CN103857751A

CN103857751A - Composition for forming an alignment layer, and alignment layer and phase difference film manufactured using same

Info

Publication number: CN103857751A
Application number: CN201280049523.4A
Authority: CN
Inventors: 宋昺勋; 赵敏成; 崔凤珍
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2011-10-07
Filing date: 2012-09-28
Publication date: 2014-06-11
Also published as: WO2013051831A3; WO2013051831A2

Abstract

The present invention relates to a composition for forming an alignment layer and to an alignment layer manufactured using same. More particularly, the present invention relates to a composition for forming an alignment layer for aligning liquid crystal compounds. The composition includes an adhesion-reinforcing agent including an isocyanate group and a (meth)acrylate group at an end portion for forming a bond with a reactive group in the liquid crystal compound. While curing the composition for forming the alignment layer, a chemical bond may be formed with another layer formed at the side portion so as to manufacture a phase difference film having very strong interlayer adhesion.

Description

For the preparation of the composition of oriented layer, oriented layer prepared therefrom and phase shift films

Technical field

The present invention relates to composition and oriented layer prepared therefrom for the preparation of oriented layer, and comprise that this has the phase shift films of the oriented layer of excellent interlayer combination.

Background technology

The factor of experiencing stereoeffect can be divided into physiologic factor and sense datum.Conventionally, three-dimensional image display technology adopts the principle of binocular parallax as the principal element of perception entity (solidity) in nearly scope.

The feature of such binocular parallax principle is: by least two stereo-picture photographic cameras, in different angles, as looking over from left eye, take an image and as look over another image of shooting from right eye after, the image photographing is transferred to respectively to viewer's eyes.Aforesaid method is possible, by receive material by retina in different angles in two eyes of people, and two images that obtained by eyes is combined in brain.

Common wear a pair of spectacles or not wear a pair of spectacles carry out the observation of stereo-picture.About wearing glasses, (1) stereoscopic photograph pattern is to bring the tinted glasses every eyes to different colours; (2) polarization mode is to bring the polarising glass with different polarization direction; (3) timesharing pattern is will bring have the electronic shutter of periodic repetitions timesharing scenery and make electronic shutter and the glasses of time lock.

Wherein, the glasses of polarization mode can with viewer location-independent express stereoeffect, comprise eyestrain still less or dizzy, and can manufacture easily, therefore, attract public attention very much.

Adopt polarization mode glasses to show the display unit of stereo-picture, can there is pattern phase shift films (being formed with the base material of pattern retardation layer above), and can be by using tackiness agent or binding agent pattern phase shift films to be attached to the surface of polaroid.

This pattern phase shift films can have the structure that comprises the transparent substrate stacked by sequential order, oriented layer and hardening liquid crystal layer.In this, because phase shift films has low bonding strength at each interlayer, this cause first by phase shift films adhesives to base material and therefrom remove subsequently in the method for protective membrane, there is the problem of splitting.

Summary of the invention

summary of the invention

Therefore, an object of the present invention is will be provided for preparing the composition of oriented layer, improve the combination of oriented layer and other film.

Another object of the present invention is that the phase shift films with excellent interlayer combination will be provided, and it comprises oriented layer.

By following feature, will realize above-mentioned purpose of the present invention:

(1) for the preparation of the composition of oriented layer that is suitable for liquid crystalline cpd orientation, it comprises: have endways isocyanate group and (methyl) acrylate-based adhesiving reinforcing agent, wherein isocyanate group and (methyl) acrylate-based reactive group that is bonded to liquid crystalline cpd.

(2), according to the composition of above-mentioned (1), wherein the reactive group of liquid crystalline cpd is carbon-to-carbon unsaturated bond, hydroxyl, epoxy group(ing) or cyano group.

(3), according to the composition of above-mentioned (1), wherein adhesiving reinforcing agent is at least one of group that is selected from the compound composition of following formula 1 to 4 expression:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

R ₃and R ₇for having the alkylidene group of 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or does not replace independently of one another;

R ₄and R ₆for having the alkylidene group of 1 to 10 carbon atom, its group that is selected from the group of amide group, ketone group, ester group and thiol group composition replaces or does not replace independently of one another; With

R ₅be the alkylidene group with 1 to 10 carbon atom, its alkoxyl group with 1 to 8 carbon atom replaces or does not replace);

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₉and R ₁₁for having the alkylidene group of 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or does not replace independently of one another;

R ₁₀(a)

or (b)

wherein E ₁and E ₃the alkoxyl group independently of one another with 1 to 8 carbon atom replaces or the unsubstituted alkyl with 1 to 10 carbon atom, or has the alkoxyl group of 1 to 8 carbon atom; With E2 be the alkylidene group with 1 to 10 carbon atom, its had 1 to 8 carbon atom alkoxyl group replace or do not replace);

Formula 3

(wherein R ₁₂hydrogen or methyl,

R ₁₃be the alkylidene group with 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or does not replace); With

Formula 4

(wherein R ₁₄hydrogen or methyl,

R ₁₅be the alkylidene group with 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or does not replace).

(4), according to the composition of above-mentioned (3), wherein adhesiving reinforcing agent is by least one of the compound of formula 2 to 4 expressions and the mixture of the compound that formula 1 represents.

(5), according to the composition of above-mentioned (1), it further comprises the polymkeric substance that comprises styracin ester group as alignment agent.

(6), according to the composition of above-mentioned (5), wherein comprise adhesiving reinforcing agent taking the amount based on 100 weight part alignment agent as 0.1 to 20 weight parts.

(7), according to the composition of above-mentioned (1), it further comprises at least one and is selected from the light trigger of the group of following composition: compound in triazine class, acetophenone compounds, bisglyoxaline compounds, oxime compounds, bitter almond oil camphor compounds, benzophenone compound, thioxanthone compounds and anthracene compounds.

(8), according to the composition of above-mentioned (1), it further comprises at least one organic solvent of selecting from the group of following composition: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diglyme, diethyl carbitol, glycol ether ethyl-methyl ether, glycol ether dipropyl ether, glycol ether dibutyl ether, methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, methoxyl group butylacetic acid ester, methoxyl group amyl group acetic ester, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol ethyl-methyl ether, propylene glycol dipropyl ether, propylene glycol propyl group methyl ether, propylene glycol ethyl propyl ether, propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propandiol butyl ether propionic ester, methoxybutanol, oxyethyl group butanols, propoxy-butanols, butoxy butanols, methoxyl group butylacetic acid ester, oxyethyl group butylacetic acid ester, propoxy-butylacetic acid ester, butoxy butylacetic acid ester, methoxyl group butyl propionic ester, oxyethyl group butyl propionic ester, propoxy-butyl propionic ester, butoxy butyl propionic ester, dipropylene glycol dme, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, benzene, toluene, dimethylbenzene, sym-trimethylbenzene, methylethylketone, acetone, methyl-n-amyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ethanol, propyl alcohol, butanols, hexanol, hexalin, ethylene glycol, glycerine, methyl acetate, ethyl acetate, propyl acetate, butylacetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy-propionic acid ethyl ester, 3-hydroxy-propionic acid propyl ester, 3-hydroxy-propionic acid butyl ester, 2-hydroxy-3-methyl methyl-butyrate, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid propyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxy-methyl acetate, propoxy-ethyl acetate, propoxy-propyl acetate, propoxy-butylacetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2 – butoxy methyl propionates, 2 – butoxy ethyl propionates, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxy-methyl propionate, 3-propoxy-ethyl propionate, 3-propoxy-propyl propionate, 3-propoxy-butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, 3-butoxy butyl propionate, tetrahydrofuran (THF), pyrans and gamma-butyrolactone.

(9) oriented layer being formed according to the composition for the preparation of oriented layer described in any one of above-mentioned (1) to (8) by one.

(10) phase shift films, it comprises: base material, on base material, form according to the oriented layer of above-mentioned (9) and the liquid crystal layer that forms in oriented layer.

(11), according to the phase shift films of above-mentioned (10), wherein base material has reactive group in its surface, its can with the adhesiving reinforcing agent containing in the composition for the preparation of oriented layer in isocyanate group and (methyl) acrylate-based bonding.

(12) according to the phase shift films of above-mentioned (11), the reactive group wherein existing is in its surface at least one of group that is selected from following composition: hydroxyl, thiol group, carboxyl, (methyl) are acrylate-based, amido and epoxy group(ing).

(13), according to the phase shift films of above-mentioned (11), wherein oriented layer is attached on base material by amino-formate bond, mercaptan ethylene linkage (thiolene bond) or carbon-to-carbon saturated bond.

(14), according to the phase shift films of above-mentioned (11), wherein base material comprises surface-treated triacetyl cellulose, cycloolefin or PMMA polymkeric substance.

(15), according to the phase shift films of above-mentioned (14), wherein surface treatment is that at least one of group by being selected from following composition processed: saponification method, prime treatment, corona treatment, Cement Composite Treated by Plasma and coating.

(16) according to the phase shift films of above-mentioned (15), wherein Cement Composite Treated by Plasma is at least one of group that is selected from following composition: remote plasma treatment (remote plasma processing), directly Cement Composite Treated by Plasma (direct plasma processing) and monomer plasma processing (monomer plasma processing).

(17) according to the phase shift films of above-mentioned (13), wherein amino-formate bond is to be formed by hydroxyl, thiol group, amido or epoxy reaction in isocyanate group and base material in oriented layer compound, and described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

R ₅be the alkylidene group with 1 to 10 carbon atom, its alkoxyl group with 1 to 8 carbon atom replaces or is unsubstituted);

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b)

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

(18) according to the phase shift films of above-mentioned (13), wherein carbon-to-carbon saturated bond by compound in oriented layer (methyl) acrylate-based with base material in (methyl) acrylate radical reaction form, described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b)

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

(19) according to the phase shift films of above-mentioned (13), wherein mercaptan ethylene linkage is that (methyl) acrylate-based reaction with the thiol group in base material by the compound in oriented layer forms, and described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b) wherein E ₁and E ₃the alkoxyl group independently of one another with 1 to 8 carbon atom replaces or the unsubstituted alkoxyl group that has the alkyl of 1 to 10 carbon atom or have 1 to 8 carbon atom; With E2 be the alkylidene group with 1 to 10 carbon atom, its had 1 to 8 carbon atom alkoxyl group replace or do not replace);

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

(20), according to the phase shift films of above-mentioned (10), wherein by amino-formate bond or carbon-to-carbon saturated bond, oriented layer is attached to liquid crystal layer.

(21), according to the phase shift films of above-mentioned (10), wherein liquid crystal layer is to be formed by the liquid crystalline cpd with carbon-to-carbon unsaturated bond or hydroxyl, epoxy group(ing) or cyano group.

(22) according to the phase shift films of above-mentioned (20), wherein amino-formate bond is to be reacted and formed by hydroxyl, epoxy group(ing) or the cyano group of the isocyanate group of compound in oriented layer and the liquid crystalline cpd of liquid crystal layer, and described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

RX is the alkylidene group with 1 to 10 carbon atom, and its alkoxyl group with 1 to 8 carbon atom replaces or do not replace);

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b)

wherein E ₁and E ₃the alkoxyl group independently of one another with 1 to 8 carbon atom replaces or the unsubstituted alkoxyl group that has the alkyl of 1 to 10 carbon atom or have 1 to 8 carbon atom; And E ₂be the alkylidene group with 1 to 10 carbon atom, its alkoxyl group with 1 to 8 carbon atom replaces or does not replace);

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

(23) according to the phase shift films of above-mentioned (20), wherein carbon-to-carbon saturated bond forms by acrylate-based the reaction with the liquid crystalline cpd carbon-to-carbon unsaturated bond of liquid crystal layer of compound in oriented layer (methyl), and described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b)

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

(24) phase shift films to (23) any one according to above-mentioned (10), wherein, forms liquid crystal layer further comprising in end has isocyanate group and (methyl) acrylate-based adhesiving reinforcing agent.

(25) according to the phase shift films of above-mentioned (24), wherein by chemical bond, liquid crystal layer and oriented layer are bonded to each other, described chemical bond is included in the carbon-to-carbon saturated bond between the adhesiving reinforcing agent comprising in liquid crystal layer and oriented layer.

(26), according to the phase shift films of above-mentioned (24), wherein adhesiving reinforcing agent is at least one of group that is selected from the compound composition of following formula 1 to 4 expression:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b)

wherein E ₁and E ₃the alkoxyl group independently of one another with 1 to 8 carbon atom replaces or the unsubstituted alkoxyl group that has the alkyl of 1 to 10 carbon atom or have 1 to 8 carbon atom; With E2 be the alkylidene group with 1 to 10 carbon atom, its had 1 to 8 carbon atom alkoxyl group replace or do not replace);

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

(27), according to the phase shift films of above-mentioned (24), wherein to comprise based on 100 weight part liquid crystalline cpds be the adhesiving reinforcing agent of 0.1 to 15 weight part to liquid crystal layer.

The composition for the preparation of oriented layer according to the present invention is hardened in the method for oriented layer, said composition can Chemical bond to the different layers that is arranged on these oriented layer both sides, thereby form the phase shift films with excellent interfacial bonding strength.

Phase shift films of the present invention has very high interfacial bonding strength, therefore, during its prepares as the blooming of polarizing coating in use, peels off remarkable decline, has reduced fraction defective, thereby has increased productivity.

Brief description of the drawings

By the detailed description of doing below in conjunction with accompanying drawing, will more clearly understand above and other objects of the present invention, feature and other advantage, wherein:

Fig. 1 is the schematic cross sectional views of phase shift films.

Embodiment

The invention discloses for the preparation of the composition of oriented layer that is suitable for liquid crystalline cpd orientation, it comprises: have endways isocyanate group and (methyl) acrylate-based adhesiving reinforcing agent, wherein isocyanate group and (methyl) acrylate-based reactive group that is bonded to liquid crystalline cpd, thereby make said composition Chemical bond arrive the different layers arranging in oriented layer both sides, thereby form the phase shift films with excellent interfacial bonding strength.

Below, the present invention will be described in more detail.

According to the composition for the preparation of oriented layer of the present invention, can comprise adhesiving reinforcing agent, it can Chemical bond to another layer forming on oriented layer side.Adhesiving reinforcing agent of the present invention can have respectively at least one (methyl) acrylate-based and at least one isocyanate group at two ends.According to the present invention, (methyl) acrylate refers to acrylate or methacrylic ester.

According to the present invention, although in the time being mixed with adhesiving reinforcing agent for the preparation of the composition of oriented layer, (methyl) in adhesiving reinforcing agent acrylate-based and/or isocyanate group is not included in its end, but before this adhesiving reinforcing agent Chemical bond arrives liquid crystalline cpd and base material, by any extra processing (for example, aftertreatment, as heating) form the functional group of (methyl) acrylate-based or isocyanate group, also can be included in the definition of aforementioned (methyl) acrylate.The aforementioned group that forms isocyanate group by thermal treatment for example can comprise: the pyrazolyl that is connected to this adhesiving reinforcing agent end by amido linkage.By heating, this pyrazolyl is separated, and form endways isocyanate group.

Conventionally, oriented layer is the layer of induction liquid crystal aligning, and the in the situation that of using oriented layer in phase shift films, its surface can contact with liquid crystal layer, and another surface contacts with base material film.As mentioned above, conventional phase shift films have oriented layer and and other layer of contacting of oriented layer between interfacial bonding strength a little less than problem.But, according to the present invention, owing to being incorporated in oriented layer thering is respectively endways isocyanate group and (methyl) acrylate-based adhesiving reinforcing agent, this isocyanate group and (methyl) acrylate-based can Chemical bond to being exposed to the lip-deep reactive group of liquid crystal layer, described reactive group contacts with (methyl) is acrylate-based with isocyanate group, and more preferably, Chemical bond arrives at the lip-deep reactive group of base material film, thereby combination between enhancement layer.

Reactive group in the liquid crystalline cpd that is used to form a liquid crystal layer Surface Contact of oriented layer (it and), for example, can comprise carbon-to-carbon unsaturated bond, hydroxyl, epoxy group(ing), cyano group etc.Preferably use carbon-to-carbon unsaturated bond.More particularly, this carbon-to-carbon unsaturated bond for example can comprise: be included in the carbon-to-carbon unsaturated bond in acryloxy, alpha-cyanoacrylate ester group, allyl group, styracin ester group or allyloxy.

Therefore, any conventional liquid crystalline cpd using in association area can be for the present invention, as long as it has reactive group.Further, even if the conventional liquid crystalline cpd itself using in association area does not have reactive group as above, if can introduce this reactive group at the end of this compound by known pretreatment process in association area, also can use without restriction this compound.

More preferably, with the base material of this another Surface Contact of oriented layer, on the surface of this base material, can have can with the reactive group of isocyanate group or (methyl) acrylate radical reaction.Such reactive group for example can comprise: hydroxyl, thiol group, carboxyl, (methyl) are acrylate-based, amido or epoxy group(ing) etc.

Therefore, if the one in the conventional base material using in association area has reactive group as above, this base material can be used in the present invention, is not subject to its concrete restriction.Further, even if the conventional base material itself using in association area does not have reactive group as above, if can introduce this reactive group by known exemplary surface treatment in association area on the surface of this base material, this base material also can be for the present invention.

Can comprise at least one of group of the compound composition that the formula of being selected from 1, formula 2, formula 3 and formula 4 represent according to the specific examples of adhesiving reinforcing agent of the present invention:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

R ₃and R ₇for having 1 to 10 carbon atom alkylidene group, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or does not replace independently of one another;

R ₄and R ₆for having 1 to 10 carbon atom alkylidene group, its group that is selected from the group of amide group, ketone group, ester group and thiol group composition replaces or does not replace independently of one another; With

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₉and R ₁₁for having 1 to 10 carbon atom alkylidene group, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or does not replace independently of one another;

R ₁₀(a) or (b)

wherein E ₁and E ₃the alkoxyl group independently of one another with 1 to 8 carbon atom replaces or the unsubstituted alkyl with 1 to 10 carbon atom), or there is the alkoxyl group of 1 to 8 carbon atom and E ₂be the alkylidene group with 1 to 10 carbon atom, its alkoxyl group with 1 to 8 carbon atom replaces or does not replace);

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

About the composition for the preparation of oriented layer of the present invention, in order to ensure more excellent interlayer combination, herein can with the adhesiving reinforcing agent being represented by formula 1 to formula 4 can be: at least one selects the compound of free style 2 to 4 expressions and the mixture of the compound that formula 1 represents.

More particularly, by the adhesiving reinforcing agent of formula 1 to 4 any expression, for example, can comprise at least one of group of the compound composition that is selected from following formula 5 to 15 expressions:

Formula 5

Formula 6

Formula 7

Formula 8

Formula 9

Formula 10

Formula 11

Formula 12

Formula 13

Formula 14

Formula 15

The feature of the compound being represented by formula 4 and the example (that is: comprise the compound being represented by formula 12,13,14 and 15) is: the dimethyl pyrazole base of the each end of these compounds, in heat-processed is for example dry, separate, therefore, its end can provide isocyanate group.

Except aforesaid viscosity intensifier, the composition for the preparation of oriented layer of the present invention, can further be included in normally used any additive, for example alignment agent, light trigger and organic solvent in association area.

Alignment agent used herein, can be included in the alignment agent of normally used any routine in association area, not limited especially by it.For example, can use the polymkeric substance that contains styracin ester group and there are 10000 to 500000 weight-average molecular weight, but not be confined to especially this.

Can comprise according to adhesiving reinforcing agent of the present invention by the content that is 0.1 to 20 weight part based on 100 weight part alignment agents.In aforementioned range, can ensure enough binding propertys.In the situation that adhesiving reinforcing agent is used for to blooming, if add excessive adhesiving reinforcing agent, although its binding property increases, other physicals may be deteriorated.

Light trigger used herein can comprise the light trigger of any routine, not limited especially by it.For example, can use compound in triazine class, acetophenone compounds, bisglyoxaline compounds, oxime compounds, bitter almond oil camphor compounds, benzophenone compound, thioxanthone compounds, anthracene compounds etc., but, be not confined to especially this.

Compound in triazine class for example can comprise: 2, two (the trichloromethyl)-6-(4-p-methoxy-phenyls of 4-)-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl group naphthyls of 4-)-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-of 4-piperonyl-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrenes of 4-)-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(5-methyl furan-2-yls of 4-) vinyl]-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-yls of 4-) vinyl]-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylin-2-aminomethyl phenyls of 4-) vinyl]-1, 3, 5-triazine or 2, two (the trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.

Acetophenone compounds for example can comprise: diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, benzyl dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methyl-prop-1-ketone, 1-hydroxy-cyclohexyl benzophenone, 2-methyl isophthalic acid-(4-methyl thio phenyl)-2-morpholino third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligopolymer of third-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) second-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) second-1-ketone, 2-propyl group-2-amino (4-morpholino phenyl) second-1-ketone, 2-butyl-2-amino (4-morpholino phenyl) second-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) third-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) fourth-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) third-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) fourth-1-ketone, 2-methyl-2-methylamino (4-morpholino phenyl) third-1-ketone, 2-methyl-2-dimethylamino (4-morpholino) third-1-ketone or 2-methyl-2-diethylamino (4-morpholino phenyl) third-1-ketone etc.

Bisglyoxaline compounds for example can comprise: two (the 2-chloro-phenyl-s)-4 of 2,2'-, 4', 5,5'-tetraphenyl bisglyoxaline, 2, two (2, the 3-dichlorophenyls)-4 of 2'-, 4', 5,5'-tetraphenyl bisglyoxaline, 2, two (the 2-chloro-phenyl-s)-4 of 2'-, 4', 5,5'-tetra-(alkoxyl phenyl) bisglyoxaline, 2, two (the 2-chloro-phenyl-s)-4 of 2'-, 4', 5,5'-tetra-(tri-alkoxy phenyl) bisglyoxaline, has 4,4', replaces the imidazolium compounds of the phenyl that has carbalkoxy etc. on 5,5' position.Wherein, two (the 2-chloro-phenyl-s)-4 of 2,2'-, 4', two (2, the 3-dichlorophenyls)-4 of 5,5'-tetraphenyl bisglyoxaline and 2,2'-, 4', 5,5'-tetraphenyl bisglyoxaline is preferred.

Oxime compounds for example can comprise: adjacent ethoxycarbonyl-α-oxygen amido-1-phenyl third-1-ketone etc.

Bitter almond oil camphor compounds for example can comprise: bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether or bitter almond oil camphor isobutyl ether etc.

Benzophenone compound for example can comprise: benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenyl thioether or 3,3'; 4; 4'-tetra-(t-butyl peroxy carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone etc.

Thioxanthone compounds for example can comprise: ITX, 2,4-diethyl thioxanthone, 2,4-bis-clopenthixal ketones or the chloro-4-propoxy-of 1-thioxanthone etc.

Anthracene compounds for example can comprise: 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.

Except above-claimed cpd; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, 10-butyl-2-chloro-acridine ketone, 2-ethyl-anthraquinone, benzyl, 9; 10-phenanthrenequione, camphorquinone, methyl benzoylformate, two cyclopentadiene titanium compounds, have the Photoepolymerizationinitiater initiater of group that chain shifts can occur; this is disclosed in the announcement communique of Japanese patent application publication No. 2002-544205, or also can use analogue.

In the composition for the preparation of oriented layer according to a further aspect in the invention, can not comprise light trigger.Light trigger has advantages of can make the photopolymerization reaction of alignment agent be easy to carry out.But, using excessive light trigger in the situation that, light trigger is as impurity, reduces orientation effect and disturbs the orientation of liquid crystal, thereby during cross polarization, cause light leak, or after photocuring, can distil and pollute mask (mask).In addition,, wavelength in the time that the intensity of the reaction wavelength of light trigger is being reacted between exposure period with respect to alignment agent is much higher, may cause for example generation efficiency of side effect to reduce (linear velocity of, implementing light orientation reduces).From this aspect, that the composition for the preparation of oriented layer of the present invention can comprise minimum or do not comprise light trigger.

Organic solvent used herein can be included in any conventional organic solvent using in association area, not limited especially by it.For example, ethylene glycol monoalkyl ether, as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether and ethylene glycol monobutyl ether etc., glycol ether dialkyl ether, as diglyme, diethyl carbitol, glycol ether ethyl-methyl ether, glycol ether dipropyl ether, glycol ether dibutyl ether etc., ethylene glycol alkyl oxide acetic ester, as methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate etc., aklylene glycol alkyl oxide acetic ester, as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, methoxyl group butylacetic acid ester, methoxyl group amyl group acetic ester etc., propylene-glycol monoalky lether, as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc., propylene glycol dialkyl ether, such as Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol ethyl-methyl ether, propylene glycol dipropyl ether, propylene glycol propyl group methyl ether, propylene glycol ethyl propyl ether etc., propylene glycol alkyl ether propionic ester, such as propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propandiol butyl ether propionic ester etc., butyleneglycol monoalky lether, as methoxybutanol, oxyethyl group butanols, propoxy-butanols, butoxy butanols etc., butyleneglycol monoalky lether acetic ester, as methoxyl group butylacetic acid ester, oxyethyl group butylacetic acid ester, propoxy-butylacetic acid ester, butoxy butylacetic acid ester etc., butyleneglycol monoalky lether propionic ester, as methoxyl group butyl propionic ester, oxyethyl group butyl propionic ester, propoxy-butyl propionic ester, butoxy butyl propionic ester etc., dipropylene glycol dialkyl ether, as dipropylene glycol dme, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether etc., aromatic hydrocarbons, as benzene,toluene,xylene, sym-trimethylbenzene etc., ketone, as methylethylketone, acetone, MAK, mibk, pimelinketone etc., alcohols, as ethanol, propyl alcohol, butanols, hexanol, hexalin, ethylene glycol, glycerine etc., ester class, as methyl acetate, ethyl acetate, propyl acetate, butylacetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy-propionic acid ethyl ester, 3-hydroxy-propionic acid propyl ester, 3-hydroxy-propionic acid butyl ester, 2-hydroxy-3-methyl methyl-butyrate, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid propyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxy-methyl acetate, propoxy-ethyl acetate, propoxy-propyl acetate, propoxy-butylacetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxy-methyl propionate, 3-propoxy-ethyl propionate, 3-propoxy-propyl propionate, 3-butoxy butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, 3-butoxy butyl propionate etc., cyclic ethers class, as tetrahydrofuran (THF), pyrans etc., cyclic esters, as gamma-butyrolactone, it can use separately or be used in combination with two or more.

Optionally, the composition for the preparation of oriented layer of the present invention can further comprise any additive, such as filler, solidifying agent, levelling agent, tackifier, antioxidant, ultraviolet light absorbers, anti-agglomerating agent or chain-transfer agent etc.

Composition for the preparation of oriented layer of the present invention, by solidifying to form oriented layer, can, in any routine application that has wherein used oriented layer, not limited by it especially.Preferably, composition of the present invention can be effectively applied to: at the pattern phase shift films providing for the display unit that shows 3-D view (, pattern delayer).

Fig. 1 shows the structure of typical phase shift films.Phase shift films 100 comprises transparent substrate 110, photocuring liquid crystal layer 120 and inserts the oriented layer 130 between transparent substrate 110 and photocuring liquid crystal layer 120.

For transparent substrate 110 of the present invention, on substrate surface, can have can with the reactive group of isocyanate group or (methyl) acrylate radical reaction, for example hydroxyl, thiol group, carboxyl, (methyl) are acrylate-based, amido or epoxy group(ing).

In the conventional base material using in association area, transparent substrate 110 according to the present invention can comprise any base material with reactive group described above, not limited especially by it.In addition, even if do not contain previous reaction group, also can use in the present invention by known any pretreatment process in association area and can be incorporated into any reactive group on substrate surface, not limited especially by it.

Base material used herein can comprise the transparent film of any routine using in association area, for example, comprises (PMMA) film of polymkeric substance etc. of triacetyl cellulose (TAC) polymkeric substance, cyclic olefin polymer (COP) or poly-(methyl methacrylate).The base material being made by TAC, COP or PMMA, in its surface conventionally containing can with the reactive group of isocyanate group or (methyl) acrylate radical reaction.Therefore, can on substrate surface, introduce by surface treatment required reactive group.For example, for hydroxyl, if saponification is carried out in surface, just on TAC surface, introduce hydroxyl, and also can introduce from the teeth outwards hydroxyl to the Cement Composite Treated by Plasma on COP surface.Except aforesaid method, also can use: drying means, such as corona treatment, prime treatment etc.; Chemical treatment, for example, comprise the alkalinization of saponification; Or form coating method of wieldy bonding coat etc.Especially, preferably process cellulosefilm by the alkalization that comprises saponification, and advantageously process acrylic, polyolefine and polyester film by for example corona treatment of drying means or plasma method.More particularly, can use at least one that be for example selected from remote plasma, directly plasma body or monomer plasma to carry out Cement Composite Treated by Plasma.

Can prepare photocuring liquid crystal layer 120 by solidifying following composition, said composition comprises: have carbon-to-carbon unsaturated carbon bond or have endways the liquid crystalline cpd of hydroxyl, epoxy group(ing) or cyano group; Polymerization initiator and organic solvent.In this case, polymerization starter used herein can be Photoepolymerizationinitiater initiater or the thermopolymer initiator of any routine of using in association area.Especially, Photoepolymerizationinitiater initiater used herein can be the light trigger of as above enumerating.Organic solvent used herein also can suitably be selected from the organic solvent of as above enumerating.

According to a further aspect in the invention, the aforementioned composition for the preparation of photocuring liquid crystal layer 120 can further comprise adhesiving reinforcing agent as above as required.With regard to further improve interlayer in conjunction with regard to, this is particularly preferred, has formed carbon-to-carbon saturated bond because have endways in isocyanate group and (methyl) acrylate-based adhesiving reinforcing agent, wherein these groups are comprised in liquid crystal layer and oriented layer.In this case, consider that adhesiving reinforcing agent can make to obtain between base material and oriented layer and/or between oriented layer and liquid crystal layer effectively bonding, keep liquid crystal aligning characteristic simultaneously and prevent the reduction postponing, the content of adhesiving reinforcing agent can be 0.1 to 15 weight part based on 100 weight part liquid crystalline cpds.

According to the present invention, the reactive group in transparent substrate 110 can be with to be exposed to the lip-deep reactive group of photocuring liquid crystal layer 120 identical or different.

Oriented layer 130 of the present invention can be included in end and have isocyanate group and (methyl) acrylate-based adhesiving reinforcing agent, wherein these groups can be respectively with transparent substrate 110 on reactive group and the other reaction-ity group reaction exposing on photocuring liquid crystal layer 120, to form chemical bond.

About chemical bond as above, the isocyanate group end of this adhesiving reinforcing agent can react with hydroxyl, thiol group, carboxyl, amido, epoxy group(ing) or cyano group in transparent substrate 110 or photocuring liquid crystal layer 120, thereby forms amino-formate bond.

React with hydroxyl as above, thiol group, carboxyl, amido, epoxy group(ing) or cyano group by isocyanate group and form amino-formate bond, can be represented by reaction process 1 below.As a reference, before cyano group and isocyanic ester radical reaction, during by heating cyano group, use H2O pre-treatment, cyano group can be become to amido or carboxyl.

Reaction process 1

Reaction process 2

Reaction process 3

Reaction process 4

Reaction process 5

Reaction process 6

Except above-mentioned, chemical bond for example can comprise: by (methyl) acrylate-based end of the adhesiving reinforcing agent containing in oriented layer, and/or carbon-to-carbon unsaturated bond acrylate-based with (methyl) in transparent substrate 110 or photocuring liquid crystal layer 120 reacts the carbon-to-carbon saturated bond forming.Further, in the situation that liquid crystal layer 120 comprises adhesiving reinforcing agent described above therein, (methyl) acrylate end of the adhesiving reinforcing agent containing in oriented layer and the adhesiving reinforcing agent that contains in liquid crystal layer can react each other, so that forms carbon-to-carbon saturated bond.

Or this chemical bond for example can comprise: (methyl) acrylate end by adhesiving reinforcing agent reacts with the thiol group in transparent substrate 110 the mercaptan ethylene linkage forming.

By the such as chemical bond of amino-formate bond, carbon-to-carbon saturated bond, mercaptan ethylene linkage etc., oriented layer 130 of the present invention can be bonded to because thering is excellent adhesiveness transparent substrate 110 and photocuring liquid crystal layer 120 both.

Can prepare by the following method according to phase shift films of the present invention: the composition for the preparation of oriented layer of the present invention is applied to transparent substrate, is dried and is exposed, to form pattern in oriented layer; And will be applied to oriented layer for the preparation of the composition of photocuring liquid crystal layer, and it is dry, then carry out photocuring operation.As mentioned above, between liquid crystal layer hardening period, oriented layer of the present invention and liquid crystal layer Chemical bond, simultaneously in drying means (thermal treatment), oriented layer and transparent substrate Chemical bond.

, will describe preferred embodiment below, more specifically understand the present invention.But, it will be apparent for a person skilled in the art that: can be as defined in claims, various improvement and distortion to these embodiments are possible, and scope of the present invention should be not limited to following embodiment.These embodiments are provided, and are in order to explain the present invention to the people with this area general knowledge and technical ability completely.

Embodiment

embodiment 1 to 7 and comparative example 1 and 2

With the composition of composition shown in following table 1, by mixing all alignment agents, viscosity intensifier, light trigger (Irgacure907, manufactured by BASF Co.) and organic solvent (toluene) (unit is g), prepares the respectively composition for the preparation of oriented layer.

Table 1

the preparation of sample

After each composition of preparation in embodiment 1 to 7 and comparative example 1 and 2 is carried out to saponification respectively, the composition of processing is applied to the TAC film (being manufactured by Fuji Co.) of having introduced hydroxyl on surface, and the film applying is dried to 1 minute at 100 DEG C, dry film is exposed to cause curing reaction, thus preparation oriented layer.After the light curable liquid-crystal composition (RMS) that comprises liquid crystalline cpd (having endways carbon-to-carbon unsaturated bond) is applied to gained oriented layer, the film applying is dried to 1 minute at 60 DEG C, to prepare phase shift films.

Embodiment 8 to 14 and comparative example 3 and 4

With the composition of composition shown in following table 2, by mixing all liquid crystalline cpds (RMS), viscosity intensifier, alignment agent (Irgacure907, manufactured by BASF Co.) and organic solvent (toluene) (unit is g), for the preparation of each composition of preparing liquid crystal layer.

Further, with the composition of composition shown in table 2, by mixing all alignment agents, adhesiving reinforcing agent, light trigger (Irgacure907 is manufactured by BASF Co.) and organic solvent (toluene), (unit is g), carrys out the composition for the preparation of preparation oriented layer.

Table 2

the preparation of sample

After each composition of preparation in embodiment 8 to 14 and comparative example 3 and 4 is carried out to saponification respectively, the composition of processing is applied to the TAC film (being manufactured by Fuji Co.) of having introduced hydroxyl on surface, and the film applying is dried to 1 minute at 100 DEG C, dry film is exposed to cause curing reaction, thus preparation oriented layer.After the each composition for the preparation of liquid crystal layer of preparation in embodiment 8 to 14 and comparative example 3 and 4 being applied to respectively to the top of oriented layer and it is dried to 1 minute at 60 DEG C, dry film is exposed to promote curing reaction, thereby prepare phase shift films.

Experimental example

< orientation angle >

In the pattern A and B of the phase shift films of preparing, use the instrument WPA-100L obtaining from Rukeo Co. to carry out the orientation angle of measured pattern A.

◎: 45 ° ± 3(is for pattern A), 135 ° ± 3(is for pattern B)

Zero: 45 ° ± be less than 6 ((for pattern A), 135 ° ± be less than 6(for pattern B)

×: more than 45 ° ± 6 (for pattern A), more than 135 ° ± 6 (for pattern B)

< phase delay >

Rr: at comparative example 1(table 3) or comparative example 3(table 4) in the phase delay of phase shift films of preparation

Rs: the phase delay of phase delay film

◎：0.97<Rs/Rr<1.03

Zero: 0.95<Rs/Rr<0.97 or 1.03<Rs/Rr<1.05

△: 0.90<Rs/Rr<0.95 or 1.05<Rs/Rr<1.1

×: Rs/Rr is more than 1.1, or Rs/Rr is below 0.90

< interlayer is in conjunction with >

The pattern forming by observation by light microscope, carrys out evaluation pattern generating according to the standard of following pattern degree of taking (degrees of pattern picking) and takes.

◎: do not observe pattern and take

Zero: pattern is taked 1 to 3

△: pattern is taked 4 to 8

×: pattern takes to exceed 8

Table 3

Table 4

Described in above-mentioned table 3 and 4, can find: although the phase shift films of preparation is compared with the phase shift films of preparing in comparative example in an embodiment according to the present invention, substantially there is same or analogous optical property, but, the phase shift films that is better than preparing in comparative example according to the interlayer combination of phase shift films of the present invention.

Claims

1. one kind for the preparation of the composition of oriented layer that is suitable for liquid crystalline cpd orientation, it comprises: have endways isocyanate group and (methyl) acrylate-based adhesiving reinforcing agent, wherein said isocyanate group and described (methyl) acrylate-based reactive group that is bonded to described liquid crystalline cpd.

2. composition according to claim 1, the reactive group of wherein said liquid crystalline cpd is carbon-to-carbon unsaturated bond, hydroxyl, epoxy group(ing) or cyano group.

3. composition according to claim 1, wherein said adhesiving reinforcing agent is at least one of group that is selected from the compound composition of following formula 1 to 4 expression:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R7 and R8 are hydrogen or methyl independently of one another;

R9 and R11 are independently of one another for having the alkylidene group of 1 to 10 carbon atom, and its group that is selected from the group of ketone group, ester group and thiol group composition replaces or do not replace;

R10 is (a)

or (b)

wherein E1 and E3 are had alkoxyl group replacement or the unsubstituted alkyl with 1 to 10 carbon atom of 1 to 8 carbon atom independently of one another, or have the alkoxyl group of 1 to 8 carbon atom; With E2 be the alkylidene group with 1 to 10 carbon atom, its had 1 to 8 carbon atom alkoxyl group replace or do not replace);

Formula 3

(wherein R12 is hydrogen or methyl,

R13 is the alkylidene group with 1 to 10 carbon atom, and its group that is selected from the group of ketone group, ester group and thiol group composition replaces or do not replace); With

Formula 4

(wherein R ₁₄hydrogen or methyl,

4. composition according to claim 3, wherein said adhesiving reinforcing agent is the mixture of the compound that represented by least one of the compound of formula 2 to 4 expressions and formula 1.

5. composition according to claim 1, it further comprises the polymkeric substance that comprises styracin ester group as alignment agent.

6. composition according to claim 5, wherein comprises described adhesiving reinforcing agent taking the amount based on 100 weight part alignment agent as 0.1 to 20 weight parts.

7. composition according to claim 1, it further comprises at least one and is selected from the light trigger of the group of following composition: compound in triazine class, acetophenone compounds, bisglyoxaline compounds, oxime compounds, bitter almond oil camphor compounds, benzophenone compound, thioxanthone compounds and anthracene compounds.

8. composition according to claim 1, it further comprises at least one organic solvent of selecting from the group of following composition: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diglyme, diethyl carbitol, glycol ether ethyl-methyl ether, glycol ether dipropyl ether, glycol ether dibutyl ether, methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, methoxyl group butylacetic acid ester, methoxyl group amyl group acetic ester, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol ethyl-methyl ether, propylene glycol dipropyl ether, propylene glycol propyl group methyl ether, propylene glycol ethyl propyl ether, propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propandiol butyl ether propionic ester, methoxybutanol, oxyethyl group butanols, propoxy-butanols, butoxy butanols, methoxyl group butylacetic acid ester, oxyethyl group butylacetic acid ester, propoxy-butylacetic acid ester, butoxy butylacetic acid ester, methoxyl group butyl propionic ester, oxyethyl group butyl propionic ester, propoxy-butyl propionic ester, butoxy butyl propionic ester, dipropylene glycol dme, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, benzene, toluene, dimethylbenzene, sym-trimethylbenzene, methylethylketone, acetone, methyl-n-amyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ethanol, propyl alcohol, butanols, hexanol, hexalin, ethylene glycol, glycerine, methyl acetate, ethyl acetate, propyl acetate, butylacetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy-propionic acid ethyl ester, 3-hydroxy-propionic acid propyl ester, 3-hydroxy-propionic acid butyl ester, 2-hydroxy-3-methyl methyl-butyrate, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid propyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxy-methyl acetate, propoxy-ethyl acetate, propoxy-propyl acetate, propoxy-butylacetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2 – butoxy methyl propionates, 2 – butoxy ethyl propionates, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxy-methyl propionate, 3-propoxy-ethyl propionate, 3-propoxy-propyl propionate, 3-propoxy-butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, 3-butoxy butyl propionate, tetrahydrofuran (THF), pyrans and gamma-butyrolactone.

9. by the oriented layer forming according to the composition for the preparation of oriented layer described in claim 1 to 8 any one.

10. a phase shift films, it comprises: base material, the oriented layer according to claim 9 forming on base material and the liquid crystal layer forming in described oriented layer.

11. phase shift films according to claim 10, wherein said base material has reactive group in its surface, described reactive group can with the adhesiving reinforcing agent containing in the described composition for the preparation of oriented layer in isocyanate group and (methyl) acrylate-based bonding.

12. phase shift films according to claim 11, the reactive group wherein existing on substrate surface is at least one of group that is selected from following composition: hydroxyl, thiol group, carboxyl, (methyl) are acrylate-based, amido and epoxy group(ing).

13. phase shift films according to claim 11, wherein said oriented layer is attached on described base material by amino-formate bond, mercaptan ethylene linkage or carbon-to-carbon saturated bond.

14. phase shift films according to claim 11, wherein said base material comprises surface-treated triacetyl cellulose, cycloolefin or PMMA polymkeric substance.

15. phase shift films according to claim 14, wherein said surface treatment is processed by least one of group that is selected from following composition: saponification method, prime treatment, corona treatment, Cement Composite Treated by Plasma and coating.

16. phase shift films according to claim 15, wherein said Cement Composite Treated by Plasma is at least one of group that is selected from following composition: remote plasma treatment, directly Cement Composite Treated by Plasma and monomer plasma processing.

17. phase shift films according to claim 13, wherein said amino-formate bond is to be formed by hydroxyl, thiol group, carboxyl, amido or epoxy reaction in isocyanate group and described base material in described oriented layer compound, and described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b)

wherein E ₁and E ₃the alkoxyl group independently of one another with 1 to 8 carbon atom replaces or the unsubstituted alkyl with 1 to 10 carbon atom, or has the alkoxyl group of 1 to 8 carbon atom; And E ₂be the alkylidene group with 1 to 10 carbon atom, its alkoxyl group with 1 to 8 carbon atom replaces or does not replace);

Formula 3

(wherein R ₁₂hydrogen or methyl,

R ₁₃be the alkylidene group with 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group or thiol group composition replaces or does not replace); With

Formula 4

(wherein R ₁₄hydrogen or methyl,

R ₁₅be the alkylidene group with 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group or thiol group composition replaces or is unsubstituted).

18. phase shift films according to claim 13, wherein said carbon-to-carbon saturated bond is that (methyl) acrylate radical reaction by (methyl) acrylate-based and described base material of the compound in described oriented layer forms, and described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

R ₃and R ₇for having the alkylidene group of 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or is unsubstituted independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₉and R ₁₁for having the alkylidene group of 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or is unsubstituted independently of one another;

R ₁₀(a) or (b)

Formula 3

(wherein R ₁₂hydrogen or methyl,

R ₁₃be the alkylidene group with 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or is unsubstituted); With

Formula 4

(wherein R ₁₄hydrogen or methyl,

R ₁₅be the alkylidene group with 1 to 10 carbon atom, its group that is selected from the group of ketone group, ester group and thiol group composition replaces or is unsubstituted).

19. phase shift films according to claim 13, wherein mercaptan ethylene linkage is to be reacted and formed by the thiol group in (methyl) acrylate-based and described base material of the compound in described oriented layer, described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a) or (b)

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

20. phase shift films according to claim 10, are wherein attached to described liquid crystal layer by amino-formate bond or carbon-to-carbon saturated bond by described oriented layer.

21. phase shift films according to claim 10, wherein said liquid crystal layer is to be formed by the liquid crystalline cpd with carbon-to-carbon unsaturated bond or hydroxyl, epoxy group(ing) or cyano group.

22. phase shift films according to claim 20, wherein said amino-formate bond is to be reacted and formed by hydroxyl, epoxy group(ing) or the cyano group of the isocyanate group of the compound in described oriented layer and the liquid crystalline cpd of described liquid crystal layer, and described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b)

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

23. phase shift films according to claim 20, wherein said carbon-to-carbon saturated bond is that acrylate-based the reaction with the liquid crystalline cpd carbon-to-carbon unsaturated bond of described liquid crystal layer of (methyl) by the compound in described oriented layer forms, and described compound is by any expression of following formula 1 to 4:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b) wherein E ₁and E ₃the alkoxyl group independently of one another with 1 to 8 carbon atom replaces or the unsubstituted alkyl with 1 to 10 carbon atom, or has the alkoxyl group of 1 to 8 carbon atom; With E2 be the alkylidene group with 1 to 10 carbon atom, its had 1 to 8 carbon atom alkoxyl group replace or do not replace);

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

24. according to claim 10 to the phase shift films described in 23 any one, wherein, forms described liquid crystal layer further comprising in end has isocyanate group and (methyl) acrylate-based adhesiving reinforcing agent.

25. phase shift films according to claim 24, are wherein bonded to each other described liquid crystal layer and described oriented layer by chemical bond, and described chemical bond is included in the carbon-to-carbon saturated bond between the adhesiving reinforcing agent comprising in described liquid crystal layer and described oriented layer.

26. phase shift films according to claim 24, wherein said adhesiving reinforcing agent is at least one of group that is selected from the compound composition of following formula 1 to 4 expression:

Formula 1

(wherein R ₁and R ₂be hydrogen or methyl independently of one another;

Formula 2

(wherein R ₇and R ₈be hydrogen or methyl independently of one another;

R ₁₀(a)

or (b)

Formula 3

(wherein R ₁₂hydrogen or methyl,

Formula 4

(wherein R ₁₄hydrogen or methyl,

27. phase shift films according to claim 24, it is the described adhesiving reinforcing agent of 0.1 to 15 weight part that wherein said liquid crystal layer comprises based on 100 weight part liquid crystalline cpds.