JP4774712B2 - Polarizer - Google Patents

Description

  The present invention relates to an optical film, a polarizing plate and a liquid crystal display device using cellulose ester.

  A cellulose ester film has been used for a support for a photographic negative film, a film for protecting a polarizer used in a liquid crystal display, and the like because of its high transparency and low birefringence.

  Due to the thinness and lightness of the liquid crystal display, the production volume has increased greatly in recent years, and the demand for liquid crystal displays has increased. In addition, TVs using liquid crystal displays are being made thin and light, and large-scale TVs that could not be achieved with TVs using Brown 菅 are now being produced. The size of polarizers and polarizer protective films that are used is also demanded. The use of liquid crystal displays in automobiles, such as car navigation systems, is also spreading.

  However, as the size of the polarizer increases, it becomes more susceptible to environmental fluctuations such as temperature and humidity, which degrades the edges of the polarizer, brightens the black display, and reduces the contrast. Being easy to get up is a new issue. The same applies to applications where the temperature changes drastically, such as in a car.

  Such deterioration of the polarizer is said to be caused by a dimensional change caused by shrinkage of the polarizer protective film.

  By the way, the cellulose-ester film used as a polarizer protective film has been manufactured by the solution casting method until now. 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.

  In such a film forming method, shrinkage of the film occurs when the solvent is dried, but it is necessary to dry the film while applying tension in order to maintain the flatness of the surface. As a result, some internal stress remained, causing shrinkage over a long period of time.

  In addition, because of the solubility of cellulose ester, a halogen-based solvent such as methylene chloride is used as the solvent, and the environmental load is also a problem.

  In contrast, plastic films other than cellulose ester films (PET films and the like) are often formed by melt casting. The melt casting method is a film forming method in which a solvent is not required for forming a film by melting a plastic by heat, and there are few problems such as shrinkage and residual internal stress during drying. In addition, since a production facility such as a drying line and a solvent recovery / regeneration device is not required, the film width can be easily increased, and the environmental load can be greatly reduced, which is a preferable production method.

  However, until now, triacetyl cellulose (TAC), which is a raw material cellulose ester for optical films, is a polymer whose melting start temperature is higher than the decomposition starting temperature, so it has been difficult to obtain an optical film using the melt casting method until now. Not achieved.

  In order to allow the cellulose ester film to be melted at a low temperature below the decomposition temperature, (i) a method of adding a large amount of plasticizer, (ii) an organic acid that replaces cellulose is a linear organic compound that is longer than acetic acid. A method of using an acid (see Non-Patent Document 1) is known.

  However, the amount of plasticizer added is that when the added amount exceeds a certain level, the plasticizer precipitates from the cellulose ester film over time and deteriorates. Therefore, the added amount of the plasticizer is substantially about 10 to 20% by mass. It is a limit. When the amount is such an amount, the effect of lowering the melting point is still insufficient, and it is not possible to completely prevent decomposition of the cellulose ester at the time of melting.

  On the other hand, according to the method of lengthening the substituent of the cellulose ester, when the organic acid that replaces the cellulose is an acid longer than acetic acid, the melting point rapidly decreases, and the lowest temperature (86 ° C.) of caprylic acid, which is a C8 carboxylic acid. ) Is reported.

  However, it has been reported that the tensile strength of cellulose ester is reduced at the same time as the length of the organic acid that substitutes cellulose is reduced, and the tensile strength of tricapryl cellulose is about 1/10 that of triacetyl cellulose. It is reported to decline.

  As a polarizer protective film using a cellulose ester, it is also an important physical property that mechanical strength such as tensile strength and elastic modulus is high. Since a polarizer (PVA film) is stretched about 4 to 5 times during production, internal stress remains in the film. However, if a protective film having low tensile strength or elastic modulus is used, the internal stress of the polarizer is reduced. Cellulose ester having low tensile strength and low elastic modulus cannot be used as a polarizer protective film even if the melting point is low, because it is easy to lose and easily deform and the polarizer tends to deteriorate.

  In addition, since cellulose has a hydroxyl group that can be substituted for up to three per each repeating unit, the elastic modulus is adjusted to some extent by a mixed cellulose ester of acetic acid and propionic acid, as disclosed in Patent Document 1. be able to. It is also known that the elastic modulus can be improved by stretching a cellulose ester film.

  Moreover, in patent document 2, after melt film-forming using the cellulose ester by which the substituent of the cellulose was substituted by the specific ratio with the acetyl group and the propionyl group, it is applicable to a negative film support body by extending | stretching. Although a cellulose ester film is obtained, there is no description about birefringence, dimensional stability, and elastic modulus, which are important physical properties as an optical film.

  Patent Document 3 also discloses a polarizer protective film using a fatty acid cellulose ester such as an acetyl group, a propionyl group, and a butyryl group, and a polarizer protective film, a polarizer, and a liquid crystal display with good dimensional stability are obtained. However, the produced display is 15 inches, and application to a large liquid crystal display such as 30 inches or more in recent years has not been attempted.

Accordingly, an object of the present invention is to provide an optical film having good optical characteristics, mechanical characteristics, and dimensional stability even when used for a television having a large screen size, and optical characteristics, mechanical characteristics, and dimensional stability using the same. The object is to provide an excellent polarizer. Moreover, it is providing the manufacturing method which manufactures the above high performance optical films, without using the halogen-type solvent with a high environmental impact.
Japanese Patent Laid-Open No. 10-45804 Japanese National Patent Publication No. 6-501040 JP 2000-352620 A Industrial and Engineering Chemistry, vol. 43-3 (1951), p688-691

  Accordingly, an object of the present invention is to provide an optical film having good optical characteristics, mechanical characteristics, and dimensional stability even when used for a television having a large screen size, and optical characteristics, mechanical characteristics, and dimensional stability using the same. The object is to provide an excellent polarizer. Moreover, it is providing the manufacturing method which manufactures the above high performance optical films, without using the halogen-type solvent with a high environmental impact.

  The above problem could be solved by the following configuration.

(Claim 1)
In the polarizing plate having a sandwiched on both sides of the polarizer with two polarizing plate protective film, the two polarizing plate protective fill beam, characterized in that it contains acetate isobutyrate cellulose or acetate pivalate cellulose Polarizer.

(Claim 2)
The polarizing plate according to claim 1, wherein the polarizing plate protective film contains a benzotriazole-based ultraviolet absorber having a Td (1.0) of 250 ° C. or higher.

  Provided are optical films having good optical characteristics, mechanical characteristics, and dimensional stability even when used in large screen size televisions, etc., and polarizers having excellent optical characteristics, mechanical characteristics, and dimensional stability. I was able to. In addition, it was possible to provide a production method for producing a high-performance optical film without using a halogen-based solvent having a high environmental load.

  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 so-called solution casting method in which a film obtained by casting a solution obtained by dissolving the resin in a solvent and then evaporating and drying the solvent is used. Has been done. Since the solution casting method must remove the solvent remaining in the film, it not only affects the film physical properties such as the generation of internal stress, but also the drying line, the drying energy, and the recovery and regeneration device for the evaporated solvent, etc. In addition, capital investment and production costs on production lines are enormous, and reducing them is an important issue.

  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. 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 heat 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 optical film of the present invention is formed using a film forming material containing 80% to 99% by mass of the following cellulose ester.

  The cellulose ester used in the present invention is a cellulose ester that simultaneously satisfies the following formulas (1) and (2) when the substitution degree of the acetyl group is X and the substitution degree of isobutyric acid or pivalic acid is Y.

Formula (1) 2.4 <= X + Y <= 2.9
Formula (2) 0.3 <= Y <= 2.0
That is, it has been found that an excellent optical film can be obtained in the melt casting method by using cellulose ester of acetic acid and isobutyric acid or acetic acid and pivalic acid as the acyl group of cellulose ester. As a prior art, it has been known that cellulose ester (CAP) of acetic acid and propionic acid and cellulose ester (CAB) of acetic acid and butyric acid can be formed by a melt casting method. It has been found that by using an alkyl group of the acyl group as a branched alkyl group, it is more suitable for the melt casting method and an excellent optical film can be obtained.

The range in which the total substitution amount (X + Y) of the organic acid is larger than 2.4 and smaller than 2.9 is the substitution degree within the range in which the cellulose ester can be melted at a low temperature. Thus, the physical properties of the obtained cellulose ester film are lowered by the melting process. More preferably, it is the range of 2.5 or more and 2.7 or less.
The value of Y, which is the degree of substitution with a branched chain organic acid, is preferably in the range of more than 0.1 and less than 2.0. If it is 0.1 or less, the effect of lowering the melting temperature of the cellulose ester is small, and if it is 2.0 or more, the mechanical strength of the resulting cellulose ester is insufficient. More preferably, it is the range of 0.5 or more and 1.0 or less.

  In the present invention, a cellulose ester containing both isobutyric acid and pivalic acid may be used. For example, cellulose esters having a substitution degree with acetic acid of 1.8, a substitution degree with isobutyric acid of 0.4, and a substitution degree with pivalic acid of 0.4.

  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, and the 6th position is a primary hydroxyl group. Depending on which position the acid substitutes, the higher order structure and physical properties of the cellulose ester may slightly change, but in the optical film of the present invention, the cellulose ester in which the branched chain organic acid is located should preferably be used. Can do.

  Furthermore, these cellulose esters used as raw materials for melt film formation are required to have a weight average molecular weight of 200,000 or more, preferably 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. When it is 500,000 or more, the viscosity at the time of melting becomes too high, and the flatness of the obtained optical film may be deteriorated. In addition, it is preferable that the cellulose ester constituting the optical film formed by the melt casting method suppresses decomposition by heat melting as low as possible, and the weight average molecular weight after the melting process is preferably 150,000 or more.

  The above cellulose ester can be synthesized by a known method.

  By making the cellulose ester in the film-forming material in the range of 80% by mass to 99% by mass, excellent melt castability and stability can be obtained in the presence of a stabilizer, a plasticizer and an ultraviolet absorber described later. The obtained film can impart excellent performance as an optical film. If the cellulose ester content is 80% by mass or less, the additive bleeds out and the elastic modulus of the film becomes low, which is not preferable. Further, when the amount of other additives necessary as an optical film is 1.0% by mass or less (the content of cellulose ester is 99% or more), it is difficult to satisfy the required physical properties. More preferably, the cellulose ester content is 85 to 95% by mass.

  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.

  In the present invention, a more preferable optical film can be obtained by adding a plasticizer and a stabilizer to the film-forming material before or when the cellulose ester is heated and melted.

(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 200 ° C., it is a system in which the polymer is easily decomposed and deteriorated, and it is preferable to contain a stabilizer in the film-forming material.

  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 to contain at least one of an antioxidant and an acid scavenger as a stabilizer in the film-forming material.

  It is represented by coloring and molecular weight reduction, including decomposition reactions that have not been elucidated, such as preventing oxidation of film-forming materials, capturing acid generated by decomposition, and suppressing or prohibiting decomposition reactions caused by radical species due to light or heat. Stabilizers are used to suppress the generation of volatile components due to deterioration and material degradation.

  At least one or more stabilizers in the film-forming material used in the present invention can be selected, and the added amount is 0.001% by mass or more and 5% by mass with respect to the mass of the cellulose ester. % Or less, more preferably 0.005 mass% or more and 3 mass% or less, and still more preferably 0.01 mass% or more and 0.8 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, the transparency of the optical compensation film as a support is lowered, and 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 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher. The 1% mass reduction temperature Td (1.0) under air can be measured with a commercially available differential thermogravimetric analysis (TG-DTA) apparatus.

  The film-forming material can be stored by dividing the constituent material into one or a plurality of types of pellets for the purpose of avoiding material alteration and hygroscopicity. Pelletization may improve the mixing or compatibility of the melt during heating, or may ensure the optical uniformity of the resulting film.

  When the film-forming material is heated and melted, the presence of the above-mentioned stabilizer is from the viewpoint of suppressing the deterioration based on the deterioration and decomposition of the material and the deterioration of optical transparency, or maintaining the inherent strength of the material. Are better.

  If the film constituting material is significantly deteriorated by heating, coloring may occur and the film may not be used as an optical film. In addition, when the optical film of the present invention is used as an optical compensation film, a retardation imparting step (stretching step) is performed next to the casting step. However, when the film constituent material is significantly deteriorated by heating, the formed film May become brittle and may be easily broken in the stretching process, or the retardation value of the target optical compensation film 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 can suppress or eliminate deterioration that is undesirable as an optical film, such as a decrease in the thickness.

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

  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. Can be used in combination with the method of 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 of time.

(Antioxidant)
Since cellulose ester is decomposed not only by heat but also by oxygen at a high temperature, 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, the 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 deterioration due to thermal oxidation without lowering transparency, heat resistance and the like. These antioxidants can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention, but the polymer 100 according to the present invention. Preferably it is 0.001-5 mass parts with respect to a mass part, More preferably, it is 0.01-2 mass parts.

  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, a preferable compound includes a compound 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 from Ciba Specialty Chemicals under the trade names “Irganox 1076” and “Irganox 1010”, for example.

  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.

(Acid scavenger)
Since cellulose ester is also decomposed by an acid at a high temperature, the optical film of the present invention preferably contains 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. 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 various polyglycol diglycidyl ethers, particularly about 8-40 moles of ethylene oxide per mole of polyglycol. Glycol, diglycidyl ether of glycerol, metal epoxy compounds (such as those conventionally used in and together with vinyl chloride polymer compositions), epoxidized ether condensation products, diphenols of bisphenol A Glycidyl ether (i.e., 4,4'-dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester (especially an ester of an alkyl of about 4 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 (2) can also be preferably used.

  In the above formula, n represents 0-12.

  Furthermore, examples of 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. Is included.

In addition, although an acid scavenger may be called an acid scavenger, an acid capture agent, an acid catcher, etc., in this invention, it can use without a difference by these names.
(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 (3).

  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-tert-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.

(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 relatively strong material against ultraviolet rays, but other additives may be compounds that are weak against ultraviolet rays, and polarizers and liquid crystal cells are also formed from compounds that are weak against 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 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.

  In the present invention, the ultraviolet absorber is preferably added in an amount of 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass. Two or more of these may be used in combination.

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

  Generally, a plasticizer is an additive having an effect of improving brittleness or imparting flexibility by adding it to a polymer. In the present invention, a plasticizer is melted. It is used as an additive that lowers the temperature or as an additive that lowers the viscosity of the film-forming material at the same temperature. Since it is possible to suppress the degradation of the cellulose ester during the melting process by lowering the melting temperature or lowering the melt viscosity, in the present invention, any material having such an effect can be used as a plasticizer without limitation. Can do. 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, the addition of a plasticizer may improve the mechanical properties of the cellulose ester film, improve the tear strength, impart water resistance resistance, and reduce moisture permeability. It is more preferable to use 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, 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. Thermally, it is preferably stable at a higher temperature, and the 1% mass reduction temperature Td (1.0) in air is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher. The addition amount may be as long as the optical properties and mechanical properties are not adversely affected, and the blending amount is appropriately selected within the range not impairing the object of the present invention, and preferably 0.001 with respect to 100 parts by mass of the polymer according to the present invention. -50 mass parts, More preferably, it is 0.01-30 mass parts. 0.1-15 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, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane- 1,3,5-triol, pinacol, sorbitol, glycerin, diglycerin, trimethylolethane, trimethylolpropane, xylitol, pentaerythritol, dipentaerythritol, glucose, cello Mention may be made of the Oath, and the like. Particularly preferred are ethylene glycol polyhydric alcohols such as diethylene glycol, triethylene glycol and tetraethylene glycol, glycerin polyhydric alcohols such as glycerin and diglycerin, trimethylolethane, trimethylolpropane, pentaerythritol and dipentaerythritol.

  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 , 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 the plasticizers described in paragraphs 30 to 33 of JP-A-2003-12823.

  In the above-mentioned plasticizer, both the polyhydric alcohol part or the organic acid part may be further substituted with an alkylate group, a cycloalkyl carboxylate group or an arylate group, and these substituents are covalently bonded to each other. It may be combined. Alternatively, these structures may be part of the polymer, or may be regularly pendant, and are introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, and UV absorbers. May be.

  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 alkyl dicarboxylic acid alkyl ester plastics such as didodecyl malonate (C1), dioctyl adipate (C4), and dibutyl sebacate (C8). Agents, alkyl dicarboxylic acid cycloalkyl ester plasticizers such as dicyclopentyl succinate and dicyclohexyl adipate, alkyl dicarboxylic acid aryl ester plasticizers such as diphenyl succinate and di4-methylphenyl glutarate, dihexyl-1, Cycloalkyl dicarboxylic acid alkyl ester plasticizers such as 4-cyclohexanedicarboxylate and didecylbicyclo [2.2.1] heptane-2,3-dicarboxylate, dicyclohexyl-1,2-cyclobutanedicarboxylate , Cycloalkyl dicarboxylic acid cycloalkyl ester plasticizers such as dicyclopropyl-1,2-cyclohexyl dicarboxylate, diphenyl-1,1-cyclopropyl dicarboxylate, di-2-naphthyl-1,4-cyclohexanedi Cycloalkyl dicarboxylic acid aryl ester plasticizers such as carboxylate, aryl dicarboxylic acid alkyl ester plasticizers such as diethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dicyclopropyl phthalate, Aryl dicarboxylic acid cycloalkyl ester plasticizers such as dicyclohexyl phthalate, and aryl dicarboxylic acid aryl ester systems such as diphenyl phthalate and di-4-methylphenyl phthalate 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. In addition, the partial structure of phthalate ester may be part of the polymer or may be regularly pendant to the polymer, and introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc. May be.

  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.

  The amount of these compounds added is preferably 0.5% by mass to less than 50% by mass, more preferably 1% by mass to 30% with respect to the cellulose ester in which the plasticizer constitutes the film. It exists in the range below 1 mass%, More preferably, it exists in the range below 1 mass%-less than 11 mass%. The addition amount of these compounds can be adjusted from the above-mentioned viewpoint.

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

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

  For example, matting agents, fillers, inorganic compounds such as silica and silicates, dyes, pigments, phosphors, dichroic dyes, retardation control agents, refractive index regulators, gas permeation inhibitors, antibacterial agents, biodegradable Examples include an imparting agent. 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.

(Film formation)
The optical film of the present invention can be formed by an ordinary solution casting method as described in, for example, Japanese Patent No. 3341134, but it can be formed by a melt casting method. Thus, a high-quality optical film with higher dimensional stability can be obtained.
Examples of the melt casting method include U.S. Pat. Nos. 2,492,978, 2,739,070, 2,739,069, 2,492,977, No. 336,310, No. 2,367,603, No. 2,607,704, British Patent Nos. 64,071, 735,892, No. 45-9074, No. 49-4554 49-5614, 60-27562, 61-39890, and 62-4208.

  For example, the cellulose ester and additive mixture of the present invention is hot-air dried or vacuum dried, then melt extruded, extruded into a film from a T-die, and brought into close contact with a cooling drum by an electrostatic application method or the like, and cooled and solidified. To obtain an unstretched film. The temperature of the cooling drum is preferably maintained at 90 to 150 ° C.

  Melt extrusion may be used by connecting a single screw extruder, a twin screw extruder, and a single screw extruder downstream of the twin screw extruder. From the viewpoint of the mechanical properties and optical properties of the obtained film, the single screw extruder is used. Is preferably used. Furthermore, it is preferable to replace or depressurize the raw material supply and melting processes such as the raw material tank, the raw material charging section, and the inside of the extruder with an inert gas such as nitrogen gas.

  The temperature during the melt extrusion of the present invention is preferably in the range of 150 to 250 ° C. Furthermore, it is preferable that it is the range of 200-240 degreeC.

  When a polarizing plate is produced using the optical film of the present invention as a polarizer protective film, the cellulose ester film is particularly preferably a film stretched in the width direction or the film forming direction.

  The unstretched film peeled off from the cooling drum described above is heated in a range of Tg + 100 ° C. from the glass transition temperature (Tg) of the cellulose ester via a heating device such as a plurality of roll groups and / or an infrared heater, It is preferable to perform single-stage or multistage longitudinal stretching. Next, the cellulose ester film stretched in the longitudinal direction obtained as described above is preferably stretched transversely within a temperature range of Tg to Tg-20 ° C. and then heat-set.

  In the case of transverse 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 the transverse stretching, it is preferable that the film is held at a temperature of Tg-40 ° C. or higher at a temperature equal to or lower than the final transverse stretching temperature for 0.01 to 5 minutes because the distribution of physical properties in the width direction can be further reduced.

  In the heat setting, heat setting is usually performed for 0.5 to 300 seconds at a temperature higher than the final transverse stretching temperature and within a temperature range of Tg-20 ° C or lower. At this time, it is preferable to heat-fix while sequentially raising the temperature difference in the range of 1 to 100 ° C. in the region divided into two 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 carry out 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 cellulose ester constituting the film, so the physical properties of the obtained biaxially stretched film should be measured and adjusted appropriately to have desirable characteristics. It may be determined by.

(Functional layer)
In producing the optical film of the present invention, before and / or after stretching, an antistatic layer, a transparent conductive layer, a hard coat layer, an antireflection layer, an antifouling layer, a slippery layer, an easy adhesion layer, an antiglare layer, and a gas barrier. A functional layer such as a 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.

  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 film material of the same product type or as a film material of a different product type. It may be reused.

  The optical film of the present invention can be used for a polarizer protective film. When using as a polarizer protective film, the production method of a polarizing plate is not specifically limited, It can produce by a general method. The obtained optical film is alkali-treated, and a polarizer protective film is bonded to both sides of the polarizer using a completely saponified polyvinyl alcohol aqueous solution on both sides of the polarizer prepared by immersing and stretching the polyvinyl alcohol film in an iodine solution. There is a method, and the optical film which is the polarizer protective film of the present invention on at least one side is preferable from the viewpoint that it can be directly bonded to the polarizer.

  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 at the time of shipping the polarizing plate and at the time of product inspection. 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. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal board, and is used for the surface side which bonds a polarizing plate to a liquid crystal cell.

(Stretching operation, refractive index control)
The optical film of the present invention can be controlled in refractive index by a stretching operation. As the stretching operation, the refractive index is controlled within a preferable range by stretching 1.0 to 2.0 times in one direction of the cellulose ester and 1.01 to 2.5 times in the direction perpendicular to the film plane. Can do.

  For example, the film can be stretched sequentially or simultaneously in the longitudinal direction of the film and the direction perpendicular to the longitudinal direction of the film, that is, the width direction. At this time, if the stretching ratio in at least one direction is too small, a sufficient phase difference cannot be obtained, and if it is too large, stretching becomes difficult and breakage may occur.

  For example, when the film is stretched in the direction of melting and casting, if the contraction in the width direction is too large, the refractive index in the thickness direction of the film becomes too large. In this case, the width shrinkage of the film can be suppressed or improved by stretching in the width direction. When stretching in the width direction, the refractive index may be distributed with a width. This is sometimes seen when the tenter method is used, but it is a phenomenon that occurs when the film is stretched in the width direction, causing contraction force at the center of the film and the ends being fixed. It is thought to be called a phenomenon. Even in this case, by stretching in the casting direction, the bowing phenomenon can be suppressed, and the distribution of width retardation can be reduced.

  Furthermore, the film thickness fluctuation | variation of the film obtained can be reduced by extending | stretching in the biaxial direction orthogonal to each other. If the variation in the film thickness of the optical film is too large, the retardation will be uneven, and unevenness such as coloring may be a problem when used in a liquid crystal display.

  The film thickness variation of the cellulose ester film support is preferably in the range of ± 3%, more preferably ± 1%. For the purposes as described above, the method of stretching in the biaxial directions perpendicular to each other is effective, and the stretching ratio in the biaxial directions perpendicular to each other is finally 1.0 to 2.0 times in the casting direction. The width direction is preferably 1.01 to 2.5 times, the casting direction is 1.01 to 1.5 times, and the width direction is 1.05 to 2.0 times. preferable.

  When cellulose ester that obtains positive birefringence with respect to stress is used, the slow axis of the optical film can be provided in the width direction by stretching in the width direction. In this case, in the present invention, in order to improve display quality, the slow axis of the optical film is preferably in the width direction, and satisfies (stretch ratio in the width direction)> (stretch ratio in the casting direction). is required.

  There is no particular limitation on the method of stretching the web. For example, a method in which a difference in peripheral speed is applied to a plurality of rolls, and the roll peripheral speed difference is used to stretch in the longitudinal direction between the rolls. And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions, and the like. Of course, these methods may be used in combination. In the case of the so-called tenter method, driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the risk of breakage and the like can be reduced.

  It is preferable to perform the width maintenance or the transverse stretching in the film forming process by a tenter, and it may be a pin tenter or a clip tenter.

  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. In particular, it is preferably 20 μm or more, and more preferably 35 μm or more. Moreover, 150 micrometers or less, Furthermore 120 micrometers or less are preferable. Most preferably, it is 25 or more and 90 micrometers. If the optical film is thicker than the above region, the polarizing plate after polarizing plate processing becomes too thick, so that it is not suitable for the purpose of thin and light in liquid crystal displays used for notebook personal computers and mobile electronic devices. On the other hand, if it is thinner than the above-mentioned region, it is not preferable because it becomes difficult to develop retardation, the moisture permeability of the film becomes high, and the ability to protect the polarizer from humidity decreases.

  The slow axis or the fast axis of the optical film of the present invention is present in the film plane, and θ1 is preferably −1 ° or more and + 1 ° or less, assuming that the angle formed with the film forming direction is θ1. More preferably, it is 5 ° or more and + 0.5 ° or less. This θ1 can be defined as an orientation angle, and θ1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).

  Each of θ1 satisfying the above relationship can contribute to obtaining high luminance in a display image, suppressing or preventing light leakage, and contributing to obtaining faithful color reproduction in a color liquid crystal display device.

(Liquid crystal display device)
In a liquid crystal display device, a substrate containing liquid crystal is usually arranged between two polarizing plates. However, a polarizer protective film to which the optical film of the present invention is applied has high dimensional stability, so it can be placed at any position. Excellent display properties can be obtained. A polarizer protective film provided with a clear hard coat layer, an antiglare layer, an antireflection layer and the like is preferably used for this part as the polarizer protective film on the outermost surface of the display side of the liquid crystal display device. In the case of a polarizer protective film provided with an optical compensation layer, or a polarizer protective film imparted with an appropriate optical compensation capability by stretching operation, etc. 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 also suitable for improving viewing angle dependency and improving 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.

Example 1
<Molecular weight measurement of cellulose ester>
Since the average molecular weight and molecular weight distribution of 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 and acid other than acetic acid measured by ion chromatography X: degree of substitution with acetic acid Y: degree of substitution with isobutyric acid or pivalic acid SA: 70.09 when Y is isobutyric acid, pivalic acid At 84.12
<Preparation of cellulose>
Indian J. Chem. Tech. , Vol. 3 (1996) p333, cellulose having different molecular weights was fractionated.

  After 10 parts by weight of α-cellulose extracted from Guinem tree (Leucaena Leucocephala) and 12 parts by weight of paraformaldehyde were dissolved in 360 parts by weight of dimethyl sulfoxide (hereinafter abbreviated as DMSO) at 100 ° C. for 5 hours. Then, 620 parts by mass of DMSO was added and cooled to 5 ° C.

  While stirring this DMSO solution, 100 parts by mass of pure water was added, and a solid obtained by filtering the produced precipitate was designated as cellulose H. 100 parts by mass of pure water was again added to the filtered filtrate, and the produced precipitate was designated as cellulose M. Further, 200 parts by mass of pure water was added to the filtrate, and the obtained solid content was defined as cellulose L.

  The obtained cellulose a to c were dissolved in a solution of water: acetone = 50: 50, then refrigerated at 5 ° C. for 24 hours, and then the generated suspended matter was filtered, and water and acetone were distilled off. It refine | purified by drying at 100 degreeC under vacuum for 24 hours.

《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 M, 420 parts by mass (1600 parts by mol) of lithium chloride, 30 parts by mass (80 parts by mol) of acetic acid, 138 parts by mass (220 parts by mol) of pivalic acid, To a solution mixed with 1000 parts by mass (10 times by volume) of acetamide, 380 parts by mass (300 parts by mol) of dicyclohexylcarbodiimide (DCC), 130 parts by mass (170 parts by mol) of dimethylaminopyridine, and dimethylaminopyridine-tosylate 130 parts by weight (70 moles) was 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>
Similar to cellulose ester a1, except that 30 parts by weight (80 parts by mole) of acetic acid was changed to 63 parts by weight (170 parts by weight) and 138 parts by weight (220 parts by weight) of pivalic acid were changed to 82 parts by weight (130 parts by weight). To obtain cellulose ester a2.

<Cellulose ester a3>
Similar to cellulose ester a1, except that 30 parts by weight (80 parts by mole) of acetic acid was changed to 81 parts by weight (220 parts by weight) and 138 parts by weight (220 parts by weight) of pivalic acid were changed to 50 parts by weight (80 parts by weight). To obtain cellulose ester a3.

<Cellulose ester a4>
The same procedure as in the cellulose ester a1 except that 30 parts by weight (80 parts by mole) of acetic acid was changed to 93 parts by weight (250 parts by weight) and 138 parts by weight (220 parts by weight) of pivalic acid was changed to 31 parts by weight (50 parts by weight). Synthesis was performed to obtain cellulose ester a4.

<Cellulose ester a5>
The cellulose ester a3 was changed except that 81 parts by mass (220 parts by mole) of acetic acid was changed to 74 parts by weight (200 parts by weight) and 380 parts by weight (300 parts by weight) of DCC was changed to 355 parts by weight (280 parts by weight). Synthesis was performed to obtain cellulose ester a5.

<Cellulose ester a6>
The same as cellulose ester a3 except that 81 parts by mass (220 parts by mole) of acetic acid was changed to 93 parts by weight (250 parts by mole), and 380 parts by weight (300 parts by weight) of DCC was changed to 418 parts by weight (330 parts by weight). Synthesis was performed to obtain cellulose ester a6.

<Cellulose ester a7>
A cellulose ester a5 was obtained in the same manner as the cellulose ester a3 except that the cellulose ester raw material, cellulose M, was changed to cellulose H.

<Cellulose ester a8>
The cellulose ester a6 was obtained by synthesizing in the same manner as the cellulose ester a3 except that cellulose L was used as the cellulose ester raw material.

<Cellulose ester b1>
Synthesis was carried out in the same manner as the cellulose ester a1 except that 138 parts by mass (220 parts by mol) of pivalic acid was changed to 120 parts by mass (220 parts by mol) of isobutyric acid to obtain a cellulose ester b1.

<Cellulose ester b2>
Synthesis was performed in the same manner as cellulose ester a2 except that 82 parts by mass (130 parts by mol) of pivalic acid was changed to 71 parts by mass (130 parts by mol) of isobutyric acid to obtain cellulose ester b2.

<Cellulose ester b3>
Synthesis was performed in the same manner as cellulose ester a3 except that 50 parts by mass (80 parts by mol) of pivalic acid was changed to 43 parts by mass (80 parts by mol) of isobutyric acid to obtain cellulose ester b3.

<Cellulose ester b4>
Synthesis was carried out in the same manner as cellulose ester a4 except that 12 parts by mass (20 mols) of pivalic acid was changed to 10 parts by mass (20 mols) of isobutyric acid to obtain cellulose ester b4.

<Cellulose ester b5>
A cellulose ester b5 was obtained in the same manner as the cellulose ester b3 except that the cellulose ester raw material, cellulose M, was changed to cellulose H.

<Cellulose ester b6>
A cellulose ester b6 was obtained in the same manner as the cellulose ester b3 except that the cellulose ester raw material, cellulose M, was changed to cellulose L.

<Cellulose ester c1>
Synthesis was performed in the same manner as cellulose ester a3 except that 50 parts by mass (80 parts by mol) of pivalic acid was changed to 36 parts by mass (80 parts by mol) of propionic acid to obtain cellulose ester c1.

<Cellulose ester c2>
Synthesis was performed in the same manner as cellulose ester b3 except that 43 parts by mass (80 mols) of isobutyric acid was changed to 43 parts by mass (80 mols) of butyric acid to obtain cellulose ester c2.

<Film forming method>
90 parts by mass of cellulose ester (a1 to a8, b1 to b6, c1 to c2) synthesized in Synthesis Example, 10 parts by mass of plasticizer, 1.0 part by mass of antioxidant, and 1.0 part by mass of ultraviolet absorber After mixing with the part and powder, it was fed to a twin screw extruder. Since the acid scavenger is a liquid at normal temperature, it was fed into the barrel by a separate liquid feeder. The temperature in the barrel (melting temperature) was the temperature shown in Table 1, the screw rotation speed was 200 rpm, and the film thickness of the optical film finally obtained was 80 μm. The experimental prescriptions such as the types of additives in each sample are also shown in Table 1.

The various additives used for each sample and their 1% mass reduction temperature (Td1.0) are shown below. About 1% mass reduction | decrease temperature (Td1.0), 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.
Polyhydric alcohol ester plasticizer TMPTB (Asahi Denka Trimethylolpropane tribenzoate): 262 ° C., EPEG (Tokyo Kasei ethyl phthalyl ethyl glycolate): 200 ° C.
-Phosphate ester plasticizer PFR (Adeka Stub PFR manufactured by Asahi Denka Co., Ltd.): 273 ° C., TPP (manufactured by Tokyo Chemical Industry Co., Ltd., triphenyl phosphate): 237 ° C.
-Hindered phenol antioxidant I1010 (Irganox 1010 manufactured by Ciba Specialty Chemicals): 295 ° C
-Hindered amine light stabilizer C2020 (Ciba Specialty Chemicals' Cimasorb 2020): 278 ° C
・ Epoxy-based acid scavenger V7190 (Batoflex 7190 manufactured by Atofina): 286 ° C
・ Benzotriazole UV absorber T360 (Cinubin 360 manufactured by Ciba Specialty Chemicals): 323 ° C
Benzophenone UV absorber MBHMB (Aldrich 5,5'-methylenebis (2-hydroxy-4methoxybenzophenone)): 303 ° C

The optical film A1 to A8, B1 to B6, C1 to C2, and E1 to E7 obtained based on the prescription in Table 1 and Konica Minolta Konicattak 8UX as the solution casting film D1 of the comparative example are evaluated as follows. The results are shown in Table 2.
The following evaluation was performed about A1-A7, B1-B5, C1-C3, E1-E4.

<Measurement of elastic modulus>
Each of the produced film samples was cut out by 10 mm in the width direction (TD direction) and 200 mm in the transport direction (MD direction), and conditioned for 12 hours in an atmosphere of 23 ° C. and 55% relative humidity. Tensilon (RTA-100) manufactured by the company is used, the upper and lower ends of the conveying direction (MD direction) are fixed with a chuck, the distance between the chucks is set to 100 mm, and the tensile speed is 100 mm / min. The rate (GPa) was measured. The larger the value, the higher the strength against tension.

<Measurement of in-plane birefringence R0>
Measured using an automatic birefringence meter KOBRA-21ADH manufactured by Oji Scientific Instruments Co., Ltd. under an environment of 23 ° C. and 55% RH, and the thickness is 80 μm due to the difference in refractive index between the X and Y directions in the plane of each transparent film. The value multiplied by assuming that is expressed as birefringence (nm).

<Dimensional stability>
About a film sample, it is cut into a size of 150 mm in the longitudinal direction and 120 mm in the width direction, and is cross-shaped with a sharp blade such as a razor in each of the longitudinal direction (MD) and the width direction (TD) at 100 mm intervals on the film surface. The humidity is adjusted for 24 hours or more in an environment of 23 ° C. and 55% RH, and the distance L1 between the marks in the longitudinal direction and the width direction before processing is measured with a factory microscope. Next, the sample is subjected to high-temperature treatment (conditions: left for 120 hours in an environment of 90 ° C.) or high-temperature and high-humidity treatment (conditions; left for 120 hours in an environment of 80 ° C. and 90% RH). . Again, the sample was conditioned for 24 hours in an environment of 23 ° C. and 55% RH, and the distance L2 between the marks in the longitudinal direction and the width direction after processing was measured with a factory microscope. The rate of change before and after this processing is obtained by the following equation.
(Expression) Dimensional change rate (%) = (L2−L1) / L1 × 100
L1: Distance between marks before treatment L2: Distance between marks after treatment <Light resistance evaluation>
The produced cellulose ester film was put into a light resistance evaluation tester manufactured by Suga Corporation for 500 hours, the light transmittance at 380 nm before and after the feeding was measured, and the attenuation rate ΔT (%) was evaluated.

A: Change rate of less than 2% (a level that does not cause a problem as a polarizer protective film)
○: degree of change 2% or more and less than 10%
Δ: degree of change 10% or more and less than 20% (a level that can be managed as a polarizer protective film)
×: Change of 20% or more (problem level as a polarizer protective film)
Moreover, according to the following procedures, the obtained polarizer protective film was bonded on both surfaces of the polarizer, and the durability as a polarizing plate was evaluated.
(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 E6 were alkali-treated with a 2.5 M / L-sodium hydroxide aqueous solution at 40 ° C. for 60 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 E4 from both sides using a completely saponified polyvinyl alcohol 5% aqueous solution as an adhesive. E4 was produced.

<Polarizing plate durability test: white spot>
Heat treatment (condition: left at 90 ° C. for 100 hours) of two 500 mm × 500 mm polarizing plate samples, and the length of the blank portion of the larger edge of the vertical or horizontal center line portion when it is placed in an orthogonal state The thickness was measured to calculate the ratio to the side length (500 mm), and the following determination was made according to the ratio. The whiteness of the edge can be determined visually by the fact that the edge portion of the polarizing plate that does not allow light to pass through in a straight state is allowed to pass light. In the state of the polarizing plate, the display of the edge portion becomes invisible.

A: Edge blank is less than 5% (a level at which there is no problem as a polarizing plate)
○: White edge of the edge is 5% or more and less than 10% (a level that does not cause a problem as a polarizing plate)
Δ: White edge of edge is 10% or more and less than 20% (a level that can be managed as a polarizing plate)
X: White outline of edge is 20% or more (a problematic level as a polarizing plate)
The evaluation results are shown in Table 2.

  In Table 2, when comparing the film A3 of the present invention formed by melt casting and the film D1 formed by solution casting, the film of the present invention has high dimensional stability and dimensional stability in MD and TD. It can be seen that it is a preferred polarizer protective film with little difference in properties and with few whiteout failures even when it is made into a polarizer.

  Further, when the films A3 and A4 are compared, when the substitution degree Y by pivalic acid is larger than 0.3, the melting temperature can be reduced, the molecular weight is hardly lowered by the melt film forming process, and the dimensional stability of the obtained film is improved. It turns out that it is favorable. Further, when the films A1 and A3 are compared, it can be seen that when the pivalic acid substitution degree Y is less than 2.0, the dimensional stability is high and whiteout failure is less likely to occur.

  Such a tendency is the same even when the substituent is isobutyric acid. However, using pivalic acid tends to lower the melting temperature, which is advantageous in terms of energy and is preferable.

  Furthermore, the film E1 added with an acid scavenger as a stabilizer in the film forming material, the film E2 added with a hindered amine light stabilizer, and the film E3 added with a hindered phenolic antioxidant have a molecular weight in the melt casting method. Can be prevented, and a film with high dimensional stability can be obtained.

  Further, when the films E5 and A3 are compared, it can be seen that the use of a polyhydric alcohol ester type plasticizer as the plasticizer causes less deterioration of the cellulose ester, and the dimensional stability of the obtained film is enhanced. Further, as in the case of the film E6, if the ultraviolet absorber is not a benzotriazole type, the light resistance is low and the ultraviolet absorption ability is deteriorated by the light resistance test. However, since the film has high dimensional stability, it is not exposed to external light. It was an optical film that can be used only for the inner polarizer protective film.

Example 2
(Characteristic evaluation as a liquid crystal display device)
The polarizing plate of 32 type TFT type color liquid crystal display Vega (manufactured by Sony Corporation) was peeled off, and each polarizing plate produced above was cut according to the size of the liquid crystal cell. With the liquid crystal cell sandwiched, the two polarizing plates prepared above were stuck so as to be orthogonal to each other so that the polarizing axis of the polarizing plate was not changed, and a 32 type TFT type color liquid crystal display was prepared. When the characteristics as a polarizing plate were evaluated, the polarizing plates A3 to A6, B2 to B4, and E2 to E4 of the present invention showed high contrast and excellent display properties. Thereby, it was confirmed that it is excellent as a polarizing plate for an image display device such as a liquid crystal display.

Claims (2)

In the polarizing plate having a sandwiched on both sides of the polarizer with two polarizing plate protective film, the two polarizing plate protective fill beam, characterized in that it contains acetate isobutyrate cellulose or acetate pivalate cellulose Polarizer. The polarizing plate according to claim 1, wherein the polarizing plate protective film contains a benzotriazole-based ultraviolet absorber having a Td (1.0) of 250 ° C. or higher.