JP2006249221A - Cellulose ester film, polarizing plate and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a cellulose ester film that is stably drawn even in a high draw ratio, has sufficient planarity as a polarizer protecting film and satisfies plasticizer retention and low birefringence and to provide a polarizing plate and a liquid crystal display that use the cellulose ester film and have excellent stability. <P>SOLUTION: The cellulose ester film is obtained by melt film-forming of a composition consisting essentially of a cellulose ester. The cellulose ester satisfies formula (1) 2.4≤X+Y≤2.8 and formula (2) 0.3≤Y≤1.3 (X is a substitution degree by acetic acid; Y is a substitution degree by a 5-22C straight-chain carboxylic acid). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides a cellulose ester film, a polarizing plate and a liquid crystal display device. More specifically, the film can be stably stretched even at a high magnification, and sufficient planarity can be obtained as a polarizer protective film, and the plasticizer has low retention and low The present invention relates to a cellulose ester film that can satisfy birefringence.

  Cellulose ester film is a film that protects photographic negative film supports and polarizers used in liquid crystal displays because of its high transparency, low birefringence, and easy adhesion to polarizers. Has been used.

  The production volume of liquid crystal displays has been increasing in recent years due to its thin depth and lightness. In particular, a television using a liquid crystal display is producing a large-sized television that has not been achieved with a television using a brown screen, which has been the mainstream until now. Accordingly, the demand for polarizers and polarizer protective films constituting liquid crystal displays is increasing rapidly.

  Until now, these cellulose ester films have been produced exclusively by the solution casting method. The solution casting method is a film forming method in which a solution obtained by dissolving cellulose ester in a solvent is cast to obtain a film shape, and then the solvent is evaporated and dried to obtain a film. Since a film formed by the solution casting method has high flatness and uniformity, a high-quality liquid crystal display without unevenness can be obtained using this film.

  However, the solution casting method is not self-supporting until the solvent used for dissolving the cellulose ester is volatilized to some extent, so a drying process is essential before it is discharged from the die and peeled off and wound. Since the drying process requires a certain amount of time, the production speed cannot be increased, and it has become difficult to meet the demand for increased production in the market. In addition, since an organic solvent is used in the solution casting method, a large environmental load has been a problem. In particular, cellulose ester films are formed using halogen-based solvents with high environmental impact due to their dissolution characteristics, so reduction of solvent usage is required, and production of cellulose ester films is increased by solution casting film formation. It has become difficult to do.

  Therefore, in recent years, attempts have been made to melt-form a composition mainly composed of cellulose ester for silver salt photography (for example, see Patent Document 1) or for a polarizer protective film (for example, see Patent Document 2). Yes. Since the melt casting method does not use a solvent, the drying process is not required, so the production speed can be improved, and the production line such as a drying line and a solvent recovery / regeneration device is not required. This is a preferable manufacturing method because it can be easily increased in size and the environmental load can be greatly reduced.

  However, triacetyl cellulose, a cellulose ester that has been used for silver salt photography and polarizer protective films, is a polymer that has a melting temperature higher than the decomposition start temperature. The film obtained is not obtained by melt casting.

  On the other hand, in the cellulose ester for melt molding used for melt molding of toothbrushes and the like, cellulose esters mainly using propionic acid or butyric acid (CAP482-20 or CAB381-20 manufactured by Eastman Chemical Co., Ltd.) are used as organic acids for replacing cellulose. Etc.) are used.

  Such a cellulose ester has a glass transition temperature significantly lower than that of triacetyl cellulose, so that it can be melt-molded. On the other hand, the thermal deformation temperature and the wet heat deformation temperature are lowered, and a polarizer protective film for a liquid crystal display. As a result, the necessary physical properties cannot be obtained.

  As described above, it is known that the thermal properties of cellulose esters vary greatly depending on the type and degree of substitution of the organic acid that replaces cellulose (see, for example, Non-Patent Document 1).

  However, as a result of investigation by the inventors of the present invention, a combination of acetic acid and propionic acid as in Patent Document 1 or propionic acid (C3 carboxylic acid) to palmitic acid (C16 carboxylic acid) as in Non-Patent Document 1 It has been found that it is difficult to achieve both melt film-forming properties and wet heat resistance of the obtained film. That is, cellulose ester with a low melting temperature does not achieve moisture and heat resistance, while cellulose ester with sufficient moisture and heat resistance has a high melting temperature and melt viscosity, resulting in high apparatus load and flatness of the resulting film. It has been found that cellulose ester having an appropriate degree of substitution cannot be obtained due to problems such as inferior to the above, or thermal decomposition that causes coloring or brittleness of the film.

  Above all, the flatness of the film is a big problem of the melt film-forming process itself, and even for polymers other than cellulose esters, films used for optics are formed by solution film-forming. This is because in the melt film forming process, the time from the discharge of the fluid polymer from the die to solidification is short, and the time for the film to be leveled is short. Furthermore, the cellulose ester has a problem that its melt viscosity is high, and a melt-formed cellulose ester film having a quality that can be used for optics by melt film formation has not been obtained.

  It is known that the stretchability of a film can be improved by stretching uniaxially or biaxially. For example, a film such as polyethylene terephthalate (PET) is stretched about 10 times to improve the flatness. In Patent Document 1 as well, in order to obtain a cellulose ester film with good flatness, a film obtained by melt-forming a composition comprising cellulose acetate propionate containing about 14% of a plasticizer, 4 times stretching is performed.

  However, cellulose ester is a polymer that is difficult to stretch, and the cellulose ester obtained in the above patent document is a film that can be stretched only by about 20% to 40% at room temperature. The stretching ratio can be increased to some extent by performing the stretching operation at a high temperature. However, as a result of the study by the researchers of the present invention, a known publicly used cellulose ester has a high ratio of 2 to 4 times even at a high temperature. It was difficult to perform stretching with high productivity.

In addition, a film with such a high plasticizer composition lacks plasticizer retention as a polarizer protective film used in liquid crystal displays that can be used under high-temperature and high-humidity conditions such as in midsummer cars. It was found that the film lacks stability over time.
Japanese National Patent Publication No. 6-501040 JP 2000-352620 A Industrial and Engineering Chemistry, vol. 34-4 (1942), p430-435

  Therefore, the object of the present invention is a cellulose ester film that can be stably stretched even at a high magnification, has sufficient flatness as a polarizer protective film, and can satisfy the retentivity and low birefringence of the plasticizer, An object of the present invention is to provide a polarizing plate and a liquid crystal display device excellent in stability using the same.

  When the researchers of the present invention diligently studied the above problems, by using a mixed fatty acid cellulose ester in which a linear carboxylic acid having 5 to 22 carbon atoms and acetic acid are bound at a specific ratio as the cellulose ester. The inventors have found that a film having low birefringence and having a flatness that can be used as an optical film can be obtained even when stretched at a high magnification, and the present invention has been completed. At the same time, it is possible to provide a high-performance optical film having good optical properties, flatness, mechanical properties, and heat-and-moisture resistance by a melt film-forming method that does not use a halogen-based solvent having a high environmental load.

  Therefore, the above-described problem of the present invention is achieved by the following configuration.

(Claim 1)
A cellulose ester film obtained by melt-forming a composition mainly comprising cellulose ester, wherein the cellulose ester satisfies the following formulas (1) and (2).

Formula (1) 2.4 <= X + Y <= 2.8
Formula (2) 0.3 <= Y <= 1.3
(Wherein X represents the degree of substitution with acetic acid, and Y represents the degree of substitution with linear carboxylic acid having 5 to 22 carbon atoms)
(Claim 2)
The cellulose ester film according to claim 1, wherein the cellulose ester has a weight average molecular weight of 150,000 or more.

(Claim 3)
The cellulose ester film according to claim 1 or 2, wherein the temperature at the time of melt film formation is 180 ° C or higher and 230 ° C or lower.

(Claim 4)
The cellulose ester film according to claim 1, wherein the cellulose ester film is a film stretched 1.5 to 4.0 times.

(Claim 5)
The cellulose ester film according to any one of claims 1 to 4, wherein the linear carboxylic acid having 5 to 22 carbon atoms replacing the cellulose ester is caproic acid.

(Claim 6)
The cellulose ester film according to any one of claims 1 to 5, wherein the cellulose ester film contains 5 to 13% by mass of a polyhydric alcohol ester plasticizer.

(Claim 7)
The cellulose ester film according to any one of claims 1 to 6, wherein the cellulose ester film contains 0.1 to 5% by mass of a hindered phenol-based antioxidant.

(Claim 8)
The cellulose ester film according to any one of claims 1 to 7, wherein the cellulose ester film contains 0.1 to 5% by mass of a hindered amine light stabilizer.

(Claim 9)
The cellulose ester film according to any one of claims 1 to 8, wherein the cellulose ester film contains 0.1 to 5% by mass of an epoxy acid scavenger.

(Claim 10)
The cellulose ester film according to any one of claims 1 to 8, wherein the cellulose ester film contains 0.1 to 5% by mass of a benzotriazole-based ultraviolet absorber.

(Claim 11)
A polarizing plate comprising the cellulose ester film according to claim 1 as a protective film.

(Claim 12)
A liquid crystal display device comprising the polarizing plate according to claim 11.

  According to the present invention, a cellulose ester film that can be stably stretched even at a high magnification, has sufficient flatness as a polarizer protective film, and can satisfy the retentivity and low birefringence of a plasticizer, is used. It is possible to provide a polarizing plate and a liquid crystal display device excellent in stability.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  Conventionally, when a film is produced using a cellulose ester resin as a material for a polarizer protective film, a solution in which the resin is dissolved in a solvent is cast, and then the solvent is evaporated and dried to form a film, so-called solution casting. The law is being done. In the solution casting method, the self-supporting property of the film cannot be obtained until the dope discharged from the die is dried to some extent, so there is a limit in improving the production rate, and the solvent used is a solvent with a high environmental load. In addition, since facilities such as solvent recovery are necessary, it is necessary to make a capital investment that is higher than the production volume, making it difficult to meet the demand for increased production from the market.

  Therefore, if there is no solvent to be evaporated and dried at the time of film formation, it can be expected that the problems of the solution casting method can be avoided.

  The present invention was made in order to investigate a method for forming a film by thermally melting cellulose ester, and by forming a film by melting and casting a specific cellulose ester at an optimum temperature. An optical film can be provided, and a liquid crystal display device with improved display quality can be provided by using these as an optical compensation film or a polarizer protective film to form a polarizing plate. In addition, the present inventors have found that an optical film having excellent performance can be formed even when the specific cellulose ester used in the present invention is used in the solution casting method.

  The present invention is described in detail below.

  The present invention is characterized by using a cellulose film formed by melt casting as an optical film. In the present invention, it is defined as melt casting that the film constituent material is cast in a flowable state by heating without dissolving in the solvent as in the solution casting.

  More specifically, the heating and melting molding method can be classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like. Among these, in order to obtain an optical film excellent in mechanical strength and surface accuracy, the melt extrusion method is excellent.

  Here, the method of heating the film-forming material to develop its fluidity and then extruding it onto a drum or an endless belt is included in the melt casting method of the present invention as a melt casting film forming method.

(Cellulose ester)
The cellulose ester film of the present invention (also referred to as an optical film in the present invention) is formed using a composition containing 85% by mass to 95% by mass of the following cellulose ester.

  As cellulose ester, triacetyl cellulose is generally formed by solution casting film formation for photographic negative films and polarizer protective films. On the other hand, cellulose acetate propionate and cellulose acetate butyrate in which propionic acid (carbon number 3) or butyric acid (carbon number 4) and acetic acid are mixed and bound to cellulose are obtained by melt film formation. However, generally, the film obtained by melt film formation is inferior in flatness, and is used as a film for optical applications such as a polarizer protective film in which a triacetyl cellulose film obtained by solution casting film formation is used. Absent.

  On the other hand, as described above, the solution casting film production is relatively slow, and it is difficult to meet the demand for increased production from the market due to environmental demands.

  The minimum required properties as a polarizer protective film are colorless and transparent, and have uniform planarity and low birefringence. Therefore, as long as the material can satisfy such characteristics, the polymer material constituting the polarizer protective film can be used without being limited to other than triacetylcellulose.

  However, in the melt film forming process, there is no load such as drying of the solvent, so the time from discharging from the die to solidification can be shortened and the production speed can be increased, but the time for the film to level and flatten is short. There is a problem that it is difficult to obtain a film having high flatness, and ensuring the flatness of the film is an important problem.

  Stretching is generally performed as a means for improving the flatness of the film. However, since the stretching operation causes a significant increase in the birefringence of the film, an optical film is used in general transparent plastics such as PET. I can't get it. In recent years, melt film formation of cycloolefin polymers that hardly generate birefringence even when stretched has been studied. However, since cycloolefin polymers are very hydrophobic polymers, hydrophilic polymers cannot be used. The film is inferior in adhesiveness with the polarizer formed by use, and is difficult to use as a polarizer protective film.

  On the other hand, cellulose ester is a polymer that has little occurrence of birefringence during stretching and is excellent in adhesiveness with a polarizer, but it is a polymer that can be stretched low and difficult to stretch at high magnification. Are known.

  The inventors of the present invention have studied that triacetyl cellulose is a cellulose ester substituted with acetic acid (linear carboxylic acid having 2 carbon atoms), and is used as an optical film by solution casting film formation. The film could only be stretched about 1.2 to 1.4 times.

  However, with CAP482-20 (manufactured by Eastman Chemical), which is a commercially available cellulose ester substantially substituted by propionic acid (a linear carboxylic acid having 3 carbon atoms), it is possible to stretch about 1.5 to 1.7 times. Thus, it was found that CAB500-5, which is a cellulose ester substantially substituted by butyric acid (linear carboxylic acid having 4 carbon atoms), can be stretched by about 1.8 to 2.1 times.

  Thus, the researchers of the present invention have found that the stretch ratio of the cellulose ester greatly depends on the number of carbon atoms of the organic acid that binds to the cellulose. The main factor is the carbon number of the linear carboxylic acid that binds to the cellulose ester, although the stretchability of the cellulose ester varies depending on the addition of plasticizer, stretching temperature, stretching speed, molecular weight of the cellulose ester, etc. .

  In addition, as disclosed in Non-Patent Document 1, it is known that the melting point of cellulose ester varies greatly depending on the number of carbon atoms of the organic acid that binds to cellulose, and triacetyl cellulose has a melting point of 306 ° C. In contrast, tripropionyl cellulose is reported to be 234 ° C., tributyryl cellulose is 183 ° C., trivaleryl cellulose is 122 ° C., and tricapryl cellulose is reported to be 88 ° C. In the case of a linear carboxylic acid longer than caprylic acid (carbon number 8), the melting point of the cellulose ester gradually starts to rise, and in the case of tripalmityryl cellulose (carbon number 16), it rises to 105 ° C.

  As a result of the study by the researchers of the present invention, cellulose ester has a lower melting point and is formed by melting film formation because cellulose ester begins to decompose from a temperature of about 180 ° C. to 220 ° C. regardless of the substituent. Although it is considered to be a highly suitable material, on the other hand, the polarizer protective film needs to have heat resistance and heat and moisture resistance that can withstand even under high-temperature and high-humidity conditions such as in midsummer cars.

  As described above, cellulose ester having a structure satisfying the following formulas (1) and (2) can be used as a cellulose ester having sufficient heat resistance and capable of high draw ratio while having melt-forming ability. preferable.

Formula (1) 2.4 <= X + Y <= 2.8
Formula (2) 0.3 <= Y <= 1.5
(X represents the degree of substitution with acetic acid, Y represents the degree of substitution with linear carboxylic acid having 5 to 22 carbon atoms)
In the present invention, by replacing 0.3 or more hydroxyl groups per unit of cellulose ester with a linear carboxylic acid having 5 to 22 carbon atoms, the melt film-forming property is high and can withstand a high-magnification stretching process. A cellulose ester film can be obtained.

  The upper limit of the degree of substitution with a linear carboxylic acid having 5 to 22 carbon atoms is preferably 1.5 or less. By setting it to 1.5 or less, the heat resistance of the formed cellulose ester film can be made sufficient. More preferably, the degree of substitution with a linear carboxylic acid having 5 to 22 carbon atoms is 0.5 to 1.0.

  Examples of the linear carboxylic acid bonded to cellulose include valeric acid (carbon number 5), caproic acid (carbon number 6), enanthic acid (carbon number 7), caprylic acid (carbon number 8), pelargonic acid (carbon 9), decanoic acid (10 carbon atoms), undecanoic acid (11 carbon atoms), lauric acid (12 carbon atoms), tridecanoic acid (13 carbon atoms), myristic acid (14 carbon atoms), pentadecanoic acid (15 carbon atoms) ), Palmitic acid (16 carbon atoms), margaric acid (17 carbon atoms), stearic acid (18 carbon atoms), nonadecanoic acid (19 carbon atoms), arachidic acid (20 carbon atoms), heneicosanoic acid (21 carbon atoms), Examples include behenic acid (carbon number 22). It may be an unsaturated fatty acid, such as 2-pentenoic acid, 4-pentenoic acid (5 carbon atoms), 2-hexenoic acid, 3-hexenoic acid (6 carbon atoms), 2-octenoic acid (8 carbon atoms), 2-decenoic acid. (C10), undecylenic acid (C11), oleic acid, elaidic acid, linoleic acid, linolenic acid (C18), etc. may be sufficient. In addition, even if it is an aliphatic carboxylic acid having a branched chain or a substituent, a cellulose ester having the same effect can be obtained if the aliphatic alkyl carboxylic acid has a continuous alkyl chain length of 4 or more. -Methylhexanoic acid (carbon number 7), 2-propylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid (carbon number 8), 8-methylnonanoic acid (carbon number 10), and the like may be used.

  On the other hand, if a carboxylic acid having a large number of carbon atoms is used, the resulting cellulose ester becomes too hydrophobic and may have poor adhesion to a polarizer composed of a hydrophilic polymer. Is preferably an organic acid having 22 or less carbon atoms. More preferred is an organic acid having 5 to 8 carbon atoms, and most preferred is caproic acid (6 carbon atoms).

  The molecular weight also affects the stretchability of the cellulose ester film. When the molecular weight of the cellulose ester constituting the film is small, breakage is likely to occur during stretching of the film, and production cannot be stably performed. In order to maintain the mechanical strength and toughness of the resulting film, the weight average molecular weight of the cellulose ester constituting the film (after undergoing the melting process) is preferably 150,000 or more. If it is less than 150,000, the film may frequently break during production as described above. More preferably, it is 180,000 or more, more preferably 200,000 or more. The weight average molecular weight can be measured by commercially available gel permeation chromatography (GPC).

  The cellulose ester begins to thermally decompose from about 180 ° C. to 220 ° C., and the molecular weight decreases. Therefore, in order to set the weight average molecular weight of the cellulose ester constituting the film after the melting process to 150,000 or more, it is preferable that the weight average molecular weight of the raw material (before the melting process) is 200,000 or more. More preferably, it is 250,000 or more, and more preferably 300,000 or more. There is no particular upper limit, but it is usually in the range of 1 million or less. If it is 500,000 or more, the viscosity at the time of melting becomes too high, and the burden on the extrusion molding machine may be increased. The molecular weight reduction during the melting process can be suppressed by adding a plasticizer to reduce the melting temperature, or by using an antioxidant, a hindered amine light stabilizer, an acid scavenger, etc., which will be described later.

  However, even if the above-mentioned additives are used, it is difficult to make the weight average molecular weight of the cellulose ester 150,000 or more when the melting temperature is 250 ° C. or higher. Therefore, the temperature during melt film formation is preferably 250 ° C. or lower, More preferably, it is 230 degreeC, More preferably, it is 220 degrees C or less. On the other hand, if the temperature at the time of melt film formation is too low, the film is melted unevenly or foaming is observed. Therefore, it is preferable to melt at a temperature of 150 ° C. or higher. Moreover, in the case of a cellulose ester that can be melted at a very low temperature, the heat and heat resistance of the resulting film is insufficient, so that the temperature is preferably 180 ° C. or higher, and more preferably 190 ° C. or higher.

  The cellulose ester having the structure and molecular weight as described above can be synthesized by a known method.

  The positions where cellulose is substituted with organic acid are the 2nd, 3rd and 6th positions of the glucose unit, the 2nd and 3rd positions are secondary hydroxyl groups, the 6th position is a primary hydroxyl group, and the number of carbon atoms is 5. Although the higher order structure and physical properties of the cellulose ester may change somewhat depending on which position the -22 linear carboxylic acid substitutes, in the optical film of the present invention, the linear carboxylic acid having 5 to 22 carbon atoms. Cellulose esters in which the acid is in any substitution position can be preferably used.

  The cellulose ester raw material cellulose used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferred. A cotton linter is preferably used from the viewpoint of peelability during film formation. The cellulose ester made from these can be mixed suitably or can be used independently.

  For example, the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 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.

  The cellulose ester in the film-forming composition is in the range of 85% by mass to 95% by mass, and additionally contains 1 to 20% by mass as a material constituting the film, and the stabilizer, plasticizer and ultraviolet absorber described later are contained. As a result, it is possible to suppress a decrease in melt viscosity and melting temperature and a decrease in molecular weight during the melting process. When the cellulose ester content is 85% by mass or less, the additive may bleed out, which is not preferable. Moreover, when the addition amount of other additives required as an optical film is 1.0% by mass or less (the content of cellulose ester is 99% or more), various physical properties required for the optical film are satisfied. Is difficult. More preferably, the cellulose ester content is 88 to 93% by mass, and more preferably 89 to 92% by mass.

(Plasticizer)
In forming the optical film by melt casting according to the present invention, it is preferable to add at least one plasticizer in the film forming material.

  Generally, a plasticizer is an additive having an effect of improving brittleness, imparting flexibility, or improving stretchability by being added to a polymer. Is used as an additive that lowers the melting temperature of the film-forming material or as an additive that lowers the viscosity of the film-forming material at the same melting temperature. By lowering the melting temperature or melt viscosity, it is possible to suppress the degradation of the cellulose ester during the melting process, and as a result, the stretchability of the film can be improved. For example, it can be used as a plasticizer without limitation. Such a melting point lowering effect / viscosity reduction lowering can be more easily obtained when a plasticizer to be added has a melting point or glass transition temperature lower than the glass transition temperature of the cellulose ester.

  In addition, by adding a plasticizer, effects such as improvement of mechanical properties of cellulose ester film, improvement of tear strength (stretchable elongation), water absorption resistance, and reduction of moisture permeability may be seen. It is more preferable to use a material having an advantageous effect as a plasticizer.

  In addition, the plasticizer also has an effect of suppressing degradation in the hot melt process of the cellulose ester by adding as described above, but the effect is due to a physical effect and not due to a chemical effect. In the present invention, it is not classified as a stabilizer.

  Examples of plasticizers that satisfy the above conditions and are used in the present invention include phosphate ester plasticizers, polyhydric alcohol ester plasticizers (ethylene glycol ester plasticizers, glycerin ester plasticizers, diglycerin). Ester plasticizers), polycarboxylic acid ester plasticizers, polymer plasticizers, phosphazene plasticizers, siloxane plasticizers, and the like. Of these, polyhydric alcohol ester plasticizers and polycarboxylic acid ester plasticizers are preferred, and polyhydric alcohol ester plasticizers are more preferred. Further, the plasticizer may be a liquid or a solid, and is preferably colorless due to restrictions on the composition. It is preferably thermally stable at higher temperatures and does not volatilize, and the 1% mass reduction temperature Td (1.0) in dry air is 200 ° C. or higher, more preferably 230 ° C. or higher, and particularly preferably 250 ° C. or higher. The 1% mass reduction temperature Td (1.0) under dry air can be measured with a commercially available differential thermogravimetric analysis (TG-DTA) apparatus.

  The addition amount may be as long as it does not adversely affect the optical properties and mechanical properties, and the blending amount is appropriately selected within a range not impairing the object of the present invention, and is preferably 1 to 20 parts by mass in the film composition according to the present invention. Is 5 to 13 parts by mass. 8-12 mass% is especially preferable.

  Hereinafter, although the plasticizer used for this invention is demonstrated to a specific example, this invention is not limited to these.

  Polyhydric alcohol ester plasticizer: In the present invention, a compound in which a compound having a plurality of hydroxyl groups in one molecule and a plurality of monovalent organic acids are condensed is referred to as a polyhydric alcohol ester plasticizer.

  Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethylpentane- 1,3-diol, 1,6-hexanediol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, glycerin, diglycerin, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, gas Kuchitoru, glucose, cellobiose, inositol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol. In particular, diethylene glycol, triethylene glycol, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol are preferable.

  Examples of preferable organic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, acrylic acid, methacrylic acid, cyclohexanecarboxylic acid, benzoic acid, naphthoic acid, and the like. It is preferable that the polyhydric alcohol ester is formed of an unsaturated carboxylic acid having a high effect of reducing.

  The unsaturated carboxylic acid used in the polyhydric alcohol ester may be one type or a mixture of two or more types. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.

  Among specific examples of such polyhydric alcohol ester plasticizers, for example, ethylene glycol plasticizers include ethylene glycol alkyl ester plasticizers such as ethylene glycol diacetate and ethylene glycol dibutyrate, and ethylene glycol dibutylate. Examples thereof include ethylene glycol cycloalkyl ester plasticizers such as cyclopropylcarboxylate and ethylene glycol dicyclohexylcarboxylate, ethylene glycol dibenzoate, and ethylene glycol di4-methylbenzoate.

  Specific examples of glycerin ester plasticizers include glycerin alkyl esters such as triacetin, tributyrin, glycerin diacetate caprylate, glycerin oleate propionate, and glycerin cycloesters such as glycerin tricyclopropyl carboxylate and glycerin tricyclohexyl carboxylate. Diglycerol alkyl esters such as alkyl esters, glycerol aryl esters such as glycerol tribenzoate, glycerol 4-methylbenzoate, diglycerol tetraacetylate, diglycerol tetrapropionate, diglycerol acetate tricaprylate, diglycerol tetralaurate, etc. , Diglycerin tetracyclobutylcarboxylate, diglycerin tetracyclopentylcarboxylate, etc. Diglycerol cycloalkyl esters, diglycerin tetrabenzoate, diglycerin 3-methylbenzoate or the like.

  Specific examples of the polyhydric alcohol ester plasticizer other than the above include compounds described in paragraphs 30 to 33 of JP-A No. 2003-12823, or compounds described in chemical formulas 2 to 12 of Japanese Patent Application No. 2004-356546. Can be mentioned.

  The plasticizer listed above may be further substituted with an alkyl group, an alkoxy group, an acyl group, an oxycarbonyl group, a carbonyloxy group or the like in both the polyhydric alcohol part or the organic acid part. They may be bonded by a covalent bond. Alternatively, these structures may be part of the polymer, or may be regularly pendant, and the molecular structure of additives such as antioxidants, acid scavengers, and UV absorbers may be part of the structure. It may be introduced.

  Polycarboxylic acid ester plasticizer: In the present invention, a compound obtained by condensing a compound having a plurality of carboxylic acid groups in one molecule and a plurality of monovalent alcohols or phenols is a polyvalent carboxylic acid ester It is called a plasticizer.

  Specific examples of dicarboxylic acid ester plasticizers composed of divalent carboxylic acids include didodecyl malonate (the number of carbons connecting the divalent carboxylic acid is 1), dioctyl adipate (C4), dibutyl Alkyl dicarboxylic acid alkyl ester plasticizers such as sebacate (C8), dicyclopentyl succinate, alkyl dicarboxylic acid cycloalkyl ester plasticizers such as dicyclohexyl adipate, diphenyl succinate, di-4-methylphenyl glutarate, etc. Alkyl dicarboxylic acid aryl ester plasticizers such as dihexyl-1,4-cyclohexanedicarboxylate, didecylbicyclo [2.2.1] heptane-2,3-dicarboxylate, and the like. Plasticizer, dicyclohex Cycloalkyl dicarboxylic acid cycloalkyl ester plasticizers such as di-1,2-cyclobutane dicarboxylate, dicyclopropyl-1,2-cyclohexyl dicarboxylate, diphenyl-1,1-cyclopropyl dicarboxylate, di Cycloalkyldicarboxylic acid aryl ester plasticizers such as 2-naphthyl-1,4-cyclohexanedicarboxylate, aryl dicarboxylic acid alkyl esters such as diethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate Plasticizers, arylcyclocarboxylic acid cycloalkyl ester plasticizers such as dicyclopropyl phthalate and dicyclohexyl phthalate, diphenyl phthalate, di-4-methylphenyl phthalate Include aryl dicarboxylic acid aryl ester plasticizers.

  Specific examples of plasticizers composed of trivalent or higher carboxylic acids include alkyl polyvalent carboxylic acid alkyl esters such as tridodecyl tricarbarate and tributyl-meso-butane-1,2,3,4-tetracarboxylate. Plasticizers, alkyl polyvalent carboxylic acid cycloalkyl ester plasticizers such as tricyclohexyl tricarbarate, tricyclopropyl-2-hydroxy-1,2,3-propanetricarboxylate, triphenyl 2-hydroxy-1, Alkyl polyvalent carboxylic acid aryl ester plasticizers such as 2,3-propanetricarboxylate and tetra-3-methylphenyltetrahydrofuran-2,3,4,5-tetracarboxylate, tetrahexyl-1,2,3, 4-cyclobutanetetracarboxylate, tetrabutyl-1 Cycloalkyl polycarboxylic acid alkyl ester plasticizers such as 2,3,4-cyclopentanetetracarboxylate, tetracyclopropyl-1,2,3,4-cyclobutanetetracarboxylate, tricyclohexyl-1,3, Cycloalkyl polycarboxylic acid cycloalkyl ester plasticizers such as 5-cyclohexyl tricarboxylate, triphenyl-1,3,5-cyclohexyl tricarboxylate, hexa-4-methylphenyl-1,2,3,4, Cycloalkyl polycarboxylic acid aryl ester plasticizers such as 5,6-cyclohexylhexacarboxylate, tridodecylbenzene-1,2,4-tricarboxylate, tetraoctylbenzene-1,2,4,5-tetra Aryl polyvalent carboxylic such as carboxylate Alkyl ester plasticizers, aryl polyvalent carboxylic acid cycloalkyl ester plasticizers such as tricyclopentylbenzene-1,3,5-tricarboxylate, tetracyclohexylbenzene-1,2,3,5-tetracarboxylate Aryl polycarboxylic acid aryl ester based plasticizers such as triphenylbenzene-1,3,5-tetracartoxylate, hexa-4-methylphenylbenzene-1,2,3,4,5,6-hexacarboxylate Is mentioned.

  The alkoxy group and cycloalkoxy group in the above plasticizer may be the same or different, may be mono-substituted, and these substituents may be further substituted. The alkyl group and cycloalkyl group may be mixed, and these substituents may be bonded together by a covalent bond. Further, the aromatic ring of phthalic acid may be substituted, and a multimer such as a dimer, trimer or tetramer may be used. The partial structure of the phthalate ester may be part of the polymer or regularly pendant to the polymer, and the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc. May be introduced in the department.

  Phosphate ester plasticizers: specifically, phosphoric acid alkyl esters such as triacetyl phosphate and tributyl phosphate, phosphoric acid cycloalkyl esters such as tricyclobenthyl phosphate and cyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate And phosphoric acid aryl esters such as cresylphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, trinaphthyl phosphate, trixylyl phosphate, tris ortho-biphenyl phosphate. These substituents may be the same or different, and may be further substituted. Further, it may be a mix of an alkyl group, a cycloalkyl group, and an aryl group, and the substituents may be covalently bonded.

  Also, alkylene bis (dialkyl phosphate) such as ethylene bis (dimethyl phosphate), butylene bis (diethyl phosphate), alkylene bis (diaryl phosphate) such as ethylene bis (diphenyl phosphate), propylene bis (dinaphthyl phosphate), phenylene bis (dibutyl phosphate) ), Biphenylene bis (arylene bis (dialkyl phosphate) such as dioctyl phosphate, phenylene bis (diphenyl phosphate) such as ADK STAB PFR manufactured by Asahi Denka), phenylene bis (dixylenyl phosphate) such as ADK STAB FP500 manufactured by Asahi Denka, Asahi Denka Arylene bis (di-diyl phosphate) such as bisphenol A diphenyl phosphate such as ADK STAB FP600 Phosphoric acid esters of the reel phosphate) and the like. These substituents may be the same or different, and may be further substituted. Moreover, the mix of an alkyl group, a cycloalkyl group, and an aryl group may be sufficient, and substituents may couple | bond together by the covalent bond.

  Furthermore, the phosphate ester partial structure may be part of the polymer or regularly pendant, and may be introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, and UV absorbers. May be. Among the above-mentioned compounds, phosphoric acid aryl ester and arylene bis (diaryl phosphate) are preferable, and specifically, triphenyl phosphate and phenylene bis (diphenyl phosphate) are preferable.

  Polymer plasticizer: Specifically, aliphatic hydrocarbon polymer, alicyclic hydrocarbon polymer, acrylic polymer such as polyethyl acrylate and polymethyl methacrylate, polyvinyl isobutyl ether, poly N-vinyl pyrrolidone, etc. Examples include vinyl polymers, polystyrene, styrene polymers such as poly-4-hydroxystyrene, polybutylene succinate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethers such as polyethylene oxide and polypropylene oxide, polyamides, polyurethanes, and polyureas. It is done. The number average molecular weight is preferably about 1,000 to 500,000, particularly preferably 5,000 to 200,000. If it is 1,000 or less, a problem arises in volatility, and if it exceeds 500,000, the plasticizing ability is lowered, which adversely affects the mechanical properties of the cellulose ester derivative composition. These polymer plasticizers may be a homopolymer composed of one type of repeating unit or a copolymer having a plurality of repeating structures. Two or more of the above polymers may be used in combination, and other plasticizers, antioxidants, acid scavengers, ultraviolet absorbers, slip agents, matting agents, and the like may be included.

  Among the plasticizers, it is preferable that no volatile component is generated during heat melting.

  Examples of preferable plasticizers other than the above include phosphazene compounds such as hexaphenoxyphosphazene and octaphenoxyphosphazene, and siloxane compounds such as hexaphenyldisiloxane, hexaphenylcyclotrisiloxane and trimethyltriphenylcyclotrisiloxane. It may be used as an agent.

  Moreover, you may use these plasticizers in mixture of several types. Even in that case, the total addition amount is preferably in the range of 1 to 20% by mass.

(Stabilizer)
A stabilizer is a material that suppresses decomposition of a polymer by heat, oxygen, moisture, acid, or the like by a chemical action. Since the optical film of the present invention is molded at a high temperature of about 150 to 250 ° C., it is a system in which the polymer is easily decomposed and deteriorated, and a stabilizer is preferably contained in the film forming material.

  Addition of a stabilizer to the film-forming material prevents oxidation / thermal deterioration of the film-forming material due to radical species, acids, alkalis, etc. generated by heat, oxygen, light, etc. It can capture low molecules such as acids, and can prevent deterioration of the properties such as coloring and molecular weight reduction, process contamination due to material decomposition, and deterioration of physical properties of the resulting film.

  Examples of stabilizers include, but are not limited to, antioxidants, acid scavengers, hindered amine light stabilizers, ultraviolet absorbers, peroxide decomposers, radical scavengers, metal deactivators, and the like. Not. These are described in JP-A-3-199201, JP-A-5-1907073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, and the like. Among these, for the purpose of the present invention, it is preferable that at least one of an antioxidant, a hindered amine light stabilizer, and an acid scavenger is included in the film forming material as a stabilizer.

  At least one or more stabilizers in the film-forming material used in the present invention can be selected, and the added amount is 0.01% by mass or more and 5% by mass with respect to the mass of the cellulose ester. % Or less, more preferably 0.1% by mass or more and 3% by mass or less, and further preferably 0.3% by mass or more and 2% by mass or less.

  If the addition amount of the stabilizer is less than the range of the above addition amount, the stabilizing effect of the material at the time of heat melting is low, so the effect of the stabilizer cannot be obtained, and if the addition amount is more than the above range of the addition amount From the viewpoint of compatibility with the resin, it is not preferable because it may cause a decrease in transparency as an optical film or the film may become brittle.

  These stabilizers are preferably thermally stable at higher temperatures, and the 1% mass reduction temperature Td (1.0) is preferably 200 ° C. or higher, more preferably 230 ° C. or higher, and particularly preferably 250 ° C. or higher.

  A film-forming material can be stored as one or more kinds of pellets by mixing a plurality of materials prior to film formation for the purpose of avoiding material alteration and moisture absorption and simplifying the film formation process. . Pelletization may improve the mixing or compatibility of the melt during heating, or may ensure the optical uniformity of the resulting film. Moreover, the design of the barrel can be simplified, the generation of the accumulated matter in the barrel is suppressed, and the quality of the obtained molten film can be improved.

  Even when the film forming material is pelletized prior to film formation, it can be pelletized by heating and melting. Even when pelletizing, the presence of the above-mentioned stabilizer is excellent from the viewpoint of suppressing the strength and degradation of optical transparency based on the degradation and decomposition of the material, or maintaining the inherent strength of the material. Yes.

  If the film constituting material is significantly deteriorated by heating, coloring may occur and the film may not be used as an optical film. Further, in order to improve the flatness of the film, a stretching process is performed after the casting process. However, when the film constituent material is significantly deteriorated by heating and the molecular weight is lowered, the formed film becomes brittle, and the stretching process is performed. In this case, breakage may easily occur, and the target retardation value may not be expressed.

  Therefore, the presence of the above-mentioned stabilizer suppresses the generation of colored substances in the visible light region at the time of heating and melting, or the transmittance and haze value caused by volatile components generated by decomposition of the material constituting the film. It is also excellent in that it is possible to suppress or eliminate deterioration that is undesirable as an optical film, such as a decrease in temperature.

  In the present invention, the display image of the liquid crystal display device is affected when the haze value of the optical film used exceeds 1%. Therefore, the haze value is preferably less than 1%, more preferably less than 0.5%. The haze value can be measured based on JIS-K7136. As an index of colorability, yellowness (yellow index, YI) can be used, preferably 3.0 or less, more preferably 1.0 or less. Yellowness can be measured based on JIS-K7103.

  In the above-described film forming material storage or film forming process, deterioration reactions due to oxygen or moisture in the air may occur simultaneously. In this case, in addition to the stabilizing action of the stabilizer, reducing the humidity and oxygen concentration in the air can be preferably used in combination for realizing the present invention. This includes the use of nitrogen or argon as an inert gas as a known technique, a degassing operation under reduced pressure to vacuum, and an operation under a sealed environment, and at least one of these three methods includes the above stabilizer. It can be used in combination with the method. By reducing the probability that the film constituent material comes into contact with oxygen in the air, deterioration of the material can be suppressed, which is preferable for the purpose of the present invention.

  In addition, since the optical film of the present invention is used as a polarizer protective film, the above-mentioned in the film constituting material is also used from the viewpoint of improving storage stability with respect to the polarizing plate of the present invention and the polarizer constituting the polarizing plate. The presence of stabilizers plays an important role.

  In the liquid crystal display device using the polarizing plate of the present invention, when the above-mentioned stabilizer is present in the optical film of the present invention, the storage stability of the optical film over time can be improved from the viewpoint of suppressing the above-mentioned deterioration and deterioration, and the liquid crystal Also in improving the display quality of the display device, the optical compensation design is excellent in that the function can be expressed over a long period.

(Antioxidant)
Since the cellulose ester is decomposed not only by heat but also by oxygen at high temperatures, the optical film of the present invention preferably contains an antioxidant as a stabilizer. The antioxidant useful in the present invention can be used without limitation as long as it is a compound that suppresses the deterioration of the film-forming material due to oxygen. Among them, useful antioxidants include phenolic antioxidants and phosphorus-based antioxidants. Antioxidants, sulfur-based antioxidants, heat-resistant processing stabilizers, oxygen scavengers and the like can be mentioned. Among these, phenol-based antioxidants, particularly hindered phenol-based antioxidants are preferable. By blending these antioxidants, it is possible to prevent coloring and strength reduction of the molded product due to heat during heat molding or thermal oxidative degradation without lowering transparency and heat resistance. These antioxidants can be used alone or in combination of two or more thereof, and the blending amount thereof is appropriately selected within a range that does not impair the object of the present invention, but in the optical film according to the present invention. Is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass.

  The hindered phenolic antioxidant compound is a known compound, and is described in, for example, columns 12 to 14 of U.S. Pat. No. 4,839,405, and includes a 2,6-dialkylphenol derivative compound. It is. Among such compounds, preferred compounds are those represented by the following general formula (1).

  In the above formula, R 1, R 2 and R 3 represent a further substituted or unsubstituted alkyl substituent. Specific examples of the hindered phenol compound include n-octadecyl = 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl = 3- (3,5-di-t- Butyl-4-hydroxyphenyl) -acetate, n-octadecyl = 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl = 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n -Dodecyl = 3,5-di-tert-butyl-4-hydroxyphenylbenzoate, neo-dodecyl = 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, dodecyl = β (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, ethyl = α- (4-hydroxy-3,5-di-t-butylphenyl) isobuty Rate, octadecyl = α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl = α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n-octylthio) ethyl = 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n-octylthio) ethyl = 3,5-di-t-butyl-4-hydroxy-phenylacetate 2- (n-octadecylthio) ethyl = 3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl = 3,5-di-t-butyl-4-hydroxy -Benzoate, 2- (2-hydroxyethylthio) ethyl = 3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol = bi Su- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate, 2- (n-octadecylthio) ethyl = 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate , Stearamide-N, N-bis- [ethylene = 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino-N, N-bis- [ethylene = 3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], 2- (2-stearoyloxyethylthio) ethyl = 3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2-stearoyl) Oxyethylthio) ethyl = 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, 1,2-propylene glycol = bis- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], ethylene glycol = bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], neopentyl Glycol = bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], ethylene glycol = bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerin -Ln-octadecanoate-2,3-bis- (3,5-di-t-butyl-4-hydroxyphenylacetate), pentaerythritol-tetrakis- [3- (3 ', 5'-di -T-butyl-4'-hydroxyphenyl) propionate], 1,1,1-trimethylolethane-tris- [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate], sorbitol hexa- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl = 7- (3-methyl-5-t- Butyl-4-hydroxyphenyl) propionate, 2-stearoyloxyethyl = 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol-bis [(3 ′, 5'-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate). Hindered phenolic antioxidants of the above type are commercially available, for example from Ciba Specialty Chemicals under the trade names “Irganox 1076” and “Irganox 1010”.

  Specific examples of other antioxidants include phosphorus antioxidants such as trisnonylphenyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and dilauryl-3. , 3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), etc. System antioxidant, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5- Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate 3,4-dihydro-2H-1-benzopyran compound, 3,3′-spirodichroman compound, 1,1-spiroindane compound, morpholine, thiomorpholine, thiomorpholine oxide, described in JP-B-08-27508, Examples include thiomorpholine dioxide, compounds having a piperazine skeleton in the partial structure, oxygen scavengers such as dialkoxybenzene compounds described in JP-A-3-174150, and the like. These antioxidant partial structures may be part of the polymer or regularly pendant to the polymer.

Moreover, it may be used in combination with the above-mentioned hindered phenol antioxidant, or a compound in which a hindered phenol group and the above phosphorus antioxidant or sulfur antioxidant are combined in one molecule may be used. good.
(Hindered amine light stabilizer)
In the present invention, a hindered amine light stabilizer (HALS) is used as a stabilizer at the time of melting the film constituting material, and as a stabilizer against external light exposed as a polarizer protective film after production or light from a backlight of a liquid crystal display. Compounds, which are known compounds, such as columns 5-11 of US Pat. No. 4,619,956 and columns 3-5 of US Pat. No. 4,839,405. 2,2,6,6-tetraalkylpiperidine compounds, or their acid addition salts or complexes of them with metal compounds, as described in. Examples of such a compound include compounds represented by the following general formula (2).

  In the above formula, R1 and R2 are H or a substituent. Specific examples of hindered amine light stabilizer compounds include 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl. -4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (4-t-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyl Oxy-2,2,6,6-tetramethylpiperidine, 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6 6-pentamethylpiperidine, 1,2,2,6,6-pentamethylpiperidin-4-yl-β (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, -Benzyl-2,2,6,6-tetramethyl-4-piperidinyl maleate, (di-2,2,6,6-tetramethylpiperidin-4-yl) -adipate, (di- 2,2,6,6-tetramethylpiperidin-4-yl) -sebacate, (di-1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) -sebacate, (di -1-allyl-2,2,6,6-tetramethyl-piperidin-4-yl) -phthalate, 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, trimellitic acid- Tri- (2,2,6,6-tetramethylpiperidin-4-yl) ester, 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, dibutyl-malonic acid-di -(1,2,2,6,6-pentamethyl-piperidin-4-yl) -ester, dibenzyl-malonic acid-di- (1,2,3,6-tetramethyl-2,6-diethyl-piperidine- 4-yl) -ester, dimethyl-bis- (2,2,6,6-tetramethylpiperidine-4-oxy) -silane, tris- (1-propyl-2,2,6,6-tetramethylpiperidine- 4-yl) -phosphite, tris- (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) -phosphate, N, N′-bis- (2,2,6,6- Tetramethylpiperidin-4-yl) -hexamethylene-1,6-diamine, N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -hexamethylene-1,6- Diacetamide, 1-acetyl -4- (N-cyclohexylacetamide) -2,2,6,6-tetramethyl-piperidine, 4-benzylamino-2,2,6,6-tetramethylpiperidine, N, N'-bis- (2, 2,6,6-tetramethylpiperidin-4-yl) -N, N'-dibutyl-adipamide, N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -N , N'-dicyclohexyl- (2-hydroxypropylene), N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylene-diamine, 4- (bis-2 -Hydroxyethyl) -amino-1,2,2,6,6-pentamethylpiperidine, 4-methacrylamide-1,2,2,6,6-pentamethylpiperidine, α-cyano-β-methyl-β- [N- (2,2 6,6-tetramethyl-piperidin-4-yl)] - amino - acrylic acid methyl ester. Examples of preferred hindered amine light stabilizers include the following HALS-1 and HALS-2.

In addition, among the hindered amine light stabilizers, Tinuvin 144 (manufactured by Ciba Specialty Chemicals) having a hindered phenol structure in the same molecule is also commercially available, and such a complex type stabilizer is also preferable. It is an example of a stabilizer.

(Acid scavenger)
Cellulose ester is preferably decomposed by an acid at a high temperature, and therefore, in the optical film of the present invention, it is preferable to contain an acid scavenger as a stabilizer. Any acid scavenger useful in the present invention can be used without limitation as long as it is a compound that reacts with an acid to inactivate the acid, and is described in U.S. Pat. No. 4,137,201. Such a compound having an epoxy group is preferred. Epoxy compounds as such acid scavengers are known in the art and are derived by condensation of diglycidyl ethers of various polyglycols, particularly about 8-40 moles of ethylene oxide per mole of polyglycol. Metal glycol compounds such as polyglycols, diglycidyl ethers of glycerol (eg, those conventionally used in and together with vinyl chloride polymer compositions), epoxidized ether condensation products, bisphenol A Diglycidyl ether (ie, 4,4'-dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester (especially an ester of an alkyl of about 2 to 2 carbon atoms of a fatty acid of 2 to 22 carbon atoms (e.g. Butyl epoxy stearate And epoxidized vegetable oils and other unsaturated natural oils (sometimes these are epoxidized natural glycerides, which can be represented and exemplified by compositions of various epoxidized long chain fatty acid triglycerides and the like (eg, epoxidized soybean oil and the like) Or unsaturated fatty acids, which generally contain 12 to 22 carbon atoms). Further, as a commercially available epoxy group-containing epoxide resin compound, EPON 815C and other epoxidized ether oligomer condensation products of the following general formula (3) can also be preferably used.

  In the above formula, n represents 0-12.

  Further, acid scavengers that can be used other than the above include oxetane compounds, oxazoline compounds, organic earth salts of alkaline earth metals and acetylacetonate complexes, and paragraphs 68 to 105 of JP-A-5-194788. What is listed is included.

  The acid scavenger may be referred to as an acid scavenger, an acid scavenger, an acid catcher, etc., but can be used in the present invention without any difference due to their names.

(UV absorber)
When the optical film of the present invention is used as a polarizer protective film used on the outside of the liquid crystal cell, it is preferable to further contain an ultraviolet absorber as a stabilizer. The ultraviolet absorber is a material having an effect of preventing the material constituting the film from being decomposed by ultraviolet rays in an environment used after production. Cellulose ester itself is a material relatively resistant to ultraviolet rays, but other additives may be compounds that are weak against ultraviolet rays, and polarizers and liquid crystal cells also contain compounds that are sensitive to ultraviolet rays. Therefore, it is preferable that at least the polarizer protective film on the side exposed to external light and the polarizer protective film on the side on which the backlight of the liquid crystal display is incident contain an ultraviolet absorber.
As such an ultraviolet absorber, from the viewpoint of preventing deterioration of a polarizer and a display device with respect to ultraviolet rays, the ultraviolet absorber has an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less, and from the viewpoint of liquid crystal display properties, visible light having a wavelength of 400 nm or more. Those that absorb less are preferred. Examples include oxybenzophenone compounds, benzotriazole compounds, triazine compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. Triazole compounds and triazine compounds are preferable, and benzotriazole compounds are particularly preferable. Moreover, you may use the ultraviolet absorber of Unexamined-Japanese-Patent No. 10-182621, Unexamined-Japanese-Patent No. 8-337574, and the polymeric ultraviolet absorber of Unexamined-Japanese-Patent No. 6-148430.

  Specific examples of useful benzotriazole ultraviolet absorbers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl). ) Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis ( 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydro Cis-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy Examples include, but are not limited to, a mixture of -5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate.

  As commercially available products, TINUVIN 109, TINUVIN 171, TINUVIN 234, and TINUVIN 360 (all manufactured by Ciba Specialty Chemicals) can also be used.

  Specific examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy- 5-benzoylphenyl) methane and the like can be mentioned, but are not limited thereto.

  Furthermore, the partial structure of the above-mentioned ultraviolet absorber may be part of a polymer or regularly pendant, and part of the molecular structure of an additive such as an antioxidant, an acid scavenger, or an ultraviolet absorber. May be introduced. For example, it is also preferable to use a compound in which a triazine group and a hindered phenol group are complexed in the same molecule as disclosed in JP-T-2002-518485.

  In the present invention, the ultraviolet absorber is preferably added in an amount of 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, and further preferably 0.5 to 2% by mass. Two or more of these may be used in combination in order to interpolate the transmission of ultraviolet light by the absorption waveform.

(Matting agent)
A matting agent can be added to the cellulose ester film of the present invention in order to impart slipperiness, optical and mechanical functions. Examples of the matting agent include inorganic compound fine particles and organic compound fine particles.

  The shape of the matting agent is preferably a spherical shape, a rod shape, a needle shape, a layer shape, a flat shape or the like. Examples of the matting agent include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate. Examples thereof include inorganic fine particles such as oxides, phosphates, silicates, carbonates, and crosslinked polymer fine particles. Among these, silicon dioxide is preferable because it can reduce the haze of the film. These fine particles are preferably surface-treated with an organic substance because the haze of the film can be reduced.

  The surface treatment is preferably performed with halosilanes, alkoxysilanes, silazane, siloxane, or the like. The larger the average particle size of the fine particles, the greater the sliding effect, and the smaller the average particle size, the better the transparency. The average primary particle size of the fine particles is in the range of 0.01 to 1.0 μm. The average particle size of the primary particles of preferable fine particles is preferably 5 to 50 nm, more preferably 7 to 14 nm. These fine particles are preferably used for generating irregularities of 0.01 to 1.0 μm on the surface of the cellulose ester film.

  Examples of the fine particles of silicon dioxide include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600 manufactured by Nippon Aerosil Co., Ltd., preferably Aerosil 200V, R972. , R972V, R974, R202, R812. Two or more kinds of these fine particles may be used in combination.

  When using 2 or more types together, it can mix and use in arbitrary ratios. Fine particles having different average particle sizes and materials, for example, Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.

  These matting agents are preferably added by kneading. Further, as another form, after mixing and dispersing a matting agent previously dispersed in a solvent and a cellulose ester and / or a plasticizer and / or an ultraviolet absorber, a solid material obtained by volatilizing or precipitating the solvent is obtained. It is preferable to use it in the production process of the ester melt from the viewpoint that the matting agent can be uniformly dispersed in the cellulose resin.

  The matting agent can be added to improve the mechanical, electrical and optical properties of the film.

  The slipperiness of the resulting cellulose ester film improves as the fine particles are added, but the haze increases as the fine particles are added. Therefore, the content is preferably 0.001 to 5% by mass, more preferably 0. 0.005 to 1% by mass, and more preferably 0.01 to 0.5% by mass.

(Other additives)
In the present invention, the cellulose ester can contain various additives in addition to the plasticizer, the stabilizer and the matting agent.

  For example, fillers, inorganic compounds such as silica and silicate, organic polymers, dyes, pigments, phosphors, dichroic dyes, retardation control agents, infrared absorbers, refractive index regulators, gas permeation inhibitors, antibacterial agents Agents, biodegradability imparting agents, anti-gelling agents, viscosity modifiers, release agents and the like. Moreover, the additive which is not classified into this can be used if it has the said function.

  Then, as a method of incorporating these additives into the cellulose ester, each material is mixed in a solid or liquid state, heated and melted and kneaded to form a uniform melt, and then cast to form an optical film. Even in this method, after dissolving all the materials in advance using a solvent or the like to obtain a uniform solution, the solvent is removed to form a mixture of the additive and the cellulose ester, and this is heated and melted. It may be cast to form an optical film.

(Melt casting process)
The cellulose ester film of the present invention is characterized by being formed by melt casting.

  The molding method by melt casting, which is heated and melted without using the solvent used in the solution casting method (for example, methylene chloride, etc.), more specifically, melt extrusion molding method, press molding method, inflation method, injection molding method , Blow molding method, stretch molding method and the like. Among these, in order to obtain a polarizing plate protective film having excellent mechanical strength and surface accuracy, the melt extrusion method is excellent.

  The winding length of the cellulose ester film of the present invention is preferably 500 to 5000 m, and more preferably 1000 to 5000 m. It is also preferable to wind up by providing a knurling with a height of 0 to 25% of the film thickness at both ends of the width.

  In order to stably produce such a very long film, it is important how the molecular weight is not reduced during melt film formation. When the molecular weight is lowered, the film becomes brittle and breakage tends to occur, and it is difficult to obtain a film having the above length. In order to prevent the decrease in molecular weight, not only the above-mentioned stabilizers are added, but also solvents, impurities, oxygen, moisture, etc. mixed before the material purchase or synthesis are removed as much as possible before the melting process. It is important to keep it. Film formation by the melt casting method has a significantly higher temperature at the time of film formation than the solution casting method. Therefore, if oxygen, moisture, or chemically active impurities are mixed, the cellulose ester is decomposed. This is because it will be promoted. Even if it is not an impurity / contaminant that promotes the decomposition of cellulose ester, if there are volatile components in the material to be cast, those additives will volatilize during film formation and adhere to the film forming apparatus. This causes fluctuations in the film thickness of the film to be formed and causes various failures, which is not preferable from the viewpoint of ensuring the flatness and transparency of the film for utilizing the function as a film or a polarizing plate protective film. In particular, when it adheres to the die, it may cause a streak on the film surface and induce flatness deterioration. Therefore, when a film constituent material is formed into a film, it is not preferable that a component that volatilizes at a temperature lower than the melting temperature for film formation is present from the viewpoint of avoiding generation of a volatile component during heating and melting. As materials to be added to the cellulose ester film of the present invention, it is preferable to use materials whose 1% mass reduction temperature Td (1.0) by heat is 250 ° C. or more.

  It is preferable that volatile components such as moisture and impurities are removed before film formation or before melting. A method by drying can be applied to this removal method, and it can be performed by a method such as a heating method, a reduced pressure method, or a heated reduced pressure method. Drying may be performed in air or in an atmosphere in which an inert gas such as nitrogen or argon is selected as the inert gas. These inert gases preferably have a low water or oxygen content. The oxygen concentration is preferably 0.1% or less, and the dew point of the gas is preferably −30 ° C. or less. Most preferably, it does not contain substantially. When these known drying methods are performed, it is preferable in terms of film quality to be performed in a temperature range where the film constituting material does not decompose. For example, the moisture or solvent remaining after removal in the drying step is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the mass of the entire film constituent material. It is.

  In particular, the moisture content of the cellulose ester resin is preferably less than 0.3% by mass. These characteristic values can be measured by ASTM-D817-96. The cellulose ester is preferably used as 0.1 to 1000 ppm by further reducing the moisture by heat treatment.

  The amount of residual organic solvent can be measured by a headspace gas chromatography method. That is, a known amount of cellulose ester film is heated in a sealed container at 120 ° C. for 20 minutes, and the organic solvent contained in the gas phase in the sealed container is quantified by gas chromatography. From this result, the residual organic solvent amount (%) can be calculated.

  The film constituent material can reduce the generation of volatile components by drying before film formation, and the resin alone, or at least one mixture or compatible material other than the resin among the resin and the film constituent material. It can be divided and dried. The preferable drying temperature is preferably 80 ° C. or higher and the Tg or melting point of the material to be dried. Including the viewpoint of avoiding fusion between materials, the drying temperature is more preferably 100 to (Tg-5) ° C, and still more preferably 110 to (Tg-20) ° C. A preferable drying time is 0.5 to 24 hours, more preferably 1 to 18 hours, and still more preferably 1.5 to 12 hours. Below these ranges, the removal rate of volatile components may be low, or drying may take too long, and when Tg is present in the material to be dried, heating to a drying temperature higher than Tg will cause the material to be removed. May be difficult to handle due to fusion. Drying is preferably performed at 1 atm or less, and particularly preferably performed while reducing the pressure from vacuum to 1/2 atm. Drying is preferably performed while appropriately stirring the material such as resin, and the fluidized bed method in which drying air or dry nitrogen is fed from the lower part in the drying container can perform necessary drying in a shorter time. It is preferable because it is possible.

  The drying process may be separated into two or more stages. For example, the material may be formed using a material that has been subjected to storage of the material in the preliminary drying process and drying immediately before film formation to immediately before a week. .

  After removing volatile components such as moisture and impurities in the film forming material by the drying process, the film forming material is individually or pre-mixed / pelleted and sent to a heated barrel for melting and flowing. After being formed, it is extruded into a sheet shape by a T-die, and brought into close contact with a cooling drum or an endless belt by an electrostatic application method or the like, and cooled and solidified to be solidified into a sheet shape to obtain an unstretched sheet. These processes are called casting processes.

  Considering the physical properties of the resulting cellulose ester film, the melting temperature (temperature in the barrel) is preferably in the range of 150 to 250 ° C, more preferably 180 ° C to 230 ° C, and still more preferably 190 ° C to 220 ° C. The temperature of the cooling drum is preferably maintained at 90 to 150 ° C. When the temperature of the drum is 90 ° C. or lower, the sheet extruded from the die is rapidly cooled, and the structure in the film may become uneven or brittle in the film thickness direction. It is preferable. On the other hand, when the temperature is 150 ° C. or higher, the cooling rate of the unstretched sheet becomes slow and the productivity is lowered, which is not preferable.

  When the optical film of the present invention is used as a polarizer protective film, the thickness of the protective film is preferably 10 to 500 μm. 10-100 micrometers is especially preferable, 20-80 micrometers is preferable, Especially preferably, it is 30-60 micrometers. When the cellulose ester film is thicker than the above region, for example, when used as a polarizer protective film, the polarizing plate after polarizing plate processing becomes too thick, and is particularly thin in liquid crystal displays used for notebook computers and mobile electronic devices. Not suitable for lightweight purposes. On the other hand, if the thickness is smaller than the above region, the film has high moisture permeability, and the ability to protect the polarizer from humidity decreases, which is not preferable. Moreover, in the retardation film, since it becomes difficult to express retardation, it is not preferable.

  In the solution casting method, when the film thickness is increased, the drying load is remarkably increased. However, in the present invention, since a drying step is not necessary, a film having a large film thickness can be produced with high productivity. Therefore, there is an advantage that it is easier than ever to increase the thickness of the film in accordance with the purpose of providing a necessary phase difference or reducing moisture permeability. Moreover, even if it is a film with a thin film thickness, it has the effect that it can be produced with high productivity by extending | stretching such a thick film. In addition, the film thickness of the film at the time of extending | stretching becomes thin in inverse proportion to the draw ratio. For example, when the unstretched sheet is 200 μm, a 100 μm film can be obtained by stretching twice.

  The film thickness variation of the cellulose ester film support is preferably ± 3%, more preferably ± 1%, and still more preferably ± 0.1%. These film thickness fluctuations can be reduced by stretching.

  In view of the recent increase in the size of liquid crystal displays, the width of the polarizer protective film is preferably 1 m or more. On the other hand, if it exceeds 4 m, the apparatus becomes large and difficult to convey, so the width of the cellulose ester film of the present invention is preferably 1 to 4 m, particularly preferably 1.4 to 2 m. Since it is difficult to extrude the cellulose ester flowing from the barrel uniformly from the die to a width of 1.4 m or more, it is difficult to obtain a film having a width of 1.4 m or more unless it is laterally stretched. It is.

(Stretching process)
Next, the stretching process will be described.

  Since the cellulose ester film using the cellulose ester of the present invention can lower the melting temperature and suppress the decrease in the molecular weight of the cellulose ester after melt extrusion, it is difficult to break during transportation, and has a high yield. Can be manufactured at high speed. In addition, a film with good flatness can be obtained even if it is unstretched due to low viscosity at the time of dissolution, and furthermore, since it can be stretched at a high magnification, an optical film with better flatness can be obtained. Furthermore, a cellulose ester film can be produced with high productivity.

  After being extruded from the barrel and brought into close contact with the cooling drum, the film peeled off from the cooling drum is subjected to transverse stretching, longitudinal stretching, or stretching in an oblique direction as disclosed in JP-A-2004-226465. By doing so, the planarity can be improved and the production speed can be improved. These stretching operations may be performed a plurality of times. When performing the stretching a plurality of times, they may be performed simultaneously or sequentially. When stretching is performed a plurality of times, the product of all the stretching ratios becomes the final stretching ratio. For example, if 2 times of stretching is performed twice, the final stretching ratio is 4 times.

  The cellulose ester has a refractive index that increases in the stretched direction, and forms a slow axis. Therefore, the draw ratio is determined within the range of optical properties to be satisfied by the finally obtained film.

  When it is desired to reduce the retardation in the film plane as much as possible, biaxial stretching is preferred. By stretching at the same magnification in the direction orthogonal to the first stretching axis, the occurrence of birefringence due to the first stretching is canceled, and an isotropic film can be obtained.

  On the other hand, when obtaining a retardation film that has the effect of expanding the viewing angle of the liquid crystal display, the ratio of the first stretching and the second stretching is changed, and one of the stretching ratios is the other stretching An optically anisotropic film can be obtained by stretching so as to be larger than the magnification. In this case, the draw ratio between the width direction and the longitudinal direction is preferably 1.1 to 2.0, more preferably 1.2 to 1.5.

  When stretching a plurality of times, the film may be stretched from the longitudinal direction or from the width direction, but after the stretching process in the width direction, the transport width of the film becomes large, and the transport device Therefore, it is preferable to perform stretching in the width direction after stretching in the longitudinal direction.

  The final draw ratio of the cellulose ester film is preferably 1.5 to 4.0 times. If it is less than 1.5 times, the flatness of the resulting film may be inferior. On the other hand, stretching more than 4.0 times is difficult even if the cellulose ester of the present invention is used, and it is not preferable because there is a high possibility that fracture occurs in the stretching process. More preferably, it is stretched 2.0 to 3.0 times.

  Next, the stretching method in the longitudinal direction (MD) will be described.

  After being extruded from the barrel and brought into close contact with the cooling drum, the film peeled off from the cooling drum is heated again in the longitudinal direction through one or more roll groups and / or a heating device such as an infrared heater. Single-stage or multistage MD stretching may be performed.

  When stretching, assuming that the glass transition temperature of the film of the present invention is Tg, it is heated in the range of (Tg-30) to (Tg + 100) ° C., more preferably (Tg-20) to (Tg + 80) ° C. It is preferable to stretch in the (longitudinal direction; MD) or width direction (TD). It is preferable to perform transverse stretching within the temperature range of (Tg-20) to (Tg + 20) ° C. and then heat-set. It is also preferable to perform relaxation treatment after the stretching step.

  The Tg of the cellulose ester film can be controlled by the material type constituting the film and the ratio of the constituting materials. In the application of the present invention, the Tg when the film is dried is preferably 110 ° C. or higher, more preferably 120 ° C. or higher. This is because when the cellulose ester film of the present invention is used in a liquid crystal display device, if the Tg of the film is lower than the above, molecules fixed inside the film due to the influence of the temperature and humidity of the use environment and the heat of the backlight. The orientation state of the film is affected, and there is a high possibility that the retardation value and the dimensional stability and shape of the film will greatly change. In addition, the shape of the film may not be maintained. Conversely, if the Tg of the film is too high, it becomes difficult to produce because it approaches the decomposition temperature of the film constituting material, and the presence of a volatile component or coloring may occur due to the decomposition of the material itself used when forming a film. Accordingly, the glass transition temperature is preferably 180 ° C. or lower, more preferably 150 ° C. or lower. At this time, the Tg of the film can be determined by the method described in JIS K7121.

  Next, the extending | stretching method of a lateral direction (TD) is demonstrated.

  In the case of TD stretching, it is preferable to perform transverse stretching while sequentially raising the temperature difference in the range of 1 to 50 ° C. in a stretching region divided into two or more, because the distribution of physical properties in the width direction can be reduced. Further, after transverse stretching, it is preferable that the film is held at a temperature not higher than the final TD stretching temperature and not lower than Tg−40 ° C. for 0.01 to 5 minutes because the distribution of physical properties in the width direction can be further reduced.

  The heat setting is performed at a temperature higher than the final TD stretching temperature and usually within 0.5 to 300 seconds within a temperature range of Tg-20 ° C. or less. Under the present circumstances, it is preferable to heat-fix, heating up sequentially in the range from which a temperature difference becomes 1-100 degreeC in the area | region divided into 2 or more.

  The heat-set film is usually cooled to Tg or less, and clip holding portions at both ends of the film are cut and wound. At this time, it is preferable to perform a relaxation treatment of 0.1 to 10% in the lateral direction and / or the longitudinal direction within a temperature range of not more than the final heat setting temperature and not less than Tg. In addition, it is preferable that the cooling is gradually performed from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second. Means for cooling and relaxation treatment are not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to perform these treatments while sequentially cooling in a plurality of temperature ranges from the viewpoint of improving the dimensional stability of the film. The cooling rate is a value obtained by (T1-Tg) / t, where T1 is the final heat setting temperature and t is the time until the film reaches Tg from the final heat setting temperature.

  More optimal conditions of these heat setting conditions, cooling, and relaxation treatment conditions vary depending on the type of additives such as cellulose ester and plasticizer constituting the film, so the physical properties of the obtained biaxially stretched film are measured and preferable characteristics are obtained. What is necessary is just to determine by adjusting suitably so that it may have.

  The in-plane retardation value (Ro) and thickness direction retardation value (Rth) of the cellulose ester film according to the present invention are preferably 0 ≦ Ro and Rth ≦ 70 nm when used as a polarizer protective film. More preferably, 0 ≦ Ro ≦ 20 nm and 0 ≦ Rth ≦ 50 nm, and more preferably 0 ≦ Ro ≦ 10 nm and 0 ≦ Rth ≦ 30 nm. When used as a retardation film, 30 ≦ Ro ≦ 100 nm and 70 ≦ Rth ≦ 400 nm, and more preferably 35 ≦ Ro ≦ 65 nm and 90 ≦ Rth ≦ 180 nm. Further, the variation of Rth and the width of distribution are preferably less than ± 10%, more preferably less than ± 5%. More preferably, it is less than ± 1%, and most preferably, there is no fluctuation of Rth.

  The retardation values Ro and Rth can be obtained by the following equations.

Ro = (nx−ny) × d
Rth = ((nx + ny) / 2−nz) × d
Here, d is the thickness (nm) of the film, the refractive index nx (also referred to as the maximum refractive index in the plane of the film, the refractive index in the slow axis direction), ny (in the direction perpendicular to the slow axis in the film plane). ) (Refractive index of the film in the thickness direction).

  The retardation values (Ro) and (Rth) can be measured using an automatic birefringence meter. For example, it can be obtained at a wavelength of 590 nm using KOBRA-21ADH (Oji Scientific Instruments) under an environment of 23 ° C. and 55% RH.

  The slow axis is preferably in the width direction ± 1 ° or the longitudinal direction ± 1 ° of the film. More preferably, it is ± 0.7 ° with respect to the width direction or the longitudinal direction, and further preferably ± 0.5 ° with respect to the width direction or the longitudinal direction. By setting it as such a range, the contrast of the liquid crystal display obtained can be raised.

  Since the cellulose ester film of the present invention does not substantially use a solvent in the film forming step, the amount of residual organic solvent contained in the cellulose ester film wound up after film formation is stably less than 0.1% by mass. As a result, it is possible to provide a cellulose ester film having more stable flatness and Rth than before. In particular, it is possible to provide a cellulose ester film having stable flatness and Rth even in a long roll of 100 m or more. The cellulose ester film is not particularly limited as to the winding length, and is preferably used even if it is 1500 m, 2500 m, or 5000 m.

  It is difficult to reduce the residual organic solvent amount (%) of the cellulose ester film produced by the solution casting method to 0.1% by mass or less, and this requires a long drying step. For example, a cellulose ester film having a very low residual organic solvent content can be obtained at low cost, and a cellulose ester film having excellent characteristics as an optical film can be obtained.

  In the film forming process, the clip gripping portions at both ends of the cut film are pulverized or granulated as necessary, and then used as a raw material for the same type of film or for different types of film. It may be reused as a raw material.

(Functional layer)
In producing the optical film of the present invention, before and / or after stretching, the antistatic layer, the transparent conductive layer, the hard coat layer, the antireflection layer, the antifouling layer, the slippery layer, the easy adhesion layer, the easy saponification layer, and the smoothness. A functional layer such as a lightening layer, an antiglare layer, a gas barrier layer, or an optical compensation layer may be provided. In particular, it is preferable to provide at least one layer selected from an antistatic layer, a hard coat layer, an antireflection layer, an easy adhesion layer, an antiglare layer, and an optical compensation layer. At this time, various surface treatments such as corona discharge treatment, plasma treatment, and chemical treatment can be performed as necessary. The chemical treatment includes not only chemically active chemicals, but also operations such as simply applying an organic solvent to dissolve or swell the surface of the cellulose ester film to improve planarity.

  In the cellulose ester film of the present invention, the cellulose ester film having a laminated structure may be formed by co-extrusion of different types of cellulose ester and / or additive.

  For example, a cellulose ester film having a structure of skin layer / core layer / skin layer can be produced. For example, fine particles such as a matting agent can be contained in the skin layer in a large amount or only in the skin layer. In addition, a melt-extruded layer of diacetyl cellulose that can be easily saponified may be formed on the skin layer. Melt extrusion of diacetylcellulose can be achieved according to known methods. Further, a low-volatile plasticizer and / or an ultraviolet absorber can be contained in the skin layer, and a plasticizer having excellent plasticity or an ultraviolet absorber having excellent ultraviolet absorption can be added to the core layer. The glass transition temperature of the skin layer and the core layer may be different, and the glass transition temperature of the core layer may be lower than the glass transition temperature of the skin layer. Also, the viscosity of the melt containing the cellulose ester at the time of melt casting may be different between the skin layer and the core layer, and the viscosity of the skin layer> the viscosity of the core layer or the viscosity of the core layer ≧ the viscosity of the skin layer may be When the viscosity of the thinner layer (usually skin layer) is higher, a laminate having a uniform film thickness can be obtained.

(Polarizer)
When forming and using a polarizing plate using the cellulose ester film of the present invention as a polarizing plate protective film for a liquid crystal display device, the polarizing plate on at least one surface is preferably the polarizing plate of the present invention, and both surfaces are polarizing plates of the present invention. It is more preferable that

  In addition, as a conventional polarizing plate protective film, Konica Minoltack KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC12UR, KC8UXW-H, KC8UYW-HA, HC A cellulose ester film such as Konica Minolta Opto Co., Ltd.) is used.

  The production method of the polarizing plate of the present invention is not particularly limited, and can be produced by a general method. The obtained polarizing plate protective film was treated with an alkali, and a polyvinyl alcohol film was immersed and stretched in an iodine solution, using a completely saponified polyvinyl alcohol aqueous solution on both sides of the polarizer, and polarizing plate protective films on both sides of the polarizer. Can be pasted together. This method is preferable in that the polarizing plate protective film of the present invention can be directly bonded to a polarizer on at least one side.

  Further, instead of the alkali treatment, easy-adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be applied to perform polarizing plate processing.

  The polarizing plate is composed of a polarizer and a protective film for protecting both surfaces of the polarizer, and can further be constructed by laminating a protective film on one surface of the polarizing plate and a separate film on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate when the polarizing plate is shipped or transported. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. The separate film is used for the purpose of covering the adhesive layer.

(Liquid crystal display device)
In a liquid crystal display device, a substrate containing liquid crystal is usually disposed between two polarizing plates. However, a polarizer protective film to which the optical film of the present invention is applied has high uniformity in flatness and retardation. Even if it is arranged, excellent display properties can be obtained. A polarizer protective film provided with a clear hard coat layer, an antiglare layer, an antireflection layer, or the like is preferably used for this part of the polarizer protective film on the outermost display side of the liquid crystal display device. In addition, in the case of a polarizer protective film provided with an optical compensation layer, or a polarizer protective film provided with an appropriate optical compensation capability by itself, such as stretching operation, it is excellent in being disposed at a site in contact with the liquid crystal cell. Displayability is obtained. In particular, the use of the present invention for a multi-domain type liquid crystal display device, more preferably a multi-domain type liquid crystal display device with a birefringence mode, can further exhibit the effects of the present invention.

  Multi-domain is a method of dividing a liquid crystal cell that constitutes one pixel into a plurality of parts, and is suitable for improving the viewing angle dependency and the symmetry of image display. Various methods have been reported. “Okita, Yamauchi: Liquid Crystal, 6 (3), 303 (2002)”. The liquid crystal display cell is also shown in “Yamada, Yamabara: Liquid Crystal, 7 (2), 184 (2003)”, but is not limited thereto.

  The display quality of the display cell is preferably symmetrical with respect to human observation. Therefore, when the display cell is a liquid crystal display cell, the domains can be multiplied substantially giving priority to the symmetry on the observation side. A known method can be used to divide the domain, and can be determined by taking into account the properties of the known liquid crystal mode by a two-division method, more preferably a four-division method.

  The polarizing plate of the present invention includes an MVA (Multi-domain Vertical Alignment) mode represented by a vertical alignment mode, in particular, an MVA mode divided into four, a known PVA (Patterned Vertical Alignment) mode and an electrode multi-domained by electrode arrangement. It can be effectively used in a CPA (Continuous Pinwheel Alignment) mode in which arrangement and chiral ability are fused. In addition, a proposal of an optically biaxial film in the adaptation to the OCB (Optical Compensated Bend) mode has been disclosed, and “T. Miyashita, T. Uchida: J. SID, 3 (1), 29 ( 1995) ", the polarizing plate of the present invention can also exhibit the effect of the present invention in display quality. If the effect of this invention can be expressed by using the polarizing plate of this invention, arrangement | positioning of a liquid crystal mode and a polarizing plate will not be limited.

  Since the liquid crystal display device has high performance as a device for colorization and moving image display, the display quality of the liquid crystal display device using the optical film of the present invention, particularly a large-sized liquid crystal display device is less fatigued and faithful. Display is possible.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
《Synthesis of cellulose ester》
Polymers for Advanced Technologies, vol. 14 (2003), p478, various cellulose esters were synthesized.

<Cellulose ester a1>
100 parts by mass (100 parts by mol) of cellulose, 420 parts by mass (1600 parts by mol) of lithium chloride, 26 parts by mass (70 parts by mol) of acetic acid, 165 parts by mass (230 parts by mol) of caproic acid, and dimethylacetamide To a solution mixed in 1000 parts by mass (10 times by volume), 380 parts by mass (300 parts by mol) of dicyclohexylcarbodiimide (DCC), 130 parts by mass (170 parts by mol) of dimethylaminopyridine, 130 of dimethylaminopyridine-tosylate 130 Mass parts (70 mol parts) were added at room temperature and stirred for 24 hours until the DCC was completely consumed. After completion of the reaction, a white precipitate formed by adding 5000 parts by mass of distilled water was filtered off. The solid matter separated by filtration was washed several times with pure water, then subjected to Soxhlet extraction with methanol for 24 hours, and finally dried in vacuo at 70 ° C. to obtain cellulose ester a1. The substitution degree and molecular weight of the obtained cellulose ester were carried out according to the measurement method described later, and the measurement results are shown in Table 1.

<Cellulose ester a2>
The same as cellulose ester a1 except that 26 parts by mass (70 mols) of acetic acid was changed to 56 parts by mass (150 parts by mol) and 165 parts by mass (230 parts by mol) of caproic acid were changed to 108 parts by mass (150 parts by mol). To obtain cellulose ester a2.

<Cellulose ester a3>
It is the same as cellulose ester a1 except that acetic acid 26 parts by mass (70 mol parts) is changed to 78 parts by mass (210 mol parts) and caproic acid 165 parts by mass (230 mol parts) is changed to 64 parts by mass (90 mol parts). To obtain cellulose ester a3.

<Cellulose ester a4>
The same as cellulose ester a1, except that acetic acid 26 parts by mass (70 mol parts) was changed to 93 parts by mass (250 mol parts) and caproic acid 165 parts by mass (230 mol parts) were changed to 36 parts by mass (50 mol parts). And cellulose ester a4 was obtained.

<Cellulose ester a5>
The same as cellulose ester a1, except that acetic acid 26 parts by mass (70 mol parts) was changed to 104 parts by mass (280 mol parts) and caproic acid 165 parts by mass (230 mol parts) was changed to 14 parts by mass (20 mol parts). To obtain cellulose ester a5.

<Cellulose ester b1>
Synthesis was carried out in the same manner as cellulose ester a3 except that 78 parts by mass (210 parts by mol) of acetic acid was changed to 63 parts by mass (170 parts by mol) to obtain cellulose ester b1.

<Cellulose ester b2>
Synthesis was carried out in the same manner as cellulose ester a3 except that 78 parts by mass (210 parts by mol) of acetic acid was changed to 70 parts by mass (190 parts by mol) to obtain cellulose ester b2.

<Cellulose ester b3>
Synthesis was performed in the same manner as cellulose ester a3 except that 78 parts by mass (210 parts by mol) of acetic acid was changed to 85 parts by mass (230 parts by mol) to obtain cellulose ester b3.

<Cellulose ester b4>
Synthesis was carried out in the same manner as cellulose ester a3 except that 78 parts by mass (210 parts by mol) of acetic acid was changed to 93 parts by mass (250 parts by mol) to obtain cellulose ester b4.

<Cellulose ester c1>
Synthesis was performed in the same manner as cellulose ester a3 except that 165 parts by mass (230 mols) of caproic acid was changed to 145 parts by mass (230 mols) of valeric acid to obtain cellulose ester c1.

<Cellulose ester c2>
Synthesis was performed in the same manner as in the cellulose ester a3 except that 165 parts by mass (230 mols) of caproic acid was changed to 185 parts by mass (230 mols) of enanthic acid to obtain cellulose ester c2.

<Cellulose ester c3>
Synthesis was performed in the same manner as in the cellulose ester a3 except that 165 parts by mass (230 mols) of caproic acid was changed to 205 parts by mass (230 mols) of caprylic acid to obtain cellulose ester c3.

<Cellulose ester c4>
Synthesis was carried out in the same manner as cellulose ester a3 except that 165 parts by mass (230 mols) of caproic acid was changed to 244 parts by mass (230 mols) of decanoic acid to obtain cellulose ester c4.

<Cellulose ester c5>
Synthesis was carried out in the same manner as cellulose ester a3 except that 165 parts by mass (230 mols) of caproic acid was changed to 284 parts by mass (230 mols) of lauric acid to obtain cellulose ester c5.

<Cellulose ester c6>
Synthesis was performed in the same manner as cellulose ester a3 except that 165 parts by mass (230 mols) of caproic acid was changed to 404 parts by mass (230 mols) of stearic acid to obtain cellulose ester c6.

<Cellulose ester d1>
It was synthesized by the method described in Section 8 Example B of Patent Document 1. The obtained cellulose ester d1 was used to form cellulose ester films D1 to D3 as a comparative film.

<Cellulose ester d4>
Eastman Chemical cellulose acetate propionate, CAP482-20 was used.
<Cellulose ester d5>
Eastman Chemical Cellulose Acetate Butyrate, CAB171-15 was used.
<Cellulose ester d6>
Eastman Chemical Cellulose Acetate Butyrate, CAB381-20 was used.

  Each cellulose ester obtained by the above synthesis example was measured for molecular weight and substitution degree by the following method.

<Molecular weight measurement of cellulose ester>
Since the average molecular weight and molecular weight distribution of a cellulose ester can be measured using high performance liquid chromatography, the weight average molecular weight (Mw) can be calculated using this.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803 (used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

<Measurement of substitution degree of cellulose ester>
Based on ASTM D817-96, substitution degree DS was calculated | required as follows.

  1.90 g of the dried cellulose ester was precisely weighed, 70 ml of acetone and 30 ml of dimethyl sulfoxide were added and dissolved, and then 50 ml of acetone was further added. While stirring, 30 ml of 1 mol / L sodium hydroxide aqueous solution was added and saponified for 2 hours. After adding 100 ml of hot water and washing the sides of the flask, titration was performed with 0.5 mol / L sulfuric acid using phenolphthalein as an indicator. Separately, a blank test was performed in the same manner as the sample. The supernatant of the solution after titration was diluted 100 times, and the composition of the organic acid was measured by an ordinary method using an ion chromatograph. From the measurement result and the acid composition analysis result by ion chromatography, the substitution degree was calculated by the following formula.

TA = (B−A) × F / (1000 × W)
X = (162.14 * TA) / {1-42.14 * TA + (1-SA * TA) * (Y / X)}
Y = X × (Y / X)
DS = X + Y
A: Sample titration (ml)
B: Blank test titration (ml)
F: Potency of 0.5 mol / L sulfuric acid W: Mass of sample (g)
TA: Total organic acid amount (mol / g)
Y / X: molar ratio of acetic acid to acid other than acetic acid measured by ion chromatography X: degree of substitution with acetic acid Y: degree of substitution with acid other than acetic acid SA: acid other than acetic acid substituted hydroxyl group of cellulose ester This is a molecular weight that increases when the molecular weight of water other than acetic acid is subtracted from the molecular weight of water (18.02).

For example, 56.06 for propionic acid and 116.16 for caproic acid.
<Synthesis of Phosphate Plasticizer Di-TPP>
The synthesis was carried out with reference to Example A on page 8 of Patent Document 1.

  Under nitrogen, 32.7 g of hydroquinone was dissolved in 500 ml of pyridine, and then cooled to 5 ° C. To this solution, 200 g of diphenyl chlorophosphate was added, and after completion of the dropwise addition, the reaction vessel was warmed to room temperature and kept for a whole day and night. After this solution was mixed with 200 ml of water, this solution was put into a 3 L water container to obtain a white precipitate. The white precipitate was collected by filtration and then recrystallized from methanol to obtain a white solid. The yield was 90% and the melting point was 107 ° C.

<Film forming method>
90 parts by mass of cellulose esters (a1 to a5, b1 to b4, c1 to c6, d1, and d4 to d6) prepared in the synthesis example, 10 parts by mass of a plasticizer, and 1.0 part by mass of an ultraviolet absorber Was mixed in powder form and fed to a twin screw extruder. The screw rotation speed was 100 rpm, and the temperature (melting temperature) in the barrel was selected as the lowest temperature at which a transparent film was obtained. The film was formed so that the film thickness was 180 μm.

  The various additives used and their 1% mass reduction temperature Td (1.0) are shown below. About 1% mass reduction | decrease temperature Td (1.0), it measured with the temperature increase rate of 10 degree-C / min and dry air (dew point -30 degreeC) with the Seiko Instruments differential thermal-thermal mass simultaneous measurement apparatus and EXSTAR6000TG / DTA.

-Plasticizer: Trimethylolpropane tribenzoate (TMPTB, 262 ° C) manufactured by Asahi Denka
UV absorber: Tinuvin 360 (323 ° C) manufactured by Ciba Specialty Chemicals
<Evaluation>
The optical films A1 to A5, B1 to B4, C1 to C6, and D1 to D6 obtained based on the formulation of Table 1 were evaluated as follows, and the results are also shown in Table 1.

<Measurement of molecular weight after film formation>
The obtained cellulose ester film was sampled, and the molecular weight was measured by GPC in the same manner.

<Evaluation of heat and humidity resistance>
The film sample was cut into a size of 50 mm in the width direction and 150 mm in the longitudinal direction, stored in an environmental chamber at 23 ° C. and 55% RH for 24 hours, and then a 10 g weight was hung on the short axis side of the rectangular sample. After storing for 48 hours in an environmental chamber at 90 ° C. and RH for 23 hours in an environmental chamber at 23 ° C. and 55% RH, the amount of deformation of the film was evaluated.

◎: Change in length in the long axis direction after removal from the environmental chamber is 1% or less ○: Change in length in the long axis direction after removal from the environmental chamber is 3% or less △: After removal from the environmental chamber Change in length in the long axis direction of 10% or less ×: Change in length in the long axis direction after removal from the environmental chamber is 10% or more <Bleed-out property>
The film sample was cut into a size of 50 mm in the width direction and 150 mm in the longitudinal direction and stored in an environmental chamber at 23 ° C. and 55% RH for 24 hours, and then a rectangular sample was stored in an environmental chamber at 80 ° C. and 90% RH. The surface of the film at the time of 48 hours and 300 hours was observed, and the bleeding out property was evaluated according to the following criteria.

A: No powder is generated on the film surface even after 300 hours. O: No powder is generated on the film surface even after 48 hours. Δ: Some powder is observed on the film surface after 48 hours. After 48 hours, a large amount of powder is observed on the film surface <Measurement of Yellowness>
The yellowness of each transparent film before stretching was measured for the absorption spectrum of the obtained cellulose ester film using a spectrophotometer U-3310 manufactured by Hitachi High-Technologies under a 23 ° C. and 55% RH environment. X, Y, and Z were calculated. From these tristimulus values X, Y, and Z, yellowness YI was calculated based on JIS-K7103.

<Evaluation of stretchability>
Ten film samples cut to 10 cm × 10 cm were prepared and biaxially stretched. First, 50% MD stretching was performed, and then 50% TD stretching was performed (the final stretching ratio was 125% = 2.25 times). The stretching temperature was 140 ° C. and the stretching speed was 100% per minute.

  Such stretching operation was performed on 10 films, and the number of films that could be biaxially stretched without breaking was evaluated.

◎: All 10 sheets could be stretched ○: 8 sheets or more could be stretched △: 5 sheets or more could be stretched ×: Less than 5 sheets could be stretched XX: 1 sheet could not be stretched <Evaluation of flatness>
The flatness (sag) of the film surface prepared by the above stretching operation was evaluated by the degree of reflection of the fluorescent lamp.

◎: Fluorescent light is reflected straight and fine irregularities are hardly seen. ○: Fluorescent light is reflected straight and very slight irregularities are observed. △: Fluorescent light is slightly distorted. A stretched film that can be seen in or evaluated was not obtained. <Measurement of Birefringence Values Ro and Rth>
In-plane birefringence Ro and film thickness direction of each transparent film after measurement using an automatic birefringence meter KOBRA-21ADH manufactured by Oji Scientific Instruments Co., Ltd. under an environment of 23 ° C. and 55% RH. The birefringence Rth of was measured. Of the 10 films that were attempted to be stretched, all the stretched films were measured, and the average value was listed in the table (the film that could not be stretched was not measured).

  In Table 1, it turns out that the comparative films D1-D6 using a well-known cellulose ester have low stretchability, and cannot endure high magnification stretching like 2.25 times. Further, it can be seen that the cellulose ester having a composition capable of producing a film having a high moisture and heat resistance is low when it can be melted at a low temperature, and the molecular weight after film formation is reduced and coloring is also generated.

  On the other hand, in cellulose ester films A1 to A5 using caproic acid as an organic acid for replacing cellulose, cellulose ester having a caproic acid substitution degree within the scope of the present invention has moisture and heat resistance despite its low melting temperature. In addition, it can be seen that a cellulose ester film having stretchability is obtained. Moreover, even if it carries out high magnification extending | stretching, it turns out that it is settled in the range of the preferable retardation.

  Further, when the films B1 to B4 are compared, if the total substitution degree is out of the range of 2.4 to 2.8, the melt suitability is lowered, the yellowness of the resulting film is increased, and the molecular weight after film formation is decreased. The tendency to do is seen. In addition, the stretchability of the film also decreases.

  In addition, when films D1, D3, A3, and C1 to C6 are compared, since the organic acid that substitutes cellulose exceeds valeric acid having 5 carbon atoms, it can withstand high magnification stretching of 2.1 times. It turns out that the cellulose ester which can be obtained is obtained. On the other hand, since the compatibility with the used plasticizer or ultraviolet absorber is reduced from the cellulose ester using caprylic acid to decanoic acid, the organic acid to be substituted is a carboxylic acid having 5 to 8 carbon atoms. It turns out that it is preferable to use. The best balance of physical properties was cellulose ester using caproic acid having 6 carbon atoms.

Example 2
Cellulose ester used for melt film formation is fixed to cellulose ester a3 (substitution degree 1.9 with acetic acid, degree of substitution 0.7 with cyclohexanecarboxylic acid, molecular weight 231000 before film formation), and additives such as plasticizer and ultraviolet absorber The film was formed by changing the thickness. Melting conditions were a barrel temperature of 220 ° C., a screw rotation speed of 100 rpm, and the types of additives are shown in Table 2. The abbreviations in Table 2 represent the following compounds.

-I1010: Irganox 1010 manufactured by Ciba Specialty Chemicals, hindered phenol antioxidant-LP63P: Asahi Denka, hindered amine light stabilizer-T144: Tinuvin 144 manufactured by Ciba Specialty Chemicals, hindered phenol-hindered amine combined antioxidant Agent V7190: Atofina Bicoflex 7190, acid scavenger MBHMB Aldrich 5,5'-methylenebis (2-hydroxy-4methoxybenzophenone), benzophenone UV absorber The amount of each additive added is The plasticizer is 10%, and the antioxidant and the acid scavenger are both 0.5% by mass. The addition amount of the ultraviolet absorber was such that the transmittance of the cellulose ester film at 380 nm was 8.0%.

  About the obtained films E1-E6, the molecular weight, bleed-out, wet heat resistance, yellowness, stretchability, flatness, and birefringence value of the film after film formation were evaluated in the same manner as in Example 1.

  Comparing film A3 of Example 1 and E1 of Example 2, it can be seen that the use of a polyhydric alcohol ester type plasticizer as the plasticizer causes less deterioration and coloring of the cellulose ester. In addition, bleed-out hardly occurs.

  Moreover, it turns out that molecular weight retention can be raised by adding antioxidant and an acid scavenger like films E2-E5. As a result, it can be seen that the stretchability is improved.

  In addition, the film E6 using a benzophenone-based compound as an ultraviolet absorber has a small gram extinction coefficient, so that a large amount of ultraviolet absorber is required to impart a predetermined ultraviolet absorption performance to the cellulose ester film. Since it is easy to generate | occur | produce, it was the cellulose ester film with the more preferable using a benzotriazole type ultraviolet absorber.

Example 3
The unstretched film E4 obtained in Example 2 was subjected to evaluation of stretchability and planarity and birefringence in the same manner as in Examples 1 and 2 by changing the stretch elongation to the stretch ratios described in Table 3. The value was measured.

  As is clear from Table 3, it can be seen that the planarity of the cellulose ester film is improved as the draw ratio is increased. Practically, it is a cellulose ester having a final draw ratio of 1.5 times or more, preferably 2.0 times.

  On the other hand, when the draw ratio exceeds 4.0 times, stable stretching becomes difficult, and the birefringence value of the film, particularly Rth increases. It can be seen that 0 times is preferable.

Example 4
The optical films obtained in Examples 1, 2, and 3 were bonded to both surfaces of a polarizer according to the following procedure to produce polarizing plates.

(Preparation of polarizing plate)
A 120 μm-thick polyvinyl alcohol film was immersed in an aqueous solution containing 1 part by mass of iodine, 2 parts by mass of potassium iodide, and 4 parts by mass of boric acid, and stretched 4 times at 50 ° C. to produce a polarizer.

  Examples or Comparative Films A1 to F5 were alkali-treated with a 2.0 M / L-sodium hydroxide aqueous solution at 90 ° C. for 120 seconds, further washed with water and dried to be alkali-treated.

  Polarizing plates A1 to A1 having protective films formed on both surfaces of the polarizer by bonding the alkali-treated surfaces of Examples or Comparative Films A1 to F5 from both sides with a completely saponified polyvinyl alcohol 5% aqueous solution as an adhesive. F5 was produced.

(Characteristic evaluation as a liquid crystal display device)
The polarizing plate of the 6-type TFT color liquid crystal television “Exfer XF-600” (manufactured by Casio Co., Ltd.) was peeled off, and each of the polarizing plates produced above was cut according to the size of the liquid crystal cell. The two polarizing plates produced as described above were bonded so that the polarizing axes of the polarizing plates were not perpendicular to each other so as to sandwich the liquid crystal cell, thereby producing a 6-type TFT color liquid crystal display, and the polarization of the cellulose ester film. When the characteristics as a plate were evaluated, the polarizing plates A2 to A4, B2, B3, C1 to C6, E1 to E6, and F1 to F5 of the present invention showed high contrast and excellent display properties. Thereby, it was confirmed that it is excellent as a polarizing plate for image display apparatuses, such as a liquid crystal display.

Claims (12)

A cellulose ester film obtained by melt-forming a composition mainly comprising cellulose ester, wherein the cellulose ester satisfies the following formulas (1) and (2).
Formula (1) 2.4 <= X + Y <= 2.8
Formula (2) 0.3 <= Y <= 1.3
(Wherein X represents the degree of substitution with acetic acid, and Y represents the degree of substitution with linear carboxylic acid having 5 to 22 carbon atoms) The cellulose ester film according to claim 1, wherein the cellulose ester has a weight average molecular weight of 150,000 or more. The cellulose ester film according to claim 1 or 2, wherein the temperature at the time of melt film formation is 180 ° C or higher and 230 ° C or lower. The cellulose ester film according to claim 1, wherein the cellulose ester film is a film stretched 1.5 to 4.0 times. The cellulose ester film according to any one of claims 1 to 4, wherein the linear carboxylic acid having 5 to 22 carbon atoms replacing the cellulose ester is caproic acid. The cellulose ester film according to any one of claims 1 to 5, wherein the cellulose ester film contains 5 to 13% by mass of a polyhydric alcohol ester plasticizer. The cellulose ester film according to any one of claims 1 to 6, wherein the cellulose ester film contains 0.1 to 5% by mass of a hindered phenol-based antioxidant. The cellulose ester film according to any one of claims 1 to 7, wherein the cellulose ester film contains 0.1 to 5% by mass of a hindered amine light stabilizer. The cellulose ester film according to any one of claims 1 to 8, wherein the cellulose ester film contains 0.1 to 5% by mass of an epoxy acid scavenger. The cellulose ester film according to any one of claims 1 to 8, wherein the cellulose ester film contains 0.1 to 5% by mass of a benzotriazole-based ultraviolet absorber. A polarizing plate comprising the cellulose ester film according to claim 1 as a protective film. A liquid crystal display device comprising the polarizing plate according to claim 11.