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CN1834705A - Optical film, optical compensation film and production method, polarizing plate and liquid crystal display device - Google Patents

Optical film, optical compensation film and production method, polarizing plate and liquid crystal display device Download PDF

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Publication number
CN1834705A
CN1834705A CN 200610055064 CN200610055064A CN1834705A CN 1834705 A CN1834705 A CN 1834705A CN 200610055064 CN200610055064 CN 200610055064 CN 200610055064 A CN200610055064 A CN 200610055064A CN 1834705 A CN1834705 A CN 1834705A
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phenyl
film
ester
acid
group
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村上隆
清水邦夫
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Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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Abstract

An object of the present invention is to provide an optical film with little change in retardation due to long-term use, an optical compensation film with excellent uniformity of retardation and little change in retardation with environmental change by using the optical film as a support, and a polarizing plate and a liquid crystal display device with excellent color reproducibility by significantly reducing heat generation by an LED backlight and change in visibility with environmental change. A method for producing an optical film, which comprises melt-casting a composition comprising a cellulose resin and a plasticizer to form a film, wherein the amount of residual sulfuric acid in the cellulose resin is in the range of 0.1 to 50 ppm, and the composition comprises a polymer having a weight-average molecular weight of 500 to 30000 or less obtained by polymerizing an ethylenically unsaturated monomer or an acrylic polymer having a weight-average molecular weight of 500 to 30000 or less.

Description

Optical thin film and optical compensating film and method for making, Polarizer and liquid crystal indicator
Technical field
The present invention relates to optical thin film, the preparation method of optical thin film, optical compensating film, the preparation method of optical compensating film, Polarizer and liquid crystal indicator, in more detail, relate to because the long-term optical path difference optical thin film with low uncertainty that is caused that uses, even and if then relate to by making and carry out hot-stretch used as support, its transparency and planarity can be not destroyed yet, the excellent in uniform of optical path difference, optical compensating film with low uncertainty with environmental change, and then also relate to owing to the heating of optics LED-backlit and the reduction that is changed significantly of the visibility that environmental change causes, the Polarizer that color reproduction is good, liquid crystal indicator.
Background technology
Because LCD (LCD) is low-voltage, low power consumption, particularly can slimming, be widely adopted as the display device of PC, TV, monitor, portable data assistance etc.The basic comprising of this LCD is for example in the both sides of liquid crystal cell Polarizer to be set.
, Polarizer only allows the light of the plane of polarization of certain orientation to pass through, and bearing the variation that makes liquid crystal aligning in LCD becomes visual vital role.That is, the performance of Polarizer is being controlled the performance of LCD to a great extent.Polarizer generally be by by absorption iodine or dyestuff and the positive and negative both sides that the polarizing film that the polyvinyl alcohol film etc. of orientation constitutes takes place constitute with transparent resin bed lamination.As this transparent resin bed, cellulose ester films such as tri acetyl cellulose very suitablely use as protective film because its birefringence is little.
In recent years, LCD is developed in order to make as an alternative the monitor of CRT reach big picture high image qualityization.The thing followed is; liquid crystal is with Polarizer strict to protective film; because particularly cellulose ester film has water absorptivity; be subjected to the influence of environment easily; its result; in situation about being assembled into owing to change of optical property in the liquid crystal indicator, exist the problem that characteristics such as visibility change easily.Particularly cellulose ester film is as the situation of the optical compensating film or its supporting carrier film that are used to enlarge the visual angle, and strong request improves the stability of optical path difference to environmental change.
On the other hand, the preparation method of cellulose ester film generally adopts solution casting method.This method is cellulose esters to be dissolved in the solvent of halogenated hydrocarbon solvent etc. form the so-called solution that mixes, with this solution casting on endless metal belt that rotates as the metal support or rotary drum and form film.After the curtain coating, a part of solvent is dry on support, the film that curing obtains to be peeled off from support, the solvent seasoning with remnants obtains cellulose ester film.
This method be owing to must remove the inner remaining solvent of film, make drying production line, drying energy and be used for the equipment and the preparation cost of the recovery of vaporized solvent and regenerating unit etc. huge, thereby make cutting down cost also become problem.
As the means that solve above-mentioned problem, for example, the optical thin film of record has the cellulose ester film that adopts the fusion The tape casting to form in the patent documentation 1.By such formation, can obtain optical thin film optics, physics, excellent size stability, but people require further to improve the stability of above-mentioned optical path difference to environmental change.
In addition; about optical compensating film; technology as described below was once disclosed; promptly; the tri acetyl cellulose film that the solution casting system of use film forms is as support; being coated with the polymeric layer with optical compensation function on support also at high temperature stretches with support; can easily provide thus given desired phase differential optical compensating film (for example; with reference to patent documentation 2); but in the past; for can be used as the tri acetyl cellulose film that employing solution casting system embrane method that protective film for polarizing plate uses makes; if except film making process; polymeric layer with optical compensation function is set in addition again, at high temperature stretches then, will occur being easy to generate because the problem of the irregular optical path difference unevenness that causes that stretches.Therefore, as support, even require a kind of employing pyroprocessing to carry out the optical thin film that hot-stretch also is difficult to destroy the excellent in uniform of the transparency and planarity, optical path difference.
In addition, in the situation that optical compensating film is assembled into liquid crystal indicator, also require to improve heating that causes by type optics LED-backlit under using in the liquid crystal indicator and the visibility variation that brings by environmental change.
(patent documentation 1) spy opens the 2000-352620 communique
(patent documentation 2) spy opens the 2004-4474 communique
Summary of the invention
Therefore, the present invention finishes in view of above-mentioned problem, its purpose is, provide a kind of because the long-term optical thin film with low uncertainty that uses the optical path difference that causes, and then pass through used as support, a kind of hot-stretch also is difficult to destroy the transparency and planarity, optical path difference excellent in uniform, the optical compensating film with low uncertainty of the optical path difference brought because of environmental change even provide, and then provides a kind of because the optics LED-backlit is generated heat and the good Polarizer and the liquid crystal indicator of the reduction that is changed significantly, color reproduction of the visibility that brings because of environmental change.
In addition, also provide that the high halogenated hydrocarbons series solvent of a kind of not environment for use load is made, high performance optical thin film and optical compensating film.
Above-mentioned problem of the present invention can be finished by following formation.
1. the preparation method of optical thin film, it is characterized in that, this method is the preparation method who the composition that contains celluosic resin and plastifier is carried out the optical thin film of fusion casting film, wherein, the residual sulfuric acid amount of above-mentioned celluosic resin in the scope of 0.1～50ppm, above-mentioned composition contain by the weight-average molecular weight that the alkene polymerization of unsaturated monomers is obtained be more than 500 to polymkeric substance below 30000 or weight-average molecular weight be to the acrylic acid series polymeric compounds below 30000 more than 500.
2. the preparation method of the optical thin film described in above-mentioned 1 is characterized in that, above-mentioned celluosic resin is the mixed aliphatic ester of total acyl substituted degree 2.5～2.9, number-average molecular weight (Mn) 70000～200000.
3. the preparation method of the optical thin film described in above-mentioned 1 or 2 is characterized in that, it is that plastifier, polyester are that plastifier, citrate are that plastifier and phthalic ester are plastifier that in the above-mentioned plastifier at least a kind is selected from polyol ester.
4. the preparation method of above-mentioned 1～3 optical thin film described in wantonly 1 is characterized in that above-mentioned residual sulfuric acid amount is in the scope of 0.1～45ppm.
5. the preparation method of above-mentioned 1～4 optical thin film described in wantonly 1 is characterized in that above-mentioned composition contains ultraviolet light absorber, and the weight-average molecular weight of this ultraviolet light absorber is in 490～50000 scope.
6. the preparation method of above-mentioned 1～5 optical thin film described in wantonly 1 is characterized in that, above-mentioned composition contains hindered amine system or the hindered phenol based compound of 0.01～5 quality %.
7. optical thin film is characterized in that, this optical thin film is to adopt the preparation method of above-mentioned 1～6 optical thin film described in wantonly 1 to prepare.
8. the preparation method of optical compensating film is characterized in that, polymeric layer is set on the optical thin film described in above-mentioned 7 and stretches.
9. the preparation method of the optical compensating film described in above-mentioned 8 is characterized in that, above-mentioned polymeric layer constitutes by a kind that is selected from polyetherketone, polyamide, polyester, polyimide, polyamidoimide and the polyester-imide at least.
10. the preparation method of the optical compensating film described in above-mentioned 8 or 9 is characterized in that, the draft temperature B during above-mentioned stretching represents with following formula (I).
Melt temperature A-100 ℃≤draft temperature of formula (I) B≤melt temperature A-40 ℃
(in the formula, melt temperature A represents the temperature of optical thin film melt-flow time-delay)
11. optical compensating film is characterized in that, this optical compensating film is to adopt the preparation method of above-mentioned 8～10 optical compensating films described in wantonly 1 to prepare.
12. Polarizer is characterized in that, has the optical compensating film described in the optical thin film described in above-mentioned 7 or above-mentioned 11 at least one side surface.
13. liquid crystal indicator is characterized in that, has the Polarizer described in above-mentioned 12 at least one side surface.
14. the liquid crystal indicator described in above-mentioned 13 is characterized in that, backlight is LED.
(effect of invention)
One class can be provided in the present invention because the long-term optical thin film with low uncertainty that uses the optical path difference that is caused.And then pass through used as support, even provide a class to carry out its transparency of hot-stretch and planarity is not fragile yet, the optical compensating film with low uncertainty of optical path difference excellent in uniform, the optical path difference that causes because of environmental change, and then can provide heating that a class causes by the optics LED-backlit and the good Polarizer and the liquid crystal indicator of the reduction that is changed significantly, color reproduction of the visibility that brings because of environmental change.
In addition, the present invention also provides class preparation, the high performance optical thin film of halogen series solvent that the environment for use load is not high.
Embodiment
Below explain and be used to implement preferred plan of the present invention, but the present invention is not subjected to their qualification.
The 1st purpose of the present invention is, obtain because the long-term optical thin film with low uncertainty (being also referred to as cellulose ester film among the present invention) that uses the optical path difference that is caused, and then, the 2nd purpose of the present invention is, by with this optical thin film as support, can easily obtain desirable phase differential, obtain the excellent in uniform of the transparency, planarity, optical path difference, with the optical path difference of environmental change optical compensating film with low uncertainty.And then the 3rd purpose of the present invention is by using above-mentioned optical thin film, optical compensating film, to obtain the reduction that is changed significantly owing to the visibility that heating and environmental change caused of optics LED-backlit, Polarizer, liquid crystal indicator that color reproduction is good.
The present inventor has carried out deep research to above-mentioned problem, found that, above-mentioned problem can reach by the preparation method of the following stated optical thin film, this method is to contain the preparation method of optical thin film of the composition fusion casting film of celluosic resin and plastifier, it is characterized in that, in the method, the residual sulfuric acid amount of above-mentioned celluosic resin is in the scope of 0.1～50ppm, and above-mentioned composition contains and obtains by the alkene polymerization of unsaturated monomers, weight-average molecular weight be more than 500 to polymkeric substance below 30000 or weight-average molecular weight be to the acrylic acid series polymeric compounds below 30000 more than 500.
Promptly, the present inventor is through detailed research, found that, in the heat fusing method, promptly adopt in the method for fusion curtain coating legal system film of the not big halogen series solvent of the load of environment for use, good in order to obtain a class optical characteristics and moisture-penetrability, even long-term simultaneously the use, the optical thin film that the stability of its optical path difference is also very high, as long as when carrying out casting film, select some specific compound as specific celluosic resin and the polymkeric substance that contains at this celluosic resin, just can improve the stability of the optical path difference of optical thin film significantly.
And then find, by on above-mentioned optical thin film, being provided with by at least a kind that is selected from polyetherketone, polyamide, polyester, polyimide, polyamidoimide and polyester-imide polymeric layer that constitutes, the optical compensating film of making together with support stretches can obtain the excellent in uniform of the transparency, planarity, optical path difference, with the optical path difference of environmental change optical compensating film with low uncertainty.
The special discovery, optical compensating film of the present invention preferably adopts the preparation method of the following stated optical compensating film to prepare, and it is characterized in that, on the optical thin film that the fusion casting film obtains polymeric layer is set, draft temperature B when stretching together with support is represented by following formula (I)
Melt temperature A-100 ℃≤draft temperature of formula (I) B≤melt temperature A-40 ℃
(in the formula, melt temperature A represents the temperature of the melt-flow time-delay of optical thin film).
Said fusion curtain coating among the present invention is meant under the condition of not using solvent actually the celluosic resin heating and melting and then, will contains the fused mass curtain coating of mobile celluosic resin to demonstrating mobile temperature, and it is defined as the fusion curtain coating.The method of forming of heating and melting in more detail, can be divided into several classes such as melt extruding the method for forming, shaping method to suppress, blown film method, injection moulding, blow molding method, drawing and forming method.Wherein, in order to obtain all good optical compensating films of performance such as physical strength and surface accuracy, preferred molten extrusion molding.Herein, with film constituent material heating, make it flowability occur after, be expressed on rotary drum or the endless belt and make film, this method is called fusion curtain coating system embrane method, this method is included among the preparation method of fused films of the present invention.
Below describe each key element of the present invention respectively in detail.
(polymkeric substance)
Optical thin film of the present invention is characterised in that it contains the weight-average molecular weight that obtains by the alkene polymerization of unsaturated monomers is to the polymkeric substance below 30000, plastifier and celluosic resin more than 500.
And then, optical thin film of the present invention is characterised in that, its contain weight-average molecular weight be more than 500 to the acrylic acid series polymeric compounds below 10000, plastifier and celluosic resin, this acrylic acid series polymeric compounds is preferably the acrylic acid series polymeric compounds that has cyclohexyl on the acrylic acid series polymeric compounds that has aromatic rings on the side chain or the side chain.
As long as the weight-average molecular weight of polymkeric substance of the present invention is 500～30000, then the intermiscibility with celluosic resin is good, and also can not cause evaporation and volatilization in film-forming process.Especially; for the acrylic acid series polymeric compounds that has cyclohexyl on acrylic acid series polymeric compounds that has aromatic rings on acrylic acid series polymeric compounds, the side chain or the side chain; if its weight-average molecular weight is preferably 500～10000; more preferably 500～5000; so just can make except above-mentioned effect; the cellulose ester film of system behind the film transparent good, moisture permeability is also extremely low, demonstrates the good performance as Polarizer usefulness protective film.
Since the weight-average molecular weight of polymkeric substance of the present invention be 500 or more to below 30000, so can think and be between oligomer and the low-molecular weight polymer.For synthetic this polymkeric substance, wish to adopt the following stated method, that is,, be not difficult to control molecular weight and the excessive situation of molecular weight in the common polymerization with regard to not occurring in, thereby molecular weight is met the requirements according to this method.As this class polymerization, can list the method for peroxidic polymerization initiators such as using cumene peroxide or tert-butyl hydroperoxide, use is than the common polymerization method of the polymerization initiator of volume more, except polymerization initiator, also use the method for chain-transferring agents such as sulfhydryl compound or phenixin, except polymerization initiator, also use the method for polymerization terminators such as benzoquinones or dinitro benzene, and the spy opens 2000-128911 number or special opening used the compound with a mercapto and secondary hydroxyl in the 2000-344823 communique, perhaps, the polymerization catalyst of this compound and organometallics and usefulness is carried out method of bulk polymerization etc., any method is all preferably used in the present invention, especially preferably adopts the method for putting down in writing in this communique.
List monomer below, but be not subjected to their qualification the monomeric unit of the useful conduct formation polymkeric substance of the present invention.
As the alkene unsaturated monomer unit that constitutes the polymkeric substance that obtains by the alkene polymerization of unsaturated monomers: as vinyl esters, for example can list vinyl acetate, propionate, vinyl butyrate, valeric acid vinyl acetate, new vinyl acetate acid, vinyl caproate, capric acid vinyl acetate, vinyl laurate, myristic acid ethene ester, palmitic acid vinyl acetate, stearic acid vinyl ester, cyclohexane-carboxylic acid vinyl acetate, sad vinyl acetate, metering system vinyl acetate, Vinyl crotonate, sorbic acid vinyl acetate, vinyl benzoate, vinyl cinnamate etc.; As acrylate, for example can list methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), acrylic acid pentyl ester (n-, i-, s-), Hexyl 2-propenoate (n-, i-), acrylic acid heptyl ester (n-, i-), 2-ethyl hexyl acrylate (n-, i-), acrylic acid ester in the ninth of the ten Heavenly Stems (n-, i-), acrylic acid myristin (n-, i-), cyclohexyl acrylate, acrylic acid (2-ethylhexyl) ester, benzyl acrylate, phenylethyl, acrylic acid (6-caprolactone), acrylic acid (2-hydroxyethyl) ester, acrylic acid (2-hydroxypropyl) ester, acrylic acid (3-hydroxypropyl) ester, acrylic acid (4-hydroxybutyl) ester, acrylic acid (2-hydroxybutyl) ester, acrylic acid is to the hydroxymethyl phenyl ester, acrylic acid is to (2-hydroxyethyl) phenyl ester etc.; As methacrylate, can list those ester classes that the aforesaid propylene acid esters changed to methacrylate; As unsaturated acid, can list for example acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid etc.The polymkeric substance that is made of above-mentioned monomer can be a multipolymer, also can be homopolymer, the multipolymer of the homopolymer of preferred vinyl ester, the multipolymer of vinyl esters, vinyl esters and acrylic or methacrylic acid esters.
In the present invention, so-called acrylic acid series polymeric compounds (being called acrylic acid series polymeric compounds simply) is meant the alkyl acrylate of the monomeric unit that does not have aromatic rings or cyclohexyl or the homopolymer or the multipolymer of alkyl methacrylate.The acrylic acid series polymeric compounds that has aromatic rings on the so-called side chain is meant and contains the acrylate monomeric units that must have aromatic rings or the acrylic acid series polymeric compounds of methacrylate monomers unit.In addition, have the acrylic acid series polymeric compounds of cyclohexyl on the so-called side chain, be meant and contain the acrylate monomeric units with cyclohexyl or the acrylic acid series polymeric compounds of methacrylate monomers unit.
As the acrylate monomer that does not have aromatic rings and cyclohexyl, for example can list methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), acrylic acid pentyl ester (n-, i-, s-), Hexyl 2-propenoate (n-, i-), acrylic acid heptyl ester (n-, i-), 2-ethyl hexyl acrylate (n-, i-), acrylic acid ester in the ninth of the ten Heavenly Stems (n-, i-), acrylic acid myristin (n-, i-), acrylic acid (2-ethylhexyl) ester, acrylic acid (6-caprolactone), acrylic acid (2-hydroxyethyl) ester, acrylic acid (2-hydroxypropyl) ester, acrylic acid (3-hydroxypropyl) ester, acrylic acid (4-hydroxybutyl) ester, acrylic acid (2-hydroxybutyl) ester, acrylic acid (2-methoxy ethyl) ester, acrylic acid (2-ethoxyethyl group) etc., perhaps the aforesaid propylene acid esters is changed to those ester classes of methacrylate.
Acrylic acid series polymeric compounds is the homopolymer or the multipolymer of above-mentioned monomer, preferably has more than the methacrylate monomer unit 30 quality %, and, preferably have more than the methyl methacrylate monomer unit 40 quality %.The homopolymer of preferred especially methyl acrylate or methyl methacrylate.
As acrylic or methacrylic acid ester monomer with aromatic rings, for example can list, phenyl acrylate, phenyl methacrylate, acrylic acid (2 or 4-chlorphenyl) ester, methacrylic acid (2 or 4-chlorphenyl) ester, acrylic acid (2 or 3 or 4-ethoxy carbonyl phenyl) ester, methacrylic acid (2 or 3 or 4-ethoxy carbonyl phenyl) ester, acrylic acid (o or m or p-tolyl) ester, methacrylic acid (o or m or p-tolyl) ester, benzyl acrylate, benzyl methacrylate, phenylethyl, the methacrylic acid phenethyl ester, acrylic acid (2-naphthyl) esters etc. preferably use benzyl acrylate, benzyl methacrylate, acrylic acid ethoxyphenyl ester, the methacrylic acid phenethyl ester.
Have on the side chain in the acrylic acid series polymeric compounds of aromatic rings, preferably contain acrylate monomeric units or methacrylate monomers unit 20～40 quality %, and contain methacrylate monomer unit or methyl methacrylate monomer unit 50～80 quality % with aromatic rings.In this polymkeric substance, preferably contain acrylate monomeric units or methacrylate monomers unit 2～20 quality % with hydroxyl.
As acrylate monomer with cyclohexyl, for example can list, cyclohexyl acrylate, cyclohexyl methacrylate, acrylic acid (4-methylcyclohexyl) ester, methacrylic acid (4-methylcyclohexyl) ester, acrylic acid (4-ethyl cyclohexyl) ester, methacrylic acid (4-ethyl cyclohexyl) ester etc. preferably use cyclohexyl acrylate and cyclohexyl methacrylate.
Have on the side chain in the acrylic acid series polymeric compounds of cyclohexyl, suit to contain acrylate monomeric units or methacrylate monomers unit 20～40 quality %, and preferably contain 50～80 quality % with cyclohexyl.In addition, in this polymkeric substance, preferably contain acrylate monomeric units or methacrylate monomers unit 2～20 quality % with hydroxyl.
Have on the polymkeric substance that obtains by above-mentioned alkene polymerization of unsaturated monomers, acrylic acid series polymeric compounds, the side chain appointing in the acrylic acid series polymeric compounds that has cyclohexyl on the acrylic acid series polymeric compounds of aromatic rings and the side chain-kind all good with the intermiscibility of celluosic resin; can not evaporate or volatilize at the film-forming process that adopts the fusion curtain coating; highly productive; good as Polarizer with the retention of protective film; moisture permeability is little, excellent size stability.
Of the present invention have the acrylate monomer of hydroxyl or the situation of methacrylate monomers is not a homopolymer, but the formation unit of multipolymer.Under this situation, the acrylate monomeric units or the methacrylate monomers unit that preferably have hydroxyl contain 2～20 quality % at acrylic acid series polymeric compounds.
In the present invention, the also preferred polymkeric substance that has hydroxyl on the side chain that uses.As monomeric unit with hydroxyl, same with above-mentioned monomer, preferred acrylate or methacrylate, for example can list, acrylic acid (2-hydroxyethyl) ester, acrylic acid (2-hydroxypropyl) ester, acrylic acid (3-hydroxypropyl) ester, acrylic acid (4-hydroxybutyl) ester, acrylic acid (2-hydroxybutyl) ester, acrylic acid-p-hydroxymethyl phenyl ester, acrylic acid-p-(2-hydroxyethyl) phenyl ester or these acrylic acid are replaced to those ester classes that methacrylic acid forms are preferably 2-Hydroxy ethyl acrylate and methacrylic acid-2-hydroxy methacrylate.The acrylate monomeric units or the methacrylate monomers unit that have hydroxyl in polymkeric substance preferably contain 2～20 quality % at polymkeric substance, more preferably contain 2～10 quality %.
If resembling, above-mentioned polymkeric substance contains the monomeric unit that 2～20 quality % have hydroxyl above-mentioned; then can have following effect; promptly; no matter be all good with intermiscibility, retention, the dimensional stability of celluosic resin; not only moisture permeability is little; and, can improve the permanance of Polarizer with good especially with the cementability of the polarizer of protective film as Polarizer.
In addition, in the present invention, has hydroxyl on the end of at least one side of preferred polymers main chain.Make the main chain end have the method for hydroxyl, so long as the method that makes the main chain end have hydroxyl does not just have particular determination, can adopt following method to obtain: use azo two (2-hydroxyethyl butyric ester) etc. has the method for the radical polymerization initiator of hydroxyl, use 2 mercapto ethanol etc. has the method for the chain-transferring agent of hydroxyl, use has the method for the polymerization terminator of hydroxyl, make end have the method for hydroxyl by the active ion polymerization, use special open 2000-128911 number or the 2000-344823 communique in such compound with a mercapto and secondary hydroxyl, perhaps the polymerization catalyst of this compound and organometallics and usefulness is carried out the method for bulk polymerization etc., the method for putting down in writing in preferred especially this communique.Adopt with this communique in put down in writing the polymkeric substance that relevant method is made, preferably use the commercially available comprehensive ア Network ト Off ロ that grinds chemical company's system a series of.
Above-mentioned end has the polymkeric substance that has hydroxyl on the polymkeric substance of hydroxyl and/or the side chain, in the present invention, has the intermiscibility that significantly improves polymkeric substance, the effect of the transparency.
These polymkeric substance preferably contain 1～20 quality % at optical thin film, especially preferably contain 3～15 quality %.
(celluosic resin)
Be described in detail the celluosic resin that uses among the present invention below.
Optical thin film of the present invention adopts fusion curtain coating legal system to be equipped with.Because the fusion The tape casting can reduce the organic solvent use amount when the preparation film significantly, therefore compare with a large amount of solution casting methods with an organic solvent in the past, can obtain the film that environmental suitability increases substantially.
Said fusion curtain coating among the present invention, be in fact do not use solvent but with the celluosic resin heating and melting to demonstrating mobile temperature and making the method for film with it, be for example the celluosic resin of flowability to be extruded the method for making film from the mouth mould.
As the celluosic resin that constitutes optical thin film, so long as celluosic resin that can fusion system film does not just have particular determination, also can use for example aromatic carboxylic acid esters etc., if, preferably use cellulosic low-grade fatty acid ester in view of the characteristic of the film that can access optical characteristics etc.Among the present invention, lower fatty acid in the cellulosic low-grade fatty acid ester is meant that carbon number is at the fatty acid below 5, as the preference of cellulosic low-grade fatty acid ester, can list for example cellulose ethanoate, cellulose propionate, cellulose butylate, cellulose pivalate etc.In order to have mechanical characteristic and fusion system film both sides concurrently, can use the mixed aliphatic ester of cellulose ethanoate propionic ester, cellulose ethanoate propionic ester butyric ester, cellulose propionate butyric ester or cellulose acetate butyrate etc.In addition, for the general tri acetyl cellulose that belongs to celluosic resin that uses in the solution casting system film, owing to be the decomposition temperature celluosic resin higher than melt temperature, so in the fusion system of the being difficult to use in embrane method.
Therefore; most preferred cellulosic low-grade fatty acid ester is the following stated cellulose esters: the acyl group with carbon number 2～4 is as substituting group; when the degree of substitution of acetate, be that the degree of substitution of acetyl group is as X; by the organic acid degree of substitution of carbon number 3～5, promptly, the acyl group of particularly deriving, for example by the aliphatics organic acid of carbon number 3～5; the degree of substitution of acyl group such as propiono or bytyry preferably satisfies following formula (2), (3) during as Y.
Formula (2) 2.5≤X+Y≤2.9
Formula (3) 0.1≤Y≤2.0
Wherein, especially preferably use the cellulose ethanoate propionic ester, wherein preferably use the cellulose esters of 1.5≤X≤2.5,0.5≤Y≤1.0.Do not existed as hydroxyl usually by the part of acyl substituted.They can synthesize according to known method.
The acyl substituted degree of 2,3,6 acyl groups of the glucose unit of preferred use cellulose esters adds up to 2.0～2.9 scope, and the average substitution degree of 6 acyl groups is 0.5～0.9 cellulose esters.
The ratio of its weight-average molecular weight of the celluosic resin that uses among the present invention Mw/ number-average molecular weight Mn is preferably 1.0～5.5, is preferably 1.4～5.0 especially, and more preferably 2.0～3.0.In addition, use preferably that Mw is 100,000～500,000, preferred especially 200,000～400,000 celluosic resin.
The mean molecular weight of celluosic resin and molecular weight distribution can use high performance liquid chromatograph to carry out according to known method.Calculate number-average molecular weight, weight-average molecular weight with it.
Condition determination is as follows.
Solvent: methylene chloride
Post: Shodex K806, K805, K803 (clear and electrician's (strain) system couples together use with 3 posts)
Column temperature: 25 ℃
Sample solution concentration: 0.1 quality %
Detecting device: RI Model 504 (GL サ イ エ Application ス corporate system)
Pump: L6000 (Hitachi (strain) system)
Flow: 1.0ml/min
Calibration curve: use 13 calibration curves that sample is made by polystyrene standard STK standard polystyrene (eastern ソ one (strain) system) Mw=1000000～500.13 samples are preferably roughly uniformly-spaced gathered.
The raw cellulose of the celluosic resin that uses among the present invention can be wood pulp or velveteen, and wood pulp can also can be from broad leaf tree from conifer, more preferably conifer.The viewpoint of fissility is considered during from the system film, preferably uses velveteen.Can mix use aptly by these celluosic resins of making, perhaps use separately.
For example, celluosic resin from velveteen: from the celluosic resin of wood pulp (conifer): the ratio from the celluosic resin of wood pulp (broad leaf tree), can use according to 100: 0: 0,90: 10: 0,85: 15: 0,50: 50: 0,20: 80: 0,10: 90: 0,0: 100: 0,0: 0: 100,80: 10: 10,85: 0: 15,40: 30: 30 ratio.
Celluosic resin, for example, can by with the hydroxyl of raw cellulose with acetic anhydride, propionic andydride and/or butyric anhydride, acetyl group, propiono and/or bytyry replaced in above-mentioned scope according to conventional method and to obtain.The synthetic method of this celluosic resin does not have particular determination, can reference example as, spy open flat 10-45804 number or special table flat 6-501040 number in the method for record synthesize.Perhaps can use the spy to open the cellulose esters of putting down in writing among the 2005-281645.
The degree of substitution of acyl groups such as acetyl group, propiono, bytyry can be measured according to ASTM-D817-96.
In addition, industrial is that sulfuric acid is come the synthetic cellulose resin as catalyzer, but this sulfuric acid can't be removed fully, residual sulfuric acid can cause various decomposition reactions when fusion system film, thereby the quality to the cellulose ester film that obtains exerts an influence, and therefore, the residual sulphur acid content in the celluosic resin that uses among the present invention should be scaled by element sulphur in the scope of 0.1～50ppm, this is a feature of the present invention, preferably in the scope of 0.1～45ppm.Can think that they are contained with the form of salt.If the content of residual sulfuric acid surpasses 50ppm, then can not get effect of the present invention, if below 45ppm, then except obtaining effect of the present invention, therefore the attachment of the extruding dies in the time of can also reducing heat fusing (ダ イ リ Star プ) portion is preferred.In addition, owing to be difficult to breakage during hot-stretch and during the shearing after the hot-stretch, be preferred therefore.Preferred residual sulphur acid content is few, but in order to make it less than 0.1ppm, makes the burden of washing procedure of celluosic resin excessive, therefore not only bad, and opposite, often becomes damaged easily, is not preferred therefore.This is because along with the increase of washing times, may exert an influence to resin, but its reason is still not fully aware of.The more preferably scope of 0.1～30ppm.The content of residual sulfuric acid can adopt following determination method to measure.
(residual sulphur acid content determination method)
＜pre-service 〉
Take by weighing sample 500mg (M) in the container of polypropylene system, add ultrapure water 10ml.
After it was disperseed 30 minutes with ultrasonic washer, (0.45 μ m) filtered with the water system chromatodisk.With it as sample.
(SO 4Quantitatively)
＜device〉ion chromatograph DIONEX makes DX-120
＜post〉IonPac AG14 (4mm)+IonPac AS14 (4mm)
＜canceller〉ASRS-ULTRAII (4mm)
＜eluent〉3.5mM-Na 2CO 31.0mM-NaHCO 3
＜SRS electric current〉50mA
＜flow velocity〉1.0ml/min
＜injection rate IR〉25 μ l
＜conversion method 〉
Content (ppm)=measured value (mg/l)/1000 * 10/M (mg) * 1000000
The wash ratio of synthetic celluosic resin adopts the situation of solution casting method to carry out more fully, thus, the residual sulphur acid content is in the above-mentioned scope, when adopting fusion curtain coating thin films, can obtain the film that adhering to of die orifice portion alleviates, planarity is good, can obtain change in size, physical strength, the transparency, anti-moisture-penetrability, Rt value described later, the equal good film of Ro value.
In addition, the limiting viscosity of celluosic resin is preferably 1.5～1.75g/cm 3, 1.53～1.63 scope more preferably.
In addition, the preferred bright spot few foreign when making film of the celluosic resin that uses among the present invention.So-called bright spot foreign matter is meant, when 2 Polarizer square crossing ground are disposed, dispose cellulose ester film between the two, when accepting to observe cellulose ester film, because light leak and can see the bright spot of the light of light source from the light of the light source of a side and from the another side.Wish that estimate the Polarizer that uses this moment is to be made of the protective film that does not have the bright spot foreign matter, glass plate is preferably used in the protection of polarizer.The bright spot foreign matter is considered to be in not acetoxylation that celluosic resin contains or the cellulose of low acetate degree is one of its reason, if use the celluosic resin of bright spot few foreign, then with fusion celluosic resin filter, perhaps also can or be used for obtaining at least one operation of sedimentary operation in the operation of celluosic resin post-synthesis phase, it as a solution state, is similarly removed the bright spot foreign matter via filtering operation.Molten resin is owing to the viscosity height, so the latter's method efficient height.
The thickness of film is thin more, and the bright spot foreign matter number of per unit area is just few more, and the content of the celluosic resin that film contains is few more, and then the bright spot foreign matter is just few more, and the number of the bright spot foreign matter of bright spot diameter more than 0.01mm is preferably at 200/cm 2Below, more preferably at 100/cm 2Below, more preferably at 50/cm 2Below, further preferably at 30/cm 2, further preferably at 10/cm 2Below, most preferably do not have fully.In addition, for the bright spot below 0.005～0.01mm, preferably at 200/cm 2Below, more preferably at 100/cm 2Below, more preferably at 50/cm 2Below, further preferably at 30/cm 2Below, further preferably at 10/cm 2Below, most preferably do not have fully.
In the situation of removing the bright spot foreign matter by melt filteration, with the celluosic resin fusion is filtered compare, filter by interpolation being mixed with the composition that plastifier, deterioration preventing agent, antioxidant etc. form, its bright spot foreign matter remove the efficient height, be preferred.Certainly, when the synthetic cellulose resin, it is dissolved in the solvent filters again, so also can reduce the bright spot foreign matter.The solution that has mixed ultraviolet light absorber and other additives aptly also can filter.The preferred viscosity at the fused mass that contains celluosic resin of filtration is that the condition below the 10000P is carried out, more preferably below 5000P, especially preferably below 1000P, further preferably below 500P.As filtering material, preferably use known in the past those filtering materials of the fluororesin etc. of glass fibre, cellulose fibre, filter paper, tetrafluoroethylene resin etc., preferred especially pottery, the metal etc. of using.As absolute filtering accuracy, preferably use the following aperture of 50 μ m, more preferably below the 30 μ m, further below the preferred 10 μ m, below the further preferred 5 μ m.Also can be with they suitable being used in combination.Filtering material can use plane or depth type, and the depth type is difficult to stop up mesh, therefore preferred the use.
In other embodiment, the celluosic resin of raw material also can use by the celluosic resin that after being dissolved in solvent at least solvent seasoning is obtained.At this moment, use in plastifier, ultraviolet light absorber, anti-degradation, antioxidant and matting agent be dissolved in the solvent at least more than a kind after carry out drying and the celluosic resin that obtains.As solvent, can use methylene chloride, methyl acetate, dioxolanes etc. to can be used for the good solvent of solution casting method, also can use the lean solvent of methyl alcohol, ethanol, butanols etc. simultaneously.In course of dissolution, also can be cooled to below-20 ℃, perhaps be heated to more than 80 ℃.If use this celluosic resin, each additive in the time of often can easily making molten condition becomes evenly, makes optical characteristics become even.
(plastifier)
In the optical thin film of the present invention, with above-mentioned polymkeric substance and with and add plastifier, from improve engineering properties, give flexibility, give water absorption resistance, the viewpoint of upgrading that reduces the film of moisture transmitance etc. considers it is necessary.In addition, in the fusion The tape casting of carrying out in the present invention, comprise: according to the purpose of adding plastifier, interpolation by plastifier, the melt temperature that makes the film constituent material is also lower than the glass transition temperature of employed independent celluosic resin, perhaps can make the viscosity of the independent celluosic resin of the viscosity ratio of the film constituent material that contains plastifier low under identical heating-up temperature.
Herein, in the present invention, the melt temperature of so-called film constituent material is meant that this material is heated under the state that flowability occurs the heated temperature of material.
In the independent celluosic resin, if lower than glass transition temperature, the flowability of filming then can not appear being used for.But celluosic resin is more than glass transition temperature, and by absorbing heat, spring rate or viscosity reduce, thereby occur mobile.In order to make the fusion of film constituent material, the plastifier that is added has fusing point or the glass transition temperature also lower than the glass transition temperature of celluosic resin, owing to satisfy above-mentioned purpose, is preferred therefore.
As said plastifier among the present invention, there is not particular determination, preferably having can be by with the hydrogen bond of cellulose derivative or other adjuvant etc. interactional functional group taking place, so that do not make film generation preformed casse (mist degree) or can not ooze out (bleed out) from film or volatilization.
As this functional group; hydroxyl, ether, carbonyl, ester group, carboxylic acid residues, amino, imino group, amide group, imide, cyano group, nitro, sulfonyl, sulfonic acid moieties, phosphono, phosphonic acids residue etc. be can list, carbonyl, ester group, phosphono are preferably.
Example as this plastifier, preferred to use phosphate be that plastifier, phthalic ester are that plastifier, trimellitate are that plastifier, Pyromellitic Acid are that plastifier, polyol ester are that plastifier, ethyl glycolate are that plastifier, citrate are that plastifier, fatty acid ester are that plastifier, carboxylate are that plastifier, polyester are plastifier etc., and the non-phosphate that is preferably polyol ester especially and is plastifier, polyester and be plastifier, citrate and be plastifier, phthalic acid ester and be plastifier etc. is a plastifier.Aspect intermiscibility, preferably the ultraviolet light absorber of they and molecular weight described later 490～50000 is merged and use.
Polyol ester is that the ester by aliphatic polyol more than 2 yuan and monocarboxylic acid forms, and preferably has aromatic rings or cycloalkyl ring in molecule.
The polyvalent alcohol that uses among the present invention is represented by following formula (1).
Formula (1) R 1-(OH) n
(in the formula, R 1The organic group of expression n valency, n represents the positive integer more than 2)
As the example of preferred polyhydric alcohols, for example can list following those, but the present invention is not subjected to their qualification.Adonitol, arabite, ethylene glycol, diglycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1, ammediol, dipropylene glycol, tripropylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, dibutylene glycol, 1,2,4-butantriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpent-1,3,5-triol, pinacol, D-sorbite, trimethylolpropane, trimethylolethane, xylitol etc.Preferred especially triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, D-sorbite, trimethylolpropane, xylitol.
Wherein, the polyol ester that especially preferably uses the polyvalent alcohol of carbon number more than 5 to form.Preferred especially carbon number is 5～20.
Do not have particular restriction as the monocarboxylic acid that uses in the polyol ester of the present invention, can use known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylate etc.If use alicyclic monocarboxylic acid, aromatic monocarboxylate, be preferred aspect raising moisture-penetrability, the retention then.
As the example of preferred monocarboxylic acid, can list following those, but the present invention is not subjected to their qualification.
As aliphatic monocarboxylic acid, preferably use the straight chain of carbon number 1～32 or have the fatty acid of side chain.Carbon number more preferably 1～20 is preferably 1～10 especially.If make it contain acetate,, therefore be preferred then owing to the intermiscibility with cellulose derivative increases, also preferably acetate is mixed use with other monocarboxylic acid.
As preferred aliphatic monocarboxylic acid, can list acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, 2-ethyl-cyclohexane carboxylic-acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, Heptadecanoic acide, stearic acid, nonadecylic acid, arachidic acid behenic acid, lignoceric acid, hexacosoic acid, carboceric acid acid, montanic acid, melissic acid, the saturated fatty acid of lacceroic acid etc., undecenoic acid, oleic acid, sorbic acid, linoleic acid, leukotrienes, the unsaturated fatty acid of arachidonic acid etc. etc.
As the example of preferred alicyclic monocarboxylic acid, can list cyclopentane-carboxylic acid, cyclohexane-carboxylic acid, cyclooctane carboxylic acid or their derivant.
Example as preferred aromatic monocarboxylate, can list the aromatic monocarboxylate with 2 above phenyl ring of the compound that on benzoic phenyl ring, imports alkyl, biphenyl carboxylic acids, naphthalene-carboxylic acid, tetralin carboxylic acid etc. of benzoic acid, phenylacetic acid etc. or their derivant, preferred especially benzoic acid.
The molecular weight of polyol ester does not have particular restriction, is preferably 300～3000, and more preferably 350～1500.Therefore the polyol ester that molecular weight is big is difficult to volatilization, is not preferred, moisture-penetrability, and the intermiscibility of cellulose derivative aspect, the polyol ester that preferred molecular weight is little.
The carboxylic acid that uses in the polyol ester can be a kind, also can be the potpourri more than 2 kinds.In addition, the OH base in the polyvalent alcohol can be esterified fully, also can residual a part of OH base.
The concrete compound of polyol ester below is shown.
Figure A20061005506400231
Figure A20061005506400241
Figure A20061005506400251
In addition, preferably using the polyester that has aromatic rings or cycloalkyl ring in molecule is plastifier.As preferred polyester is plastifier, does not have particular determination, and preference is as the plastifier by following general formula (2) expression.
General formula (2) B-(G-A) n-G-B
(in the formula, B represents benzene monocarboxylic acid residue; G represents that the aryl-diol residue of the aklylene glycol residue of carbon number 2～12 or carbon number 6～12 or carbon number are 4～12 alkylidene oxide diol residue; A represents the alkylene dicarboxylic acids residue of carbon number 4～12 or aryl dicarboxylic acid's residue of carbon number 6～12; And n represents the integer more than 0).
The compound that the alkylene dicarboxylic acids residue that general formula (2) is the benzene monocarboxylic acid residue represented by B and the aklylene glycol residue of being represented by G or alkylidene oxide diol residue or aryl-diol residue, represented by A or aryl dicarboxylic acid's residue constitute, it can by with common polyester be that the same reaction of plastifier makes.
As the polyester that uses among the present invention is the benzene monocarboxylic acid composition of plastifier, for example have, benzoic acid, p-tert-butyl benzoic acid, o-benzene acetic acid, a phenylacetic acid, to phenylacetic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, aminobenzoic acid, acetoxy-benzoic acid etc., they can be respectively by a kind or use as the potpourri more than 2 kinds.
As polyester of the present invention is the aklylene glycol composition of the carbon number 2～12 of plastifier, and ethylene glycol is arranged, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butylene glycol, 1,3 butylene glycol, 2-methyl 1, ammediol, 1, the 4-butylene glycol, 1, the 5-pentanediol, 2,2-dimethyl-1, ammediol (neopentyl glycol), 2,2-diethyl-1, ammediol (3,3-dihydroxymethyl pentane), 2-normal-butyl-2-ethyl-1,3 propylene glycol (3,3-dihydroxymethyl heptane), the 3-methyl isophthalic acid, 5-pentanediol 1, the 6-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1, the 3-hexanediol, 2-methyl 1, the 8-ethohexadiol, 1, the 9-nonanediol, 1, the 10-decanediol, 1,12-octacosanols etc., these glycol can or use as the potpourri more than 2 kinds by a kind.
In addition, the alkylidene oxide diol component as the carbon number 4～12 of aromatic series terminal ester of the present invention for example has, diglycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol etc., and these glycol can or use as the potpourri more than 2 kinds by a kind.
Alkylene dicarboxylic acids composition as the carbon number 4～12 of aromatic series terminal ester of the present invention, for example have, succinic acid, maleic acid, fumaric acid, glutaric acid, hexane diacid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid etc., they can be respectively by a kind or use as the potpourri more than 2 kinds.Arlydene dicarboxylic acid composition as carbon number 6～12 has phthalic acid, terephthalic acid (TPA), 1,5 naphthalene dicarboxylic acids, 1,4 naphthalene dicarboxylic acids etc.
The polyester that uses among the present invention is a plastifier, and its number-average molecular weight is preferably 250～2000, more preferably in 300～1500 scope.In addition, preferably its acid number below the 0.5mgKOH/g, hydroxyl value below 25mgKOH/g, more preferably its acid number below the 0.3mgKOH/g, hydroxyl value is below 15mgKOH/g.
It is the synthesis example of plastifier that the aromatic series terminal ester of using among the present invention below is shown.
＜sample No.1 (aromatic series terminal ester sample) 〉
In reaction vessel, add 365 parts of hexane diacids (2.5 moles), 1 in the lump, 2-propylene glycol 418 parts (5.5 moles), benzoic acid 610 parts (5 moles) and as 0.30 part of the tetraisopropyl titanate of catalyzer, in nitrogen stream, stir down, install back flow condenser, Yi Bian make 1 yuan of superfluous alcohol reflux, Yi Bian continue 130～250 ℃ of heating down, acid number is reached below 2, remove the water of generation continuously.Then, under 200～230 ℃, 1.33 * 10 4～final 4 * 10 2Under the decompression below the Pa, remove and distillate branch, filter then, obtain having the aromatic series terminal ester of following proterties.
Viscosity (25 ℃, mPa.s); 815
Acid number; 0.4
＜sample No.2 (aromatic series terminal ester sample) 〉
In reaction vessel, use hexane diacid 365 parts (2.5 moles), benzoic acid 610 parts (5 moles), diglycol 583 parts (5.5 moles) and as 0.45 part of the tetraisopropyl titanate of catalyzer, in addition, fully similarly carry out with sample No.1, obtain having the aromatic series terminal ester of following proterties.
Viscosity (25 ℃, mPa.s); 90
Acid number; 0.05
＜sample No.3 (aromatic series terminal ester sample) 〉
In reaction vessel, use phthalic acid 410 parts (2.5 moles), benzoic acid 610 parts (5 moles), dipropylene glycol 737 parts (5.5 moles) and as 0.40 part of the tetraisopropyl titanate of catalyzer, in addition, fully similarly carry out with sample No.1, the aromatic series terminal ester that obtains having following proterties is a plastifier.
Viscosity (25 ℃, mPas); 43400
Acid number; 0.2
The particular compound that the aromatic series terminal ester is a plastifier below is shown, but the present invention is not subjected to their qualification.
Figure A20061005506400291
Figure A20061005506400301
The polyester that uses among the present invention is the content of plastifier, preferably contains 1～20 quality % at optical thin film, especially preferably contains 3～11 quality %.
Optical thin film of the present invention also preferably contains the plastifier beyond the above-mentioned plastifier.
By making it contain plastifier more than 2 kinds, can reduce the stripping of plastifier.Though its reason is not verified as yet, can think, can reduce per a kind addition like this, by 2 kinds of plastifier each other and and celluosic resin between interaction, can suppress stripping.
As phthalic ester is plastifier, can list diethyl phthalate, DMEP, repefral, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, terephthalic acid (TPA) two cyclohexyls or derivant etc., in addition, it is dipolymer that preferred use is opened the phthalic ester of putting down in writing in flat 11-349537 number by general formula (1) expression the spy, preferably uses paragraph numbering 23 particularly, the compound-1 of record in 26, compound-2.
General formula (1)
A:-(CH 2) n-or-(CH 2CH 2O) n-
The integer of n:1～10
R 1: the also alkyl of the carbon number 1～12 that can replace with alkoxy carbonyl
Compound-1
Figure A20061005506400322
Compound-2
Figure A20061005506400323
Phthalic ester is that the dipolymer compound is the compound that has by the structural formula of above-mentioned general formula (1) expression, can its esterification of dewatering be made by with two phthalic acids and dibasic alcohol Hybrid Heating.Phthalic ester is that the mean molecular weight of the xenyl bis-phenol based compound of dipolymer, terminal hydroxyl is preferably about 250～3000, is preferably 300～1000 especially.If below 250, then can produce the problem of thermal stability, plasticizer volatility and metastatic aspect, if and surpass 3000, then reduce, processability, the transparency and the engineering properties of fatty acid cellulose ester based resin composition had harmful effect as the intermiscibility of plastifier, plasticization capacity.
As citrate is that plastifier does not have special qualification, can list citric acid acetyl three methyl esters, acetyl triethyl citrate, acetyl tributyl citrate etc., preferably the citric acid ester compound of being represented by following general formula (3).
General formula (3)
In the formula, R 1Be hydrogen atom or aliphatic acyl radical, R 2Be alkyl.
In general formula (3), as R 1Aliphatic acyl radical do not have special restriction, preferred carbon number is 1～12, preferred especially carbon number is 1～5.Can list formoxyl, acetyl group, propiono, bytyry, valeryl, palmityl, oleoyl etc. particularly.In addition, as R 2Alkyl do not have special restriction, and can be to have in straight chain shape, the side chain any, be preferably the alkyl of carbon number 1～24, be preferably the alkyl of carbon number 1～4 especially.Can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group particularly.Especially, be the plastifier of resin, preferably R as cellulose acetate ester 1Be hydrogen atom, R 2Be the compound of methyl or ethyl, and R 1Be acetyl group, R 2Compound for methyl or ethyl.
＜R 1Method for making for the citric acid ester compound of hydrogen atom 〉
R in the citric acid ester compound that uses among the present invention 1Be the compound of hydrogen atom, can adopt known method to prepare.As known method, what can list record in No. 931781, the British patent gazette for example prepares the method for phthalyl glycolic acid ester by phthalic acid half ester and alpha-halogen alkyl acetate.Specifically, trisodium citrate, citric acid tri potassium or citric acid (following they are abbreviated as the citric acid raw material)., preferably, make and R with respect to 1 mole of trisodium citrate 2Corresponding Arrcostab α-an alkyl halogen acetates, for example monochloracetic acid methyl esters, monochloracetic acid ethyl ester etc. are with the amount more than the chemical theory, and preferred 1～10 mole, more preferably 2～5 moles are reacted.If there is moisture in the reaction system, then the yield of purpose compound reduces, and therefore, raw material uses anhydrous compound as far as possible.Can use the chain of trimethylamine, triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, dimethyl cyclohexyl amine etc. or annular aliphatic tertiary amine as catalyzer in the reaction, wherein, preferred triethylamine.Catalyst consumption with respect to 1 mole of citric acid raw material, is 0.01～1.0 mole, is preferably 0.2～0.5 mole scope.Temperature of reaction is 60～150 ℃, 1～24 hour reaction time.Reaction dissolvent is not necessary especially, can use toluene, benzene, dimethylbenzene, butanone etc.After the reaction, for example add entry, remove accessory substance and catalyzer,, go out unreacted starting compound by separated then, thereby object can be separated the oil reservoir washing.
＜R 1Method for making for the citric acid ester compound of aliphatic acyl radical 〉
R 1Be aliphatic acyl radical, R 2Citric acid ester compound of the present invention for alkyl can use above-mentioned R 1For the citric acid ester compound of hydrogen atom prepares.
That is,, make to be equivalent to R with respect to 1 mole of this citric acid ester compound 1The acyl halide, for example formyl chloride, acetyl chloride etc. of aliphatic acyl radical react for 1～10 mole.As catalyzer,, can use 0.1～2 mole of the pyridine etc. of alkalescence with respect to 1 mole of this citric acid ester compound.Solvent can not be used in reaction, carries out 1～5 hour under 80～100 ℃ of temperature.After the reaction, in reaction mixture, add entry and water-fast organic solvent, for example toluene, object is dissolved in the organic solvent, water layer is separated with organic solvent layer, with after the organic solvent layer washing, can adopt the conventional method of distillation etc. that object is separated.
The combination of the ultraviolet light absorber of citric acid ester compound that uses among the present invention and weight-average molecular weight 490～50000 aspect acquisition effect of the present invention, is preferred.
The amount of the citric acid ester compound that is added in the celluosic resin with respect to celluosic resin 100 mass parts, is preferably 5～200 mass parts, is preferably 10～200 mass parts especially.
In addition, the content of citric acid ester compound in film is preferably 1～30 quality %, is preferably 2～20 quality % especially.
Ethyl glycolate is that plastifier does not have particular determination, and can use the ethyl glycolate that has aromatic rings or cycloalkyl ring in molecule is plastifier.As ethyl glycolate is plastifier, can list for example butyl phthalyl butyl alcohol acid esters, ethyl phthalyl ethyl hexanol acid esters, methyl phthalyl ethyl hexanol acid esters etc.
As phosphate is plastifier, can list triphenyl, three cresyl phosphates, cresyl diphenyl phosphoester, octyl group diphenyl phosphoester, diphenyl xenyl phosphate, trioctylphosphine phosphate, Tributyl phosphate ester etc., among the present invention, phosphate is containing below the 40 quality % that ratio is preferably total plasticizer loading of plastifier, and the content that special preferably phosphoric acid ester is a plastifier is less than 1 quality %.More preferably do not add.
The plastifier of glycol ester system: the plastifier that can list ethylene glycol Arrcostab systems such as ethylene acetate, ethylene glycol dibutyrate particularly; The plastifier of ethylene glycol cycloalkyl esters such as ethylene glycol bisthioglycolate cyclopropyl carboxylic acid esters, ethylene glycol bisthioglycolate cyclohexane carboxylic acid ester system; The plastifier of ethylene glycol aryl esters such as ethylene glycol bisthioglycolate benzoic ether, ethylene glycol bisthioglycolate 4-methyl benzoic acid ester system.These alkylates bases, cycloalkylation thing base, aryl can be identical or different, also can further be substituted.In addition, they also can be the potpourris of alkylates base, cycloalkylation thing base, arylide base, and these substituting groups also can be used covalent bonding each other.And then, the ethylene glycol part also can be substituted, the part-structure of glycol ester also can become the part of polymkeric substance or become side group regularly, and, also can import in the part of molecular structure of adjuvants such as antioxidant, sour remover, ultraviolet light absorber.
The plastifier of glyceride system: can list glycerine Arrcostabs such as glycerol triacetate, glycerin tributyrate, glycerin diacetate caprylate, glyceryl oleate propionic ester particularly; The glycerine cycloalkyl ester of glycerine three cyclopropyl carboxylic acid esters, glycerine thricyclohexyl carboxylate etc.; Glycerine aryl esters such as tribenzoin, glycerine 4-methyl benzoic acid ester; Two glycerine Arrcostabs such as two glycerine tetracetates, two glycerine, four propionic esters, two glyceryl acetates, three caprylates, two glycerine cinnamic acid in April esters; Two glycerine cycloalkyl esters such as two glycerine Fourth Ring butyl carboxylates, two glycerine Fourth Ring amyl group carboxylates; Two glycerine aryl esters such as two glycerine, four benzoic ethers, two glycerine 3-methyl benzoic acid esters etc.These alkylates bases, naphthenic base carboxylic acid ester groups, the arylide base can be identical or different, also can further be substituted.In addition, they also can be the potpourris of alkyl, naphthenic base carboxylic acid ester groups, aryl, and these substituting groups also can be used covalent bonding each other.And then, glycerine, two glycerine portions also can be substituted, the part-structure of glyceride, two glyceride, also can become the part of polymkeric substance, perhaps become side group regularly, and, also can import in the part of molecular structure of adjuvants such as antioxidant, sour remover, ultraviolet light absorber.
The plastifier of dicarboxylic ester system: the plastifier that can list malonic acid two (dodecyl) ester (C1), dioctyl adipate (C4), dibutyl sebacate alkyl dicarboxylic aid's Arrcostabs such as (C8) system particularly; The plastifier of alkyl dicarboxylic aid's cycloalkyl ester systems such as succinic acid two ring pentyl esters, dicyclohexyl adipate; The plastifier of alkyl dicarboxylic aid's aryl esters such as succinic acid diphenyl ester, two 4-aminomethyl phenyl glutaric acid esters system; Dihexyl-1,4-cyclohexanedicarboxyester ester, didecyl dicyclo [2.2.1] heptane-2, the plastifier of naphthenic base dicarboxylic acid Arrcostabs such as 3-dicarboxylic ester system; Dicyclohexyl-1,2-cyclobutane dicarboxylic acid ester, two cyclopropyl-1, the plastifier of naphthenic base dicarboxylic acid cycloalkyl esters such as 2-cyclohexyl dicarboxylic acid ester system; Diphenyl-1,1-cyclopropyl dicarboxylic ester, two 2-naphthyls-1, the plastifier of naphthenic base dicarboxylic acid aryl esters such as 4-cyclohexanedicarboxyester ester system; The plastifier of aryl dicarboxylic acid's Arrcostabs such as diethyl phthalate, repefral, dioctyl phthalate, dibutyl phthalate, two-2-ethylhexyl phthalic ester system; The plastifier of aryl dicarboxylic acid's cycloalkyl ester systems such as phthalic acid two ring propyl ester, dicyclohexyl phthalate; The plastifier of aryl dicarboxylic acid's aryl esters such as diphenyl phthalate, two 4-aminomethyl phenyl phthalic esters system.These alkoxys, cycloalkyloxy can be identical or different, and can one replace, and these substituting groups also can further be substituted.Alkyl, naphthenic base also can be potpourris, and these substituting groups also can be used covalent bonding each other.And then the aromatic rings of phthalic acid also can be substituted, and also can be polymers such as dipolymer, trimer, tetramer.And the part-structure of phthalic ester also can become the part of polymkeric substance, perhaps becomes the side group of polymkeric substance regularly, also can import in the part of molecular structure of adjuvants such as antioxidant, sour remover, ultraviolet light absorber.
The plastifier of multi-carboxylate system: can list three (dodecyls), three cabalate, tributyl-meso-butane-1,2,3 particularly, the plastifier of alkyl polybasic carboxylic acid Arrcostabs such as 4-tetrabasic ester system; Thricyclohexyl three cabalate, three cyclopropyl-2-hydroxyl-1,2, the plastifier of alkyl polybasic carboxylic acid cycloalkyl esters such as 3-tricarballylic acid ester system; Triphenyl 2-hydroxyl-1,2,3-tricarballylic acid ester, four 3-aminomethyl phenyl tetrahydrofurans-2,3,4, the plastifier of alkyl polybasic carboxylic acid aryl esters such as 5-tetrabasic ester system; Four hexyls-1,2,3,4-cyclobutane tetracarboxylic ester, the tetrabutyl-1,2,3, the plastifier of naphthenic base polybasic carboxylic acid Arrcostabs such as 4-cyclopentane tetrabasic ester system; Fourth Ring propyl group-1,2,3,4-cyclobutane tetracarboxylic ester, thricyclohexyl-1,3, the plastifier of naphthenic base polybasic carboxylic acid cycloalkyl esters such as 5-cyclohexyl tricarboxylic ester system; Triphenyl-1,3,5-cyclohexyl tricarboxylic ester, six (4-aminomethyl phenyl)-1,2,3,4,5, the plastifier of naphthenic base polybasic carboxylic acid aryl esters such as 6-cyclohexyl hexacarboxylic acid ester system; Three (dodecyl) benzene-1,2,4-tricarboxylic ester, four octyl group benzene-1,2,4, the plastifier of aryl polybasic carboxylic acid Arrcostabs such as 5-tetrabasic ester system; Three cyclopentyl benzene-1,3,5-tricarboxylic ester, Fourth Ring hexyl benzene-1,2,3, the plastifier of aryl polybasic carboxylic acid cycloalkyl esters such as 5-tetrabasic ester system; Triphenylbenzene-1,3,5-tetrabasic ester, six 4-aminomethyl phenyl benzene-1,2,3,4,5, the plastifier of aryl polybasic carboxylic acid aryl esters such as 6-hexacarboxylic acid ester system.These alkoxys, cycloalkyloxy can be identical or different, and can one replace, and these substituting groups also can further be substituted.Alkyl, naphthenic base also can be potpourris, and these substituting groups also can be used covalent bonding each other.And then the aromatic rings of phthalic acid also can be substituted, and also can be polymers such as dipolymer, trimer, tetramer.And the part-structure of phthalic ester also can become the part of polymkeric substance, perhaps becomes the side group of polymkeric substance regularly, also can import among an one of molecular structure of adjuvants such as antioxidant, sour remover, ultraviolet light absorber.
Polymeric plasticizer: can list vinyl based polymers such as aliphatic hydrocarbon based polymer, ester ring type hydrocarbon system polymkeric substance, polyvinyl isobutyl ether, poly N-vinyl pyrrolidone particularly; Styrenics such as polystyrene, poly-4-hydroxy styrenes; Polyester such as polybutylene succinate, polyethylene terephthalate, polyethylene glycol phthalate; Polyethers such as polyethylene oxide, polypropyleneoxide; Polyamide, polyurethane, polyureas etc.Number-average molecular weight is preferably about 1000～500000, is preferably 5000～200000 especially.If below 1000, then can produce volatile problem, and if surpass 500000, then plasticization capacity reduces, and the engineering properties of celluosic resin derivative composition is had harmful effect.These polymeric plasticizers can be the homopolymer that is made of a kind of repetitive, also can be the multipolymers with multiple repetitive structure body.In addition, also above-mentioned polymkeric substance can be merged use more than 2 kinds, also can contain other plastifier, antioxidant, sour remover, ultraviolet light absorber, lubricant and matting agent etc.
These plastifier can be used singly or two or more kinds mixed.The total content of the plastifier in the film, if with respect to celluosic resin less than 1 quality %, the effect of moisture permeability that then reduces film is few, therefore be bad, if and surpass 30 quality %, problem, the rerum natura generation deterioration of film such as then cause intermiscibility easily and ooze out, therefore, be preferably 1～30 quality %.More preferably 3～25 quality % are preferably 5～20 quality % especially, and its addition can aspect acquisition effect of the present invention, be determined aptly according to the polymkeric substance that the said alkene polymerization of unsaturated monomers of the present invention is obtained and the total amount of acrylic acid series polymeric compounds.
(ultraviolet light absorber)
Said ultraviolet light absorber among the present invention, be preferably the ultraviolet light absorber of weight-average molecular weight in 490～50000 scope, as the UVA skeleton, the preferred compound that has 2 above benzotriazole skeletons at least, and this ultraviolet light absorber preferably contains the compound of weight-average molecular weight 490～2000 and the ultraviolet light absorber of weight-average molecular weight 2000～50000.
Below describe said ultraviolet light absorber among the present invention in detail.
As ultraviolet light absorber, the viewpoint of deterioration is considered from preventing polarizer or display device to be subjected to the ultraviolet ray conduct, the following ultraviolet ray of reply wavelength 370nm has the excellent absorption ability, and consider preferably few ultraviolet light absorber to the absorption of the visible light more than the wavelength 400nm from the viewpoint of liquid crystal expressivity.For example can list, oxidation of benzophenone based compound, benzotriazole based compound, salicylate based compound, cyanoacrylate based compound, triazine based compound, nickel complex salt based compound etc., preferred benzophenone based compound and painted few benzotriazole based compound.In addition, also can use the spy to open flat 10-182621 communique, spy and open the polymeric UV absorber that ultraviolet light absorber, the spy of flat 8-337574 communique record open flat 6-148430 communique record.
In these ultraviolet light absorbers, weight-average molecular weight is the ultraviolet light absorber in 490～50000 the scope, present effect of the present invention aspect, be preferred.If molecular weight is excessive, then with the intermiscibility deterioration of celluosic resin, therefore, usually use molecular weight at the ultraviolet light absorber below 490, but, less than 490 situation, can observe and cause the tendency of oozing out to film surface in weight-average molecular weight, simultaneously, have in time and pass through and painted tendency.Surpass 50000 situation in weight-average molecular weight, the tendency with the remarkable variation of intermiscibility of film resin is arranged.
In addition, the another kind of preferred version of said ultraviolet light absorber is to contain the weight-average molecular weight 490～ultraviolet light absorber (A) less than 2000 and the ultraviolet light absorber (B) of weight-average molecular weight 2000～50000 among the present invention.The ultraviolet light absorber that molecular weight is different merges use, can satisfy above-mentioned exudative and intermiscibility again when improving effect of the present invention, consider from this respect, and be preferable methods.The mixture ratio of ultraviolet light absorber (A), (B) is suitable selection the in 1: 99～99: 1 scope preferably.
Be in the scope of the present invention and have the example of ultraviolet light absorber of the compound of at least 2 above benzotriazole skeletons as the UVA skeleton as weight-average molecular weight, preferably by two benzotriazole phenol of following general formula (4) expression.
General formula (4)
(0146)
(in the formula, R 1, R 2Represent hydrogen atom respectively, replace or do not have the alkyl of the carbon number 1～20 of replacement; R 3, R 4Represent hydrogen atom, halogen atom respectively; L represents the alkylidene of carbon number 1～4.〕
As replacement atom, the substituting group of alkyl, can list halogen atom, for example chlorine atom, bromine atoms, fluorine atom etc.; Hydroxyl, phenyl (in this phenyl also can by replacements such as alkyl or halogen atoms) etc.
As concrete example by two benzotriazole base oxybenzene compounds of general formula (4) expression, those below for example can listing.But, be not subjected to their qualification.
1) RUVA-100/110 (Da mound chemistry system)
2) RUVA-206 (Da mound chemistry system)
3) Tinuvin-360 (Chiba particularization length of schooling)
4) ア デ カ ス Block LA-31 (rising sun electrification system)
5) ア デ カ ス Block LA-31RG (rising sun electrification system)
In addition, among the present invention in the said ultraviolet light absorber at least a kind is at the molar extinction coefficient at the 380nm place multipolymer at ultraviolet-absorbing monomer more than 4000 and alkene unsaturated monomer, and then, as this alkene unsaturated monomer composition, preferably has the alkene unsaturated monomer composition that has a kind of hydrophilic radical at least.
Promptly, the present invention is the multipolymer of the molar extinction coefficient at 380nm place at ultraviolet-absorbing monomer more than 4000 and alkene unsaturated monomer, if making this multipolymer contain weight-average molecular weight is 490～50000 ultraviolet-absorbing multipolymer, then can obtain to improve the optical compensating film of above-mentioned problem.
380nm place molar extinction coefficient is in the situation more than 4000, it is good to demonstrate UV absorbing properties, can obtain the effect of abundant block ultraviolet, can improve problems such as this skin turning yellow of optical compensating film is painted thus, thereby improve the transparency of optical compensating film itself.
As the ultraviolet-absorbing monomer that uses in the ultraviolet-absorbing multipolymer among the present invention, the molar extinction coefficient that can use the 380nm place is more than 4000, preferably more than 8000, more preferably at the monomer more than 10000.The molar extinction coefficient at 380nm place, must add in order to obtain desirable UV absorptive character in a large number less than 4000 situation, because the separating out to wait and bring significantly reduction of the transparency of the rising of mist degree or ultraviolet light absorber, and film strength has the tendency of reduction.
And then, as the ultraviolet-absorbing monomer that uses in the above-mentioned ultraviolet-absorbing multipolymer, be more than 20 with respect to the ratio of the molar extinction coefficient at 380nm place preferably at the molar extinction coefficient at 400nm place.
That is, in order to suppress more the absorption near near the light visible region, 400nm, and obtain desirable UV absorptive character, should contain the ultraviolet-absorbing monomer with the performance that absorbs ultraviolet light as much as possible, this is preferred in the present invention.
A. ultraviolet-absorbing monomer
The molar extinction coefficient at its 380nm place of ultraviolet-absorbing monomer (ultraviolet light absorber) is more than 4000, and the molar extinction coefficient at preferred especially 400nm place is more than 20 with respect to the ratio of the molar extinction coefficient at 380nm place.
As the ultraviolet-absorbing monomer, known for example have that salicylic acid is a ultraviolet light absorber (phenyl salicytate, salicylic acid is to tert-butyl ester etc.) or benzophenone series ultraviolet light absorber (2, the 4-dihydroxy benaophenonel, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone etc.), benzotriazole be ultraviolet light absorber (2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary pentyls-phenyl) benzotriazole etc.), cyanoacrylate be ultraviolet light absorber (2 '-ethylhexyl-2-cyano group-3,3-diphenylacrylate ester, ethyl-2-cyano group-3-(3 ', 4 '-methylene titanium dioxide phenyl)-acrylate etc.), triazine be ultraviolet light absorber (2-(2 '-hydroxyl-4 '-own oxygen base phenyl)-4,6-diphenyl triazine etc.) or the spy open clear 58-185677 number, the spy opens the compound of clear 59-149350 number record etc.
As the ultraviolet-absorbing monomer among the present invention, from known all kinds ultraviolet light absorber as implied above, select basic framework aptly, to wherein importing the substituting group that contains the alkene unsaturated link, form polymerisable compound, and the preferred molar extinction coefficient at use 380nm place of selecting is at those monomers more than 4000.As ultraviolet-absorbing monomer of the present invention, consider from the storage stability aspect, preferably use the benzotriazole based compound.Particularly preferred ultraviolet-absorbing monomer is represented by following general formula (5).
General formula (5)
In the general formula (5), by R 11～R 16Short of the specializing of each substituting group of expression also can further have substituting group.
In the general formula (5), by R 11～R 16Wantonly 1 of group of expression has the polymerizable group represented by the group of said structure as its part-structure.
In the formula, L represents the linking group or the singly-bound of divalent, R 1Expression hydrogen atom or alkyl.As R 1, the alkyl of preferred hydrogen atom or carbon number 1～4.The group that contains above-mentioned polymerizable group can be by R 11～R 16Any group of expression, preferred R 11Or R 13, R 14, R 15, preferred especially R 14
In the general formula (5), R 11Represent by halogen atom, oxygen atom, nitrogen-atoms or sulphur atom at the nuclear substituted group of benzene.As halogen atom, can list fluorine atom, chlorine atom, bromine atoms etc., preferred chlorine atom.
As by oxygen atom and at the nuclear substituted group of benzene, can list hydroxyl, alkoxy (for example methoxyl, ethoxy, tert-butoxy, 2-ethoxy ethoxy etc.), aryloxy group (for example phenoxy group, 2,4-two tertiary pentyl phenoxy groups, 4-(4-hydroxy phenyl sulfonyl) phenoxy group etc.), heterocyclic oxy group (for example 4-pyridine oxygen base, 2-six hydrogen pyran oxygen bases etc.), carbonyl oxygen base (alkyl carbonyl oxies such as acetoxyl group, trifluoroacetyl oxygen base, new pentane acyloxy for example; Aryloxy group such as benzoyloxy, phenyl-pentafluoride formyloxy etc.), urethane ester group (N for example, alkyl amino group-4 ethyl formates such as N-dimethylamino group-4 ethyl formate; Arylamino group-4 ethyl formates such as N-euphorin base, N-(to cyano-phenyl) urethane ester group), sulfonyloxy (alkylsulfonyloxies such as mesyloxy, trifluoro-methanesulfonyl oxy, n-dodecane sulfonyloxy for example; Aryl-sulfonyl oxygens such as phenylsulfonyloxy, tolysulfonyl oxygen base) etc., the alkoxy of preferred carbon number 1～6, the alkoxy of preferred especially carbon number 2～4.
As by nitrogen-atoms and, can list nitro, amino (alkylaminos such as dimethylamino, cyclohexyl amino, n-dodecane amino for example at the nuclear substituted group of benzene; Anilino-, to arylaminos such as uncle's octyl group anilino-etc.), sulfonamido (methanesulfonamido for example, seven fluorine, third sulfonamido, alkyl sulfonyl amino such as cetyl sulfonamido, tolysulfonyl amino, Arenesulfonyl aminos such as phenyl-pentafluoride sulfonamido), sulfamoylamino group (N for example, alkyl sulfamoylamino groups such as N-dimethylamino sulfonamido, aryl sulfonamide amino such as N-phenyl sulfamoyl amino), acylamino-(acetylamino for example, alkyl-carbonyl-aminos such as myristoyl amino, aryl-amino-carbonyls such as benzamido), urea groups (N for example, alkyl urea groups such as N-dimethylamino urea groups, N-phenyl urea groups, aryl-ureidos such as N-(to cyano-phenyl) urea groups) etc., preferred acylamino-.
As by sulphur atom and at the nuclear substituted group of benzene; can list alkylthio group (methyl mercapto for example; the hot sulfenyl of uncle etc.); arylthio (for example thiophenyl etc.); heterocycle sulfenyl (1-phenyltetrazole-5-sulfenyl for example; the 5-methyl isophthalic acid; 3; 4-oxadiazoles-2-sulfenyl etc.); sulfinyl (methanesulfinyl for example; alkyl sulfinyls such as fluoroform sulfinyl; and to aryl sulfinyls such as toluene sulfinyls); sulfonyl (mesyl for example; alkyl sulphonyls such as trifyl; and aryl sulfonyl such as p-toluenesulfonyl); sulfamoyl (dimethylamino sulfonyl for example; 4-(2; 4-two tertiary pentyl phenoxy groups) alkylsulfamoyl group such as butyl amino-sulfonyl; ammonia aryl sulfonyls such as phenyl sulfamoyl base); preferred sulfinyl, the alkyl sulfinyl of preferred especially carbon number 4～12.
In the general formula (5), n represents 1～4 integer, preferred 1 or 2.N is the situation more than 2, by R 11A plurality of groups of expression can be identical or different.By R 11Substituent the position of substitution of expression does not have particular restriction, preferred 4 or 5.
In the general formula (5), R 12Expression hydrogen atom or fat base (for example alkyl, alkenyl, alkynyl etc.), aryl (for example phenyl, rubigan etc.), heterocyclic radical (for example 2-tetrahydrofuran base, 2-thiophenyl, 4-imidazole radicals, indoline full-1-base and 2-pyridine radicals etc.).As R 12, preferred hydrogen atom and alkyl.
In the general formula (5), R 13Expression hydrogen atom, fat base, aryl, heterocyclic radical are as R 13, the alkyl of preferred hydrogen atom or carbon number 1～12, branched alkyls such as isopropyl, the tert-butyl group, tertiary pentyl especially preferably are because its permanance is good.
In the general formula (5), R 14Expression oxygen atom or by nitrogen-atoms and at the nuclear substituted group of benzene, can list particularly with by R 11The passing through oxygen atom or nitrogen-atoms of expression and at the same group of the nuclear substituted group of benzene.As R 14, preferred acylamino-or alkoxy.R 14Contain the situation of above-mentioned polymerizable group, as R as part-structure 14, preferred following radicals:
Figure A20061005506400431
In the formula, L 2The alkylidene of expression carbon number 1～12, the alkylidene of preferred 3～6 straight chain shape, a chain or ring-type.R 1Expression hydrogen atom or methyl, R 2The alkyl of expression carbon number 1～12, preferred 2～6 alkyl.
In the general formula (5), R 15Expression hydrogen atom, fat base, aryl, heterocyclic radical; As R 15, the alkyl of preferred hydrogen atom or carbon number 1～12, branched alkyls such as preferred especially isopropyl, the tert-butyl group, tertiary pentyl.
In the general formula (5), R 16Expression hydrogen atom, fat base, aryl, heterocyclic radical are as R 16, preferred hydrogen atom.
The preferred ultraviolet-absorbing monomer that uses among following example the present invention, but the present invention is not subjected to their qualification.
Figure A20061005506400451
Figure A20061005506400461
B. to the explanation of polymkeric substance
The ultraviolet-absorbing multipolymer that uses among the present invention is the multipolymer of above-mentioned ultraviolet-absorbing monomer and alkene unsaturated monomer, it is characterized in that, the weight-average molecular weight of this multipolymer is in 490～50000 scope.
By forming multipolymer, can obtain the optical compensating film that mist degree is low, transparency is good.Among the present invention, weight-average molecular weight is preferably 2000～20000 in 490～50000 scope, and more preferably 7000～15000.Weight-average molecular weight is less than 490 situation, and thinking has the tendency of oozing out that causes to film surface, simultaneously, can observe in time process and painted tendency.In addition, greater than 50000 situation, the tendency with the intermiscibility variation of resin is arranged in weight-average molecular weight.
As can with the alkene unsaturated monomer of above-mentioned ultraviolet-absorbing monomer copolymerization, can list for example methacrylic acid and ester derivant (methyl methacrylate thereof, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, the metering system tert-butyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, the methacrylic acid tetrahydro furfuryl ester, benzyl methacrylate, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate etc.), perhaps acrylic acid and ester derivant (methyl acrylate thereof, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl hexyl acrylate, cyclohexyl acrylate, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, the acrylic acid tetrahydro furfuryl ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid diglycol hydroxyethyl ester, acrylic acid 3-methoxyl butyl ester, benzyl acrylate, the acrylic acid dimethylamino ethyl ester, acrylic acid diethylamino ethyl ester etc.), alkyl vinyl ether (methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether etc.), alkyl vinyl ester (vinyl formate, vinyl acetate, vinyl butyrate, vinyl caproate, stearic acid vinyl ester etc.), vinyl cyanide, vinyl chloride, styrene etc.
In these alkene unsaturated monomers, the acrylate or the methacrylate (for example, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, methacrylic acid tetrahydro furfuryl ester, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid tetrahydro furfuryl ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid diglycol hydroxyethyl ester, acrylic acid 3-methoxyl butyl ester) that preferably have hydroxyl or ehter bond.They can carry out copolymerization with the ultraviolet-absorbing monomer by a kind with mixing more than 2 kinds individually or.
Can with the usage ratio of the above-mentioned alkene unsaturated monomer of above-mentioned ultraviolet-absorbing monomer copolymerization, should be taken into account that the intermiscibility to resulting ultraviolet-absorbing multipolymer and transparent resin, the transparency of optical thin film and the influence of physical strength select.Preferably, according to the ratio that contains ultraviolet-absorbing monomer 20～70 quality % at above-mentioned multipolymer, more preferably contains 30～60 quality % the two is cooperated.The content of ultraviolet-absorbing monomer is less than the situation of 20 quality %, in order to obtain desirable UV absorbing properties, must a large amount of add, because the separating out to wait and cause transparent reduction of the rising of mist degree or ultraviolet light absorber, and make film strength that the tendency of reduction be arranged.The content of ultraviolet-absorbing monomer has the tendency of variation greater than the situation of 70 quality % with the intermiscibility of transparent resin, and makes operation variation in film forming situation.
C. to the explanation of polymerization
The said method of ultraviolet-absorbing copolymer polymerization that makes does not have particular determination among the present invention, can extensively adopt known method in the past, for example can list free radical polymerization, anionic polymerisation, cationic polymerization etc.As the initiating agent of radical polymerization, for example can list, azo-compound, superoxide etc. can list azoisobutyronitrile (AIBN), azo two isobutyric acid diester derivs, benzoyl peroxide etc.Polymer solvent is not had particular determination, for example can list aromatic hydrocarbon series solvents such as toluene, chlorobenzene; Halogenated hydrocarbons such as ethylene dichloride, chloroform series solvent; Ether series solvents such as tetrahydrofuran, diox; Acid amides series solvents such as dimethyl formamide; Pure series solvent such as methyl alcohol; Ester such as methyl acetate, ethyl acetate series solvent; Ketone series solvents such as acetone, cyclohexanone, butanone; Hydrosolvent etc.By choice of Solvent, also can carry out following polymerization: carry out with homogeneous system polymerization solution polymerization, generation polymer precipitation precipitation polymerization, carry out the emulsion polymerization of polymerization with the micella state.
The weight-average molecular weight of above-mentioned ultraviolet-absorbing multipolymer can be adjusted according to known Methods of molecular weight regulation.As this Methods of molecular weight regulation, can list method of adding chain-transferring agents such as phenixin, lauryl mercaptan, mercaptoacetic acid monooctyl ester for example etc.Polymerization is usually in room temperature～130 ℃, preferably carry out under 50～100 ℃ temperature.
Above-mentioned ultraviolet-absorbing multipolymer preferably mixes with the ratio of 0.01～20 quality % with respect to the transparent resin that forms optical thin film, more preferably mixes with the ratio of 0.1～10 quality %.At this moment, if the mist degree when forming optical thin film does not then have particular restriction below 0.5, preferred mist degree is below 0.2.Mist degree when more preferably forming optical thin film is below 0.2, and the transmitance at 380nm place is below 10%.
And then, at least a kind of polymkeric substance that also contains by the UVA monomer derived thing of following general formula (6) expression of preferred ultraviolet light absorber.
General formula (6)
(in the formula, n represents 0～3 integer, R 1～R 5Expression hydrogen atom, halogen atom or substituting group; X represents-COO-,-CONR 7-,-OCO-or-NR 7CO-, R 6Expression hydrogen atom, alkyl, alkenyl, alkynyl or aryl, R 7Expression hydrogen atom, alkyl or aryl.But, by R 6The group of expression has polymerizable group as part-structure.〕
In the above-mentioned general formula (6), n is 2 when above, a plurality of R 5Between can be identical or different, and, can link mutually and form 5～7 yuan ring.
R 1～R 5Represent hydrogen atom, halogen atom or substituting group respectively.As halogen atom, for example can list, fluorine atom, chlorine atom, bromine atoms, iodine atom etc. are preferably fluorine atom, chlorine atom.In addition; as substituting group; for example can list; alkyl (for example; methyl; ethyl; isopropyl; hydroxyethyl; methoxy; trifluoromethyl; the tert-butyl group etc.); alkenyl (for example; vinyl; allyl; 3-butene-1-Ji etc.); aryl (for example; phenyl; naphthyl; p-methylphenyl; rubigan etc.); heterocyclic radical (for example; pyridine radicals; benzimidazolyl; benzothiazolyl benzoxazolyl etc.); alkoxy (for example; methoxyl; ethoxy; isopropoxy; n-butoxy etc.); aryloxy group (for example; phenoxy group etc.); heterocyclic oxy group (for example; 1-phenyltetrazole-5-oxygen base; 2-tetrahydro-pyran oxy etc.); acyloxy (for example; acetoxyl group; new pentane acyloxy; benzoyloxy etc.); acyl group (for example; acetyl group; propiono; bytyry etc.); alkoxy carbonyl (for example; methoxycarbonyl; ethoxy carbonyl etc.); aryloxycarbonyl (for example; phenyloxycarbonyl etc.); carbamyl (for example; the methylamino formoxyl; the ethylamino formoxyl; formyl-dimethylamino etc.); amino; alkylamino (for example; methylamino; ethylamino; lignocaine etc.); anilino-(for example; anilino-; methylphenylamine base etc.); acylamino-(for example; acetylamino; propionamido etc.); hydroxyl; cyano group; nitro; sulfoamido (for example; the methylsulfonyl amido; benzene sulfonamido etc.); sulfamoylamino group (for example; dimethylamino sulfonamido etc.); sulfonyl (for example; mesyl; the fourth sulfonyl; benzenesulfonyl etc.); sulfamoyl (for example; the ethyl sulfamoyl; dimethylamino sulfonyl etc.); sulfonamido (for example; methanesulfonamido; benzenesulfonamido-etc.); urea groups (for example; 3-methyl urea groups; 3; 3-dimethyl urea groups; 1; 3-dimethyl urea groups etc.); imide (for example; phthalimide etc.);. silicyl is (for example; trimethyl silyl; triethylsilyl; t-butyldimethylsilyl etc.); alkylthio group (for example; methyl mercapto; ethylmercapto group; positive butylthio etc.); arylthio (for example; thiophenyl etc.) etc., be preferably alkyl; aryl.
In the general formula (6), by R 1～R 5Each group of expression also can further have substituting group for the situation of the group that can further replace, in addition, and adjacent R 1～R 4Also can link mutually, form 5～7 yuan ring.
R 6Expression hydrogen atom, alkyl, naphthenic base, alkenyl, alkynyl, aryl or heterocycle, for example can list methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, hexyl etc. as alkyl.In addition; abovementioned alkyl also can further have halogen atom; substituting group; as halogen atom; for example can list; fluorine atom; the chlorine atom; bromine atoms; iodine atom etc.; as substituting group; for example can list; aryl (for example; phenyl; naphthyl; p-methylphenyl; rubigan etc.); acyl group (for example; acetyl group; propiono; bytyry etc.); alkoxy (for example; methoxyl; ethoxy; isopropoxy; n-butoxy etc.); aryloxy group (for example; phenoxy group etc.); amino; alkylamino (for example; methylamino; ethylamino; lignocaine etc.); anilino-(for example; anilino-; methylphenylamine base etc.); acylamino-(for example; acetylamino; propionamido etc.); hydroxyl; cyano group; carbamyl (for example; the methylamino formoxyl; the ethylamino formoxyl; formyl-dimethylamino etc.); acyloxy (for example; acetoxyl group; new pentane acyloxy; benzoyloxy etc.); alkoxy carbonyl (for example; methoxycarbonyl; ethoxy carbonyl etc.); aryloxycarbonyl (for example, phenyloxycarbonyl etc.).
As naphthenic base, for example can list, saturated ring type hydrocarbon such as cyclopentyl, cyclohexyl, norborny, adamantyl, they can not have replacement, can be substituted yet.
As alkenyl, for example can list, vinyl, allyl, 1-methyl-2-propenyl, 3-butenyl group, 2-butenyl group, 3-methyl-2-butene base, oleyl etc. are preferably vinyl, 1-methyl-2-propenyl.
As alkynyl, for example can list, ethinyl, diacetylene base, phenylacetylene base, propargyl, 1-methyl-2-propynyl, 2-butynyl, 1,1-dimethyl-2-propynyls etc. are preferably ethinyl, propargyl.
As aryl; for example can list; phenyl; naphthyl; anthryl etc.; above-mentioned aryl also can further have halogen atom; substituting group; as halogen atom; for example can list; fluorine atom; the chlorine atom; bromine atoms; iodine atom etc.; as substituting group; for example can list; alkyl (for example; methyl; ethyl; isopropyl; hydroxyethyl; methoxy; trifluoromethyl; the tert-butyl group etc.); acyl group (for example; acetyl group; propiono; bytyry base etc.); alkoxy (for example; methoxyl; ethoxy; isopropoxy; n-butoxy etc.); aryloxy group (for example; phenoxy group etc.); amino; alkylamino (for example; methylamino; ethylamino; lignocaine etc.); anilino-(for example; anilino-; methylphenylamine base etc.); acylamino-(for example; acetylamino; propionamido etc.); hydroxyl; cyano group; carbamyl (for example; the methylamino formoxyl; the ethylamino formoxyl; formyl-dimethylamino etc.); acyloxy (for example; acetoxyl group; new pentane acyloxy; benzoyloxy etc.); alkoxy carbonyl (for example; methoxycarbonyl; ethoxy carbonyl etc.); aryloxycarbonyl (for example, phenyloxycarbonyl etc.).
As heterocyclic radical, for example can list pyridine radicals, benzimidazolyl, benzothiazolyl, benzoxazolyl etc.As R 6, be preferably alkyl.
In the general formula (6), X represents-COO-,-CONR 7-,-OCO-or-NR 7CO-.
R 7Expression hydrogen atom, alkyl, naphthenic base, aryl or heterocyclic radical, for example can list methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, hexyl etc. as alkyl.This class alkyl can further have halogen atom; substituting group; as halogen atom; for example can list; fluorine atom; the chlorine atom; bromine atoms; iodine atom etc.; as substituting group; for example can list; aryl (for example; phenyl; naphthyl; p-methylphenyl; rubigan etc.); acyl group (for example; acetyl group; propiono; bytyry etc.); alkoxy (for example; methoxyl; ethoxy; isopropoxy; n-butoxy etc.); aryloxy group (for example; phenoxy group etc.); amino; alkylamino (for example; methylamino; ethylamino; lignocaine etc.); anilino-(for example; anilino-; methylphenylamine base etc.); acylamino-(for example; acetylamino; propionamido etc.); hydroxyl; cyano group; carbamyl (for example; the methylamino formoxyl; the ethylamino formoxyl; formyl-dimethylamino etc.); acyloxy (for example; acetoxyl group; new pentane acyloxy; benzoyloxy etc.); alkoxy carbonyl (for example; methoxycarbonyl; ethoxy carbonyl etc.); aryloxycarbonyl (for example, phenyloxycarbonyl etc.).
As naphthenic base, for example can list, saturated ring type hydrocarbon such as cyclopentyl, cyclohexyl, norborny, adamantyl, they can not have replacement, can be substituted yet.
As aryl; for example can list; phenyl; naphthyl; anthryl etc.; this class aryl can further have halogen atom; substituting group; as halogen atom; can list fluorine atom; the chlorine atom; bromine atoms; iodine atom etc.; as substituting group; for example can list; alkyl (for example; methyl; ethyl; isopropyl; hydroxyethyl; methoxy; trifluoromethyl; the tert-butyl group etc.); acyl group (for example; acetyl group; propiono; bytyry etc.); alkoxy (for example; methoxyl; ethoxy; isopropoxy; n-butoxy etc.); aryloxy group (for example; phenoxy group etc.); amino; alkylamino (for example; methylamino; ethylamino; lignocaine etc.); anilino-(for example; anilino-; methylphenylamine base etc.); acylamino-(for example; acetylamino; propionamido etc.); hydroxyl; cyano group; carbamyl (for example; the methylamino formoxyl; the ethylamino formoxyl; formyl-dimethylamino etc.); acyloxy (for example; acetoxyl group; new pentane acyloxy; benzoyloxy etc.); alkoxy carbonyl (for example; methoxycarbonyl; ethoxy carbonyl etc.); aryloxycarbonyl (for example, phenyloxycarbonyl etc.).
As heterocyclic radical, for example can list pyridine radicals, benzimidazolyl, benzothiazolyl, benzoxazolyl etc.As R 7, be preferably hydrogen atom.
Said polymerizable group is meant that unsaturated ethylene is that polymerizable group or two senses are the polycondensation group among the present invention, and being preferably unsaturated ethylene is polymerizable group.As unsaturated ethylene is the concrete example of polymerizable group; can list vinyl, allyl, acryloyl group, methacryl, styryl, acrylamido, methacryl amido, vinyl cyanide base, 2-cyano group propenyloxy group, 1; 2-epoxy radicals, vinyl benzyl, vinyl ether group etc. are preferably vinyl, acryloyl group, methacryl, acrylamido, methacryl amido.In addition, what is called has polymerizable group as part-structure, be meant that above-mentioned polymerizable group directly or by the linking group more than the divalent is bonded together, the linking group that so-called divalent is above, for example can list, alkylidene (for example, methylene, 1, the 2-ethylidene, 1, the 3-propylidene, 1, the 4-butylidene, cyclohexane-1,4-two bases etc.), alkylene group (for example, ethene-1,2-two bases, butadiene-1,4-two bases etc.), alkynylene (for example, acetylene-1,2-two bases, butane-1,3-diine-1,4-two bases etc.), linking group by the compound deriving that contains an aromatic group at least (for example, replaces or does not have the benzene of replacement, hydrocarbon with condensed rings, heteroaromatic, the set of aromatic hydrocarbon ring, heteroaromatic set etc.), heteroatoms linking group (oxygen, sulphur, nitrogen, silicon, phosphorus atoms etc.), preferred alkylidene, and the group that links together by heteroatoms.These linking groups also can further be combined to form compound group.By the weight-average molecular weight of the polymkeric substance of ultraviolet-absorbing monomer derived preferably more than 2000 to below 30000, more preferably more than 5000 to below 20000.
The weight-average molecular weight of the ultraviolet-absorbing polymkeric substance that uses among the present invention can be adjusted according to known Methods of molecular weight regulation.As this Methods of molecular weight regulation, can list method of adding chain-transferring agents such as phenixin, lauryl mercaptan, mercaptoacetic acid monooctyl ester for example etc.Polymerization is carried out under room temperature～130 ℃, preferred 50 ℃～100 ℃ temperature usually.
The ultraviolet-absorbing polymkeric substance that uses among the present invention, be preferably the multipolymer of ultraviolet-absorbing monomer and other polymerizable monomer, but other polymerizable monomers as copolymerization, for example can list, styrene derivative (for example, styrene, α-Jia Jibenyixi, o-methyl styrene, between methyl styrene, p-methylstyrene, vinyl naphthalene etc.), acrylate derivative (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl hexyl acrylate, cyclohexyl acrylate, benzyl acrylate etc.), methacrylate derivative (for example, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, the metering system tert-butyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, cyclohexyl methacrylate, benzyl methacrylate etc.), alkyl vinyl ether (for example, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether etc.), alkyl vinyl ester (for example, vinyl formate, vinyl acetate, vinyl butyrate, vinyl caproate, stearic acid vinyl ester etc.), crotonic acid, maleic acid, fumaric acid, itaconic acid, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, unsaturated compounds such as Methacrylamide.Be preferably methyl acrylate, methyl methacrylate, vinyl acetate.
Copolymerization composition by beyond the ultraviolet-absorbing monomer in the polymkeric substance of ultraviolet-absorbing monomer derived preferably also contains at least a kind of hydrophilic alkene unsaturated monomer.
As hydrophilic alkene unsaturated monomer, so long as water wettability and in molecule, have the monomer of polymerisable unsaturated double-bond, just there is not particular restriction, for example can list, unsaturated carboxylic acids such as acrylic or methacrylic acid, (for example perhaps have the acrylate of hydroxyl or ehter bond or methacrylate, methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, the methacrylic acid tetrahydro furfuryl ester, acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, 2,3-dihydroxy-2-methyl-propyl (methacrylate), the acrylic acid tetrahydro furfuryl ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid diglycol hydroxyethyl ester, acrylic acid 3-methoxyl butyl ester etc.), acrylamide, N, (N-replacement) (methyl) acrylamides such as N-dimethyl (methyl) acrylamide, the N-vinyl pyrrolidone, N-Yi Xi oxazolidinone etc.
As hydrophilic alkene unsaturated monomer, preferably in molecule, has (methyl) acrylate of hydroxyl or carboxyl, special preferable methyl acrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate.
These polymerizable monomers can use by merging more than a kind or 2 kinds, carry out copolymerization with the ultraviolet-absorbing monomer.
The polymerization of the ultraviolet-absorbing multipolymer that uses among the present invention does not have particular determination, can extensively adopt known method in the past, for example can list free radical polymerization, anionic polymerisation, cationic polymerization etc.As the initiating agent of radical polymerization, for example can list, azo-compound, superoxide etc. can list azoisobutyronitrile (AIBN), azo two isobutyric acid diester derivs, benzoyl peroxide, hydrogen peroxide etc.Polymer solvent is not had particular determination, for example can list aromatic hydrocarbons series solvents such as toluene, chlorobenzene; Halogenated hydrocarbons such as ethylene dichloride, chloroform series solvent; Ether series solvents such as tetrahydrofuran, diox; Acid amides series solvents such as dimethyl formamide; Pure series solvent such as methyl alcohol; Ester such as methyl acetate, ethyl acetate series solvent; Ketone series solvents such as acetone, cyclohexanone, butanone; Hydrosolvent etc.By choice of Solvent, also can carry out following polymerization: carry out with homogeneous system polymerization solution polymerization, generation polymer precipitation precipitation polymerization, carry out the emulsion polymerization of polymerization, carry out the suspension polymerization of polymerization with suspended state with the micella state.
Above-mentioned ultraviolet-absorbing monomer, can with the usage ratio of the polymerizable monomer and the hydrophilic alkene unsaturated monomer of its copolymerization, should be taken into account that the intermiscibility to resulting ultraviolet-absorbing multipolymer and other transparent polymers, the transparency of optical compensating film and the influence of physical strength suit to select.
By the ratio that contains of the ultraviolet-absorbing monomer in the polymkeric substance of ultraviolet-absorbing monomer derived, be preferably 1～70 all quality %, more preferably 5～60 quality %.The situation of ratio that contain of the ultraviolet monomer in the ultraviolet-absorbing polymkeric substance less than 1 quality %, in the situation of wanting to satisfy desirable UV absorbing properties, must use a large amount of ultraviolet-absorbing polymkeric substance, because the separating out to wait of the rising of mist degree or ultraviolet-absorbing polymkeric substance brings the transparency to reduce, and becomes the main cause of film strength reduction.On the other hand, the situation of ratio above 70 quality % that contain of the ultraviolet monomer in the ultraviolet-absorbing polymkeric substance owing to the intermiscibility with other polymkeric substance reduces, causes often being difficult to obtain transparent optical compensating film.
Water wettability alkene unsaturated monomer preferably contains 0.1～50 quality % at above-mentioned ultraviolet-absorbing multipolymer.If content below 0.1 quality %, then can not be found the effect of improving of the intermiscibility that brought by water wettability alkene unsaturated monomer, and if be higher than 50 quality %, the separation and purification of the multipolymer difficulty that becomes then.The preferred content of water wettability alkene unsaturated monomer is 0.5～20 quality %.In the situation that ultraviolet-absorbing monomer itself is replaced by hydrophilic radical, the total content of hydrophilic ultraviolet-absorbing monomer and water wettability alkene unsaturated monomer is preferably in above-mentioned scope.
In order to satisfy the preferred content of ultraviolet-absorbing monomer and hydrophilic monomer,, also preferably make itself and a class in molecule, not have the alkene unsaturated monomer of hydrophilic radical to carry out copolymerization except the two.
Ultraviolet-absorbing monomer and (non-) water wettability alkene unsaturated monomer liquid can mix more than 2 kinds respectively and carries out copolymerization.
The typical example of the preferred ultraviolet-absorbing monomer that uses among the present invention below is shown, but is not subjected to their qualification.
Figure A20061005506400561
Figure A20061005506400591
Figure A20061005506400601
Figure A20061005506400621
The ultraviolet light absorber that uses among the present invention, ultraviolet-absorbing monomer and intermediate thereof can synthesize with reference to known document.For example, can with reference to No. the 3072585th, United States Patent (USP), No. the 3159646th, United States Patent (USP), No. the 3399173rd, United States Patent (USP), No. the 3761272nd, United States Patent (USP), No. the 4028331st, United States Patent (USP), No. the 5683861st, United States Patent (USP), No. the 86300416th, European patent, spy open clear 63-227575 number, spy open clear 63-185969 number, PolymerBulletin.V.20 (2), 169-176 and Chemical Abstracts V.109, No.191389 etc. synthesizes.
Ultraviolet light absorber that uses among the present invention and ultraviolet-absorbing polymkeric substance also can merge as required and use low molecular compound or macromolecular compound, mineral compound etc. in being mixed into other transparent polymer the time.For example, the ultraviolet-absorbing polymkeric substance that uses among the present invention and other the lower ultraviolet light absorber of molecular weight are mixed in other the transparent polymer simultaneously, perhaps the ultraviolet-absorbing polymkeric substance that uses among the present invention and other the lower ultraviolet light absorber of molecular weight being mixed in other the transparent polymer simultaneously, also is one of preferred version.Being mixed into adjuvants such as antioxidant, plastifier, fire retardant equally, simultaneously also is one of preferred version.
The adding method of ultraviolet light absorber that uses among the present invention and ultraviolet-absorbing polymkeric substance does not have particular determination, can be mixing with resin, or all be dissolved in the solvent and its dry solid shapeization is used with resin.
The use amount of ultraviolet light absorber that uses among the present invention and ultraviolet-absorbing polymkeric substance, according to the kind of compound, service condition etc. and different, under the situation that is ultraviolet light absorber, every 1m 2Preferred 0.1～the 5.0g of optical thin film, more preferably 0.1～3.0g, further preferred 0.4～2.0, preferred especially 0.5～1.5.In addition, under the situation that is ultraviolet ray absorbing polymer, every 1m 2Preferred 0.1～the 10g of optical thin film, more preferably 0.6～9.0g, further preferred 1.2～6.0g, preferred especially 1.5～3.0g.
And then, as mentioned above, consider from the viewpoint that prevents the liquid crystal deterioration, the good person of UV absorbing properties that optimal wavelength 380nm is following, and consider the few person of visible absorption that preferred 400nm is above from the viewpoint of good liquid crystal expressivity.In the present invention, particularly in the transmitance at wavelength 380nm place preferably below 8%, more preferably below 4%, particularly preferably in below 1%.
As the ultraviolet light absorber monomer of the commercially available product that can use in the present invention, 1-(2 benzotriazole)-2-hydroxyl-5-(2-methacryloxyethyl) benzene or the similar compounds of response type ultraviolet light absorber RUVA-93 of 1-(2 benzotriazole)-2-hydroxyl-5-(2-vinyl oxidation carbonyl ethyl) benzene, Da mound chemical company system of UVM-1 arranged.Preferred use polymkeric substance these homopolymerizations or copolymerization or multipolymer, but be not subjected to their qualification.For example, as the polymeric UV absorber of commercially available product, the PUVA-30M of also preferred Shi Yong Da mound chemistry (strain) system.Ultraviolet light absorber also can use more than 2 kinds.
(celluosic resin mixes with adjuvant)
The present invention preferably mixed adjuvants such as celluosic resin and polymkeric substance, plastifier, ultraviolet light absorber before heating and melting.
As the method for additive package, can list the method for mixing by with celluosic resin, adjuvant micropowderization together; After being dissolved in celluosic resin in the solvent, adjuvant dissolving or differential are dispersed in wherein, remove the method for desolvating etc. then.Remove the method for desolvating and to adopt known method, for example can list, seasoning, solvent coprecipitation method, freeze-dried method, solution casting method etc. in seasoning, the gas in the liquid, the celluosic resin after solvent is removed and the potpourri of adjuvant can be adjusted into shapes such as powder, particle, pellet, film.
The mixing of adjuvant as mentioned above, can be undertaken by the celluosic resin solid is dissolved, and also can and separate out curing in the synthesis procedure of celluosic resin and carry out simultaneously.
Seasoning in the liquid for example, adds the aqueous solution of lauryl sodium sulfate isoreactivity agent and carries out the emulsification dispersion in the solution that is dissolved with celluosic resin and adjuvant.Then, normal pressure or decompression distillation remove and to desolvate, and can obtain the dispersion thing of the celluosic resin that mixes with adjuvant.And then, in order to remove deactivators, preferably carry out centrifuging or decant.As emulsion process, can adopt the whole bag of tricks, the preferred emulsification diverting device that utilizes ultrasound wave, high speed rotating shearing, high pressure that uses.
Utilize hyperacoustic emulsification to disperse, can use 2 kinds of methods of so-called batch (-type) and continous way.Batch (-type) is applicable to more a spot of sample making, and continous way is applicable to a large amount of sample makings.In the continous way, for example can use UH-600SR devices such as (the エ ス エ of Co., Ltd. system テ one systems).The situation of this continous way, hyperacoustic irradiation time can be obtained according to dispersing chamber volume/flow velocity * cycle index.The ultrasonic irradiation device has a plurality of situations, according to the total ascent time calculating of each irradiation time.Hyperacoustic irradiation time was actually below 10000 seconds.In addition, more than 10000 seconds, then the load of operation is big if desired, in fact is necessary by selecting methods such as emulsifying agent to shorten the emulsification jitter time again.Therefore, need be more than 10000 seconds.More preferably more than 10 seconds to 2000 seconds in.
Emulsification diverting device as utilizing high speed rotating to shear can use dispersing and mixing machine, homomixer, hypervelocity mixer etc., and the solution viscosity when these patterns can be disperseed according to emulsification is distinguished use.
Utilize in the emulsification dispersion of high pressure, can use LAB2000 (エ ス エ system テ one corporate system) etc., its emulsification dispersibility depends on the sample applied pressure.Pressure is preferably 10 4KPa～5 * 10 5In the scope of kPa.
As activating agent, can use cationic surfactant, anionic surface active agent, amphoteric surfactant, macromolecule dispersing agent etc., can determine according to the particle diameter of solvent and purpose emulsion.
Seasoning for example is to use in the gas, and GS310 spray dryers such as (ヤ マ ト scientific company systems) will be dissolved with the method for the solution spray drying of celluosic resin and adjuvant.
The solvent coprecipitation method is that to add to respect to celluosic resin and adjuvant be in the solvent of lean solvent and the method that it is separated out for the solution that will be dissolved with celluosic resin and adjuvant.Lean solvent can mix arbitrarily with above-mentioned solvent that can the dissolving cellulos resin.Lean solvent also can be a mixed solvent.In addition, in the solution of celluosic resin and adjuvant, also can add lean solvent.
The celluosic resin of separating out can separate by filtration, drying with the potpourri of adjuvant.
In the potpourri of celluosic resin and adjuvant, the particle diameter of the adjuvant in the potpourri is preferably below the 1 μ m, more preferably below the 500nm, is preferably below the 200nm especially.The particle diameter of adjuvant is more little, and the mechanical property of melt molding thing, the distribution of optical characteristics are even more, are preferred.
The adjuvant that is added when the potpourri of above-mentioned celluosic resin and adjuvant and heating and melting wishes to be dried before heating and melting or when heating and melting.Herein, so-called drying is meant the moisture of removing any moisture absorption in melted material, any in the solvent of also will remove water used when the potpourri of celluosic resin and adjuvant is adjusted or solvent, sneaking into when adjuvant is synthetic.
This method of removing can adopt known drying means, for example can adopt methods such as heating, decompression method, heating decompression method to carry out, can be in air or selecting nitrogen to carry out under as the ambiance of inert gas.When carrying out these known drying means, consider from the quality aspect of film, preferably in the temperature province that can not cause material breakdown, carry out.
For example, make and remove the back in the above-mentioned drying process and remaining moisture or solvent is below the 5 quality % with respect to all quality of each film constituent material, be preferably below the 1 quality %, more preferably below the 0.1 quality %, more preferably below the 0.01 quality %.The baking temperature of this moment preferably more than 100 ℃ and below the Tg of dry material.If want to avoid molten sticking between the material, baking temperature is more preferably more than 100 ℃ below (Tg-5) ℃, more preferably more than 110 ℃ below (Tg-20) ℃.Be 0.5～24 hour preferred drying time, more preferably 1～18 hour, and more preferably 1.5～12 hours.If also lower, then often or aridity is low, or want the drying time of overspending than above-mentioned scope.In addition, when dry material when having Tg, if be heated to the baking temperature higher than Tg, then material often takes place molten sticking and make operation become difficult.
Drying process can divide more than 2 stages and carries out, and for example can carry out the keeping of material by predrying operation, and before will fusion system film～before 1 week during drying process before carrying out making film, carry out fusion system film then.
(other adjuvant)
As other adjuvant, except above-mentioned polymkeric substance, plastifier, ultraviolet light absorber, metallic compound, the optical path difference that also can list antioxidant, sour agent for capturing, light stabilizer, peroxide decomposer, scavenger of free radicals, metal passivator, matting agent etc. are adjusted agent, dyestuff, pigment etc.In addition, so long as have the material of above-mentioned functions, also can be used as the adjuvant that does not belong to above-mentioned classification and use.
Use adjuvant be for: prevent the film constituent material oxidation, capture owing to decompose the acid, inhibition or the prevention that produce owing to the decomposition reaction of the free radical kind gene that light and heat caused etc., suppress that not clear for some reason decomposition reaction is caused to be reduced to the rotten of representative or because the generation of the caused volatile ingredient of material breakdown etc. with painted or molecular weight, and give moisture-penetrability, the easy function of sliding property to the film constituent material.
On the other hand, if with film constituent material heating and melting, then decomposition reaction becomes significantly, and this decomposition reaction tends to make constituent material to cause this constituent material to follow the deterioration that intensity takes place owing to painted and molecular weight reduce.In addition, because undesirable volatile ingredient takes place toward contact in the decomposition reaction of film constituent material simultaneously.
During with film constituent material heating and melting, preferably contain above-mentioned adjuvant, consider that from the deterioration of the intensity that suppresses to cause or from the viewpoint of keeping the intrinsic intensity of material above-mentioned measure is preferred based on the deterioration of material and decomposition.
Suppress painted when in addition, above-mentioned adjuvant is for heating and melting, keep high permeability or the low haze valus aspect is effective.This can list as nitrogen or the argon of technique known use as inert gas, under decompression～vacuum, outgas and operate and the operation under closed environment, at least a kind of method in this can be merged with the method that above-mentioned adjuvant is existed and use.By reducing the probability that the film constituent material contacts with airborne oxygen, can suppress the deterioration of this material, can reach purpose of the present invention like this, be preferred therefore.
Use in order to make optical thin film of the present invention or optical compensating film can be effective as protective film for polarizing plate; from improve Polarizer of the present invention and constitute Polarizer polarizer through the time conservatory viewpoint consider, also preferably make to have above-mentioned adjuvant in the film constituent material.
In the liquid crystal indicator that uses Polarizer of the present invention, owing to have above-mentioned adjuvant in optical thin film of the present invention or the optical compensating film, consider from suppressing above-mentioned viewpoint rotten and deterioration, can improve optical thin film and optical compensating film through the time keeping quality, simultaneously aspect the display quality that improves liquid crystal indicator, have the optical compensation design of optical thin film or optical compensating film can be in long-time the performance function, this is its advantage.
Below more be described in detail adjuvant.
(antioxidant)
The following describes the antioxidant that uses among the present invention.
As antioxidant, can list phenol and be antioxidant, phosphorous antioxidant, sulphur is antioxidant, heat-resisting processing stabilizers, oxygen scavenger etc., and wherein preferred phenol is antioxidant, and special preferred alkyl fortified phenol is an antioxidant.By cooperating these antioxidants, can be under the condition that does not reduce the transparency, thermotolerance etc., the painted and intensity of the formed body that heat when preventing owing to moulding or oxidative degradation etc. cause reduces.These antioxidants can be distinguished use separately, perhaps will be used in combination more than 2 kinds, its use level can be selected in the scope of not destroying purpose of the present invention aptly, with respect to said polymkeric substance 100 mass parts among the present invention, be preferably 0.001～5 mass parts, more preferably 0.01～1 mass parts.
As antioxidant, preferred hindered phenol antioxidant compound for example comprises 2 of the compound of putting down in writing in the 12nd～14 hurdle of No. 4839405 instructions of United States Patent (USP) etc., 6-dialkyl benzene amphyl compound.The compound that comprises following general formula (7) in this compound.
General formula (7)
Figure A20061005506400681
In the following formula, R1, R2 and R3 represent by alkyl substituent that further replace or unsubstituted.The concrete example of hindered phenol compound comprises: n-octadecane base 3-(3, the 5-di-tert-butyl-hydroxy phenyl)-propionic ester, n-octadecane base 3-(3, the 5-di-tert-butyl-hydroxy phenyl)-acetic acid esters, n-octadecane base 3,5-di-tert-butyl-4-hydroxybenzoic acid ester, n-hexyl 3,5-di-tert-butyl-hydroxy phenyl benzoic ether, dodecyl 3,5-di-tert-butyl-hydroxy phenyl benzoic ether, new dodecyl 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, dodecyl β (3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, ethyl α-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) isobutyrate, octadecyl α-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) isobutyrate, octadecyl α-(4-hydroxyl-3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 2-(positive hot sulfenyl) ethyl 3,5-di-t-butyl-4-hydroxy-benzoic acid ester, 2-(positive hot sulfenyl) ethyl 3,5-di-t-butyl-4-hydroxyl-phenylacetic acid ester, 2-(n-octadecane sulfenyl) ethyl 3,5-di-tert-butyl-hydroxy phenyl acetic acid esters, 2-(n-octadecane sulfenyl) ethyl 3,5-di-t-butyl-4-hydroxy-benzoic acid ester, 2-(2-hydroxyl ethylmercapto group) ethyl 3,5-di-tert-butyl-4-hydroxybenzoic acid ester, diethyl glycol two-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic ester, 2-(n-octadecane sulfenyl) ethyl 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, stearoyl amido N, N-pair-[ethylidene 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], normal-butyl imino group N, N-pair-[ethylidene 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2-(2-stearoyl-oxy ethylmercapto group) ethyl 3,5-di-tert-butyl-4-hydroxybenzoic acid ester, 2-(2-stearoyl-oxy ethylmercapto group) ethyl 7-(3-methyl-5-tert-butyl-hydroxy phenyl) heptanoate, 1, the 2-propylene glycol is two-and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], ethylene glycol bis-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], dimethyltrimethylene glycol is two-and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], ethylene glycol bis-(3,5-di-tert-butyl-hydroxy phenyl acetic acid esters), glycerine-1-n-octadecane acid esters-2,3-two-(3,5-di-tert-butyl-hydroxy phenyl acetic acid esters), pentaerythrite-four-[3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester], 1,1,1-trimethylolethane-three-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], D-sorbite six-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2-hydroxyethyl 7-(3-methyl-5-tert-butyl-hydroxy phenyl) propionic ester, 2-stearoyl-oxy ethyl 7-(3-methyl-5-tert-butyl-hydroxy phenyl) heptanoate, 1, the positive hexanediol of 6--two [(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester], pentaerythrite-four (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide).The hindered phenol of the above-mentioned type is an anti-oxidant compounds, for example, is sold with the trade name of " Irganox1076 " and " Irganox1010 " by Ciba Specialty Chemicals.
As other antioxidant, can list phosphorous antioxidants such as three nonyl phenyl phosphites, triphenyl phosphite ester, three (2, the 4-di-tert-butyl-phenyl) phosphite ester particularly; Dilauryl-3,3 '-thiodipropionate, myristyl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate, pentaerythrite base four sulphur such as (3-lauryl thiopropionates) are antioxidant; The 2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) ethyl]-4, heat-resisting processing stabilizers such as 6-di-tert-pentyl-phenyl acrylate, 3 of special fair 8-27508 record, 4-dihydro-2H-1-chromene based compound, 3,3 '-spiral shell, two chroman based compounds, 1,1-spiral shell indane based compound, morpholine, thiomorpholine, the thiomorpholine oxide, the thiomorpholine dioxide, the compound that has the piperazine skeleton in the part-structure, the oxygen scavenger of the dialkoxy benzene compounds of Te Kaiping 3-174150 record etc. etc.The part-structure of these antioxidants, can be the part of polymkeric substance or the side chain that becomes polymkeric substance regularly, also can import in the part of molecular structure of adjuvants such as plastifier, sour remover (acidscavenger), ultraviolet light absorber.
(sour agent for capturing (acid capturing agent))
As sour agent for capturing, preferably contain the epoxy compound of the conduct acid agent for capturing of in No. 4137201 instructions of United States Patent (USP), putting down in writing.Epoxy compound as this sour agent for capturing is known in this technical field, comprise: the diglycidyl ether of various polyglycol, the polyglycol of deriving particularly by the condensation of about 8～40 moles oxirane of per 1 mole of polyglycol etc., the diglycidyl ether of glycerine etc., the becket oxygen compound (for example, in the vinyl chloride polymer composition, and the compound that in the past was utilized with vinyl chloride polymer composition), epoxidation ether condensation product, the diglycidyl ether of xenyl bisphenol-A (promptly, 4,4 '-dihydroxy diphenyl dimethylmethane), (particularly the ester that is formed by the alkyl of the fatty acid of 2～22 carbon atoms and 4～2 left and right sides carbon atoms (for example for the epoxidation unsaturated fatty acid ester, stearic acid butyl epoxy radicals ester) etc.), and various epoxidation long-chain fatty acid glyceryl esters etc. (for example, with compositions such as epoxidised soybean oil is representative, can be used as illustrative epoxidized vegetable oil and other unsaturated natural oil (at this moment, they are called as epoxidation natural glycerin ester or unsaturated fatty acid, and these fatty acid generally contain 12～22 carbon atoms)).Particularly preferably be other epoxidation ether oligomer condensation product of commercially available epoxy resin compound EPON815c that contains epoxy radicals (miller-stephenson chemical company, inc. system) and general formula (8).
General formula (8)
In the following formula, n equals 0～12.As other sour agent for capturing that can use, comprise that the spy opens those compounds of putting down in writing in the paragraph 87～105 of flat 5-194788 communique.
(light stabilizer)
As light stabilizer, can list hindered amine as light stabilizer (HALS) compound, it is a compound known, for example comprise in the 3rd～5 hurdle of the 5th～11 hurdle of No. 4619956 instructions of United States Patent (USP) and No. 4839405 instructions of United States Patent (USP), put down in writing 2,2,6, the complex of 6-tetraalkyl piperidine compounds or their acid-addition salts or their metallizing things.Those compounds that comprise following general formula (9) in this compound.
General formula (9)
Figure A20061005506400711
In the following formula, R1 and R2 are H or substituting group.Comprise in the concrete example of hindered amine as light stabilizer compound: 4-hydroxyl-2,2,6; the 6-tetramethyl piperidine; 1-allyl-4-hydroxyl-2,2,6; the 6-tetramethyl piperidine; 1-benzyl-4-hydroxyl-2,2,6; the 6-tetramethyl piperidine; 1-(the 4-tert-butyl group-2-butenyl group)-4-hydroxyl-2; 2,6, the 6-tetramethyl piperidine; 4-stearoyl-oxy-2; 2; 6, the 6-tetramethyl piperidine; 1-ethyl-4-bigcatkin willow acyloxy-2,2; 6; the 6-tetramethyl piperidine; 4-methacryloxy-1,2,2; 6; 6-pentamethyl piperidines; 1,2,2; 6; 6-pentamethyl piperidin-4-yl-β (3, the 5-di-tert-butyl-hydroxy phenyl)-propionic ester; 1-benzyl-2,2; 6; 6-tetramethyl-4-piperidyl maleate (maleinate); (two-2,2,6; 6-tetramethyl piperidine-4-yl)-adipate; (two-2; 2,6,6-tetramethyl piperidine-4-yl)-sebacate; (two-1; 2; 3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)-sebacate; (two-1-allyl-2; 2; 6,6-tetramethyl-piperidin-4-yl)-phthalic ester; 1-acetyl group-2,2; 6; 6-tetramethyl piperidine-4-base-acetic acid esters; trimellitic acid-three-(2,2,6; 6-tetramethyl piperidine-4-yl) ester; 1-acryloyl group-4-benzyloxy-2; 2,6, the 6-tetramethyl piperidine; dibutyl-malonic acid-two-(1; 2; 2,6,6-pentamethyl-piperidin-4-yl)-ester; dibenzyl-malonic acid-two-(1; 2; 3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)-ester; dimethyl-two-(2; 2; 6,6-tetramethyl piperidine-4-oxygen base)-silane, three-(1-propyl group-2; 2; 6,6-tetramethyl piperidine-4-yl)-phosphate; three-(1-propyl group-2,2; 6; 6-tetramethyl piperidine-4-yl)-and phosphate, N, N '-two-(2; 2; 6,6-tetramethyl piperidine-4-yl)-hexa-methylene-1, the 6-diamines; N; N '-two-(2; 2,6,6-tetramethyl piperidine-4-yl)-hexa-methylene-1; the 6-diacetayl amide; 1-acetyl group-4-(N-cyclohexyl acetamide)-2; 2,6,6-tetramethyl-piperidines; 4-benzylamino-2; 2; 6, the 6-tetramethyl piperidine; N, N '-two-(2; 2; 6,6-tetramethyl piperidine-4-yl)-N, N '-dibutyl-adipamide; N; N '-two-(2; 2,6,6-tetramethyl piperidine-4-yl)-N; N '-dicyclohexyl-(2-hydroxy propylidene); N; N '-two-(2,2,6; 6-tetramethyl piperidine-4-yl)-terephthaldehyde's base diamines; 4-(two-the 2-hydroxyethyl)-amino-1; 2,2,6; 6-pentamethyl piperidines; 4-Methacrylamide-1; 2,2,6; 6-pentamethyl piperidines; alpha-cyano-Beta-methyl-β-[N-(2; 2,6,6-tetramethyl piperidine-4-yl)]-amino-methyl acrylate.The example of preferred hindered amine as light stabilizer comprises following HALS-1 and HALS-2.
Figure A20061005506400721
These hindered amines are that fast light stabilizing agent can use separately respectively or be used in combination more than 2 kinds, and can be adjuvant and usefulness such as fast light stabilizing agent and plastifier, sour remover, ultraviolet light absorber with these hindered amines, also can import in the part of molecular structure of adjuvant.Its use level can be selected in the scope of not damaging the object of the invention aptly, preferably cooperates 0.01～10 quality % in film, more preferably cooperates 0.01～5 quality %, especially preferably cooperates 0.05～1 quality %.
(optical path difference adjustment agent)
Optical thin film of the present invention or optical compensating film, particularly optical compensating film, in order to improve the liquid crystal display quality, can in film, add optical path difference and adjust agent, perhaps form alignment films thereon and liquid crystal layer is set, with compound, give the optical compensation ability with optical compensating film thus from the optical path difference of liquid crystal layer.Particularly optical path difference is adjusted agent, does not need excessive stretching also can give desirable phase differential, and it is painted and reduce the effect of mist degree therefore can to expect to reduce film.
The compound that is used to regulate optical path difference and adds also can use in the patent 911656A2 instructions of Europe aromatics that put down in writing, that have two above aromatic rings to adjust agent as optical path difference.Can list for example following bar-shaped compound.And, also two or more aromatics can be merged and use.In the aromatic ring of this aromatics, except the aromatic hydrocarbon ring, also comprise the aromatic series heterocycle.Be preferably the aromatic series heterocycle especially, the aromatic series heterocycle generally is a unsaturated heterocycle.Wherein preferred 1,3,5-triazines ring.
(bar-shaped compound)
Optical thin film of the present invention or optical compensating film, particularly optical compensating film preferably make the bar-shaped compound of its maximum absorption wavelength that contains the ultra-violet absorption spectrum of a class solution (λ max) wavelength shorter than 250nm.
Adjust the functional point of view of agent from optical path difference and consider that bar-shaped compound preferably has at least one aromatic ring, more preferably has at least two aromatic rings.Bar-shaped compound preferably has the molecular structure of straight line.The molecular structure of so-called straight line is meant that on thermodynamics the molecular structure of bar-shaped compound in the stable structure is a straight line.Stable structure can be resolved or Molecular Orbital Calculation be obtained by crystalline texture on the thermodynamics.For example, use Molecular Orbital Calculation software (for example WinMOPAC2000, Fujitsu's (strain) system) to carry out Molecular Orbital Calculation, can obtain the minimum molecular structure of generation heat of compound.So-called molecular structure is a straight line, is meant that on the thermodynamics of obtaining according to calculating like that as mentioned above the angle of molecular structure is more than 140 degree in the stable structure.Bar-shaped compound preferably shows liquid crystal liquid crystal property.Bar-shaped compound more preferably shows liquid crystal liquid crystal property (having the thermotropic liquid crystal liquid crystal property) by heating.Liquid crystal phase is preferably nematic phase or smectic phase.
As bar-shaped compound, preferably by the anti-form-1 of following general formula (10) expression, 4-cyclohexanedicarboxyester ester compound.
General formula (10) Ar 1-L 1-Ar 2
In the formula (10), Ar 1And Ar 2Independent separately is aromatic group.In this manual, aromatic group comprises aryl (aromatic series alkyl), substituted aryl, aromatic series heterocyclic radical and substituted aromatic heterocyclic radical.Compare with the substituted aromatic heterocyclic radical with the aromatic series heterocyclic radical, more preferred with aryl and substituted aryl.The heterocycle of aromatic series heterocyclic radical generally is undersaturated.The aromatic series heterocycle is preferably 5 yuan of rings, 6 yuan of rings or 7 yuan of rings, more preferably 5 yuan of rings or 6 yuan of rings.The aromatic series heterocycle generally has maximum two keys.As heteroatoms, preferred nitrogen atom, oxygen atom or sulphur atom, more preferably nitrogen-atoms or sulphur atom.The example of aromatic series heterocycle comprises furan nucleus, thiphene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazoles ring, furazan ring, triazole ring, pyranoid ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and 1,3, the 5-triazine ring.As the aromatic ring of aromatic group, preferred phenyl ring, furan nucleus, thiphene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring and pyrazine ring, preferred especially phenyl ring.
The substituent example of substituted aryl and substituted aromatic heterocyclic radical; comprise: halogen atom (F; Cl; Br; I); hydroxyl; carboxyl; cyano group; amino; alkylamino (for example; methylamino; ethylamino; fourth amino; dimethylamino); nitro; sulfo group; carbamyl; alkyl-carbamoyl (for example; N-methyl (carbamyl); N-ethyl (carbamyl); N; N-dimethyl (carbamyl)); sulfonamide; alkylsulfamoyl group (for example; N-methyl sulfonamide; N-ethyl sulfonamide; N; N-dimethylamino sulphonyl); urea groups; the alkyl urea groups (for example; N-methyl urea groups; N; N-dimethyl urea groups; N; N; N '-trimethyl urea groups); alkyl (for example; methyl; ethyl; propyl group; butyl; amyl group; heptyl; octyl group; isopropyl; sec-butyl; tertiary pentyl; cyclohexyl; cyclopentyl); alkenyl (for example; vinyl; allyl; hexenyl); alkynyl (for example; ethinyl; butynyl); acyl group (for example; formoxyl; acetyl group; bytyry; caproyl; lauroyl); acyloxy (for example; acetoxyl group; butyryl acyloxy; hexylyloxy; the bay acyloxy); alkoxy (for example; methoxyl; ethoxy; propoxyl group; butoxy; amoxy; heptan the oxygen base; octyloxy); aryloxy group (for example; phenoxy group); alkoxy carbonyl (for example; methoxycarbonyl; ethoxy carbonyl; propoxycarbonyl; butoxy carbonyl; pentyloxy carbonyl; heptan oxygen base carbonyl); aryloxycarbonyl (for example; phenyloxycarbonyl); alkoxycarbonyl amino (for example; butoxy carbonyl amino; hexyloxy carbonyl amino); alkylthio group (for example; methyl mercapto; ethylmercapto group; the rosickyite base; butylthio; penta sulfenyl; heptan sulfenyl; hot sulfenyl); arylthio (for example; thiophenyl); alkyl sulphonyl (for example; methyl sulphonyl; ethylsulfonyl; the sulfonyl propyl base; the butyl sulfonyl; the amyl group sulfonyl; the heptyl sulfonyl; the octyl group sulfonyl); amide group (for example; acetamide; the butyl amide base; the hexyl acid amides; the lauryl acid amides) and non-aromatic heterocyclic radical (for example, morpholinyl; pyrazinyl).
As the substituting group of substituted aryl and substituted aromatic heterocyclic radical, preferred halogen atom, cyano group, carboxyl, hydroxyl, amino, alkyl-substituted amino, acyl group, acyloxy, amide group, alkoxy carbonyl, alkoxy, alkylthio group and alkyl.The moieties of alkylamino, alkoxy carbonyl, alkoxy and alkylthio group and alkyl also can further have substituting group.The substituent example of moieties and alkyl comprises halogen atom, hydroxyl, carboxyl, cyano group, amino, alkylamino, nitro, sulfo group, carbamyl, alkylamino formoxyl, sulfonamide, alkylsulfamoyl group, urea groups, alkyl urea groups, alkenyl, alkynyl, acyl group, acyloxy, alkoxy, aryloxy group, alkoxy carbonyl, aryloxycarbonyl, alkoxycarbonyl amino, alkylthio group, arylthio, alkyl sulphonyl, amide group and non-aromatic heterocyclic radical.As the substituting group of moieties and alkyl, preferred halogen atom, hydroxyl, amino, alkylamino, acyl group, acyloxy, acylamino-, alkoxy carbonyl and alkoxy.
In the formula (10), L 1For from the saturated heterocyclyl of alkylidene, alkylene group, alkynylene, divalence ,-O-,-divalent linker selected CO-and their combination.Alkylidene also can have ring texture.As cyclic alkylidene, preferred cyclohexylidene, preferred especially 1, the 4-cyclohexylidene.As the chain alkylidene, compare preferred straight chain shape alkylidene with alkylidene with side chain.The carbon number of alkylidene is preferably 1～20, more preferably is 1～15, and more preferably 1～10, further be preferably 1～8, most preferably be 1～6.
Compare with ring texture, alkylene group and alkynylene preferably have chain structure, compare with the chain structure with side chain, more preferably have straight chain structure.The carbon number of alkylene group and alkynylene is preferably 2～10, more preferably is 2～8, and more preferably 2～6, more preferably 2～4, most preferably be 2 (1,2-ethenylidene or ethynylene).The saturated heterocyclyl of divalence preferably has 3 yuan～9 yuan heterocycle.Heteroatoms preferred oxygen atom, nitrogen-atoms, boron atom, sulphur atom, silicon atom, phosphorus atoms or the germanium atom of heterocycle.The example of saturated heterocyclic comprises piperidine ring, piperazine ring, morpholine ring, pyrrolidine ring, imidazolidine ring, tetrahydrofuran ring, amylene oxide ring, 1,3-diox ring, 1,4-diox ring, thiophane ring, 1,3-thiazolidine ring, 1,3-oxazolidine ring, 1,3-dioxolanes ring, 1,3-dithiolane ring and 1,3,2-dioxobororane.Particularly preferred divalence saturated heterocyclyl is a piperazine-1,4-diylene, 1,3-diox-2,5-diylene and 1,3,2-dioxobororane-2,5-diylene.
The example of the divalent linker that constitutes is shown below.
L-1:-O-CO-alkylidene-CO-O-
L-2:-CO-O-alkylidene-O-CO-
L-3:-O-CO-alkylene group-CO-O-
L-4:-CO-O-alkylene group-O-CO-
L-5:-O-CO-alkynylene-CO-O-
L-6:-CO-O-alkynylene-O-CO-
L-7:-O-CO-divalence saturated heterocyclyl-CO-O-
L-8:-CO-O-divalence saturated heterocyclyl-O-CO-
In the molecular structure of general formula (10), Ar 1With Ar 2Clip L 1Formed angle is preferably more than 140 degree.As bar-shaped compound, more preferably by the compound of following general formula (11) expression.
General formula (11) Ar 1-L 2-X-L 3-Ar 2
In the formula (11), Ar 1And Ar 2Be aromatic group independently of one another.The Ar of the definition of aromatic group and example and formula (10) 1And Ar 2Identical.
In the formula (11), L 2And L 3Independently of one another for alkylidene ,-O-,-CO-and the divalent linker from their combination, selected.Compare with ring texture, alkylidene preferably has chain structure, compares with the chain structure with side chain, more preferably has straight chain structure.The carbon number of alkylidene is preferably 1～10, more preferably is 1～8, and more preferably 1～6, more preferably 1～4, most preferably be 1 or 2 (methylene or ethylidene).L 2And L 3Be preferably especially-O-CO-or-CO-O-.
In the formula (11), X is 1,4-cyclohexylidene, 1,2-ethenylidene or ethynylene.Concrete example by the compound of formula (10) expression below is shown.
Figure A20061005506400821
Concrete example (1)～(34), (41), (42), (46), (47), (52), (53) have two unsymmetrical carbons on 1 and 4 of cyclohexane ring.But, because concrete example (1), (4)～(34), (41), (42), (46), (47), (52), (53) have the molecular structure of the meso-form of symmetry, not optical isomer (optical activity), only have geometric isomeride (trans type and cis type).The trans type (1-trans) and the cis type (1-cis) of concrete example (1) below are shown.
As mentioned above, bar-shaped compound preferably has the molecular structure of straight line.Therefore, compare more preferably trans type with the cis type.Concrete example (2) and (3) except geometric isomeride, also have optical isomer (adding up to 4 kinds of isomeride).For geometric isomeride, same, compare more preferably trans type with the cis type.For optical isomer, not special good and bad, can be D, L or raceme any.In concrete example (43)～(45), there are trans type and cis type in 1 of center on the 2-ethenylidene key.According to above-mentioned same reason, compare more preferably trans type with the cis type.
Also can be the two or more merging uses of bar-shaped compound with maximum absorption wavelength in the ultra-violet absorption spectrum of solution (λ max) than the wavelength of 250nm weak point.Bar-shaped compound can reference literature the method for record synthetic.As document, can list Mol.Cryst.Liq.Cryst., 53 volumes, 229 pages (1979), the same magazine 89 volumes, 93 pages (nineteen eighty-two), the same magazine 145 volumes, 111 pages (1987), the same magazine 170 volumes, 43 pages (1989); J.Am.Chem.Soc., 113 volumes, 1349 pages (1991), the same magazine 118 volumes, 5346 pages (1996), the same magazine 92 volumes, 1582 pages (1970); J.Org.Chem., 40 volumes, 420 pages (1975); Tetrahedron, No. 16,48 volumes, 3437 pages (1992).
In addition, as the discoid compound that uses among the present invention, the preferred compound that uses with 1,3,5-triazines ring.
Compound with 1,3,5-triazines ring, wherein, preferably by the compound of following general formula (12) expression.
General formula (12)
In the general formula (12), X 1For singly-bound ,-NR 4-,-O-or-S-; X 2For singly-bound ,-NR 5-,-O-or-S-; X 3For singly-bound ,-NR 6-,-O-or-S-; R 1, R 2And R 3Be alkyl, alkenyl, aryl or heterocyclic radical; In addition, R 4, R 5And R 6Be hydrogen atom, alkyl, alkenyl, aryl or heterocyclic radical.Compound by general formula (12) expression is preferably melamine compound especially.
In the melamine compound, in general formula (12), X 1, X 2And X 3Be respectively-NR 4-,-NR 5-and-NR 6-, perhaps, X 1, X 2And X 3Be singly-bound, and R 1, R 2And R 3For on nitrogen-atoms, having the heterocyclic radical of free atomicity.-X 1-R 1,-X 2-R 2With-X 3-R 3Be preferably identical substituting group.R 1, R 2And R 3Be preferably aryl especially.R 4, R 5And R 6Be preferably hydrogen atom especially.
Compare with cyclic alkyl, abovementioned alkyl is chain-like alkyl more preferably.Compare with chain-like alkyl, more preferably straight chain shape alkyl with side chain.
The carbon number of alkyl is preferably 1～30, more preferably is 1～20, and more preferably 1～10, more preferably 1～8, most preferably be 1～6.Alkyl also can have substituting group.
As substituent concrete example, can list for example halogen atom, alkoxy (for example each base such as methoxyl, ethoxy, epoxy ethoxy) and acyloxy (for example, acryloxy, methacryloxy) etc.Compare with the closed chain thiazolinyl, above-mentioned alkenyl is the chain alkenyl more preferably.Compare with chain alkenyl, more preferably straight chain shape alkenyl with side chain.The carbon number of alkenyl is preferably 2～30, more preferably is 2～20, and more preferably 2～10, more preferably 2～8, most preferably be 2～6.Alkenyl also can have substituting group.
As substituent concrete example, can list halogen atom, alkoxy (for example, various groups such as methoxyl, ethoxy, epoxy ethoxy) or acyloxy (for example, various groups such as acryloxy, methacryloxy).
Above-mentioned aryl is preferably phenyl or naphthyl, is preferably phenyl especially.Aryl also can have substituting group.
As substituent concrete example; for example comprise halogen atom; hydroxyl; cyano group; nitro; carboxyl; alkyl; alkenyl; aryl; alkoxy; alkenyl oxy; aryloxy group; acyloxy; alkoxy carbonyl; the alkenyl oxy carbonyl; aryloxycarbonyl; sulfonamide; alkyl replaces sulfamoyl; alkenyl replaces sulfamoyl; aryl replaces sulfamoyl; sulfoamido; carbamyl; the alkyl-substituted amino formoxyl; alkenyl substituted-amino formoxyl; aryl substituted-amino formoxyl; amide group; alkylthio group; alkenyl thio; arylthio and acyl group.The definition of abovementioned alkyl is identical with above-mentioned alkyl.
Alkoxy, acyloxy, alkoxy carbonyl, alkyl replace the moieties of sulfamoyl, sulfoamido, alkyl-substituted amino formoxyl, amide group, alkylthio group and acyl group, and also the alkyl with above-mentioned is identical in its definition.
The definition of above-mentioned alkenyl is identical with above-mentioned alkenyl.
Alkenyl oxy, acyloxy, alkenyl oxy carbonyl, alkenyl replace the alkenyl part of sulfamoyl, sulfoamido, alkenyl substituted-amino formoxyl, amide group, alkenyl thio and acyl group, and also the alkenyl with above-mentioned is identical in its definition.
As the concrete example of above-mentioned aryl, for example can list phenyl, Alpha-Naphthyl, betanaphthyl, 4-methoxyphenyl, 3, various groups such as 4-diethoxy phenyl, 4-octyloxyphenyl or 4-dodecyloxy phenyl.
Aryloxy group, acyloxy, aryloxycarbonyl, aryl replace the example of the part of sulfamoyl, sulfoamido, aryl substituted-amino formoxyl, amide group, arylthio and acyl group, and its definition is identical with above-mentioned aryl.
Work as X 1, X 2Or X 3For-NR-,-O-or-heterocyclic radical during S-, preferably have aromatic series.
Heterocycle as in the heterocyclic radical with aromatic series is generally unsaturated heterocycle, is preferably the heterocycle with at most two keys.Heterocycle is preferably 5 yuan of rings, 6 yuan of rings or 7 yuan of rings, and more preferably 5 yuan of rings or 6 yuan of rings most preferably are 6 yuan of rings.
Heteroatoms in the heterocycle is preferably various atoms such as N, S or O, is preferably the N atom especially.
As heterocycle with aromatic series, and preferred especially pyridine ring (as heterocyclic radical, for example, various groups such as 2-pyridine radicals or 4-pyridine radicals).Heterocyclic radical also can have substituting group.The substituent example of heterocyclic radical is identical with the substituent example of above-mentioned aryl moiety.
Work as X 1, X 2Or X 3Heterocyclic radical during for singly-bound is preferably the heterocyclic radical that has free atomicity on nitrogen-atoms.The heterocyclic radical that has free atomicity on nitrogen-atoms is preferably 5 yuan of rings, 6 yuan of rings or 7 yuan of rings, and more preferably 5 yuan of rings or 6 yuan of rings most preferably are 5 yuan of rings.Heterocyclic radical also can have a plurality of nitrogen-atoms.
In addition, the heteroatoms in the heterocyclic radical also can have nitrogen-atoms heteroatoms (for example, O atom, S atom) in addition.Heterocyclic radical also can have substituting group.The substituent concrete example of heterocyclic radical, its definition is identical with the substituent concrete example of above-mentioned aryl moiety.
Below be illustrated in the concrete example of the heterocyclic radical that has free atomicity on the nitrogen-atoms.
Figure A20061005506400871
Molecular weight with compound of 1,3,5-triazines ring is preferably 300～2000.The boiling point of this compound is preferably more than 260 ℃.Boiling point can use commercially available determinator (for example, TG/DTA100, セ イ コ one electronics industry (strain) system) to measure.
The concrete example of the compound with 1,3,5-triazines ring below is shown.
In addition, a plurality of R that below illustrate represent identical group.
(1) butyl
(2) 2-methoxyl-2-ethoxyethyl group
(3) 5-undecenyl
(4) phenyl
(5) 4-ethoxy carbonyl phenyl
(6) 4-butoxy phenyl
(7) to xenyl
(8) 4-pyridine radicals
(9) 2-naphthyl
(10) 2-aminomethyl phenyl
(11) 3,4-Dimethoxyphenyls
(12) 2-furyl
Figure A20061005506400891
(14) phenyl
(15) 3-ethoxy carbonyl phenyl
(16) 3-butoxy phenyl
(17) xenyl between
(18) 3-phenyl thiophenyl
(19) 3-chlorphenyl
(20) 3-benzoyl phenyl
(21) 3-acetoxyl group phenyl
(22) 3-benzoyloxy phenyl
(23) 3-phenyloxycarbonyl phenyl
(24) 3-methoxyphenyl
(25) 3-anilino-phenyl
(26) 3-isobutyryl aminophenyl
(27) 3-phenyloxycarbonyl aminophenyl
(28) 3-(3-ethyl urea groups) phenyl
(29) 3-(3,3-diethyl urea groups) phenyl
(30) 3-aminomethyl phenyl
(31) 3-Phenoxyphenyl
(32) 3-hydroxy phenyl
(33) 4-ethoxy carbonyl phenyl
(34) 4-butoxy phenyl
(35) to xenyl
(36) 4-phenyl thiophenyl
(37) 4-chlorphenyl
(38) 4-benzoyl phenyl
(39) 4-acetoxyl group phenyl
(40) 4-benzoyloxy phenyl
(41) 4-phenyloxycarbonyl phenyl
(42) 4-methoxyphenyl
(43) 4-anilino-phenyl
(44) 4-isobutyryl aminophenyl
(45) 4-phenyloxycarbonyl aminophenyl
(46) 4-(3-ethyl urea groups) phenyl
(47) 4-(3,3-diethyl urea groups) phenyl
(48) 4-aminomethyl phenyl
(49) 4-Phenoxyphenyl
(50) 4-hydroxy phenyl
(51) 3,4-di ethoxy carbonyl phenyl
(52) 3,4-dibutoxy phenyl
(53) 3,4-diphenyl phenyl
(54) 3,4-diphenyl benzene sulfenyls
(55) 3,4-dichlorophenyls
(56) 3,4-dibenzoyl phenyl
(57) 3,4-diacetoxy phenyl
(58) 3,4-dibenzoyl oxygen base phenyl
(59) 3,4-two phenoxy carbonyl phenyl
(60) 3,4-Dimethoxyphenyls
(61) 3,4-hexichol aminocarbonyl phenyls
(62) 3,4-3,5-dimethylphenyls
(63) 3,4-two Phenoxyphenyls
(64) 3,4-dihydroxy phenyls
(65) 2-naphthyl
(66) 3,4,5-triethoxy carbonyl phenyl
(67) 3,4,5-three butoxy phenyls
(68) 3,4,5-triphenyl phenyl
(69) 3,4,5-triphenylbenzene sulfenyl
(70) 3,4, the 5-trichlorophenyl
(71) 3,4,5-tri-benzoyl phenyl
(72) 3,4,5-triacetyl oxygen base phenyl
(73) 3,4,5-thribenzoyl phenyl
(74) 3,4,5-triple phenoxyl carbonyl phenyl
(75) 3,4, the 5-trimethoxyphenyl
(76) 3,4,5-triphen aminocarbonyl phenyl
(77) 3,4, the 5-trimethylphenyl
(78) 3,4,5-triple phenoxyl phenyl
(79) 3,4,5-trihydroxy phenyl
Figure A20061005506400921
(80) phenyl
(81) 3-ethoxy carbonyl phenyl
(82) 3-butoxy phenyl
(83) xenyl between
(84) 3-phenyl thiophenyl
(85) 3-chlorphenyl
(86) 3-benzoyl phenyl
(87) 3-acetoxyl group phenyl
(88) 3-benzoyloxy phenyl
(89) 3-phenyloxycarbonyl phenyl
(90) 3-methoxyphenyl
(91) 3-anilino-phenyl
(92) 3-isobutyryl aminophenyl
(93) 3-phenyloxycarbonyl aminophenyl
(94) 3-(3-ethyl urea groups) phenyl
(95) 3-(3,3-diethyl urea groups) phenyl
(96) 3-aminomethyl phenyl
(97) 3-Phenoxyphenyl
(98) 3-hydroxy phenyl
(99) 4-ethoxy carbonyl phenyl
(100) 4-butoxy phenyl
(101) to xenyl
(102) 4-phenyl thiophenyl
(103) 4-chlorphenyl
(104) 4-benzoyl phenyl
(105) 4-acetoxyl group phenyl
(106) 4-benzoyloxy phenyl
(107) 4-phenyloxycarbonyl phenyl
(108) 4-methoxyphenyl
(109) 4-anilino-phenyl
(110) 4-isobutyryl aminophenyl
(111) 4-phenyloxycarbonyl aminophenyl
(112) 4-(3-ethyl urea groups) phenyl
(113) 4-(3,3-diethyl urea groups) phenyl
(114) 4-aminomethyl phenyl
(115) 4-Phenoxyphenyl
(116) 4-hydroxy phenyl
(117) 3,4-di ethoxy carbonyl phenyl
(118) 3,4-dibutoxy phenyl
(119) 3,4-diphenyl phenyl
(120) 3,4-diphenyl benzene sulfenyls
(121) 3,4-dichlorophenyls
(122) 3,4-dibenzoyl phenyl
(123) 3,4-diacetoxy phenyl
(124) 3,4-dibenzoyl oxygen base phenyl
(125) 3,4-two phenoxy carbonyl phenyl
(126) 3,4-Dimethoxyphenyls
(127) 3,4-hexichol aminocarbonyl phenyls
(128) 3,4-3,5-dimethylphenyls
(129) 3,4-two Phenoxyphenyls
(130) 3,4-dihydroxy phenyls
(131) 2-naphthyl
(132) 3,4,5-triethoxy carbonyl phenyl
(133) 3,4,5-three butoxy phenyls
(134) 3,4,5-triphenyl phenyl
(135) 3,4,5-triphenylbenzene sulfenyl
(136) 3,4, the 5-trichlorophenyl
(137) 3,4,5-tri-benzoyl phenyl
(138) 3,4,5-triacetyl oxygen base phenyl
(139) 3,4,5-thribenzoyl phenyl
(140) 3,4,5-triple phenoxyl carbonyl phenyl
(141) 3,4, the 5-trimethoxyphenyl
(142) 3,4,5-triphen aminocarbonyl phenyl
(143) 3,4, the 5-trimethylphenyl
(144) 3,4,5-triple phenoxyl phenyl
(145) 3,4,5-trihydroxy phenyl
Figure A20061005506400941
(146) phenyl
(147) 4-ethoxy carbonyl phenyl
(148) 4-butoxy phenyl
(149) to xenyl
(150) 4-phenyl thiophenyl
(151) 4-chlorphenyl
(152) 4-benzoyl phenyl
(153) 4-acetoxyl group phenyl
(154) 4-benzoyloxy phenyl
(155) 4-phenyloxycarbonyl phenyl
(156) 4-methoxyphenyl
(157) 4-anilino-phenyl
(158) 4-isobutyryl aminophenyl
(159) 4-phenyloxycarbonyl aminophenyl
(160) 4-(3-ethyl urea groups) phenyl
(161) 4-(3,3-diethyl urea groups) phenyl
(162) 4-aminomethyl phenyl
(163) 4-Phenoxyphenyl
(164) 4-hydroxy phenyl
Figure A20061005506400951
(165) phenyl
(166) 4-ethoxy carbonyl phenyl
(167) 4-butoxy phenyl
(168) to xenyl
(169) 4-phenyl thiophenyl
(170) 4-chlorphenyl
(171) 4-benzoyl phenyl
(172) 4-acetoxyl group phenyl
(173) 4-benzoyloxy phenyl
(174) 4-phenyloxycarbonyl phenyl
(175) 4-methoxyphenyl
(176) 4-anilino-phenyl
(177) 4-isobutyryl aminophenyl
(178) 4-phenyloxycarbonyl aminophenyl
(179) 4-(3-ethyl urea groups) phenyl
(180) 4-(3,3-diethyl urea groups) phenyl
(181) 4-aminomethyl phenyl
(182) 4-Phenoxyphenyl
(183) 4-hydroxy phenyl
Figure A20061005506400961
(184) phenyl
(185) 4-ethoxy carbonyl phenyl
(186) 4-butoxy phenyl
(187) to xenyl
(188) 4-phenyl thiophenyl
(189) 4-chlorphenyl
(190) 4-benzoyl phenyl
(191) 4-acetoxyl group phenyl
(192) 4-benzoyloxy phenyl
(193) 4-phenyloxycarbonyl phenyl
(194) 4-methoxyphenyl
(195) 4-anilino-phenyl
(196) 4-isobutyryl aminophenyl
(197) 4-phenyloxycarbonyl aminophenyl
(198) 4-(3-ethyl urea groups) phenyl
(199) 4-(3,3-diethyl urea groups) phenyl
(200) 4-aminomethyl phenyl
(201) 4-Phenoxyphenyl
(202) 4-hydroxy phenyl
(203) phenyl
(204) 4-ethoxy carbonyl phenyl
(205) 4-butoxy phenyl
(206) to xenyl
(207) 4-phenyl thiophenyl
(208) 4-chlorphenyl
(209) 4-benzoyl phenyl
(210) 4-acetoxyl group phenyl
(211) 4-benzoyloxy phenyl
(212) 4-phenyloxycarbonyl phenyl
(213) 4-methoxyphenyl
(214) 4-anilino-phenyl
(215) 4-isobutyryl aminophenyl
(216) 4-phenyloxycarbonyl aminophenyl
(217) 4-(3-ethyl urea groups) phenyl
(218) 4-(3,3-diethyl urea groups) phenyl
(219) 4-aminomethyl phenyl
(220) 4-Phenoxyphenyl
(221) 4-hydroxy phenyl
Figure A20061005506400981
(222) phenyl
(223) 4-butyl phenyl
(224) 4-(2-methoxyl-2-ethoxyethyl group) phenyl
(225) 4-(5-nonene base) phenyl
(226) to xenyl
(227) 4-ethoxy carbonyl phenyl
(228) 4-butoxy phenyl
(229) 4-aminomethyl phenyl
(230) 4-chlorphenyl
(231) 4-phenyl thiophenyl
(232) 4-benzoyl phenyl
(233) 4-acetoxyl group phenyl
(234) 4-benzoyloxy phenyl
(235) 4-phenyloxycarbonyl phenyl
(236) 4-methoxyphenyl
(237) 4-anilino-phenyl
(238) 4-isobutyryl aminophenyl
(239) 4-phenyloxycarbonyl aminophenyl
(240) 4-(3-ethyl urea groups) phenyl
(241) 4-(3,3-diethyl urea groups) phenyl
(242) 4-Phenoxyphenyl
(243) 4-hydroxy phenyl
(244) 3-butyl phenyl
(245) 3-(2-methoxyl-2-ethoxyethyl group) phenyl
(246) 3-(5-nonene base) phenyl
(247) xenyl between
(248) 3-ethoxy carbonyl phenyl
(249) 3-butoxy phenyl
(250) 3-aminomethyl phenyl
(251) 3-chlorphenyl
(252) 3-phenyl thiophenyl
(253) 3-benzoyl phenyl
(254) 3-acetoxyl group phenyl
(255) 3-benzoyloxy phenyl
(256) 3-phenyloxycarbonyl phenyl
(257) 3-methoxyphenyl
(258) 3-anilino-phenyl
(259) 3-isobutyryl aminophenyl
(260) 3-phenyloxycarbonyl aminophenyl
(261) 3-(3-ethyl urea groups) phenyl
(262) 3-(3,3-diethyl urea groups) phenyl
(263) 3-Phenoxyphenyl
(264) 3-hydroxy phenyl
(265) 2-butyl phenyl
(266) 2-(2-methoxyl-2-ethoxyethyl group) phenyl
(267) 2-(5-nonene base) phenyl
(268) adjacent xenyl
(269) 2-ethoxy carbonyl phenyl
(270) 2-butoxy phenyl
(271) 2-aminomethyl phenyl
(272) 2-chlorphenyl
(273) 2-phenyl thiophenyl
(274) 2-benzoyl phenyl
(275) 2-acetoxyl group phenyl
(276) 2-benzoyloxy phenyl
(277) 2-phenyloxycarbonyl phenyl
(278) 2-methoxyphenyl
(279) 2-anilino-phenyl
(280) 2-isobutyryl aminophenyl
(281) 2-phenyloxycarbonyl aminophenyl
(282) 2-(3-ethyl urea groups) phenyl
(283) 2-(3,3-diethyl urea groups) phenyl
(284) 2-Phenoxyphenyl
(285) 2-hydroxy phenyl
(286) 3,4-dibutyl phenyl
(287) 3,4-two (2-methoxyl-2-ethoxyethyl group) phenyl
(288) 3,4-diphenyl phenyl
(289) 3,4-di ethoxy carbonyl phenyl
(290) 3,4-two (dodecyloxy) phenyl
(291) 3,4-3,5-dimethylphenyls
(292) 3,4-dichlorophenyls
(293) 3,4-dibenzoyl phenyl
(294) 3,4-diacetoxy phenyl
(295) 3,4-Dimethoxyphenyls
(296) 3,4-two-N-methylamino phenyl
(297) 3,4-two isobutyryl aminophenyls
(298) 3,4-two Phenoxyphenyls
(299) 3,4-dihydroxy phenyls
(300) 3,5-dibutyl phenyl
(301) 3,5-two (2-methoxyl-2-ethoxyethyl group) phenyl
(302) 3,5-diphenyl phenyl
(303) 3,5-di ethoxy carbonyl phenyl
(304) 3,5-two (dodecyloxy) phenyl
(305) 3,5-3,5-dimethylphenyls
(306) 3,5-dichlorophenyls
(307) 3,5-dibenzoyl phenyl
(308) 3,5-diacetoxy phenyl
(309) 3,5-Dimethoxyphenyls
(310) 3,5-two-N-methylamino phenyl
(311) 3,5-two isobutyryl aminophenyls
(312) 3,5-two Phenoxyphenyls
(313) 3,5-dihydroxy phenyls
(314) 2,4-dibutyl phenyl
(315) 2,4-two (2-methoxyl-2-ethoxyethyl group) phenyl
(316) 2,4-diphenyl phenyl
(317) 2,4-di ethoxy carbonyl phenyl
(318) 2,4-two (dodecyloxy) phenyl
(319) 2,4-3,5-dimethylphenyls
(320) 2,4-dichlorophenyls
(321) 2,4-dibenzoyl phenyl
(322) 2,4-diacetoxy phenyl
(323) 2,4-Dimethoxyphenyls
(324) 2,4-two-N-methylamino phenyl
(325) 2,4-two isobutyryl aminophenyls
(326) 2,4-two Phenoxyphenyls
(327) 2,4-dihydroxy phenyls
(328) 2,3-dibutyl phenyl
(329) 2,3-two (2-methoxyl-2-ethoxyethyl group) phenyl
(330) 2,3-diphenyl phenyl
(331) 2,3-di ethoxy carbonyl phenyl
(332) 2,3-two (dodecyloxy) phenyl
(333) 2,3-3,5-dimethylphenyls
(334) 2,3-dichlorophenyls
(335) 2,3-dibenzoyl phenyl
(336) 2,3-diacetoxy phenyl
(337) 2,3-Dimethoxyphenyls
(338) 2,3-two-N-methylamino phenyl
(339) 2,3-two isobutyryl aminophenyls
(340) 2,3-two Phenoxyphenyls
(341) 2,3-dihydroxy phenyls
(342) 2,6-dibutyl phenyl
(343) 2,6-two (2-methoxyl-2-ethoxyethyl group) phenyl
(344) 2,6-diphenyl phenyl
(345) 2,6-di ethoxy carbonyl phenyl
(346) 2,6-two (dodecyloxy) phenyl
(347) 2,6-3,5-dimethylphenyls
(348) 2,6-dichlorophenyls
(349) 2,6-dibenzoyl phenyl
(350) 2,6-diacetoxy phenyl
(351) 2,6-Dimethoxyphenyls
(352) 2,6-two-N-methylamino phenyl
(353) 2,6-two isobutyryl aminophenyls
(354) 2,6-two Phenoxyphenyls
(355) 2,6-dihydroxy phenyls
(356) 3,4,5-tributyl phenyl
(357) 3,4,5-three (2-methoxyl-2-ethoxyethyl group) phenyl
(358) 3,4,5-triphenyl phenyl
(359) 3,4,5-triethoxy carbonyl phenyl
(360) 3,4,5-three (dodecyloxy) phenyl
(361) 3,4, the 5-trimethylphenyl
(362) 3,4, the 5-trichlorophenyl
(363) 3,4,5-tri-benzoyl phenyl
(364) 3,4,5-triacetyl oxygen base phenyl
(365) 3,4, the 5-trimethoxyphenyl
(366) 3,4,5-three-N-methylamino phenyl
(367) 3,4,5-three isobutyryl aminophenyls
(368) 3,4,5-triple phenoxyl phenyl
(369) 3,4,5-trihydroxy phenyl
(370) 2,4,6-tributyl phenyl
(371) 2,4,6-three (2-methoxyl-2-ethoxyethyl group) phenyl
(372) 2,4,6-triphenyl phenyl
(373) 2,4,6-triethoxy carbonyl phenyl
(374) 2,4,6-three (dodecyloxy) phenyl
(375) 2,4, the 6-trimethylphenyl
(376) 2,4, the 6-trichlorophenyl
(377) 2,4,6-tri-benzoyl phenyl
(378) 2,4,6-triacetyl oxygen base phenyl
(379) 2,4, the 6-trimethoxyphenyl
(380) 2,4,6-three-N-methylamino phenyl
(381) 2,4,6-three isobutyryl aminophenyls
(382) 2,4,6-triple phenoxyl phenyl
(383) 2,4,6-trihydroxy phenyl
(384) pentafluorophenyl group
(385) five chlorophenyl
(386) pentamethoxyl phenyl
(387) 6-N-methyl sulfonamide-8-methoxyl-2-naphthyl
(388) 5-N-methyl sulfonamide-2-naphthyl
(389) 6-N-phenyl sulfamoyl-2-naphthyl
(390) 5-ethoxy-7-N-methyl sulfonamide-2-naphthyl
(391) 3-methoxyl-2-naphthyl
(392) 1-ethoxy-2-naphthyl
(393) 6-N-phenyl sulfamoyl-8-methoxyl-2-naphthyl
(394) 5-methoxyl-7-N-phenyl sulfamoyl-2-naphthyl
(395) 1-(4-aminomethyl phenyl)-2-naphthyl
(396) 6,8-two-N-methyl sulfonamide-2-naphthyl
(397) 6-N-2-acetoxyl group ethyl sulfonamide-8-methoxyl-2-naphthyl
(398) 5-acetoxyl group-7-N-phenyl sulfamoyl-2-naphthyl
(399) 3-benzoyloxy-2-naphthyl
(400) 5-acetylaminohydroxyphenylarsonic acid 1-naphthyl
(401) 2-methoxyl-1-naphthyl
(402) 4-phenoxy group-1-naphthyl
(403) 5-N-methyl sulfonamide-1-naphthyl
(404) 3-N-methyl (carbamyl)-4-hydroxyl-1-naphthyl
(405) 5-methoxyl-6-N-ethyl sulfonamide-1-naphthyl
(406) 7-tetradecyloxyaniline-1-naphthyl
(407) 4-(4-methylphenoxy)-1-naphthyl
(408) 6-N-methyl sulfonamide-1-naphthyl
(409) 3-N, N-dimethyl (carbamyl)-4-methoxyl-1-naphthyl
(410) 5-methoxyl-6-N-benzyl sulfonamide-1-naphthyl
(411) 3,6-two-N-phenyl sulfamoyl-1-naphthyl
(412) methyl
(413) ethyl
(414) butyl
(415) octyl group
(416) dodecyl
(417) 2-butoxy-2-ethoxyethyl group
(418) benzyl
(419) 4-methoxy-benzyl
Figure A20061005506401051
(424) methyl
(425) phenyl
(426) butyl
(430) methyl
(431) ethyl
(432) butyl
(433) octyl group
(434) dodecyl
(435) 2-butoxy 2-ethoxyethyl group
(436) benzyl
(437) 4-methoxy-benzyl
Figure A20061005506401081
Among the present invention,, also can use the melamine polymkeric substance as compound with 1,3,5-triazines ring.The melamine polymkeric substance preferably adopts by the melamine compound of following general formula (13) expression and the polyreaction of carbonyls and synthesizes.
In the above-mentioned synthetic reaction process flow diagram, R 11, R 12, R 13, R 14, R 15And R 16Be hydrogen atom, alkyl, alkenyl, aryl or heterocyclic radical.
Illustrated various groups in abovementioned alkyl, alkenyl, aryl and heterocyclic radical and their substituting group, its definition and above-mentioned general formula (12), their substituting group are identical.
The polyreaction of melamine compound and carbonyls is identical with the synthetic method of common melamine resin (for example, melamino-formaldehyde resin etc.).In addition, also can use commercially available melamine polymkeric substance (melamine resin).
The molecular weight of melamine polymkeric substance is preferably 2,000～400,000.The concrete example of the repetitive of melamine polymkeric substance below is shown.
Figure A20061005506401092
MP-1：R 13、R 14、R 15、R 16：CH 2OH
MP-2：R 13、R 14、R 15、R 16：CH 2OCH 3
MP-3：R 13、R 14、R 15、R 16：CH 2O-i-C 4H 9
MP-4：R 13、R 14、R 15、R 16：CH 2O-n-C 4H 9
MP-5：R 13、R 14、R 15、R 16：CH 2NHCOCH＝CH 2
MP-6：R 13、R 14、R 15、R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-7：R 13、R 14、R 15：CH 2OH；R 16：CH 2OCH 3
MP-8：R 13、R 14、R 16：CH 2OH；R 15：CH 2OCH 3
MP-9：R 13、R 14：CH 2OH；R 15、R 16：CH 2OCH 3
MP-10：R 13、R 16：CH 2OH；R 14、R 15：CH 2OCH 3
MP-11：R 13：CH 2OH；R 14、R 15、R 16：CH 2OCH 3
MP-12：R 13、R 14、R 16：CH 2OCH 3；R 15：CH 2OH
MP-13：R 13、R 16：CH 2OCH 3；R 14、R 15：CH 2OH
MP-14：R 13、R 14、R 15：CH 2OH；R 16：CH 2O-i-C 4H 9
MP-15：R 13、R 14、R 16：CH 2OH；R 15：CH 2O-i-C 4H 9
MP-16：R 13、R 14：CH 2OH；R 15、R 16：CH 2O-i-C 4H 9
MP-17：R 13、R 16：CH 2OH；R 14、R 15：CH 2O-i-C 4H 9
MP-18：R 13：CH 2OH；R 14、R 15、R 16：CH 2O-i-C 4H 9
MP-19：R 13、R 14、R 16：CH 2O-i-C 4H 9；R 15：CH 2OH
MP-20：R 13、R 16：CH 2O-i-C 4H 9；R 14、R 15：CH 2OH
MP-21：R 13、R 14、R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-22：R 13、R 14、R 16：CH 2OH；R 15：CH 2O-n-C 4H 9
MP-23：R 13、R 14：CH 2OH；R 15、R 16：CH 2O-n-C 4H 9
MP-24：R 13、R 16：CH 2OH；R 14、R 15：CH 2O-n-C 4H 9
MP-25：R 13：CH 2OH；R 14、R 15、R 16：CH 2O-n-C 4H 9
MP-26：R 13、R 14、R 16：CH 2O-n-C 4H 9；R 15：CH 2OH
MP-27：R 13、R 16：CH 2O-n-C 4H 9；R 14、R 15：CH 2OH
MP-28：R 13、R 14：CH 2OH；R 15：CH 2OCH 3；R 16：CH 2O-n-C 4H 9
MP-29：R 13、R 14：CH 2OH；R 15：CH 2O-n-C 4H 9；R 16：CH 2OCH 3
MP-30：R 13、R 16：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2O-n-C 4H 9
MP-31：R 13：CH 2OH；R 14、R 15：CH 2OCH 3；R 16：CH 2O-n-C 4H 9
MP-32：R 13：CH 2OH；R 14、R 16：CH 2OCH 3；R 15：CH 2O-n-C 4H 9
MP-33：R 13：CH 2OH；R 14：CH 2OCH 3；R 15、R 16：CH 2O-n-C 4H 9
MP-34：R 13：CH 2OH；R 14、R 15：CH 2O-n-C 4H 9；R 16：CH 2OCH 3
MP-35：R 13、R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-36：R 13、R 16：CH 2OCH 3；R 15：CH 2OH；R 15：CH 2O-n-C 4H 9
MP-37：R 11：CH 2OCH 3；R 14、R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-38：R 13、R 16：CH 2O-n-C 4H 9；R 14：CH 2OCH 3；R 15：CH 2OH
MP-39：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2O-n-C 4H 9；R 16：CH 2NHCOCH＝CH 2
MP-40：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2O-n-C 4H 9
MP-41：R 13：CH 2OH；R 14：CH 2O-n-C 4H 9；R 15：CH 2NHCOC
H＝CH 2；R 16：CH 2OCH 3
MP-42：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2O-n-C 4H 9；R 16：CH 2NHCOCH＝CH 2
MP-43：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2O-n-C 4H 9
MP-44：R 13：CH 2O-n-C 4H 9；R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2NHCOCH＝CH 2
MP-45：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 16：CH 2NHCOCH＝CH 2
MP-46：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-47：R 13：CH 2OH；R 14：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2OCH 3
MP-48：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 16：CH 2NHCOCH＝CH 2
MP-49：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-50：R 13：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2NHCOCH＝CH 2
Figure A20061005506401121
MP-51：R 13、R 14、R 15、R 16：CH 2OH
MP-52：R 13、R 14、R 15、R 16：CH 2OCH 3
MP-53：R 13、R 14、R 15、R 16：CH 2O-i-C 4H 9
MP-54：R 13、R 14、R 15、R 16：CH 2O-n-C 4H 9
MP-55：R 13、R 14、R 15、R 16：CH 2NHCOCH＝CH 2
MP-56：R 13、R 14、R 15、R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-57：R 13、R 14、R 15：CH 2OH；R 16：CH 2OCH 3
MP-58：R 13、R 14、R 16：CH 2OH；R 15：CH 2OCH 3
MP-59：R 13、R 14：CH 2OH；R 15、R 16：CH 2OCH 3
MP-60：R 13、R 16：CH 2OH；R 14、R 15：CH 2OCH 3
MP-61：R 13：CH 2OH；R 14、R 15、R 16：CH 2OCH 3
MP-62：R 13、R 14、R 16：CH 2OCH 3；R 15：CH 2OH
MP-63：R 13、R 16：CH 2OCH 3；R 14、R 15：CH 2OH
MP-64：R 13、R 14、R 15：CH 2OH；R 16：CH 2O-i-C 4H 9
MP-65：R 13、R 14、R 16：CH 2OH；R 15：CH 2O-i-C 4H 9
MP-66：R 13、R 14：CH 2OH；R 15、R 16：CH 2O-i-C 4H 9
MP-67：R 13、R 16：CH 2OH；R 14、R 15：CH 2O-i-C 4H 9
MP-68：R 13：CH 2OH；R 14、R 15、R 16：CH 2O-i-C 4H 9
MP-69：R 13、R 14、R 16：CH 2O-i-C 4H 9；R 15：CH 2OH
MP-70：R 13、R 16：CH 2O-i-C 4H 9；R 14、R 15：CH 2OH
MP-71：R 13、R 14、R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-72：R 13、R 14、R 16：CH 2OH；R 15：CH 2O-n-C 4H 9
MP-73：R 13、R 14：CH 2OH；R 15、R 16：CH 2O-n-C 4H 9
MP-74：R 13、R 16：CH 2OH；R 14、R 15：CH 2O-n-C 4H 9
MP-75：R 13：CH 2OH；R 14、R 15、R 16：CH 2O-n-C 4H 9
MP-76：R 13、R 14、R 16：CH 2O-n-C 4H 9；R 15：CH 2OH
MP-77：R 13、R 16：CH 2O-n-C 4H 9；R 14、R 15：CH 2OH
MP-78：R 13、R 14：CH 2OH；R 15：CH 2OCH 3；R 16：CH 2O-n-C 4H 9
MP-79：R 13、R 14：CH 2OH；R 15：CH 2O-n-C 4H 9；R 16：CH 2OCH 3
MP-80：R 13、R 16：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2O-n-C 4H 9
MP-81：R 13：CH 2OH；R 14、R 15：CH 2OCH 3；R 16：CH 2O-n-C 4H 9
MP-82：R 13：CH 2OH；R 14、R 16：CH 2OCH 3；R 15：CH 2O-n-C 4H 9
MP-83：R 13：CH 2OH；R 14：CH 2OCH 3；R 15、R 16：CH 2O-n-C 4H 9
MP-84：R 13：CH 2OH；R 14、R 15：CH 2O-n-C 4H 9；R 16：CH 2OCH 3
MP-85：R 13、R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-86：R 13、R 16：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2O-n-C 4H 9
MP-87：R 13：CH 2OCH 3；R 14、R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-88：R 13、R 16：CH 2O-n-C 4H 9；R 14：CH 2OCH 3；R 15：CH 2OH
MP-89：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2O-n-C 4H 9；R 16：CH 2NHCOCH＝CH 2
MP-90：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2O-n-C 4H 9
MP-91：R 13：CH 2OH；R 14：CH 2O-n-C 4H 9；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2OCH 3
MP-92：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2O-n-C 4H 9；R 16：CH 2NHCOCH＝CH 2
MP-93：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2O-n-C 4H 9
MP-94：R 13：CH 2O-n-C 4H 9；R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2NHCOCH＝CH 2
MP-95：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 16：CH 2NHCOCH＝CH 2
MP-96：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-97：R 13：CH 2OH；R 14：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2OCH 3
MP-98：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 16：CH 2NHCOCH＝CH 2
MP-99：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-100：R 13：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2NHCOCH＝CH 2
MP-101：R 13、R 14、R 15、R 16：CH 2OH
MP-102：R 13、R 14、R 15、R 16：CH 2OCH 3
MP-103：R 13、R 14、R 15、R 16：CH 2O-i-C 4H 9
MP-104：R 13、R 14、R 15、R 16：CH 2O-n-C 4H 9
MP-105：R 13、R 14、R 15、R 16：CH 2NHCOCH＝CH 2
MP-106：R 13、R 14、R 15、R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-107：R 13、R 14、R 15：CH 2OH；R 16：CH 2OCH 3
MP-108：R 13、R 14、R 16：CH 2OH；R 15：CH 2OCH 3
MP-109：R 13、R 14：CH 2OH；R 15、R 16：CH 2OCH 3
MP-110：R 13、R 16：CH 2OH；R 14、R 15：CH 2OCH 3
MP-111：R 31：CH 2OH；R 14、R 15、R 16：CH 2OCH 3
MP-112：R 13、R 14、R 16：CH 2OCH 3；R 15：CH 2OH
MP-113：R 13、R 16：CH 2OCH 3；R 14、R 15：CH 2OH
MP-114：R 13、R 14、R 15：CH 2OH；R 16：CH 2O-i-C 4H 9
MP-115：R 13、R 14、R 16：CH 2OH；R 15：CH 2O-i-C 4H 9
MP-116：R 13、R 14：CH 2OH；R 15、R 16：CH 2O-i-C 4H 9
MP-117：R 13、R 16：CH 2OH；R 14、R 15：CH 2O-i-C 4H 9
MP-118：R 13：CH 2OH；R 14、R 15、R 16：CH 2O-i-C 4H 9
MP-119：R 13、R 14、R 16：CH 2O-i-C 4H 9；R 15：CH 2OH
MP-120：R 13、R 16：CH 2O-i-C 4H 9；R 14、R 15：CH 2OH
MP-121：R 13、R 14、R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-122：R 13、R 14、R 16：CH 2OH；R 15：CH 2O-n-C 4H 9
MP-123：R 13、R 14：CH 2OH；R 15、R 16：CH 2O-n-C 4H 9
MP-124：R 13、R 16：CH 2OH；R 14、R 15：CH 2O-n-C 4H 9
MP-125：R 13：CH 2OH；R 14、R 15、R 16：CH 2O-n-C 4H 9
MP-126：R 13、R 14、R 16：CH 2O-n-C 4H 9；R 15：CH 2OH
MP-127：R 13、R 16：CH 2O-n-C 4H 9；R 14、R 15：CH 2OH
MP-128：R 13、R 14：CH 2OH；R 15：CH 2OCH 3；R 16：CH 2O-n-C 4H 9
MP-129：R 13、R 14：CH 2OH；R 15：CH 2O-n-C 4H 9；R 16：CH 2OCH 3
MP-130：R 13、R 16：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2O-n-C 4H 9
MP-131：R 13：CH 2OH；R 14、R 15：CH 2OCH 3；R 16：CH 2O-n-C 4H 9
MP-132：R 13：CH 2OH；R 14、R 16：CH 2OCH 3；R 15：CH 2O-n-C 4H 9
MP-133：R 13：CH 2OH；R 14：CH 2OCH 3；R 15、R 16：CH 2O-n-C 4H 9
MP-134：R 13：CH 2OH；R 14、R 15：CH 2O-n-C 4H 9；R 16：CH 2OCH 3
MP-135：R 13、R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-136：R 13、R 16：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2O-n-C 4H 9
MP-137：R 13：CH 2OCH 3；R 14、R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-138：R 13、R 16：CH 2O-n-C 4H 9；R 14：CH 2OCH 3；R 15：CH 2OH
MP-139：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2O-n-C 4H 9；R 16：CH 2NHCOCH＝CH 2
MP-140：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2O-n-C 4H 9
MP-141：R 13：CH 2OH；R 14：CH 2O-n-C 4H 9；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2OCH 3
MP-142：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2O-n-C 4H 9；R 16：CH 2NHCOCH＝CH 2
MP-143：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2O-n-C 4H 9
MP-144：R 13：CH 2O-n-C 4H 9；R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2NHCOCH＝CH 2
MP-145：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 16：CH 2NHCOCH＝CH 2
MP-146：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCOCH＝CH 2；R 14：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-147：R 13：CH 2OH；R 14：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2OCH 3
MP-148：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 16：CH 2NHCOCH＝CH 2
MP-149：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-150：R 13：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2NHCOCH＝CH 2
Figure A20061005506401171
MP-151：R 13、R 14、R 15、R 16：CH 2OH
MP-152：R 13、R 14、R 15、R 16：CH 2OCH 3
MP-153：R 13、R 14、R 15、R 16：CH 2O-i-C 4H 9
MP-154：R 13、R 14、R 15、R 16：CH 2O-n-C 4H 9
MP-155：R 13、R 14、R 15、R 16：CH 2NHCOCH＝CH 2
MP-156：R 13、R 14、R 15、R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-157：R 13、R 14、R 15：CH 2OH；R 16：CH 2OCH 3
MP-158：R 13、R 14、R 15：CH 2OH；R 15：CH 2OCH 3
MP-159：R 13、R 14：CH 2OH；R 15、R 16：CH 2OCH 3
MP-160：R 13、R 16：CH 2OH；R 14、R 15：CH 2OCH 3
MP-161：R 13：CH 2OH；R 14、R 15、R 16：CH 2OCH 3
MP-162：R 13、R 14、R 16：CH 2OCH 3；R 15：CH 2OH
MP-163：R 13、R 16：CH 2OCH 3；R 14、R 15：CH 2OH
MP-164：R 13、R 14、R 15：CH 2OH；R 16：CH 2O-i-C 4H 9
MP-165：R 13、R 14、R 16：CH 2OH；R 15：CH 2O-i-C 4H 9
MP-166：R 13、R 14：CH 2OH；R 15、R 16：CH 2O-i-C 4H 9
MP-167：R 13、R 16：CH 2OH；R 14、R 15：CH 2O-i-C 4H 9
MP-168：R 13：CH 2OH；R 14、R 15、R 16：CH 2O-i-C 4H 9
MP-169：R 13、R 14、R 16：CH 2O-i-C 4H 9；R 15：CH 2OH
MP-170：R 13、R 16：CH 2O-i-C 4H 9；R 14、R 15：CH 2OH
MP-171：R 13、R 14、R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-172：R 13、R 14、R 16：CH 2OH；R 15：CH 2O-n-C 4H 9
MP-173：R 13、R 14：CH 2OH；R 15、R 16：CH 2O-n-C 4H 9
MP-174：R 13、R 16：CH 2OH；R 14、R 15：CH 2O-n-C 4H 9
MP-175：R 13：CH 2OH；R 14、R 15、R 16：CH 2O-n-C 4H 9
MP-176：R 13、R 14、R 16：CH 2O-n-C 4H 9；R 15：CH 2OH
MP-177：R 13、R 16：CH 2O-n-C 4H 9；R 14、R 15：CH 2OH
MP-178：R 13、R 14：CH 2OH；R 15：CH 2OCH 3；R 16：CH 2O-n-C 4H 9
MP-179：R 13、R 14：CH 2OH；R 15：CH 2O-n-C 4H 9；R 16：CH 2OCH 3
MP-180：R 13、R 16：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2O-n-C 4H 9
MP-181：R 13：CH 2OH；R 14、R 15：CH 2OCH 3；R 16：CH 2O-n-C 4H 9
MP-182：R 13：CH 2OH；R 14、R 16：CH 2OCH 3；R 15：CH 2O-n-C 4H 9
MP-183：R 13：CH 2OH；R 14：CH 2OCH 3；R 15、R 16：CH 2O-n-C 4H 9
MP-184：R 13：CH 2OH；R 14、R 15：CH 2O-n-C 4H 9；R 16：CH 2OCH 3
MP-185：R 13、R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-186：R 13、R 16：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2O-n-C 4H 9
MP-187：R 13：CH 2OCH 3；R 14、R 15：CH 2OH；R 16：CH 2O-n-C 4H 9
MP-188：R 13、R 16：CH 2O-n-C 4H 9；R 14：CH 2OCH 3；R 15：CH 2OH
MP-189：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2O-n-C 4H 9；R 16：CH 2NHCOCH＝CH 2
MP-190：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2O-n-C 4H 9
MP-191：R 13：CH 2OH；R 14：CH 2O-n-C 4H 9；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2OCH 3
MP-192：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2O-n-C 4H 9；R 16：CH 2NHCOCH＝CH 2
MP-193：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2O-n-C 4H 9
MP-194：R 13：CH 2O-n-C 4H 9；R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2NHCOCH＝CH 2
MP-195：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 16：CH 2NHCOCH＝CH 2
MP-196：R 13：CH 2OH；R 14：CH 2OCH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3
MP-197：R 13：CH 2OH；R 14：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 15：CH 2NHCOCH＝CH 2；R 16：CH 2OCH 3
MP-198：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 16：CH 2NHCOCH＝CH 2
MP-199：R 13：CH 2OCH 3；R 14：CH 2OH；R 15：CH 2NHCOCH ＝CH 2；R 16：CH 2NHCO(CH 2) 7CH ＝CH(CH 2) 7CH 3
MP-200：R 13：CH 2NHCO(CH 2) 7CH＝CH(CH 2) 7CH 3；R 14：CH 2OCH 3；R 15：CH 2OH；R 16：CH 2NHCOCH＝CH 2
Among the present invention, also can use the multipolymer that two or more above-mentioned repetitives are combined.Also two or more homopolymer or multipolymer can be merged use.
In addition, also the two or more compounds with 1,3,5-triazines ring can be merged use.Also two or more discoid compounds (compound and the compound with porphyrin skeleton that for example, have the 1,3,5-triazines ring) can be merged and use.
The adjuvant of above-mentioned bar-shaped compound or discoid compound etc. preferably contains 0.2～30 quality % with respect to optical compensating film, especially preferably contains 1～20 quality %.
(matting agent)
In order to give lubricity, perhaps, can add particulates such as matting agent in order to improve rerum natura to optical thin film of the present invention.As particulate, can list the particulate of mineral compound or the particulate of organic compound, as its shape, can use spherical, tabular, bar-shaped, needle-like, stratiform, amorphous etc.
As particulate, for example can list inorganic particles and cross-linked polymer particulates such as metal oxide, oxyhydroxide, silicate, phosphate, carbonate such as silicon dioxide, titania, aluminium oxide, zirconia, lime carbonate, porcelain earth, talcum, roasting calcium silicate, afwillite, alumina silicate, magnesium silicate, calcium phosphate.Wherein, therefore silicon dioxide be preferred owing to can reduce the mist degree of film.Particulates such as silicon dioxide often carry out surface treatment with organism, because this particulate can reduce the mist degree of film, are preferred therefore.
As preferred organism in surface treatment, can list halogenated silanes class, alkoxyl silicone alkanes, silazane, siloxane etc.The mean grain size of particulate is big more, and the lubricity effect is good more, and on the contrary, mean grain size is more little, and the transparency is good more.In addition, the mean grain size of particulate is in the scope of 0.005～1.0 μ m.They can be primary particles, also can form offspring by cohesion.The mean grain size of the primary particle of preferred particulate is preferably 5～50nm, more preferably 7～14nm.These particulates can make film surface produce the concavo-convex of 0.01～1.0 μ m.The content of particulate in celluosic resin is preferably 0.005～10 quality % with respect to celluosic resin, is preferably 0.05～5 quality % especially.
Particulate as silicon dioxide, ア エ ロ ジ Le (AEROSIL) 200,200V, 300, R972, R972V, R974, R202, R812, OX50, the TT600 etc. of Japanese ア エ ロ ジ Le (strain) system be can list, ア エ ロ ジ Le 200V, R972, R972V, R974, R202, R812 are preferably.These particulates also can merge use more than 2 kinds.To merge situation about using more than 2 kinds, can use in ratio mixing arbitrarily.Under this situation, particulate that can mean grain size is different with material, for example, ア エ ロ ジ Le 200V and R972V use according to 0.1: 99.9～99.9: 0.1 scope of mass ratio.
Existence as the particulate in the film of above-mentioned matting agent use as other purpose, also can be used to improve the intensity of film.
These particulates can be by adding with resin is mixing, and then, also can be mixing with plastifier, hindered amine compound, hindered phenol compound, ultraviolet light absorber, sour agent for capturing etc.Perhaps, make the dry thing of its drying after also can using the particle spray that will be scattered in advance in methyl alcohol, the ethanol equal solvent to mix to the celluosic resin, also can add and be mixed into mainly with methylene chloride or methyl acetate being scattered in particulate in the solvent as in the celluosic resin solution of solvent and dry thing that this potpourri dry solidification forms is used as the starting material of fusion curtain coating.More preferably make part or all that further contains plastifier, hindered amine compound, hindered phenol compound, ultraviolet light absorber, sour agent for capturing etc. in this celluosic resin solution that contains particulate.
Film with the superficial layer that contains particulate can constitute at least at the superficial layer that contains the particulate of mean grain size below 1.0 μ m on the face by adopting coetrusion or extrusion molding system film one by one.When superficial layer contains particulate, also can contain above-mentioned particulate in the layer of formation film inside.
(system film)
Optical thin film of the present invention can adopt the fusion The tape casting to form.Do not use employed solvent in the solution casting method (for example methylene chloride etc.), but the method for forming of the fusion curtain coating of employing heating and melting, in more detail, can be divided into several classes such as melt extruding the method for forming, shaping method to suppress, blowing system embrane method, injection moulding, blow molding method, drawing and forming method.Wherein, in order to obtain the protective film for polarizing plate of function admirables such as physical strength and surface accuracy, preferred molten extrusion molding.If in view of the rerum natura of resulting optical thin film, then melt temperature preferably in 120～280 ℃ scope, more preferably 200 ℃～250 ℃.
Promptly, after being shaped to the celluosic resin heated-air drying or vacuum drying of raw material of powder or pellet, with film constituent material heating and melting, after making it demonstrate flowability, melt extrude, be extruded into sheet, for example adopt static to apply method etc. and make its driving fit on cooler drum or endless belt etc. from T type mouth mould, and, obtain not stretched sheet with its cooling curing.The temperature of cooler drum preferably maintains 90～150 ℃.
Peel off the film that obtains preferably by heating arrangements such as one or more cylinder group and/or infrared heaters from cooler drum, heat once more, carry out one or more snippets vertical back cooling that stretches in the longitudinal direction.At this moment, if with the glass transition temperature of film of the present invention as Tg, then preferably at (Tg-30)～(Tg+100) ℃, more preferably heat in the scope at (Tg-20)～(Tg+80) ℃, at throughput direction (length direction; MD) or on the Width (TD) stretch.Preferably in the temperature range of (Tg-20)～(Tg+20) ℃, carry out cross directional stretch earlier, then carry out heat fixation.But also preferably after stretching process, relax processing.
The Tg of optical thin film can control according to the ratio of material category that constitutes film and the material that is constituted.In purposes of the present invention, the Tg of film is preferably more than 120 ℃, more preferably more than 135 ℃.This be because, in the situation that optical thin film of the present invention is used for liquid crystal indicator, if the Tg of this film is lower than above-mentioned numerical value, then because the influence of the temperature of environment for use and heat backlight, state of orientation to the molecule that is fixed on film inside is influential, thereby makes the light path difference and improve as the possibility that big variation takes place for the dimensional stability and the shape of film.On the contrary, if the Tg of this film is too high, then owing to the decomposition temperature near the film constituent material is difficult to preparation, there is volatile ingredient in the decomposition of the material that uses during often owing to filming itself or presents painted.Therefore, preferably below 200 ℃, more preferably below 170 ℃.At this moment, the Tg of film can adopt the method for putting down in writing among the JIS K7121 to wait to obtain.
(Width: situation TD), in the stretch zones that is divided into more than 2, Yi Bian carry out cross directional stretch Yi Bian heat up successively in the scope of 1～50 ℃ of temperature difference, the rerum natura that can alleviate Width like this distributes carrying out cross directional stretch.And then after cross directional stretch, film was kept 0.01～5 minute below the final cross directional stretch temperature, in the scope more than Tg-40 ℃ at it, the rerum natura that can further alleviate Width like this distributes.
Heat fixation is under the temperature that final cross directional stretch temperature is high than it, in the temperature range below Tg-20 ℃, carries out common 0.5～300 second heat fixation.At this moment, preferably in the zone that is divided into more than 2, Yi Bian carry out heat fixation Yi Bian heat up successively in the scope of 1～100 ℃ of temperature difference.
The film of heat fixation is cooled to below the Tg usually, downcuts the film two ends by the part of clip clamping and batch.At this moment, preferably in the temperature range below final heat fixation temperature, more than the Tg, on transverse direction and/or longitudinal direction, carry out 0.1～10% relaxation processes.In addition, cooling preferably in final heat fixation temperature to the scope of Tg, slowly cool off with the cooling velocity of per second below 100 ℃.Cool off, the method for relaxation processes do not have special qualification, can carry out according to known method in the past, Yi Bian on one side but in a plurality of temperature provinces successively cooling carry out these and handle, aspect the dimensional stability of raising film, be particularly preferred like this.In addition, cooling velocity is in final heat fixation temperature when to be T1, film temperature from the time that final heat fixation temperature reaches T2 be t, the value of obtaining according to (T1-T2)/t.
The preferred stretching ratio of optical thin film is at length direction. all stretch 1.01～2 times multiplying power of Width.More preferably stretch 1.01～1.5 times, further preferred the stretching 1.01～1.3 times.Thus, the good optical thin film of optical isotropy can be obtained, simultaneously, planarity good optical film can be obtained.These width of film making process keep or the stretching of transverse direction is preferably carried out with stenter, and this stenter can be a pin stenter, also can be clip stenter.
In addition, the situation obtaining optical compensating film described later changes the stretch rate of length direction and Width, if make either party stretching ratio bigger than the opposing party's stretching ratio by stretching, then can obtain optically anisotropic film.The stretching ratio ratio of Width and the length direction of this moment is preferably 1.1～2.0, and more preferably 1.2～1.5.
Among the present invention, also can be with the concentration that contains additives such as above-mentioned polymkeric substance, plastifier, ultraviolet light absorber, particulate the composition coextrusion of different celluosic resins, make the optical thin film of laminar structure.For example, can make the optical thin film of the formation of so-called skin/core/cortex.For example, particulate can major part enter cortex, perhaps only enters cortex.Polymkeric substance, plastifier, ultraviolet light absorber can major part enter sandwich layer rather than cortex, also can only enter sandwich layer.In addition, in sandwich layer and cortex, also can change the kind of polymkeric substance, plastifier, ultraviolet light absorber, for example, also can make cortex contain polymkeric substance, plastifier and/or the ultraviolet light absorber of low volatility, in sandwich layer, add good plastifier or the good ultraviolet light absorber of ultraviolet-absorbing of plasticity.The Tg of cortex and sandwich layer also can be different, and the Tg of preferred sandwich layer is lower than the Tg of cortex.In addition, melt-flow time-delay contains the viscosity of the fused mass of celluosic resin, also can be different in cortex and sandwich layer, and can be the viscosity of the viscosity＞sandwich layer of cortex, also can be the viscosity of the viscosity 〉=cortex of sandwich layer.
Adopting coetrusion can keep the CONCENTRATION DISTRIBUTION of adjuvant such as plastifier along film thickness direction, also can reduce the content on surface, also can obtain along the few uniform film of the distribution of additives of film thickness direction but extrude by individual layer, therefore is preferred the employing.
Optical thin film of the present invention is as the situation of Polarizer with protective film, and the thickness of this protective film is preferably 10～500 μ m.Especially, be preferably 10～100 μ m, more preferably 20～80 μ m are preferably 30～60 μ m especially.
In addition, in the solution casting method, if the thickness of film increases, then drying load significantly increases, owing to do not need drying process among the present invention, and therefore can be by the thick film of produced with high productivity thickness.Therefore, have such advantage: according to giving purposes such as necessary phase differential and reduction moisture-penetrability, the thickness of film is increased to more than all so far thickness, this is its advantage.In addition, even the thin film of thickness by the film stretching with this thickness, also has the effect that can produce by high throughput rate.
In addition, the Thickness Variation of optical thin film support, length direction, Width all preferably ± 3%, more preferably ± 1%, further preferably in the scope ± 0.1%.
The width of optical thin film of the present invention is preferably 1～4m, is preferably 1.4～4m especially.
With the cellulose ester film that uses as plastifier by the organic acid polyol ester compound of above-mentioned general formula (1) expression of the present invention,, therefore go for the cellulose ester film of wide cut owing to obtained the good optical thin film of planarity.Especially, preferably using fabric width is 1.4～4m, is preferably the film of 1.4～2m especially.If surpass 4m, then carry the difficulty that becomes.
As the length of batching, preferred 500～5000m, more preferably 1000～5000m.In addition, thickness 0～25% high annular knurl decorative pattern preferably is set is beneficial to batch in two ends of width.
(volatile ingredient is removed)
In order stably to produce the film of this long size, importantly do not sneak into volatile composition at the material that is used for curtain coating.Adopt fusion curtain coating legal system film; temperature during its system film is significantly different with solution casting method; there is volatile ingredient if be used for the material of curtain coating; then these adjuvant volatilizations when the system film are attached on the film forming apparatus, will cause various faults; therefore; in order to effectively utilize function as film or protective film for polarizing plate, consider from planarity and the transparent viewpoint of guaranteeing film, be not preferred like this.Particularly under situation about being attached on mouthful mould, become the reason that forms striped at film surface, so often bring out the planarity deterioration.Therefore, in the situation that film constituent material system film is processed, the viewpoint that produces volatile ingredient during from the avoidance heating and melting is considered, does not wish to exist volatilization temperature to be in than the low interior volatile ingredient in zone of melt temperature that is used to make film.
Said above-mentioned volatile ingredient, can list gas such as the moisture of any moisture absorption in the film constituent material or the oxygen of sneaking into, nitrogen or material and buy accessory substance or impurity such as solvent preceding or that when synthetic, sneak into, catalyzer, unreacted monomer, can list the composition that evaporates, distil or volatilize by decomposition by heating.The solvent that uses is different to said herein solvent with being used to when the solution casting to make resin to become that solution is adjusted, and it is the solvent that trace contains in the film constituent material.Therefore, when selecting the film constituent material, the very important point is to avoid the generation volatile ingredient.
Among the present invention, the film constituent material that is used for the fusion curtain coating will be that the volatile ingredient of representative is removed with above-mentioned moisture and above-mentioned solvent or impurity etc. before the system film or during heating preferably.This method of removing can adopt dry method, can carry out according to methods such as heating, decompression method, heating decompression methods.Drying also can be carried out in air or under the atmosphere gas as inert gases such as inert gas selection nitrogen or argons.The preferred water and the content of oxygen wherein of these inert gases is low, preferably in fact not moisture and oxygen.When carrying out these known drying means, on the quality of film, preferably in the temperature province that can not cause the film constituent material to decompose, carry out.Preferably the film constituent material at liquid is the situation of liquid, and it is liquid perhaps by heating it to be become, and removes the water of sneaking into, solvent, impurity etc. by drying nitrogen is waited to bubbling wherein.
Especially, preferably use the cellulose ester resin of moisture less than 0.5 quality %.These characteristic values can be measured according to ASTM-D817-96.Celluosic resin is preferably by further thermal treatment, uses after making moisture be reduced to 0.1～1000ppm.
The film constituent material can reduce the generation of volatile ingredient by carrying out drying in system before the film, can be distinguished within independent resin or resin and the film constituent material, resin potpourri more than at least a kind or solutrope in addition carry out drying.Baking temperature is preferably more than 80 ℃ and at the Tg of institute's drying material or below the fusing point.If comprise and avoid molten sticking viewpoint between the material, then baking temperature more preferably is 100～(Tg-5) ℃, more preferably 110～(Tg-20) ℃.Being preferably 0.5～24 hour drying time, more preferably is 1～18 hour, more preferably 1.5～12 hours.If be lower than these scopes, then tend to make the rate of removing of volatile ingredient to reduce, perhaps make the dry overlong time that is spent, and work as dry material when having Tg, if be heated to the baking temperature higher than Tg, then molten gluing takes place in material, thereby often makes operation become difficult.Drying is preferably carried out below 1 air pressure, Yi Bian especially preferably be decompressed to vacuum～1/2 air pressure, Yi Bian carry out drying.Preferred on one side with the stirring of materials such as resin appropriateness, carry out drying on one side, in drying receptacle, send into dry air or drying nitrogen from the bottom on one side, Yi Bian make its dry fluidized bed mode, owing to can in the shorter time, carry out required drying, be preferred therefore.
Drying process can be separated into 2 more than the stage, for example can use and carry out so dry starting material system film, that is, adopt predrying operation to carry out the keeping of material and before will making film～drying before being about to begin to make film between before 1 week.
(light path difference)
The light path difference (Rt) of light path difference (Ro) and thickness direction in the face of said optical thin film among the present invention, in situation about using as the polarizer protective film, be preferably 0≤Ro≤300nm and-150nm≤Rt≤150nm.More preferably 0≤Ro≤200nm and-50nm≤Rt≤50nm, more preferably 0≤Ro≤70nm and-30nm≤Rt≤30nm.
In addition, the variation of Rt and the width of distribution be preferably less than ± 10nm, more preferably less than ± 8nm, is more preferably less than ± 5nm.Further preferably less than ± 3nm, further preferably less than ± 1nm.Most preferably Rt does not change.
In addition, light path difference Ro, Rt can obtain according to following formula.
Formula (i) Ro=(nx-ny) * d
Formula is Rt=((nx+ny)/2-nz) * d (ii)
Herein, d is the thickness (nm) of film, refractive index n x (largest refractive index in the face of film is also referred to as the refractive index of slow axis direction), ny (in pellicular front with slow axis meet at right angles the refractive index of direction), nz (refractive index of the film on the thickness direction).
In addition, light path difference (Ro), (Rt) can use automatic birefraction meter to measure.For example, use KOBRA-21ADH (prince's instrumentation machine (strain)), under 23 ℃, the environment of 55%RH, 590nm obtains by wavelength.
In addition, slow axis preferably is in Width ± 1 ° of long size film or length direction ± 1 °.Being ± 0.7 ° with respect to Width or length direction more preferably, is ± 0.5 ° with respect to Width or length direction more preferably, is preferably especially ± 0.1 °.
(film residual solvent, amount of moisture)
Because in fact optical thin film of the present invention does not use solvent in film making process, therefore the residual organic solvent amount that is contained in the optical thin film that batches behind the system film is stable, less than 0.1 quality %, can provide thus to have than more stable in the past planarity and the optical thin film of Rt.Especially, also can be provided in the coiling thing of the above long size of 100m and have stable planarity and the optical thin film of Rt.This optical thin film does not have particular restriction for coiling length, preferably can use 1500m, 2500m, 5000m.
The residual organic solvent amount can adopt headspace gas chromatography to measure.That is, with the cellulose ester film of known quantity place in the closed container, 120 ℃ of heating 20 minutes down, the organic solvent that is contained in the gas phase in this closed container is carried out quantitatively with gas chromatograph.Can calculate residual organic solvent amount (%) from this result.
In addition, the situation that contains moisture at film, the amount of moisture (g) that can further adopt other method to obtain in the cellulose ester film to be contained, the value of deducting the quality (g) of moisture (g) of poor quality of the cellulose ester film before and after above-mentioned heat treated and obtaining can be obtained residual organic solvent content (%).
It is very difficult that the residual organic solvent amount (%) that adopts the cellulose ester film of solution casting method making is controlled at below the 0.1 quality %, therefore, need very long drying process, if and adopt this method, then can obtain the extremely low cellulose ester film of residual organic solvent content, thereby can obtain to have cellulose ester film as the good characteristic of optical thin film by cheap cost.
If with film constituent material heating and melting, decomposition reaction is become significantly, and often be accompanied by painted and deterioration owing to this decomposition reaction.In addition, according to decomposition reaction, also tend to the generation of concurrent undesirable volatile ingredient.
In order to avoid the rotten and hydroscopicity of material, the pellet that the film constituent material can be used as more than a kind is preserved, and makes fused mass with pellet then.The Combination of film constituent material or intermiscibility when pelletization can improve fusion also help to obtain the optical homogeneity of film.Constituent material beyond the celluosic resin is evenly mixed with this resin before fusion, can help when being heated fusion, to give uniform meltbility.
(polymeric layer)
Optical compensating film of the present invention is characterised in that, on the said optical thin film in the invention described above (below be sometimes referred to as the fused fiber cellulose ester film) polymeric layer is set, and stretches together with support.Below at length describe.
Said polymeric layer can utilize rubbing method to form among the present invention.The formation operation of polymeric layer so long as make form as the cellulose ester film composition fusion curtain coating of support and as optical thin film after, just do not have particular restriction, also can for example carry out continuously in the film film making process.In addition, behind the film system film, also can use the following stated method: in case will batch the fused fiber cellulose ester film debatching that forms, just utilize micro-groove roll-coater or extrusion coated machine etc., the polymeric layer coating is dry, then, utilize to use the stretching process of stenter, together with the support dried that stretches.Consider that from the degree of freedom of producing, the viewpoint on the quality guarantee preferably the formation operation/stretching process with film film making process and polymeric layer carries out respectively.
In addition,, also can adopt on other support coating to form polymeric layer,, be transferred to the method on the said fused fiber cellulose ester film among the present invention by bonding agent etc. as additive method.
The thickness of said polymeric layer is preferably 1～20 μ m among the present invention, if less than 1 μ m, then is difficult to give desirable phase difference characteristics, and if surpass 20 μ m, then the thickness of film is blocked up, crackle can occur and fractures etc., makes the operability variation.Consider that from the slimming and the viewpoint of giving the purpose of phase difference characteristics the thickness of polymeric layer is preferably below the 15 μ m, more preferably below the 12 μ m, is preferably 2～10 μ m especially.
In the formation of polymeric layer, the preferred solid polymer that can adopt coating method to be coated with, the preferred light transmitance is more than 75%, particularly at the good solid polymer of thermotolerance that can form the good layer of light transmission more than 85%.Among the present invention, from the formation of this coating layer, utilize the viewpoint of the phase differential given of stretching etc. to consider, preferably use in polyetherketone (particularly PAEK), polyamide, polyester, polyimide, polyamidoimide or the polyester-imide a kind or with the potpourri that mixes more than 2 kinds etc.
As the concrete example of above-mentioned polyetherketone (particularly PAEK), can list (spy open the 2001-49110 communique) such as polyetherketones that for example have by the repetitive of following general formula (14) expression.
General formula (14)
In the above-mentioned general formula (14), X is halogen, alkyl or alkoxy, the X on phenyl ring in conjunction with number q, promptly the tetrafluoro benzoylene is not combined with oxyalkylene group, the value that hydrogen atom is counted q in the replacement of all the other positions is 0～4 integer.In addition, R 1Be the compound (base) by following general formula (15) expression, m is 0 or 1.And then n represents the degree of polymerization, is preferably 2～5000, is preferably 5～500 especially.
General formula (15)
Figure A20061005506401291
In addition, in above-mentioned general formula (14),, can list for example fluorine atom, bromine atoms, chlorine atom and iodine atom etc., preferred fluorine atom as the halogen of X.In addition,, can list carbon numbers such as methyl, ethyl, propyl group, isopropyl, butyl for example and be alkyl of 1～6, particularly 1～4 straight or branched etc. as alkyl, wherein, preferable methyl and ethyl, and their haloalkyl, for example trifluoromethyl etc.
And then, as alkoxy, can list carbon numbers such as methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy for example and be alkoxy of 1～6, particularly 1～4 straight or branched etc., wherein, preferred methoxyl and ethoxy, and their halogenated alkoxy, for example trifluoromethoxy etc.Particularly preferably being X in the above-mentioned alkoxy is fluorine atom.
On the other hand, in the group by above-mentioned general formula (15) expression, X ' is halogen, alkyl or alkoxy, and the value in conjunction with number q ' of X ' on phenyl ring is 0～4 integer.As the halogen of X ', as alkyl or alkoxy, can list the group identical with above-mentioned X.
Preferred X ' is fluorine atom, methyl and ethyl and their haloalkyl, for example trifluoromethyl etc.; Methoxyl and ethoxy and their halogenated alkoxy, trifluoromethoxy etc. for example, wherein preferred fluorine atom.
In addition, in above-mentioned general formula (14), (15), X and X ' can be identical or different.
In addition, be 2 above this point based on q or q ' in general formula (14), (15), X or the X ' of existence more than 2 independently of one another can be identical or different in molecule.
Particularly preferred R 1It is group by following general formula (16) expression.
General formula (16)
Figure A20061005506401301
In above-mentioned general formula (15), (16), R 2Be the divalent aromatic group, P is 0 or 1.As this divalent aromatic group, can list for example (o, m or p-) phenylene, naphthyl, xenyl, anthryl, (o, m or p-) terphenyl, phenanthryl, dibenzofuran group, xenyl ether, xenyl sulfuryl, divalent aromatic group of representing by following formula etc.In addition, this divalent aromatic group, its Direct Bonding also can be replaced by above-mentioned halogen, alkyl or alkoxy at fragrant ring hydrogen.
Figure A20061005506401302
Perhaps
Figure A20061005506401303
Preferred divalent aromatic group (R in above-mentioned 2) be the group of representing by following formula.
Figure A20061005506401311
Figure A20061005506401312
Perhaps
Figure A20061005506401313
The above-mentioned PAEK by general formula (14) expression can be made of identical repetitive, also can have repetitives different more than 2 kinds or 3 kinds.In the latter's situation, each repetitive can be block-wise and exist, and also can randomly exist.
According to foregoing,, be polyetherketone by following general formula (17) expression by the preferred polyetherketone in the PAEK of general formula (14) expression.
General formula (17)
Figure A20061005506401314
In addition, the preferred PAEK of situation that contains the group of molecular end be corresponding with general formula (14) and by the polyetherketone of following general formula (18) expression and with general formula (17) polyetherketone corresponding and that represent by following general formula (19).They be intramolecular to tetrafluoro benzoylene one side on the bonding fluorine atom, the polyetherketone of hydrogen bonding atom on oxyalkylene group one side.
General formula (18)
Figure A20061005506401321
General formula (19)
Figure A20061005506401322
On the other hand, as the above-mentioned polyamide or the concrete example of polyester, can list and for example have by the compound of the repetitive of following general formula (20) expression etc.
General formula (20)
Figure A20061005506401323
In above-mentioned general formula (20), B is the alkyl of halogen, carbon number 1～3 or its halides, by the phenyl that replaces more than a kind or 2 kinds in them or the phenyl of non-replacement.Z is 0～3 integer.
E is the alkenyl of covalent bond, carbon number 2 or its halides, CH 2Base, C (CX 3) 2Base, basic, the O atom of CO, S atom, SO 2Base, Si (R) 2Base or NR base.Above-mentioned C (CX 3) 2X in the base is hydrogen atom or halogen, Si (R) 2R in base and the NR base is alkyl or its halides of carbon number 1～3.In addition, position or contraposition between E is in respect to carbonyl or Y base.In addition, halogen is fluorine atom, chlorine atom, iodine atom or bromine atoms (following identical with general formula (20)).
And then Y is O atom or NH base.A is the alkyl of hydrogen atom, halogen, carbon number 1～3 or its halides, nitro, cyano group, the alkylthio of carbon number 1～3, alkoxy or its halides, aryl or its halides, the alkyl ester group of carbon number 1～9, the aryl ester group of carbon number 1～12 or aryl amido group or its substitutive derivative of its substitutive derivative or carbon number 1～12 of carbon number 1～3.
In addition, n is 0～4 integer, and p is 0～3 integer, and q is 1～3 integer, and r is 0～3 integer.Preferred polyamide or polyester are that above-mentioned r and q are 1, at least 1 of its cyclohexyl biphenyl go up substituted polyamide or polyester at 2 and 2 ' with repetitive of representing by following general formula (21).
General formula (21)
Figure A20061005506401331
Above-mentioned general formula (21), m is 0～3 integer, is preferably 1 or 2, x and y are 0 or 1, and can not be 0 simultaneously.In addition, other mark is identical with the implication of the situation of above-mentioned general formula (20), and E is the covalent bond of para-orientation with respect to carbonyl or Y base.
In above-mentioned general formula (20), (21), there are a plurality of situations in B, E, Y or A in molecule, and they can be identical or different.Z, n, m, x, y too can be identical or different.In addition, this situation, B, E, Y, A, z, n, m, x, y judge independently of one another.
Above-mentioned polyamide or polyester by general formula (20) expression can be made of identical repetitive, also can have repetitives different more than 2 kinds or 3 kinds.In the latter's situation, each repetitive can be block-wise and exist, and also can randomly exist.
On the other hand, concrete example as above-mentioned polyimide, for example comprise 9, the condensation polymerization product of two (aminoaryl) fluorenes of 9-and aromatic tetracarboxylic acid's dianhydride can list polymkeric substance with the above repetitive represented by following general formula (22) in Unit 1 etc.
General formula (22)
In the above-mentioned general formula (22), R is hydrogen atom, halogen, phenyl, by 1～4 halogen or have phenyl that the alkyl of 1～10 carbon atom replaces or for having the alkyl of 1～10 carbon atom.4 R can determine independently of one another, can replace in 0～4 scope.The preferred above-mentioned substituting group of its substituting group, but also can contain some different substituting group.In addition, halogen is fluorine atom, chlorine atom, iodine atom or bromine atoms (following identical in general formula (22)).
Z is the tri-substituted aromatic group with 6～20 carbon atoms.Preferred Z is polycycle aromatic group such as Pyromellitic Acid base or naphthylene, fluorenylidene, benzo fluorenylidene, anthrylene or its substitutive derivative or by the group of following general formula (23) expression.In addition, the substituting group as in the substitutive derivative of above-mentioned polycycle aromatic series base can list halogen, have the alkyl of 1～10 carbon atom or its fluoride etc.
General formula (23)
Figure A20061005506401342
In the above-mentioned general formula (23), D is covalent bond, C (R 2) 2Base, basic, the O atom of CO, S atom, SO 2Base, Si (C 2H 5) 2Base, N (R 3) 2Base or their combination, m is 1～10 integer.In addition, above-mentioned R 2Be hydrogen atom or C (R independently of one another 4) 3Base.In addition, R 3Independently for hydrogen atom, have the alkyl of 1～about 20 carbon atoms or have the aryl of about 6～about 20 carbon atoms.R 4Be hydrogen atom, fluorine atom or chlorine atom independently of one another.
In addition, as the polyimide beyond above-mentioned, also can list and have by the polyimide of the unit of following general formula (24), (25) expression etc.In addition, the polyimide that preferably has the unit of representing by general formula (26).
General formula (24)
Figure A20061005506401351
General formula (25)
General formula (26)
In above-mentioned general formula (24), (25), (26), T and L be the alkyl of halogen, carbon number 1～3 or its halides, by the phenyl that replaces more than a kind or 2 kinds in them or the phenyl of non-replacement.Above-mentioned halogen is fluorine atom, chlorine atom, iodine atom or bromine atoms (following identical in general formula (24), (25), (26)).Z is 0～3 integer.
In addition, G and J are covalent bond or connecting key, CH 2Base, C (CX 3) 2Base, basic, the O atom of CO, S atom, SO 2Base, Si (C 2H 5) 2Base or N (CH 3) base.Above-mentioned C (CX 3) 2X in the base is hydrogen atom or halogen (following identical in general formula (24), (25), (26)).
A is hydrogen atom, halogen, alkyl or its halides, nitro, cyano group, alkylthio, alkoxy or its halides, aryl or its halides or alkyl ester group or its substitutive derivative.
R is substituted-phenyl or substituted alkyls such as alkyl or its halides such as hydrogen atom, halogen, phenyl or its halides.N is 0～4 integer, and p is 0～3 integer, and q is 1～3 integer.
In addition, in above-mentioned general formula (24), (25), (26), there are a plurality of situations independently of one another in T, A, R or L in molecule, and they can be identical or different.Z, n, m too can be identical or different.In addition, in this situation, T, A, R, L, z, n, m judge independently of one another.
The above-mentioned polyimide by general formula (22), (24), (25), (26) expression can be made of identical repetitive, also can have repetitives different more than 2 kinds or 3 kinds.This different repetitive also can be to form by the acid dianhydride beyond above-mentioned and/or the copolymerization more than a kind or 2 kinds of diamines.As diamines, special optimization aromatic diamines.The latter has the situation of different repeat units, and each repetitive can be block-wise and exist, and also can randomly exist.
As the above-mentioned acid dianhydride that is used to form different repeat units, can list for example pyromellitic acid anhydride, 3,6-diphenyl pyromellitic acid anhydride, 3, two (trifluoromethyl) pyromellitic acid anhydrides, 3 of 6-, 6-dibromo pyromellitic acid anhydride, 3,6-dichloro pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-xenyl carboxylic acid dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride.
In addition, two (2,5,6-three fluoro-3,4-dicarboxyl phenyl) methane dianhydride, 2, two (3,4-dicarboxyl phenyl)-1 of 2-, 1,1,3,3-hexafluoropropane dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydrides (4,4 '-oxidation diphthalic anhydrides), two (3,4-dicarboxyl phenyl) the sulfone dianhydride (3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic anhydride), 4,4 '-(4,4 '-isopropylidene-two (to the phenylene oxidation)) two (phthalic anhydrides) example that also can be used as above-mentioned acid dianhydride is enumerated.
And then, N, N-(3,4-dicarboxyl phenyl)-N-methyl amine dianhydride, two (3,4-dicarboxyl phenyl) diethylsilane dianhydride, 2,3,6,7-naphthalene-tetracarboxylic dianhydride and 1,2,5,6-naphthalene-tetracarboxylic dianhydride, 2,6-two chloro-naphthalenes-1,4,5, the 8-tetracarboxylic dianhydride waits naphthalene tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride and pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyridine-2,3,5, hetero ring type such as 6-tetracarboxylic dianhydride aromatic tetracarboxylic acid dianhydride etc. also can be used as the example of above-mentioned acid dianhydride and is enumerated.
Preferably the acid dianhydride that can use is 2,2 '-two bromo-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride, 2,2 '-two chloro-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride, 2,2 '-three halogen replacement dianhydride etc. 2,2 '-replace dianhydride etc., preferred especially 2, two (trifluoromethyl)-4 of 2-, 4 ', 5,5 '-biphenyl tetracarboxylic dianhydride.
On the other hand, the diamines that is used to form different repetitives as above-mentioned can list for example (o, m or p-) phenylenediamine, 2, the 4-diaminotoluene, 1,4-diamido-2-methoxybenzene, 1,4-diamido-2-phenyl benzene, 1, the phenylenediamine of 3-diamido-4-chlorobenzene etc., 4,4 '-benzidine, 4, the 4-diaminodiphenyl-methane, 2, two (4-aminophenyl) propane of 2-, 2, two (the 4-aminophenyls) one 1,1,1 of 2-, 3,3, the 3-HFC-236fa, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-.
In addition, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 2, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-, 2, two (4-(4-amino-benzene oxygen) phenyl)-1,1,1 of 2-, 3,3, the 3-HFC-236fa, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 2,2 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 1,8-diaminonaphthalene and 1, naphthylenediamines such as 5-diaminonaphthalene, 2,6-diamino-pyridine and 2, the 4-diamino-pyridine, 2, hetero ring type aromatic diamines such as 4-diamido-S-triazine etc. also can be used as the example of above-mentioned diamines and are enumerated.
The polyimide that can preferably use, for for example using 2,2 '-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride and 4,4 '-two (3,4-dicarboxyl phenyl)-2, the polyimide of that fragrant family acid dianhydrides such as 2-diphenyl propane dianhydride, naphthalene tetracarboxylic acid dianhydride and two (3,4-dicarboxyl phenyl) sulfone dianhydride are made, thermotolerance and solvent soluble.
In addition, as diamines, also preferably for example use 4,4-(9-fluorenylidene)-diphenylamine and 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane and 2,2 '-two chloro-4,4 '-benzidine, 2,2 ', 5,5 '-tetrachloro benzidine and 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 2, two (the 4-amino-benzene oxygen phenyl) HFC-236fa and 1 of 2-, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene and 1 of 3-, fragrant family diamines such as two (3-amino-benzene oxygen) benzene of 3-are made, the polyimide of thermotolerance and solvent soluble.
On the other hand,, do not have particular determination, can use the polymkeric substance more than a kind or 2 kinds aptly as above-mentioned polyamidoimide or polyester-imide.Wherein, preferably use the special polyester-imide put down in writing in the polyamidoimide put down in writing in the clear 61-162512 communique and the clear 64-38472 communique of Te Kai etc. of opening.
The molecular weight that polymeric layer forms the solid polymer of usefulness does not have particular determination, is preferably in the solvent soluble.From the thickness and precision of coated film and surface accuracy and even surface smoothing, film strength, because the preventing property that the crackle that the flexible and deformation of filming situation etc. cause takes place, viewpoint consideration that the dissolubility (preventing gelation) of solvent is waited, based on weight-average molecular weight, be 10,000～1,000,000, be preferably 20,000～500,000, be preferably 50,000～200,000 especially.In addition, weight-average molecular weight be with polyethylene oxide as standard sample, use solvent dimethylformamide, the value that records with gel permeation chromatograph (GPC).
In the formation of polymeric layer, can use above-mentioned PAEK and solid polymers such as polyamide, polyester and polyimide separately, also isoplassont can be mixed use more than 2 kinds.In addition, 2 kind or more the mixture of polymers of the potpourri etc. that also can be used as for example PAEK and polyamide with different functional groups used.
In addition, in the significantly reduced scope of orientation of the above-mentioned solid polymer that can not cause forming polymeric layer, also can and with tygon, polypropylene, polystyrene, polymethylmethacrylate, ABS resin and AS resin beyond above-mentioned, gather suitable polymer blend such as acetic acid esters, polycarbonate more than a kind or 2 kinds.In addition, thermoset resins such as epoxy resin, phenolic resin, novolac resin etc. also can be used as above-mentioned and are enumerated with the example of polymkeric substance.And,, just do not have particular restriction as long as in can not causing the significantly reduced scope of orientation with the use amount of polymkeric substance, and be generally below the 50 quality %, be preferably below the 40 quality %, be preferably especially below the 30 quality %.
In order to make the solid polymer liquid stateization that forms polymeric layer, can adopt aptly thermoplastic polymer is heated mode that makes its fusion or the modes such as method of dissolution of solid polymer being made solution in solvent.Therefore, the solidification of this developer layer can perhaps carry out its drying except that desolvating from this developer layer in the latter's solution by make this developer layer cooling in the former fused solution.When polymeric layer forms, can cooperate the various adjuvants that constitute by stabilizing agent, plastifier and metal species etc. as required.
Drying after the above-mentioned polymeric layer coating can adopt air dry (air-dry) mode or heat drying mode, usually, can wait with hot blast, infrared ray, heated roller, microwave and carry out.Aspect easy, preferably carry out with hot blast.Baking temperature, stretch processing temperature in view of subsequent handling with stenter, preferably in 40～150 ℃ scope, adopt the stage drying method, the temperature province that was divided into for 3～5 stages, slowly improve, good for rerum naturas such as the anti-wound property that makes polymeric layer and dimensional stabilitys, more preferably carry out 80～140 ℃ scope.
As above-mentioned solvent, can list for example chloroform and methylene chloride, phenixin and ethylene dichloride, tetrachloroethane and trichloroethanes, tetrachloroethane and halogenated hydrocarbons such as chlorobenzene, o-dichlorobenzene; Phenol such as phenol and parachlorophenol; Benzene and toluene, dimethylbenzene and methoxybenzene, 1,2-dimethoxy benzenes etc. are aromatic hydrocarbon based; Ketones such as acetone and butanone, methyl isobutyl ketone and cyclohexanone, cyclopentanone and 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-; Ester such as ethyl acetate and butyl acetate class.
In addition, the tert-butyl alcohol and glycerine, ethylene glycol and triethylene glycol, glycol monoethyl ether and diethylene glycol dimethyl ether, propylene glycol and dipropylene glycol, 2-methyl-2, alcohols such as 4-pentanediol; Amide-type such as dimethyl formamide and dimethyl acetamide; Nitrile such as acetonitrile and butyronitrile; Ethers such as diethyl ether and butyl oxide, tetrahydrofuran; And the example that other methylene chloride and carbon disulphide, ethyl cellosolve and butyl cellosolve etc. also can be used as above-mentioned solvent is enumerated.
Solvent can use separately, perhaps suitable combined hybrid more than 2 kinds is used.Solution is considered from viewpoints such as coating viscosity, with respect to solvent 100 mass parts, makes dissolution of solid polymer 2～100 mass parts, preferred 5～50 mass parts, preferred especially 10～40 mass parts.
For the polymkeric substance that makes liquid stateization launches, can adopt the suitable film generation types such as The tape casting, extrusion molding of for example method of spin coating and cylinder rubbing method, curtain coating and printing rubbing method, dip coated method and casting filming therapy, scraping article rubbing method and grooved roller print process etc. on the fused fiber cellulose ester film.Wherein, consider, preferably adopt solution film-forming methods such as The tape casting from the viewpoints such as commercial production of the film that alleviates uneven thickness and orientation deformation fluctuation etc.
Polymeric layer is dissolved in solvent as described above and the polymer solution of liquid stateization launches on support, makes its drying, carry out stretch processing described later together with support.The stretching of stenter mode is preferably adopted in stretch processing.If adopt this mode, then can under the state that is supported on the base material, handle polymeric layer, prepare continuously with good preparation efficiency and processing accuracy.
(stretched operation)
Describe for the preferred stretched operation of optical compensating film of the present invention.
Optical compensating film of the present invention preferably after on the optical thin film that the fusion curtain coating forms above-mentioned polymeric layer being set, by following stretched operation, stretches polymeric layer and optical thin film simultaneously, carries out the control of phase differential.In addition, also the optical thin film that its fusion curtain coating is formed similarly can be stretched separately.
The preferred direction along optical thin film that stretches stretches 1.0～2.0 times, stretches about 0.8～1.5 times along other direction.
Can to the length direction of for example film and in pellicular front perpendicular intersection direction, be that Width stretches one by one or simultaneously, at this moment, if the stretching ratio at least one direction is too small, then can not get sufficient phase differential, if it is and excessive, then stretching becomes difficult, and often ruptures.
For example, along the situation that the direction of fusion curtain coating stretches, if the contraction of Width is excessive, then the refractive index of the thickness direction of film becomes excessive.In this situation, the contraction that can stretch and suppress or improve the film broad ways by the while broad ways.Index distribution often appears in the situation in that broad ways stretches on Width.This often appears at the situation that adopts the stenter method, can think, this is because broad ways stretches, and causes producing convergent force at the film middle body, and the phenomenon that is fixed and produces owing to the end, just is called as the phenomenon of so-called boing.Even but in this situation, as long as by stretching along this curtain coating direction, just can suppress the boing phenomenon, thereby the phase differential that can alleviate width distributes.
And then, by on orthogonal 2 direction of principal axis, stretching, can reduce the Thickness Variation of the film that obtains.If the Thickness Variation of optical compensating film is excessive, then often become the fluctuation of phase differential, the painted uneven problem that waits will appear when being used for LCD.
The Thickness Variation of optical compensating film of the present invention preferably ± 3%, more preferably in the scope ± 1%.For above such purpose, the method that stretches on 2 direction of principal axis of square crossing mutually is effective.
As optical compensating film, optical path difference for direction in the control plane or thickness direction, can on system film direction, carry out the free end uniaxial tension, perhaps also can on Width, stretch, also can carry out the biaxial stretch-formed of on curtain coating direction unbalanced contraction.The multiplying power of shrinkage direction is preferably 0.7～1.0 times.
For stress,,, can broad ways give slow axis to optical compensating film by on Width, stretching using the situation that obtains positive birefringent celluosic resin.This situation, in the present invention, in order to improve display quality, the slow axis of optical compensating film preferably is on the Width, preferred satisfied (stretching ratio of Width)＞(stretching ratio of curtain coating direction).
Be coated with the optical thin film of the fusion curtain coating of polymeric layer, preferably before stretching, at first below 50～180 ℃, more preferably below 60～160 ℃, further preferred below 70～150 ℃, carry out 5 seconds above to below 3 minutes, more preferably more than 10 seconds to below 2 minutes, more preferably more than 15 seconds to the thermal treatment below 90 seconds (thermal pretreatment).This thermal treatment preferably before with stenter clamping film to from be clamped to before beginning to stretch during implement.Particularly preferably in from stenter clamping film before begin to stretch during implement.
Stretch preferably according to 5～300%/minute, more preferably 10～200%/minute, more preferably 15～150%/minute speed implement.The preferred use stenter clamping film two that stretches is brought in and is carried out.
As the stretching angle, preferred 2 °～10 °, more preferably 3 °～7 °, most preferably 3 °～5 °.Draw speed can be undertaken by certain speed, also can make its variation.
Temperature during stretching preferably is controlled at draft temperature B the relation by following formula (I) expression.
Melt temperature A-100 ℃≤draft temperature of formula (I) B≤melt temperature A-40 ℃
(in the formula, melt temperature A represents the temperature of the melt-flow time-delay of optical thin film)
If draft temperature B is lower than melt temperature A-100 ℃ temperature, then, must improve stretching ratio in order to obtain sufficient phase differential, will cause the film fracture like this, perhaps make its mist degree, painted rising.On the other hand, if draft temperature B is the temperature above melt temperature A-40 ℃, then the control of phase differential and repeatability are poor, and it is inhomogeneous to be easy to generate stretching.And this situation also be increased in easily long-term between in painted.
Preferred draft temperature B should satisfy melt temperature A-90 ℃≤draft temperature B≤melt temperature A-50 ℃ relation.
The atmosphere temperature degree preferred distribution of stenter in-process is few, Width preferred ± 5 ℃ in, more preferably ± 2 ℃ in, more preferably ± 1 ℃ in, most preferably ± 0.5 ℃ in.At the stenter in-process, preferably with coefficient of heat conductivity 20J/m 2Hr～130 * 10 3J/m 2Hr heat-treats.More preferably at 40J/m 2Hr～130 * 10 3J/m 2The scope of hr most preferably is at 42J/m 2Hr～84 * 10 3J/m 2The scope of hr.
Film conveyance tension in the film making process that waits in the stenter depends on temperature, is preferably 120N/m～200N/m, more preferably 140N/m～200N/m.Most preferably be 140N/m～160N/m.
In order to prevent from film making process, to take place the elongation of undesirable film, tension force cutting roller was set before or after stenter preferably.
Said optical compensating film is preferably heat-treated after stretching among the present invention, so that alleviate remaining stress (distortion).Thermal treatment 110～150 ℃, preferably under 100～180 ℃, carry out, more preferably under 130～160 ℃, carry out.At this moment, preferably at coefficient of heat conductivity 20J/m 2Hr～130 * 10 3J/m 2Heat-treat under the hr.More preferably at 40J/m 2Hr～130 * 10 3J/m 2The scope of hr most preferably is at 42J/m 2Hr～84 * 10 3J/m 2The scope of hr.Thus, can reduce remaining stress (distortion), improve under the hot conditions of 90 ℃ of grades or the dimensional stability under the hot and humid condition of 80 ℃, 90%RH etc.
The film that has stretched is cooled to room temperature after stretching.The film that has stretched preferably begins to cool down under the condition that keeps fabric width with stenter, fabric width is shunk to be slowed down, just make its fabric width of by the stenter clamping and shrink 1～10%, more preferably be 2～9% with respect to the film fabric width after stretching, more preferably more than 2% to below 8%.Cooling velocity is preferably implemented according to 10～300 ℃/minute speed, and more preferably 30～250 ℃/minute, more preferably 50～200 ℃/minute.Can with the stenter clamping and be cooled to room temperature, but preferably in clamping process, stop clamping and be converted to roller carrying, coil into the cylinder shape then.
The optical compensating film of the present invention that below prepares like that has following characteristic.
(optical characteristics)
Under the state of optical thin film upper strata compression polymer layer, the light path difference Ro by the definition of above-mentioned formula of optical compensating film of the present invention is preferably 20～300nm and light path difference Rt preferably is in-scope of 600～600nm in.In addition, preferred scope is, the Ro value is 20～120nm, and the Rt value is the scope of-400～400nm, and particularly preferred scope is, the Ro value is 40～100nm, and the Rt value is the scope of-300～300nm.
Optical compensating film of the present invention can particularly advantageously be used as the optical compensating film of the VA type liquid crystal indicator with VA model liquid crystal cell.The optical compensating film that uses in the VA type liquid crystal indicator, preferably its Ro value is 20～150nm, the Rt value is 70～400nm.The Ro value is 30～100nm more preferably.Use the situation of two optical compensating films in VA type liquid crystal indicator, the Rt value of film is preferably 70～250nm.Use the situation of an optical compensating film in VA type liquid crystal indicator, the Rt value of film is preferably 150～400nm.
By the light path difference is in the above-mentioned scope, can fully satisfy particularly as the optical property of Polarizer with phase-contrast film.
Other rerum naturas of optical thin film of the present invention, optical compensating film below are described.Following rerum natura is for as independent optical thin film and as coated polymeric layer on optical thin film and make the preferred physics value of its immobilized optical compensating film.
(moisture permeability)
The moisture permeability of optical thin film of the present invention, optical compensating film is 1～250g/m under 25 ℃, 90%RH environment preferably 224 hours, 10～200g/m more preferably 224 hours, most preferably be 20～180g/m 224 hours.Moisture permeability can be measured according to the method for putting down in writing among the JIS Z0208.
(equilibrium moisture content)
Optical thin film, the equilibrium moisture content of optical compensating film under 25 ℃ of temperature and relative humidity 60% are preferably 0.1～3%, and more preferably 0.3～2%, be preferably 0.5～1.5% especially.
Equilibrium moisture content can use mensuration machine (Ka Er Fischer determination of moisture device CA-05, Mitsubishi Chemical's (strain) system, moisture gasification installation: VA-05, inner liquid: ア Network ア ミ Network ロ Application CX μ, outer liquid: ア Network ア ミ Network ロ Application AX, nitrogen flow: 200ml/ branch, heating-up temperature: 150 ℃) easily to measure according to karl fischer method.Particularly, 25 ℃, the accurate weighing 0.6～1.0g of the sample of 60% time damping of relative humidity more than 24 hours can be measured with the mensuration machine, obtain equilibrium moisture content from the amount of moisture that obtains.
The water cut of optical thin film of the present invention, optical compensating film in order not damage the cementability with polyvinyl alcohol (PVA) (polarizer), is 0.3～15g/m under 30 ℃ of 85%RH preferably 20.5～10g/m more preferably 2If greater than 15g/m 2, then because temperature variation or humidity change the tendency that the variation of the optical path difference of being brought has increase.
(dimensional stability)
Said optical thin film, optical compensating film among the present invention also have the feature of excellent size stability.Dimensional stability is as the rate of change (%) that adopts following determination method mensuration with respect to original length, and size up changes (contraction) rate and estimates.Size changing rate is preferably 0～-0.06%.
The mensuration of＜size changing rate 〉
Film at interval with cutter is made mark with width, each about 10cm of length in the damping to the laboratory of relative humidity 55% of 23 ℃ of temperature, damping after 24 hours, measure distance (L1).Then, film was kept 24 hours in the calibration cell of the temperature and humidity conditions that is set in defined.Once more film is measured the distance (L2) of mark in the damping to the laboratory of relative humidity 55% of 23 ℃ of temperature, damping after 24 hours.Size changing rate is estimated with following formula.
Size changing rate (%)=(L2-L1)/L1} * 100
(Polarizer)
Polarizer can adopt general method to make.Preferably the rear side of optical thin film of the present invention, optical compensating film being carried out alkalization handles, optical thin film, the optical compensating film of handling soaked in iodine solution drill and stretch, on at least one side surface of the light polarizing film of so making, fit with the polyvinyl alcohol water solution of alkalization type fully.On the opposite side surface, also can use optical thin film of the present invention; also can use thin polymer films such as norbornene-based polymer or polycarbonate, polyethersulfone or polysulfones, polyolefin or acrylic acid series polymeric compounds, polyacrylate, polystyrene or polyvinyl alcohol (PVA), Polyvinylchloride or Vingon, cellulose esters based polymer, can also use other protective film for polarizing plate.For optical thin film of the present invention, optical compensating film,, can use commercially available cellulose ester film as the protective film for polarizing plate that on the opposite side surface, uses.For example, as commercially available cellulose ester film, the preferred cellulose ester film that uses コ ニ カ ミ ノ Le Star Network KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UXW-H, KC8UYW-HA, KC8UX-RHA (コ ニ カ ミ ノ Le オ プ ト (strain) system) etc. can obtain the Polarizer that planarity is good, have stable visual angle expansion effect.
So-called light polarizing film as Polarizer main composition key element, be meant the element that a kind of light that allows the plane of polarization of certain orientation passes through, known representative light polarizing film is the polyethenol series polarizing film now, comprises iodine staining to polyvinyl alcohol film film that forms and the film that makes dichroic dye dyeing.As light polarizing film, can use by with polyvinyl alcohol water solution system film, with its uniaxial tension and dye, or after dyeing, carry out uniaxial tension, the preferred use with boron compound carries out that permanance is handled and the film that obtains.One side surface of optical compensating film of the present invention is fitted on the surface of this light polarizing film, just formed Polarizer.Preferably for the aqueous adhesive of principal ingredient it is fitted with the polyvinyl alcohol (PVA) etc. of alkalization fully.
Light polarizing film is owing to stretch on single shaft direction (being generally length direction), if Polarizer is placed under the hot and humid environment, then draw direction (being generally length direction) shrinks, and is going up elongation with the vertical direction (being generally Width) that stretches.The Polarizer protection becomes thin more with the thickness of film, and the expansion and contraction of Polarizer is big more, and particularly light polarizing film is bigger along the amount of contraction of draw direction.Generally,, therefore Polarizer is being protected the situation of making film with film, particularly importantly will suppress the expansion and contraction of curtain coating direction owing to the draw direction and the Polarizer protection of light polarizing film are fitted with the curtain coating direction (MD direction) of film.Therefore optical compensating film of the present invention is suitable as this protective film for polarizing plate and uses because dimensional stability is very good.In addition, the thickness of light polarizing film is preferably 5～30 μ m.
Even if in the endurancing under 60 ℃, the condition of 90%RH, the fluctuation situation that corrugated rises and falls can not increase, and have the Polarizer of optical compensating film overleaf on the side yet, do not change, have good visibility in endurancing back angle characteristic.
Polarizer can be further by the protective film of fitting on a side surface of this Polarizer, and the applying isolated film constitutes on opposite surfaces.Protective film and isolated film are used for protecting Polarizer when Polarizer is delivered and when goods are checked etc.This situation, the applying protective film for the surface of protecting Polarizer is used for Polarizer opposing face one side of liquid crystal board binding face.In addition, isolated film is used to cover the bonding coat that is fitted on the liquid crystal board, and Polarizer is used to fit to face side on the liquid crystal cell.
(liquid crystal indicator)
By Polarizer of the present invention is fitted at least one side surface of liquid crystal cell, make liquid crystal indicator, can make the good liquid crystal indicator of the present invention of various visibilities.Optical thin film of the present invention, optical compensating film are preferred among the LCD of various type of drive such as reflection-type, infiltration type, semi-transmission type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type.In addition, optical thin film of the present invention, optical compensating film also are preferred for the good plasma scope of planarity, field-emitter display, OLED display, inorganic EL display, electronic paper various display device such as (electron paper).Particularly more than picture is 30 types in the display device of big picture, color spot and ripple spot are few, watch the eyes also can tired effect for a long time even have.
For example, being constructed as follows of preferred liquid crystal indicator, but be not subjected to their qualification.In addition, the fused fiber cellulose ester film is meant said optical thin film among the present invention.
(visual side) fused fiber cellulose ester film/polarizer/fused fiber cellulose ester film/liquid crystal cell/polymeric layer/fused fiber cellulose ester film/polarizer/fused fiber cellulose ester film (backlight)
(visual side) fused fiber cellulose ester film/polarizer/fused fiber cellulose ester film/polymeric layer/liquid crystal cell/polymeric layer/fused fiber cellulose ester film/polarizer/protective film/(backlight)
Among the present invention, because by using the optical compensating film that carries out stretch processing together with the support that polymeric layer is set, can expect to occur sufficient optical path difference, therefore, the use that the optical compensating film of polymeric layer is set can be 1, consider that from stable aspect this is preferred as the optical path difference of the object of the invention.
On the fused fiber cellulose ester film of above-mentioned visual side, also can be coated with known functional layer such as antistatic layer, transparency conducting layer, hard conating, antiglare hardcoat, anti-reflection layer, stain-proofing layer, easy slip layer, easy bonding coat, antiglare layer, gas-barrier layer.
Use in the liquid crystal indicator of the present invention backlight can be side light type, also can be under type, can also be their combination, type is backlight under being preferably.Type is backlight for having the color liquid crystal display arrangement LED-backlit of redness (R) LED, green (G) LED and blueness (B) LED under particularly preferred, preferably uses the spike of for example above-mentioned redness (R) LED long for more than the 610nm, the spike length of above-mentioned green (G) LED is that the scope of 530 ± 10nm is interior, the spike length of above-mentioned blueness (B) LED backlight as below the 480nm.Kind as green (G) LED of spike length in above-mentioned scope, for example can list DG1112H (ス Application レ one electric (strain) system), UG1112H (ス Application レ one electric (strain) system), E1L51-3G (Toyota's synthetic (strain) system), E1L49-3G (Toyota's synthetic (strain) system), NSPG500S (day inferior chemical industry (strain) system) etc.The kind of the LED that uses as red (R) LED can list for example FR1112H (ス Application レ one electric (strain) system), FR5366X (ス Application レ one electric (strain) system), NSTM515AS (inferior chemical industry of day (strain) is made), GL3ZR2D1COS (シ ヤ one プ (strain) system), GM1JJ35200AE (シ ヤ one プ (strain) system) etc.The kind of the LED that uses as blue (B) LED can list DB1112H (ス Application レ one electric (strain) system), DB5306X (ス Application レ one electric (strain) system), E1L51-3B (Toyota's synthetic (strain) system), E1L4E-SB1A (Toyota's synthetic (strain) system), NSPB630S (day inferior chemical industry (strain) system), NSPB310A (inferior chemical industry of day (strain) is made) etc.
Can make above-mentioned 3 look LED combination backlight.Perhaps also can use White LED.
In addition, as under type backlight, can list the spy open put down in writing among the 2001-281656 under backlight, the spy of type open LED of putting down in writing among the 2001-305535 etc. the use point source of light under backlight, the spy of type open put down in writing among the 2002-311412 under mode backlight etc., but this is not had particular determination.
According to the present invention, can make because the heating that causes of LED-backlit and with the reduction that is changed significantly of the visibility that environmental change caused, the liquid crystal indicator that color reproduction is good.
(embodiment)
Below list embodiment and specifically describe the present invention, but the present invention is not subjected to their qualification.
Synthesis example 1
(synthesizing of polymkeric substance 1～12)
＜polymkeric substance 1 〉
Methyl acrylate 10 mass parts
Acrylic acid 2-hydroxy methacrylate 1 mass parts
Azoisobutyronitrile (AIBN) 1 mass parts
Benzene 30 mass parts
Above-mentioned composition is put in the four-hole boiling flask (input port, thermometer, reflux condensing tube, nitrogen inlet, stirring machine are installed), slowly be warming up to 80 ℃, carry out polymerization in 5 hours while stirring, polymerization is put into polymer solution in a large amount of methyl alcohol after finishing, and makes its precipitation, use methanol wash again, refining, drying obtains the polymkeric substance 1 of weight-average molecular weight 5000 (measuring with GPC).
＜polymkeric substance 2 〉
Methyl acrylate 10 mass parts
Acrylic acid 2-hydroxy methacrylate 1 mass parts
AIBN 2 mass parts
Toluene 30 mass parts
Similarly carry out polymerization, precipitation, refining with polymkeric substance 1, obtain the polymkeric substance 2 of weight-average molecular weight 2000.
＜polymkeric substance 3 〉
Methyl acrylate 12 mass parts
Azo two (butyric acid 2-hydroxy methacrylate) 2.4 mass parts
Toluene 30 mass parts
Similarly carry out polymerization, precipitation, refining with polymkeric substance 1, obtain the polymkeric substance 3 of weight-average molecular weight 2000.
＜polymkeric substance 4 〉
Methyl methacrylate 10 mass parts
2-hydroxyethyl methacrylate 1 mass parts
AIBN 2 mass parts
Toluene 30 mass parts
Similarly carry out polymerization, precipitation, refining with polymkeric substance 1, obtain the polymkeric substance 4 of weight-average molecular weight 2000.
＜polymkeric substance 5 〉
Methyl acrylate 6 mass parts
Ethyl acrylate 5 mass parts
Acrylic acid 2-hydroxy methacrylate 1 mass parts
AIBN 2 mass parts
Toluene 30 mass parts
Similarly carry out polymerization, precipitation, refining with polymkeric substance 1, obtain the polymkeric substance 5 of weight-average molecular weight 2000.
＜polymkeric substance 6 〉
Methyl methacrylate 6 mass parts
Jia Jibingxisuanyizhi 5 mass parts
2-hydroxyethyl methacrylate 1 mass parts
AIBN 2 mass parts
Toluene 30 mass parts
Similarly carry out polymerization, precipitation, refining with polymkeric substance 1, obtain the polymkeric substance 6 of weight-average molecular weight 2,000.
＜polymkeric substance 7 〉
Adopt the spy to open the polymerization of putting down in writing in the 2000-344823 communique and carry out bulk polymerization.That is, in the flask that has stirring machine, nitrogen ingress pipe, thermometer, input port and reflux condensing tube, Yi Bian import following methyl methacrylate and ruthenocene, Yi Bian content is heated to 70 ℃.Then, half of following β-Qiu Jibingsuan of fully carrying out nitrogen replacement under agitation added in the flask.After adding β-Qiu Jibingsuan, the content in the flask in stirring is maintained 70 ℃, carry out polymerization in 2 hours.And then, to append through the residue of the β-Qiu Jibingsuan of nitrogen replacement after half, the temperature maintenance of the content in will stirring is again carried out polymerization in 4 hours at 70 ℃.The temperature of reactant is turned back to room temperature, in reactant, add tetrahydrofuran solution 20 mass parts of 5 quality % benzoquinones, polymerization is stopped.Polymkeric substance under reduced pressure on one side slowly is heated to 80 ℃ with evaporator,, obtains polymkeric substance 7 Yi Bian remove tetrahydrofuran, remaining monomer and remaining mercaptan compound.Weight-average molecular weight is 3400.In addition, hydroxyl value (adopting following assay method) is 50.
Methyl methacrylate 100 mass parts
Ruthenocene (metallic catalyst) 0.05 mass parts
β-Qiu Jibingsuan 12 mass parts
(assay method of hydroxyl value)
This mensuration is carried out according to the method for JIS K 0070 (1992).This hydroxyl value is defined as, and when making sample 1g acetylation, mg number with the needed potassium hydroxide of acetate of hydroxyl bonding is used to neutralize.Particularly, accurate weighing sample Xg (about 1g) in flask is to wherein accurately adding acetylation reagent (in acetic anhydride 20ml adding pyridine and the solution of the 400ml that forms) 20ml.On the flask mouth, air cooled tube is installed, with 95～100 ℃ glycerol bath heating.Cooling after 1 hour 30 minutes adds distilled water 1ml from air cooled tube, makes acetic anhydride be decomposed into acetate.Then, use the potential difference (PD) titration apparatus, carry out titration with the 0.5mol/L potassium hydroxide-ethanol solution, with the flex point of the titration curve that obtains as terminal point.And then, as blank test, do not add sample and carry out titration, obtain the flex point of titration curve.Hydroxyl value is calculated by following formula.
Hydroxyl value=(B-C) * f * 28.05/X}+D
In the formula, B is the amount (ml) of the potassium hydroxide-ethanol solution of the 0.5mol/L that uses in the blank test, C is the amount (ml) of the potassium hydroxide-ethanol solution of the 0.5mol/L that uses in the titration, f is the coefficient of 0.5mol/L potassium hydroxide-ethanol solution, D is an acid number, and 28.05 are 1/2 of potassium hydroxide 1mol amount 56.11.
＜polymkeric substance 8 〉
Adopt the spy to open the polymerization of putting down in writing in the 2000-128911 communique and carry out bulk polymerization.That is, in the flask that has stirring machine, nitrogen ingress pipe, thermometer, input port and reflux condensing tube, drop into following methyl acrylate, import nitrogen, stir and in flask, add the following thioglycerin of being crossed by nitrogen replacement down.After adding thioglycerin, on one side with the temperature maintenance of content at 60 ℃, carry out polymerization in 4 hours on one side, the temperature of content is turned back to room temperature, tetrahydrofuran solution 20 mass parts to wherein adding benzoquinones 5 quality % stop polymerization.Content is transferred in the evaporator, under 80 ℃, decompression, removes tetrahydrofuran, remaining monomer and remaining thioglycerin, obtain polymkeric substance 8.Weight-average molecular weight is 2100, and hydroxyl value is 35.
Methyl acrylate 100 mass parts
Thioglycerin 5 mass parts
＜polymkeric substance 9 〉
Adopt the method same, make the mix monomer of methyl acrylate and benzyl methacrylate carry out polymerization, obtain polymkeric substance 9 with ruthenocene and β-Qiu Jibingsuan with polymkeric substance 7.Weight-average molecular weight is 1800, and hydroxyl value is 35.
Methyl acrylate 70 mass parts
Benzyl methacrylate 30 mass parts
Ruthenocene 0.05 mass parts
β-Qiu Jibingsuan 12 mass parts
＜polymkeric substance 10 〉
Adopt the method same, use the mix monomer and the thioglycerin of methyl acrylate and cyclohexyl methacrylate to carry out polymerization, obtain polymkeric substance 10 with polymkeric substance 8.Weight-average molecular weight is 2200, and hydroxyl value is 40.
Methyl acrylate 65 mass parts
Cyclohexyl methacrylate 35 mass parts
Thioglycerin 5 mass parts
＜polymkeric substance 11 〉
Similarly use vinyl acetate monomer and thioglycerin to carry out polymerization with polymkeric substance 8, obtain polymkeric substance 11.Weight-average molecular weight is 1600, and hydroxyl value is 35.
Vinyl acetate 100 mass parts
Thioglycerin 5 mass parts
＜polymkeric substance 12 〉
Similarly use the mix monomer of vinyl acetate monomer and vinyl benzoate and thioglycerin to carry out polymerization with polymkeric substance 8, obtain polymkeric substance 12.Weight-average molecular weight is 4000, and hydroxyl value is 47.
Vinyl acetate 70 mass parts
Vinyl benzoate 30 mass parts
Thioglycerin 5 mass parts
＜polymkeric substance 13 〉
Making azoisobutyronitrile (AIBN) is 2.5 mass parts, in addition, similarly carries out with the making of polymkeric substance 1, obtains polymkeric substance 13.Weight-average molecular weight is 300.
＜polymkeric substance 14 〉
Making azoisobutyronitrile (AIBN) is 2.0 mass parts, in addition, similarly carries out with the making of polymkeric substance 1, obtains polymkeric substance 14.Weight-average molecular weight is 500.
＜polymkeric substance 15 〉
Making azoisobutyronitrile (AIBN) is 0.5 mass parts, in addition, similarly carries out with the making of polymkeric substance 1, obtains polymkeric substance 15.Weight-average molecular weight is 10000.
＜polymkeric substance 16 〉
Making azoisobutyronitrile (AIBN) is 0.25 mass parts, in addition, similarly carries out with the making of polymkeric substance 1, obtains polymkeric substance 16.Weight-average molecular weight is 15000 (the present invention).
＜polymkeric substance 17 〉
Making azoisobutyronitrile (AIBN) is 0.15 mass parts, in addition, similarly carries out with the making of polymkeric substance 1, obtains polymkeric substance 17.Weight-average molecular weight is 30000 (the present invention).
＜polymkeric substance 18 〉
Making azoisobutyronitrile (AIBN) is 0.10 mass parts, in addition, similarly carries out with the making of polymkeric substance 1, obtains polymkeric substance 18.Weight-average molecular weight is 40000 (comparative examples).
(starting material)
＜celluosic resin: 90 mass parts 〉
Cellulose esters 1: the degree of substitution of propiono is 2.91, number-average molecular weight 75000, residual sulphur acid content (by element sulphur) are the cellulose tripropionate of 16ppm
Cellulose esters 2: the degree of substitution of acetyl group is 1.90, the degree of substitution of propiono is 0.75, number-average molecular weight 80000, residual sulphur acid content (by element sulphur) are the cellulose ethanoate propionic ester of 50ppm
Cellulose esters 3: the degree of substitution of acetyl group is 2.0, the degree of substitution of propiono is 0.75, number-average molecular weight 100000, residual sulphur acid content (by element sulphur) are the cellulose ethanoate propionic ester of 25ppm
Cellulose esters 4: the degree of substitution of acetyl group is 2.0, and the degree of substitution of propiono is 0.8, number-average molecular weight 95000, residual sulphur acid content (by element sulphur) are the cellulose ethanoate propionic ester of 45ppm
Cellulose esters 5: the degree of substitution of acetyl group is 2.0, the degree of substitution of bytyry is 0.70, number-average molecular weight 120000, residual sulphur acid content (by element sulphur) are the cellulose acetate butyrate of 12ppm
Cellulose esters 6: the degree of substitution of acetyl group is 1.90, the degree of substitution of propiono is 0.75, number-average molecular weight 80000, residual sulphur acid content (by element sulphur) are the cellulose ethanoate propionic ester of 75ppm
Cellulose esters 7: the degree of substitution of acetyl group is 2.0, the degree of substitution of propiono is 0.75, number-average molecular weight 100000, residual sulphur acid content (by element sulphur) are the cellulose ethanoate propionic ester of 0.1ppm (making by washing and remove residual sulfuric acid after cellulose 3 of 0.01N aqueous sodium hydroxide washes are washed)
(residual sulphur acid content determination method)
Above-mentioned residual sulphur acid content adopts following method to measure.
＜pre-service 〉
In the container of polypropylene system, take by weighing sample 500mg (M), add ultrapure water 10ml.
After it was disperseed 30 minutes with ultrasonic washer, (0.45 μ m) filtered with the water system chromatodisk.With it as sample.
(SO 4Quantitatively)
＜device〉ion chromatograph DIONEX makes DX-120
＜post〉IonPac AG14 (4mm)+IonPac AS14 (4mm)
＜canceller〉ASRS-ULTRAII (4mm)
＜eluent〉3.5mM-Na 2CO 31.0mM-NaHCO 3
＜SRS electric current〉50mA
＜flow velocity〉1.0ml/min
＜injection rate IR〉25 μ l
＜conversion method 〉
Content (ppm)=measured value (mg/l)/1000 * 10/M (mg) * 1000000
＜plastifier 〉
Plastifier 1: triphenyl phosphate 10 mass parts
Plastifier 2: trimethylolpropane tris benzoic ether 10 mass parts
Plastifier 3: polyester is plastifier sample No.3 (an aromatic series terminal ester sample)
10 mass parts
Plastifier 4: citrate is that the plastifier spy opens Compound P L-11 10 mass parts of putting down in writing among the 2002-62430
Plastifier 5: phthalic ester is plastifier following compound-1 10 mass parts
Compound-1
Figure A20061005506401551
＜ultraviolet light absorber 〉
UV-1: チ ヌ PVC Application 109 (the special chemistry of Chiba (strain) system, weight-average molecular weight :) 2 mass parts 486, in molar extinction coefficient=6780 at 380nm place
UV-2: adopt following synthetic macromolecule UV agent P-1 2 mass parts that obtain
(macromolecule UV agent P-1 synthesis example)
According to the method Synthetic 2 of record in following (2 '-hydroxyl-5 '-tert-butyl group-phenyl)-5-carboxylic acid-(2-methacryloxy) ethyl ester-2H-benzotriazole (exemplary compounds MUV-19).
3-nitro-4-amino-benzoic acid of 20.0g is dissolved in the water of 160ml, adds concentrated hydrochloric acid 43ml.After 0 ℃ adds the sodium nitrite of the 8.0g in the water that is dissolved in 20m1 down, stirred 2 hours down at 0 ℃.Be dissolved in by the 4-tert-butyl phenol among water 50ml and the ethanol 100ml to 17.3g and under 0 ℃, splash into sal tartari so that solution is remained alkalescence in the solution that forms.This solution is remained on 0 ℃ on one side, Yi Bian stir 1 hour, and then at room temperature stirred 1 hour.Reactant liquor is adjusted to acidity with hydrochloric acid, after the sediment that generates is filtered, fully washing.
With the resolution of precipitate that filters out in the NaOH aqueous solution of the 1 mole/L of 500ml, add the zinc powder of 35g after, splash into 40%NaOH aqueous solution 110g.After splashing into, stir about 2 hours filters, and washing is neutralized into neutrality with filtrate with hydrochloric acid.After the sediment filtration of separating out, washing, drying, carry out recrystallization with the mixed solvent of ethyl acetate and acetone, obtain 2 thus (2 '-hydroxyl-5 '-tert-butyl group-phenyl)-5-carboxylic acid-2H-benzotriazole.
Then, with 10.0g 2 (2 '-hydroxyl-5 '-tert-butyl group-phenyl)-5-carboxylic acid-2H-benzotriazole and 0.1g quinhydrones, 4.6g 2-hydroxyethyl methacrylate, 0.5g p-toluenesulfonic acid join among the toluene 100ml, carries out 10 hours reflux in the reaction vessel that has the ester pipe.Reaction solution is injected in the water, with crystallization filtration, washing, the drying of separating out, carry out recrystallization with ethyl acetate, obtain thus as exemplary compounds MUV-19 2 (2 '-hydroxyl-5 '-tert-butyl group-phenyl)-5-carboxylic acid-(2-methacryloxy) ethyl ester-2H-benzotriazole.
Then, according to the method Synthetic 2 of record in following (2 '-hydroxyl-5 '-tert-butyl group-phenyl)-multipolymer (macromolecule UV agent P-1) of 5-carboxylic acid-(2-methacryloxy) ethyl ester-2H-benzotriazole and methyl methacrylate.
In tetrahydrofuran 80ml, add in the above-mentioned synthesis example 3 synthetic 4.0g 2 (2 '-hydroxyl-5 '-tert-butyl group-phenyl)-methyl methacrylate of 5-carboxylic acid-(2-methacryloxy) ethyl ester-2H-benzotriazole and 6.0g, then, add azo isobutyronitrile 1.14g.Reflux is 9 hours under nitrogen atmosphere gas.After tetrahydrofuran is removed in decompression distillation, again it is dissolved in the 20ml tetrahydrofuran, splashes in the excessive methyl alcohol.Filter and collect the sediment of separating out, under 40 ℃, carry out vacuum drying, obtain the macromolecule UV agent P-1 of 9.1g as the canescence powdery polymer.It is the gpc analysis of benchmark that this multipolymer adopts with the polystyrene standard, confirms that its weight-average molecular weight is 9000.In addition, the molar extinction coefficient of the monomer component at 380nm place is 7320.
By NMR spectrum and UV spectrum confirm above-mentioned multipolymer be 2 (2 '-hydroxyl-5 '-tert-butyl group-phenyl)-multipolymer of 5-carboxylic acid-(2-methacryloxy) ethyl ester-2H-benzotriazole and methyl methacrylate.The composition of above-mentioned polymkeric substance omits, 2 (2 '-hydroxyl-5 '-tert-butyl group-phenyl)-5-carboxylic acid-(2-methacryloxy) ethyl ester-2H-benzotriazole: methyl methacrylate=40: 60.
UV-3:RUVA-100 (Da mound chemistry (strain) system, weight-average molecular weight is 494.5, the molar extinction coefficient at 380nm place is 4340) 1 mass parts
UV-4:LA-31 (rising sun electrochemical industry (strain) system, weight-average molecular weight is 658.9, the molar extinction coefficient at 380nm place is 8250) 1.6 mass parts
UV-5:PUVA-30M (Da mound chemistry (strain) system, weight-average molecular weight is 9000, the molar extinction coefficient of the monomer component at 380nm place is 600,3-(2H-1,2,3-benzotriazole-2-yl)-and the methacrylate of 4-leptodactyline and the multipolymer of methyl methacrylate, composition ratio=30: 70) 2 mass parts
But, 2 kinds of ultraviolet light absorbers are being merged situation about using, making total addition level is 2 mass parts, will and become 1: 1 with ratio.(in the table, the symbol that is expressed as UV-2/3 is meant UV-2, UV-3 is merged use for these 2 kinds.UV-2/5 etc. too).
＜adjuvant 〉
Adjuvant 1:IRGANOX1010 (the special chemistry of Chiba (strain) system, antioxidant) 0.2 mass parts
Adjuvant 2: epoxidation tar (sour agent for capturing) 0.2 mass parts
Adjuvant 3:HALS-1 (hindered amine as light stabilizer) 0.2 mass parts
＜matting agent 〉
ア エ ロ ジ Le (AEROSIL) 200V (silicon dioxide microparticle of 0.016 μ m, Japanese ア エ ロ ジ Le corporate system)
Embodiment 1
(adopt fusion curtain coating system embrane method to make support: optical thin film 1～32)
Above-mentioned cellulose esters 1 is carried out thermal treatment in 1 hour under 120 ℃, in dry air, put and be chilled to room temperature in dry air.With respect to celluosic resin 90 mass parts of drying, add plastifier, the ultraviolet light absorber of cellulose esters following mass parts in addition according to the following formation of table 1, after mixing with Henschel mixer,, make pellet with the extruder heating, put cold.
Cellulose esters 1: the degree of substitution of propiono is 2.91, number-average molecular weight is 75000, residual sulfuric acid amount (by elementary sulfur) is three cellulose propionates, 90 mass parts of 16ppm
Plastifier 1: triphenyl phosphate 10 mass parts
UV-1: チ ヌ PVC Application 109 (the special chemistry of Chiba (strain) system, weight-average molecular weight :) 2 mass parts 486, at the molar extinction coefficient-6780 at 380nm place
The pellet that obtains, use the hot-air drier that circulation of air is arranged, drying is 2 hours under 105 ℃, removes moisture.Then, use above-mentioned pellet, use has the single screw extrusion machine of T type mouth mould of clothes hanger type of the wide 1.5m of die lip, and (Mitsubishi Heavy Industries Ltd industries strain formula can corporate system: screw diameter 90mm, the die lip material of T type mouth mould is used tungsten carbide), the peristome from the additive hopper that is arranged on the extruder pars intermedia adds matting agent with the continous way feeder, to reach 0.05% of extrusion capacity, melt extrude moulding, preparation cellulose ester film.Extrusion molding is in grade is clean room below 10000, carries out under the condition of molding of 230 ℃ of melt temperatures, 240 ℃ of T type die temperatures.The film that obtains is 1.02 times of the long stretchings of length direction, then use tenter frame apparatus, on Width, stretch 1.05 times, obtain optical path difference Ro5nm, optical path difference Rt38nm, the length 3000m of thickness direction of direction in the face, the cellulose ester film of thickness 75 μ m, fabric width 1.4m.Carry out the annular knurl processing of width of cloth 1cm, average height 8 μ m at the film both ends, batch, make optical thin film 1.
Then, similarly carry out, use the kind and the consumption thereof of polymkeric substance 1～18 according to the formation preparation of table 1 record, cellulose esters 1～7, plastifier, ultraviolet light absorber, adjuvant respectively, make optical thin film 2～32 with the making of optical thin film 1.In addition, with respect to celluosic resin 90 mass parts, polymkeric substance 1～18 respectively uses 10 mass parts.
(evaluation)
Use the optical thin film 1～32 that obtains, adopt following method to measure respectively under the situation of light path difference, supposition use between for a long time, the optical path difference that changes with respect to humidity changes, and its evaluation result is shown in Table 1.
(optical path difference Ro, Rt)
Use is placed 24 hours film under 23 ℃, the environment of 55%RH, under equivalent environment, measure the optical path difference of film at wavelength 590nm place with automatic birefringence meter KOBRA-21ADH (prince's instrumentation machine (strain) system).The mean refractive index of the film constituent material that records with Abbe refractomecer and the following formula of thickness d substitution, the value of the optical path difference (Rt) of interior optical path difference (Ro) of the face that obtains and thickness direction.
Formula (i) Ro=(nx-ny) * d
Formula is Rt={ (nx+ny)/2-nz} * d (ii)
(in the formula, nx is the refractive index of the slow axis direction in the pellicular front, and ny is the refractive index of the leading phase shaft direction in the pellicular front, and nz is the refractive index of the thickness direction of film, and d represents the thickness (nm) of film).
(the light path difference that changes with respect to humidity changes)
Adopt above-mentioned optical path difference pH-value determination pH method, obtain the variation of the Rt (a) that changes with humidity according to following method.
With film sample damping after 24 hours under 23 ℃, 20%RH, the Rt value that to measure under equivalent environment is as Rt (b), identical film was continued under 23 ℃, 80%RH damping after 24 hours, obtain the Rt value that records at equivalent environment, it as Rt (c), is obtained the Rt that changes with humidity by following formula and change Rt (a).
Rt(a)＝|Rt(b)-Rt(c)|
And then, the sample after the damping is measured under the environment of 23 ℃ and 55%RH once more, confirm that this variation is reversible variation.
The formation and the gained of optical thin film the results are shown in the table 1.
Table 1
Optical thin film No. Cellulose esters No. Polymkeric substance Plastifier No. Ultraviolet light absorber No. Adjuvant No, Melt temperature (℃) Ro Rt changes Remarks
Rt(b) Rt(c) Rt(a)
1 1 - 1 UV-1 - 230 5 38 26 12 Comparative example
2 1 - 2 UV-2 1 230 3 35 25 10 Comparative example
3 1 - 2 UV-2 1，2，3 230 3 31 22 9 Comparative example
4 1 1 1 UV-1 1，2，3 230 2 13 6 7 The present invention
5 2 1 2 UV-2 1，2，3 230 1 12 7 5 The present invention
6 3 1 2 UV-2 1，2，3 230 0 5 3 2 The present invention
7 4 1 2 UV-2 1，2，3 230 0 7 4 3 The present invention
8 5 1 2 UV-2 1，2，3 230 1 9 5 4 The present invention
9 3 1 3 UV-2 1，2，3 230 1 7 4 3 The present invention
10 3 1 2 UV-2/3 1，2，3 230 0 5 3 2 The present invention
11 3 1 2 UV-3/5 1，2，3 230 0 4 2 2 The present invention
12 3 1 4 UV-3 1，2，3 230 1 6 3 3 The present invention
13 3 1 5 UV-4 1，2，3 230 1 8 5 3 The present invention
14 3 2 2 UV-2/5 1，2，3 230 0 5 3 2 The present invention
15 3 3 2 UV-2/5 1，2，3 200 1 7 5 2 The present invention
16 3 4 2 UV-2/5 1，2，3 210 1 6 3 3 The present invention
17 3 5 2 UV-2/5 1，2，3 240 0 5 3 2 The present invention
18 3 6 2 UV-2/5 1，2，3 245 0 4 2 4 The present invention
19 3 7 2 UV-2/5 1，2，3 230 0 5 3 2 The present invention
20 3 8 2 UV-2/5 1，2，3 230 1 7 4 3 The present invention
21 3 9 2 UV-2/5 1，2，3 230 2 8 5 3 The present invention
22 3 10 2 UV-2/5 1，2，3 230 0 5 3 2 The present invention
23 3 11 2 UV-2/5 1，2，3 230 1 6 4 2 The present invention
24 3 12 2 UV-2/5 1，2，3 230 1 6 4 2 The present invention
25 6 1 1 UV-1 1，2，3 230 2 21 14 9 Comparative example
26 7 1 1 UV-1 1，2，3 230 0 6 3 2 The present invention
27 3 13 2 UV-2/5 1，2，3 230 4 28 20 10 Comparative example
28 3 14 2 UV-2/5 1，2，3 230 2 12 6 6 The present invention
29 3 15 2 UV-2/5 1，2，3 230 2 10 7 5 The present invention
30 3 16 2 UV-2/5 1，2，3 230 2 11 7 6 The present invention
31 3 17 2 UV-2/5 1，2，3 230 2 12 8 6 The present invention
32 3 18 2 UV-2/5 1，2，3 230 4 22 15 10 Comparative example
As can be seen; optical thin film 4～24,26,28,29,30,31 of the present invention is with respect to for the optical thin film 1～3,25,27,32 of making comparisons; the optical thin film of using as protective film for polarizing plate; be fit to find the light path difference, and the variation of the light path difference that changes with humidity is reduced significantly.
In addition, as can be seen, using triphenyl phosphate is plastifier as phosphate, and uses the optical thin film 4 of low-molecular-weight ultraviolet light absorber (UV-1), can cause effect of the present invention to reduce a little.
In addition as can be seen, also with the optical thin film 10,11,14～24 of preferred ultraviolet light absorber, the characteristic of any is all good among the present invention.
Embodiment 2
Use the optical thin film of making among the embodiment 11,4～32, after forming polymeric layer on each optical thin film, stretch, make the optical compensating film 1～35 of table 2 record according to following method.
Will be by 2,2 '-two (3,4-dicarboxyl phenyl) HFC-236fa and 2,2 '-two (trifluoromethyl)-4, the cyclohexanone solution coat of the polyimide 15 quality % of the weight-average molecular weight 5.9 ten thousand that 4 '-benzidine is synthetic is on each optical thin film, and making its dry film thickness is 5 μ m, then, while using tenter frame apparatus clamping two ends to make its drying, continue under the temperature of regulation, on Width, to stretch 1.15 times, obtain the optical compensating film of Ro70nm, Rt270nm.
(evaluation)
The optical compensating film 1～35 that use obtains carries out following evaluation.
(transparency)
Use transparency analyzer ((strain) KOTAKI makes made), estimate the transparency of the optical compensating film that obtains.
Zero: the reduction that does not observe the transparency
△: observe the transparency and reduce a little
*: observe the transparency and reduce
(planarity; Visual valuation)
Each sample is cut into the size of wide 90cm, long 100cm, with 5 parallel connections of 50W fluorescent light, the height of stuck-at-.5m on sample bench, so that shine from the 45 degree, each film sample is placed on the sample bench, reflect see concavo-convex with the visual method observation at film surface, judge by following benchmark.According to this method, can be judged to be " fold " and " wrinkle ".
◎:, seem it also is straight even 5 fluorescent lights are arranged
Zero: can see a little warpage sometimes under the fluorescent light
△: can see a little warpage at all surfaces under the fluorescent light
*: fluorescent light can be seen big bending down
(fluctuation of optical path difference Ro, Rt)
The film sample that obtains is measured the optical path difference that it produces with the interval of 1cm on Width, with variation factor (CV) expression of the optical path difference that obtains.Use automatic birefringence meter KOBURA-21ADH (prince's tester (strain) system) in the mensuration, under 23 ℃, the environment of 55%RH, at wavelength 590nm place, sample carries out 3 with the interval of 1cm and ties up birefractions mensuration on Width.Optical path difference with thickness direction in the face that obtains adopts (n-1) method to get standard deviation respectively.Optical path difference distributes, and obtains variation factor shown below (CV), as index.When practical measurement,, be set at 130 as n.
Variation factor (CV)=standard deviation/optical path difference mean value
◎: fluctuation (CV) is lower than 1.5%
Zero: the fluctuation (CV) more than 1.5%, be lower than 5%
△: the fluctuation (CV) more than 5%, be lower than 10%
*: fluctuation (CV) is more than 10%
Above evaluation result is shown in Table 2.
(table 2)
Optical compensating film No. Optical thin film No. The formation of polymeric layer Draft temperature (℃) The transparency Planarity The fluctuation of optical path difference The visibility of liquid crystal indicator Remarks
1 1 Do not have 150 × × × × Comparative example
2 1 Have 150 × × × × Comparative example
3 4 Have 150 △ △ △ ○ The present invention
4 5 Have 150 ○ △ ○ ○ The present invention
5 6 Have 130 ○ ○ ○ ○ The present invention
6 6 Have 140 ○ ◎ ◎ ○ The present invention
7 6 Have 150 ○ ◎ ◎ ◎ The present invention
8 6 Have 155 ○ ◎ ◎ ◎ The present invention
9 6 Have 160 ○ ◎ ◎ ◎ The present invention
10 7 Have 150 ○ ◎ ◎ ◎ The present invention
11 8 Have 150 ○ ◎ ◎ ◎ The present invention
12 9 Have 150 ○ ◎ ◎ ◎ The present invention
13 10 Have 150 ○ ◎ ◎ ◎ The present invention
14 11 Have 150 ○ ◎ ◎ ◎ The present invention
15 12 Have 150 ○ ◎ ◎ ◎ The present invention
16 13 Have 150 ○ ◎ ◎ ◎ The present invention
17 14 Have 150 ○ ◎ ◎ ◎ The present invention
18 15 Have 160 ○ ○ ○ ○ The present invention
19 16 Have 160 ○ ◎ ◎ ◎ The present invention
20 17 Have 150 ○ ◎ ◎ ◎ The present invention
21 18 Have 145 ○ ○ ○ ○ The present invention
22 19 Have 150 ○ ◎ ◎ ◎ The present invention
23 20 Have 150 ○ ◎ ◎ ◎ The present invention
24 21 Have 150 ○ ◎ ◎ ◎ The present invention
25 22 Have 150 ○ ◎ ◎ ◎ The present invention
26 23 Have 150 ○ ◎ ◎ ◎ The present invention
27 24 Have 150 ○ ◎ ◎ ◎ The present invention
28 25 Have 150 ○ △ × × Comparative example
29 26 Have 150 ○ ○ ◎ ◎ The present invention
30 27 Have 150 ○ △ × × Comparative example
31 28 Have 150 ○ ○ ○ ○ The present invention
32 29 Have 150 ○ ○ ○ ○ The present invention
33 30 Have 150 × × △ × Comparative example
34 31 Have 150 ○ ○ ○ ○ The present invention
35 32 Have 150 × × △ × Comparative example
As can be seen, optical compensating film 3～27,29,31,32,33,34 of the present invention, by coated polymeric layer on optical thin film of the present invention, stretch together with support, compare with the optical compensating film of not establishing polymeric layer 1 of comparative example, the optical compensating film that polymeric layer is set on optical thin film 2,28,30,35 of comparative example, at the aspects such as fluctuation of the transparency, planarity, optical path difference, in general be good.
Embodiment 3
" making of Polarizer "
Form following hard conating and anti-reflection layer on the optical thin film of in embodiment 1, making 11, make antireflective film.
＜hard conating 〉
Be coated with following hard coating composition, making dry film thickness is 3.5 μ m, and drying is 1 minute under 80 ℃.Secondly, use high-pressure mercury-vapor lamp (80W) at 150mJ/cm 2Condition under it is solidified, make hardcoat film with hard conating.The refractive index of hard conating is 1.50.
＜hard coating composition (C-1) 〉
Dipentaerythritol acrylate (containing about 2 one-tenth the above composition of 2 polymers)
108 mass parts
イ Le ガ キ コ ア 184 (the special chemistry of Chiba (strain) system)
2 mass parts
Propylene glycol monomethyl ether 180 mass parts
Ethyl acetate 120 mass parts
＜middle index layer 〉
On the hard conating of above-mentioned hardcoat film, with the coating of extrusion coated machine following in the index layer composition, under 80 ℃, the condition of 0.1m/ second, make its dry 1 minute.At this moment, use the noncontact buoy), finish (with finger touch coated face sensation dry status) up to dry to touch.As the noncontact buoy, use the air damper of the horizontal buoy type of ベ Le マ Star テ イ Network corporate system.Static pressure is 9.8kPa in the buoy, it is evenly floated on about 2mm Width carry.After the drying, with high-pressure mercury-vapor lamp (80W) irradiation 130mJ/cm 2Ultraviolet ray, it is solidified, make middle index layer film with middle index layer.The thickness of the middle index layer of index layer film is 84nm in being somebody's turn to do, and refractive index is 1.66.
＜middle index layer composition 〉
20%ITO microparticulate thing (mean grain size 70nm, aqueous isopropanol) 100g
Dipentaerythritol acrylate 6.4g
イ Le ガ キ ア 184 (the special chemistry of Chiba (strain) system) 1.6g
Four butanols titanium 4.0g
10%FZ-2207 (Japanese ユ ニ カ one corporate system, propylene glycol monomethyl ether solution) 3.0g
Isopropyl alcohol 530g
Butanone 90g
Propylene glycol monomethyl ether 265g
＜high refractive index layer 〉
In above-mentioned, on the index layer, be coated with following high index of refraction layer composition, under 80 ℃, the condition of 0.1m/ second, make its dry 1 minute with extrusion coated machine.At this moment, use the noncontact buoy, finish (with finger touch coated face sensation dry status) up to dry to touch.The condition of noncontact buoy with form in condition during index layer identical.After the drying, with high-pressure mercury-vapor lamp (80W) irradiation 130mJ/cm 2Ultraviolet ray, it is solidified, make high index of refraction layer film with high refractive index layer.
＜high index of refraction layer composition 〉
Four normal butyl alcohol titaniums, 95 mass parts
Dimethyl polysiloxane (the system KF-96-1000CS of chemical company of SHIN-ETSU HANTOTAI) 1 mass parts
γ-methacryloxypropyl trimethoxy silane (the system KBM503 of chemical company of SHIN-ETSU HANTOTAI)
5 mass parts
Propylene glycol monomethyl ether 1750 mass parts
Isopropyl alcohol 3450 mass parts
Butanone 600 mass parts
In addition, the thickness of the high refractive index layer of this high index of refraction layer film is 50 μ m, and refractive index is 1.82.
＜low-index layer 〉
Carry out the preparation of silica-based particulate (empty particle) at first.
(preparation of silica-based particulate P-1)
With mean grain size 5nm, SiO 2The silicon dioxide gel 100g of concentration 20 quality % and the potpourri of pure water 1900g are heated to 80 ℃.The pH value of this reaction mother liquor is 10.5, adds as SiO simultaneously in this mother liquor 20.98 quality % sodium silicate aqueous solution 9000g and as Al 2O 3The sodium aluminate aqueous solution 9000g of 1.02 quality %.Therebetween, the temperature with reactant liquor remains on 80 ℃.After adding, the pH value of reactant liquor rises to 12.5 immediately, then, does not almost change.After adding end, reactant liquor is cooled to room temperature, with the ultra filtration membrane washing, the SiO of preparation solids concentration 20 quality % 2Al 2O 3The nuclear particle dispersion liquid.(operation (a))
This adds pure water 1700g in nuclear particle dispersion liquid 500g, heats to 98 ℃, Yi Bian keep this temperature, Yi Bian add silicic acid liquid (SiO by sodium silicate aqueous solution is obtained with the Zeo-karb dealkalize 2Concentration 3.5 quality %) 3000g, thus obtain forming the dispersion liquid of the nuclear particle of the 1st silica-coated layer.(operation (b))
Then, to ultra filtration membrane washing and to make solids concentration be to add pure water 1125g among the nuclear particle dispersion liquid 500g of formation the 1st silica-coated layer of 13 quality %, and then splash into concentrated hydrochloric acid (35.5%), making the pH value is 1.0, carries out dealumination treatment.Then, add aqueous hydrochloric acid solution 10L and the pure water 5L of pH3, and meanwhile with the ultra filtration membrane separate dissolved aluminium salt, the SiO of a part of the constituent of the nuclear particle that forms the 1st silica-coated layer is removed in preparation 2Al 2O 3The dispersion liquid of porous plasmid (operation (c)).With the sub-dispersion liquid 1500g of above-mentioned porous plasmid, pure water 500g, ethanol 1, the mixed liquor of 750g and 28% ammoniacal liquor 626g is heated after 35 ℃, adds silester (SiO 228 quality %) 104g uses the hydrolytie polycondensation thing of silester to coat on the surface that forms porous plasmid of the 1st kind of silica-coated layer, forms the 2nd silica-coated layer.Then, with solvent exchange the dispersion liquid of the silica-based particulate of the solids concentration 20 quality % that form of ethanol with ultra filtration membrane preparation.
Thickness, mean grain size, the MOx/SiO of the 1st silica-coated layer of this silica-based particulate 2(mol ratio) and refractive index are shown in Table 2.Herein, mean grain size adopts dynamic light scattering determination, and refractive index is measured according to following method, as standard refraction liquid, uses SeriesA, the AA of CARGILL system.
The assay method of the refractive index of＜particle 〉
(1) particle dispersion is collected in the evaporator, dispersion solvent is evaporated.
(2) it is dry under 120 ℃, make powder.
(3) mensuration of refractive index is that known standard refraction liquid is dripped 2,3 on glass plate, toward wherein mixing above-mentioned powder.
(4) carry out the operation of above-mentioned (3) with various standard refraction liquid, mixed liquor is become the refractive index of the refractive index of the standard refraction liquid when transparent as colloidal particle.
(table 3)
Numbering Nuclear particle Silica-coated layer Shell Silica-based particulate
Kind MOx/SiO 2Mol ratio The 1st layer thickness (nm) The 2nd layer thickness (nm) Thickness (nm) MOx/SiO 2Mol ratio Mean grain size (nm) Refractive index
P-1 Al/Si 0.5 3 5 8 0.0017 47 1.28
The formation of＜low-index layer 〉
According to Si (OC 2H 5) 4Be 95mol%, C 3F 7-(OC 3F 6) 24-O-(CF 2) 2-C 2H 4-O-CH 2Si (OCH 3) 3For the ratio of 5mol% the two is mixed, obtained binder, in this binder, add the above-mentioned silica-based particulate P-1 of the mean grain size 47nm of 35 quality %, 1.0N-HCl is used as catalyzer, and then uses solvent dilution, make low-refraction and apply agent.On above-mentioned high refractive index layer, adopt a mouthful pattern rubbing method to press thickness 100nm coating coating solution, after under 120 ℃ dry 1 minute, carry out the ultraviolet ray irradiation, form the low-index layer of refractive index 1.37 thus.
As above make antireflective film like that.
(making of Polarizer)
The making of＜visual lateral deviation tabula rasa 〉
Then, be that the polyvinyl alcohol film of 120 μ m carries out uniaxial tension (110 ℃ of temperature, 5 times of stretching ratios) to thickness.It was flooded for 60 seconds in the aqueous solution that is made of iodine 0.075g, potassium iodide 5g, water 100g, then be impregnated in 68 ℃ the aqueous solution that constitutes by potassium iodide 6g, boric acid 7.5g, water 100g.With its washing, drying obtains light polarizing film.
Then,, the optical thin film of making among light polarizing film, above-mentioned antireflective film, the embodiment 1 11 is fit together, make Polarizer according to following operation 1～5.
Operation 1: in the sodium hydroxide solution of 60 ℃ 2 moles/L, flooded for 90 seconds, then wash, drying, a side that obtains fitting with polarizer is by optical thin film 11, the antireflective film of saponification.
Operation 2: above-mentioned light polarizing film was flooded 1～2 second in the poly (vinyl alcohol) binder groove of solids 2 quality %.
Operation 3: the bonding agent attached to the surplus on the light polarizing film is removed in the operation 2 in wiping gently, and it is stacked and placed on the optical thin film 11 handled in the operation 1, the antireflective film, carries out lamination.
Operation 4: with optical thin film 11, light polarizing film and the antireflective film of lamination in the operation 3 at pressure 20～30N/cm 2, fit under the about 2m/ of the transporting velocity condition of dividing.
Operation 5: in 80 ℃ dryer,, make visual lateral deviation tabula rasa with the samples dried that is fitted with light polarizing film, optical thin film 11, antireflective film of making in the operation 42 minutes.
The making of＜backlight side Polarizer 〉
Use optical compensating film 1～35, the rear side of making in the light polarizing film, embodiment 2 of above-mentioned making to use the optical thin film of making among the embodiment 1 11,, make backlight side Polarizer 1～35 according to above-mentioned operation 1～5.In addition, with respect to light polarizing film, when the applying optical compensating film, make polymeric layer become the outside.
" making of liquid crystal indicator "
Following making LCDs is estimated the characteristic as liquid crystal indicator.
30 inches of シ ヤ one プ corporate system, the backlight side Polarizer and the visual lateral deviation tabula rasa of the liquid crystal cell of ア Network オ ス liquid crystal indicator are peeled off, fit on the liquid crystal cell by adhesive linkage according to the mode consistent with the polarizing axis of the Polarizer of fitting in advance, so that make the optical compensating film side of backlight side Polarizer 1～35 become liquid crystal cell, and make optical thin film 11 sides of visual lateral deviation tabula rasa become the liquid crystal cell side, so make 30 inches liquid crystal indicator 1～35.This device backlight be under formula mode backlight.
(evaluation)
＜visibility 〉
With the liquid crystal indicator made under 60 ℃, 90%RH environment, will under formula is backlight opens, carry out 1000 hours endurancing after, and then after at room temperature opening 5 hours backlight, make picture show black, carry out visualization, and provide following order.
◎: see that black is broken diffusing, vividness is arranged, can't see color spot
Zero: see that black is broken diffusing, has vividness, but sees color spot slightly
△: it is poor slightly that black broken looses, and vividness is low slightly, can see color spot
*: do not have black broken diffusing, vividness is low, and color spot is obvious
Above evaluation result is shown in Table 2.
As seen from Table 2, liquid crystal indicator 3～27,29,31,32～34 of the present invention is with respect to comparative example 1,2,28,30,35, though formula is backlight under making under hot and humid open for a long time after, visibility is also good.
Use draft temperature within the scope of the invention liquid crystal indicator or merge the liquid crystal indicator that uses the optical compensating film of preferred ultraviolet light absorber among the present invention, in general be good at aspects such as the fluctuation of the transparency, planarity, optical path difference, visibilities.

Claims (14)

1.光学薄膜的制备方法，其特征在于，该方法是通过将含有纤维素树脂和增塑剂的组合物熔融流延来制膜的光学薄膜的制备方法，其中，上述纤维素树脂中的残留硫酸量在0.1～50ppm的范围内，上述组合物含有通过烯性不饱和单体聚合而得到的重均分子量在500以上至30000以下的聚合物或者重均分子量在500以上至30000以下的丙烯酸系聚合物。1. The preparation method of optical film, it is characterized in that, this method is the preparation method of the optical film that will form film by melt-casting the composition that contains cellulose resin and plasticizer, wherein, the residual in above-mentioned cellulose resin The amount of sulfuric acid is in the range of 0.1 to 50 ppm, and the above-mentioned composition contains a polymer having a weight average molecular weight of 500 to 30,000 obtained by polymerization of an ethylenically unsaturated monomer or an acrylic acid having a weight average molecular weight of 500 to 30,000. polymer. 2.权利要求1中所述的光学薄膜的制备方法，其特征在于，上述纤维素树脂为总酰基取代度2.5～2.9、数均分子量(Mn)70000～200000的混合脂肪酸酯。2. The method for preparing an optical film according to claim 1, wherein the cellulose resin is a mixed fatty acid ester with a total acyl substitution degree of 2.5-2.9 and a number-average molecular weight (Mn) of 70,000-200,000. 3.权利要求1或2中所述的光学薄膜的制备方法，其特征在于，上述增塑剂的至少1种选自多元醇酯系增塑剂、聚酯系增塑剂、柠檬酸酯系增塑剂、以及邻苯二甲酸酯系增塑剂。3. The method for preparing an optical film according to claim 1 or 2, wherein at least one of the above plasticizers is selected from polyol ester plasticizers, polyester plasticizers, citrate plasticizers, Plasticizers, and phthalate-based plasticizers. 4.权利要求1～3任1项中所述的光学薄膜的制备方法，其特征在于，上述残留硫酸量在0.1～45ppm的范围内。4. The method for producing an optical film according to any one of claims 1 to 3, wherein the amount of residual sulfuric acid is in the range of 0.1 to 45 ppm. 5.权利要求1～4任1项中所述的光学薄膜的制备方法，其特征在于，上述组合物含有紫外线吸收剂，该紫外线吸收剂的重均分子量在490～50000的范围内。5. The method for producing an optical film according to any one of claims 1 to 4, wherein the composition contains an ultraviolet absorber, and the weight average molecular weight of the ultraviolet absorber is in the range of 490 to 50,000. 6.权利要求1～5任1项中所述的光学薄膜的制备方法，其特征在于，上述组合物含有0.01～5质量％的受阻胺系、或受阻酚系化合物。6. The method for producing an optical film according to any one of claims 1 to 5, wherein the composition contains 0.01 to 5% by mass of a hindered amine or hindered phenol compound. 7.光学薄膜，其特征在于，该光学薄膜是采用权利要求1～6任1项中所述的光学薄膜的制备方法制备的。7. An optical film, characterized in that the optical film is prepared by the method for preparing an optical film according to any one of claims 1-6. 8.光学补偿薄膜的制备方法，其特征在于，在权利要求7中所述的光学薄膜上设置聚合物层并进行拉伸。8. A method for preparing an optical compensation film, characterized in that a polymer layer is provided on the optical film according to claim 7 and stretched. 9.权利要求8中所述的光学补偿薄膜的制备方法，其特征在于，上述聚合物层由选自聚醚酮、聚酰胺、聚酯、聚酰亚胺、聚酰胺酰亚胺、以及聚酯酰亚胺中的至少1种构成。9. The preparation method of optical compensation film described in claim 8 is characterized in that, above-mentioned polymer layer is selected from polyether ketone, polyamide, polyester, polyimide, polyamideimide and poly Consists of at least one of ester imides. 10.权利要求8或9中所述的光学补偿薄膜的制备方法，其特征在于，上述拉伸时的拉伸温度B由下述式(I)表示：10. the preparation method of optical compensation film described in claim 8 or 9 is characterized in that, the stretching temperature B when above-mentioned stretching is represented by following formula (1): 式(I)熔融温度A-100℃≤拉伸温度B≤熔融温度A-40℃Formula (I) melting temperature A-100°C≤stretching temperature B≤melting temperature A-40°C (式中，熔融温度A表示光学薄膜的熔融流延时的温度)。(In the formula, the melting temperature A represents the temperature at the time of melt casting of the optical film). 11.光学补偿薄膜，其特征在于，该光学补偿薄膜是采用权利要求8～10任1项中所述的光学补偿薄膜的制备方法制备的。11. An optical compensation film, characterized in that the optical compensation film is prepared by the method for preparing an optical compensation film as described in any one of claims 8-10. 12.偏光板，其特征在于，在至少一侧表面上具有权利要求7中所述的光学薄膜或权利要求11中所述的光学补偿薄膜。12. A polarizing plate, characterized by having the optical film as claimed in claim 7 or the optical compensation film as claimed in claim 11 on at least one surface thereof. 13.液晶显示装置，其特征在于，在其至少一侧表面上具有权利要求12中所述的偏光板。13. A liquid crystal display device having the polarizing plate according to claim 12 on at least one surface thereof. 14.权利要求13中所述的液晶显示装置，其特征在于，其背光为LED。14. The liquid crystal display device as claimed in claim 13, wherein the backlight is LED.
CN 200610055064 2005-03-10 2006-03-07 Optical film, optical compensation film and production method, polarizing plate and liquid crystal display device Pending CN1834705A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
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CN102171020A (en) * 2008-10-06 2011-08-31 柯尼卡美能达精密光学株式会社 Optical film, method for producing optical film, polarizing plate and liquid crystal display device
US8168702B2 (en) 2008-01-30 2012-05-01 Konica Minolta Opto Inc. Acrylic-resin-containing film, polarizing plate and liquid crystal display device using the same
US8449955B2 (en) 2007-12-25 2013-05-28 Konica Minolta Opto, Inc. Acrylic resin containing film, and polarizing plate and a liquid crystal display device employing the same
CN103459490A (en) * 2011-06-01 2013-12-18 Lg化学株式会社 Resin composition for optical film and optical film using same
TWI475059B (en) * 2009-04-15 2015-03-01 Konica Minolta Opto Inc A polarizer protective film, a polarizing plate using the same, and a method for manufacturing the same
CN116323209A (en) * 2020-10-05 2023-06-23 住友化学株式会社 Polarizing plate and image display device

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8449955B2 (en) 2007-12-25 2013-05-28 Konica Minolta Opto, Inc. Acrylic resin containing film, and polarizing plate and a liquid crystal display device employing the same
US8168702B2 (en) 2008-01-30 2012-05-01 Konica Minolta Opto Inc. Acrylic-resin-containing film, polarizing plate and liquid crystal display device using the same
CN101925641B (en) * 2008-01-30 2012-11-21 柯尼卡美能达精密光学株式会社 Film containing acrylic resin, polarizer comprising the same, and liquid-crystal display
CN102171020A (en) * 2008-10-06 2011-08-31 柯尼卡美能达精密光学株式会社 Optical film, method for producing optical film, polarizing plate and liquid crystal display device
CN102171020B (en) * 2008-10-06 2013-09-11 柯尼卡美能达精密光学株式会社 Optical film, method for producing optical film, polarizing plate and liquid crystal display device
TWI475059B (en) * 2009-04-15 2015-03-01 Konica Minolta Opto Inc A polarizer protective film, a polarizing plate using the same, and a method for manufacturing the same
CN103459490A (en) * 2011-06-01 2013-12-18 Lg化学株式会社 Resin composition for optical film and optical film using same
CN103459490B (en) * 2011-06-01 2015-12-02 Lg化学株式会社 Blooming resin combination and use the blooming of this resin combination
CN116323209A (en) * 2020-10-05 2023-06-23 住友化学株式会社 Polarizing plate and image display device

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