JP6572532B2 - Resin composition and optical compensation film using the same - Google Patents

Description

  The present invention relates to a resin composition and an optical compensation film using the same, and more particularly to a resin composition and an optical compensation film for a liquid crystal display excellent in retardation characteristics and wavelength dispersion characteristics.

  Liquid crystal displays are widely used as the most important display devices in the multimedia society, including cellular phones, computer monitors, laptop computers, and televisions. Many optical films are used in liquid crystal displays to improve display characteristics. In particular, the optical compensation film plays a major role in improving contrast and compensating for color tone when viewed from the front or obliquely.

  There are many liquid crystal displays such as vertical alignment type (VA-LCD), in-plane alignment type liquid crystal (IPS-LCD), super twist nematic type liquid crystal (STN-LCD), reflection type liquid crystal display, and transflective type liquid crystal display. There is a method, and an optical compensation film suitable for the display is required.

  As a conventional optical compensation film, a stretched film made of cellulose resin, polycarbonate, cyclic polyolefin, or the like is used. In particular, a film made of a cellulose-based resin such as a triacetyl cellulose film is widely used because it has good adhesion to polyvinyl alcohol as a polarizer.

  However, an optical compensation film made of a cellulose resin has several problems. For example, a cellulose resin film is processed into an optical compensation film having a retardation value adapted to various displays by adjusting stretching conditions, but the three-dimensional film obtained by uniaxial or biaxial stretching of the cellulose resin film. In order to manufacture an optical compensation film having a refractive index of ny ≧ nx> nz and other three-dimensional refractive indexes, for example, a three-dimensional refractive index such as ny> nz> nx or ny = nz> nx. Requires a special stretching method such as attaching a heat-shrinkable film to one or both sides of the film, heat-stretching the laminate, and applying a shrinking force in the thickness direction of the polymer film, and the refractive index (position It is also difficult to control the phase difference value (see, for example, Patent Documents 1 to 3). Here, nx is the refractive index in the fast axis direction (the direction with the smallest refractive index) in the film surface, ny is the refractive index in the slow axis direction (the direction in which the refractive index is the largest) in the film surface, and nz is the film surface. The refractive index outside (thickness direction) is shown.

  Cellulosic resin films are generally produced by a solvent casting method. Since a cellulose resin film formed by a casting method has an out-of-plane retardation (Rth) of about 40 nm in the film thickness direction, IPS mode liquid crystal There are problems such as color shift in displays. Here, the out-of-plane phase difference (Rth) is a phase difference value represented by the following equation.

Rth = [(nx + ny) / 2−nz] × d
(Where nx is the refractive index in the fast axis direction in the film plane, ny is the refractive index in the slow axis direction in the film plane, nz is the refractive index outside the film plane, and d is the film thickness). )
Moreover, the retardation film which consists of a fumarate-type resin is proposed (for example, refer patent document 4).

  However, the three-dimensional refractive index of the stretched film made of a fumarate ester resin is nz> ny> nx, and in order to obtain an optical compensation film exhibiting the above three-dimensional refractive index, it is laminated with another optical compensation film or the like. Etc. are necessary.

  Then, as an optical compensation film which shows the said three-dimensional refractive index, the resin composition and the optical compensation film using the same are proposed (for example, refer patent document 5-patent document 7).

  Although Patent Documents 5 to 7 have excellent performance as an optical compensation film, a film thickness thicker than that of the present invention is required for the purpose of achieving the desired Re. In general, a retardation film is also used as a reflection type liquid crystal display device, a touch panel or an organic EL antireflection layer. In this application, a retardation film (hereinafter referred to as “reverse wavelength”) having a larger retardation in a longer wavelength region. However, Patent Documents 5 to 7 do not have any description about use as a reverse wavelength dispersion film.

  When a reverse wavelength dispersion film is used as the antireflection layer, the phase difference is preferably about ¼ of the measurement wavelength λ, and the ratio Re (450) / Re (550) of the retardation at 450 nm to the retardation at 550 nm is 0. It is preferably close to 81. And when the thickness reduction of a display apparatus is considered, it is calculated | required that the reverse wavelength dispersion film used is also thin. Various retardation films have been developed for the required characteristics as described above.

  As such a retardation film, a retardation plate having reverse wavelength dispersion obtained by blending a polymer having positive intrinsic birefringence and a polymer having negative intrinsic birefringence is disclosed (for example, , See Patent Document 8). However, this document includes a norbornene-based polymer as a polymer having positive intrinsic birefringence, a copolymer of styrene and maleic anhydride as a polymer having negative intrinsic birefringence, and a composition obtained by blending these polymers. Although a product is disclosed, a retardation plate using the composition does not satisfy the relationship between Re and Nz, which is desirable as a retardation property of a retardation film.

Japanese Patent No. 2818983 JP-A-5-297223 JP-A-5-323120 JP 2008-64817 A JP 2013-28741 A JP 2014-125609 A JP 2014-125610 A JP 2001-337222 A

  The present invention has been made in view of the above problems, and an object thereof is to provide a resin composition suitable for an optical compensation film and an optical compensation film excellent in retardation and wavelength dispersion characteristics using the resin composition. is there.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a specific cellulose resin and a specific fumarate ester copolymer, an optical compensation film using the same, and a method for producing the same However, the present inventors have found that the above problems can be solved and have completed the present invention. That is, the present invention comprises a resin comprising 30 to 99% by weight of a cellulose resin represented by a predetermined formula and 1 to 70% by weight of a fumaric acid ester copolymer represented by a predetermined formula as a resin component. A composition, an optical compensation film using the composition, and a method for producing the same.

  Hereinafter, the present invention will be described in detail.

  The resin composition of the present invention comprises 30 to 99% by weight of a cellulose resin represented by the following general formula (1), 20 mol% or more of a fumaric acid diester residue unit represented by the following general formula (2), and the following general formula It is a resin composition characterized by containing 1 to 70% by weight of a fumaric acid ester copolymer containing 5 mol% or more of p-substituted cinnamate residue units represented by the formula (3).

_{(Wherein, R 1, R 2, R} 3 each independently represent hydrogen or a substituent having 1 to 12 carbon atoms.)

(In formula, R < ₄ >, R < ₅ > shows a C1-C12 alkyl group.)

(In the formula, R ₆ represents an alkyl group having 1 to 12 carbon atoms. X represents a nitro group, a bromo group, an iodo group, a cyano group, a chloro group, a sulfonic acid group, a carboxylic acid group, or a phenyl group.)
Examples of the cellulose resin of the present invention include cellulose ether, cellulose ester, cellulose ether ester, and cellulose acylate. The resin composition of the present invention may contain one or more of these cellulose resins.

Since the cellulose resin of the present invention has excellent mechanical properties and excellent moldability during film formation, standard polystyrene obtained from an elution curve measured by gel permeation chromatography (GPC). The converted number average molecular weight (Mn) is preferably 1 × 10 ³ to 1 × 10 ⁶ , more preferably 5 × 10 ³ to 2 × 10 ⁵ .

  As the cellulose-based resin of the present invention, cellulose ether is preferable because it is excellent in compatibility with the fumaric acid ester polymer, has a large in-plane retardation Re, and is excellent in stretch processability.

  Hereinafter, cellulose ether preferable as the cellulose resin used in the optical compensation film of the present invention will be described.

  Cellulose ether, which is a cellulose resin of the present invention, is a polymer in which β-glucose units are linearly polymerized, and a part or all of hydroxyl groups at the 2nd, 3rd and 6th positions of the glucose unit are etherified. It is a polymer. Examples of the cellulose ether of the present invention include alkyl celluloses such as methyl cellulose, ethyl cellulose, and propyl cellulose; hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; aralkyl celluloses such as benzyl cellulose and trityl cellulose; cyanoalkyl celluloses such as cyanethyl cellulose. Carboxyalkyl celluloses such as carboxymethyl cellulose and carboxyethyl cellulose; carboxyalkyl alkyl celluloses such as carboxymethyl methyl cellulose and carboxymethyl ethyl cellulose; aminoalkyl celluloses such as aminoethyl cellulose;

  The degree of substitution (degree of etherification) of the cellulose ether through the oxygen atom of the hydroxyl group of cellulose is the ratio of etherification of the hydroxyl group of cellulose for each of the 2-position, 3-position and 6-position (100% Etherification means a substitution degree of 1). From the viewpoints of solubility, compatibility, and stretch processability, the total substitution degree DS of the ether group is preferably 1.5 to 3.0 (1.5 ≦ DS ≦ 3.0), more preferably 1.8 to 2.8. It is preferable that a cellulose ether has a C1-C12 substituent from the point of solubility and compatibility. Examples of the substituent having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decanyl group, dodecanyl group, isobutyl group, and t-butyl group. Cyclohexyl group, phenonyl group, benzyl group, naphthyl group and the like. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, which are alkyl groups having 1 to 5 carbon atoms, are preferable from the viewpoint of solubility and compatibility. The cellulose group used in the present invention may have only one type of ether group or may have two or more types of ether groups. In addition to the ether group, it may have an ester group.

  Cellulose ether is generally synthesized by alkali-decomposing cellulose pulp obtained from wood or cotton and etherifying the alkali-decomposed cellulose pulp. As the alkali, hydroxides of alkali metals such as lithium, potassium and sodium, ammonia and the like can be used. The alkalis are generally used as an aqueous solution. And the cellulose pulp made into alkalinity is etherified by contacting with the etherifying agent used according to the kind of cellulose ether. Examples of etherifying agents include halogenated alkyls such as methyl chloride and ethyl chloride; aralkyl halides such as benzyl chloride and trityl chloride; halocarboxylic acids such as monochloroacetic acid and monochloropropionic acid; ethylene oxide, propylene oxide, butylene oxide and the like. These ether oxide agents can be used alone or in combination of two or more.

  If necessary, after completion of the reaction, depolymerization treatment may be performed with hydrogen chloride, hydrogen bromide, hydrochloric acid, sulfuric acid or the like for viscosity adjustment.

  The fumaric acid ester copolymer (hereinafter referred to as the fumaric acid ester copolymer) contained in the resin composition of the present invention is 20 mol% or more of the fumaric acid diester residue unit represented by the general formula (2) and the general formula ( If it is a polymer which contains 5 mol% or more of p-position substituted cinnamic acid ester residue units shown by 3), there will be no restriction | limiting in particular. When the fumaric acid diester residue unit is less than 20 mol%, the polymerizability is lowered, and when the p-position substituted cinnamate residue unit is 5 mol% or less, the retardation development property is lowered. That is, the present invention provides a fumaric acid ester copolymer in which the fumaric acid ester copolymer contains at least 20 mol% of fumaric acid diester residue units and at least 5 mol% of p-substituted cinnamate ester residue units. By being a polymer, the copolymer has a high polymerizability, and when the resin composition according to the present invention is used as an optical compensation film, the retardation development is further improved. It is.

R _{4 and} R ₅ which are ester substituents of the fumaric acid diester residue unit represented by the general formula (2) in the fumaric acid ester copolymer are alkyl groups having 1 to 12 carbon atoms, for example, methyl group, ethyl Group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, s-pentyl group, t-pentyl group, s-hexyl group, t-hexyl group, 2-ethylhexyl group, cyclopropyl Group, cyclopentyl group, cyclohexyl group and the like. As the fumarate diester residue unit represented by the general formula (2), for example, dimethyl fumarate residue unit, diethyl fumarate residue unit, ethyl isopropyl fumarate residue unit, ethyl t-butyl fumarate residue unit , Di-n-propyl fumarate residue unit, diisopropyl fumarate residue unit, isopropyl t-butyl fumarate residue unit, di-n-butyl fumarate residue unit, di-s-butyl fumarate unit Di-t-butyl fumarate residue units, di-n-pentyl fumarate residue units, di-s-pentyl fumarate residue units, di-t-pentyl fumarate residue units, di-n fumarate units -Hexyl residue unit, di-s-hexyl fumarate unit, di-t-hexyl fumarate unit, di-2-ethylhexyl fumarate unit, dicyclopropyl fumarate unit Fumaric acid dicyclopentyl residue unit, and fumaric acid dicyclohexyl residue units. Among these, diethyl fumarate residue unit, diisopropyl fumarate residue unit, di-t-butyl fumarate residue unit, ethyl isopropyl fumarate residue unit, ethyl fumarate unit from the viewpoint of polymerizability and retardation development. A t-butyl residue unit and an isopropyl fumarate t-butyl residue unit are preferred, and a diethyl fumarate residue unit, a diisopropyl fumarate residue unit, and a di-t-butyl fumarate residue unit are more preferred.

R ₆ which is an ester substituent of the p-substituted cinnamate residue unit represented by the general formula (3) in the fumarate ester copolymer is an alkyl group having 1 to 12 carbon atoms, such as a methyl group, Ethyl group, propyl group, isopropyl group, s-butyl group, t-butyl group, s-pentyl group, t-pentyl group, s-hexyl group, t-hexyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group And a cyclohexyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group, which are alkyl groups having 1 to 4 carbon atoms, are preferable from the viewpoint of compatibility with the cellulose resin. The substituent X is a substituent that contributes to an improvement in negative retardation, and is a nitro group, bromo group, iodo group, cyano group, chloro group, sulfonic acid group, carboxylic acid group, or phenyl group. Examples of p-substituted cinnamate residue units represented by the general formula (3) include, for example, 4-nitrocinnamate methyl residue unit, 4-nitrocinnamate ethyl residue unit, 4-nitrocinnamate isopropyl residue Base unit, 4-nitrocinnamic acid n-propyl residue unit, 4-nitrocinnamic acid n-butyl residue unit, 4-nitrocinnamic acid sec-butyl residue unit, 4-nitrocinnamic acid tert-butyl residue unit 4-Nitrocinnamic acid 2-ethylhexyl residue unit, 4-bromocinnamic acid methyl residue unit, 4-bromocinnamic acid ethyl residue unit, 4-bromocinnamic acid isopropyl residue unit, 4-bromocinnamic acid n- Propyl residue unit, 4-bromocinnamic acid n-butyl residue unit, 4-bromocinnamic acid sec-butyl residue unit, 4-bromocinnamic acid tert-butyl residue unit, 4-bromocinnamic acid 2-ethyl ester Ruhexyl residue unit, 4-iodocinnamate methyl residue unit, 4-iodocinnamate ethyl residue unit, 4-iodocinnamate isopropyl residue unit, 4-iodocinnamate n-propyl residue unit, 4-iodosilicate Cinnamic acid n-butyl residue unit, 4-iodocinnamic acid sec-butyl residue unit, 4-iodocinnamic acid tert-butyl residue unit, 4-iodocinnamic acid 2-ethylhexyl residue unit, 4-cyanocinnamic acid Methyl residue unit, 4-cyanocinnamic acid ethyl residue unit, 4-cyanocinnamic acid isopropyl residue unit, 4-cyanocinnamic acid n-propyl residue unit, 4-cyanocinnamic acid n-butyl residue unit, 4 -Cyanocinnamic acid sec-butyl residue unit, 4-cyanocinnamic acid tert-butyl residue unit, 4-cyanocinnamic acid 2-ethylhexyl residue unit, 4-sulfonic acid methyl cinnamate residue Position, 4-sulfonic acid ethyl cinnamate residue unit, 4-sulfonic acid cinnamate isopropyl residue unit, 4-sulfonic acid cinnamate n-propyl residue unit, 4-sulfonic acid cinnamate n-butyl Residue unit, 4-sulfonic acid cinnamate sec-butyl residue unit, 4-sulfonic acid cinnamate tert-butyl residue unit, 4-sulfonic acid cinnamate 2-ethylhexyl residue unit, 4-carboxylic acid Ethyl cinnamate residue units, 4-carboxylic acid isopropyl cinnamate residue units, 4-carboxylic acid cinnamate n-propyl residue units, 4-carboxylate cinnamate n-butyl residue units, 4- Carboxylic cinnamate sec-butyl residue unit, 4-carboxylic cinnamate tert-butyl residue unit, 4-carboxylic cinnamate 2-ethylhexyl residue unit, 4-phenyl cinnamate methyl residue unit 4-Phenylcinnamic acid Residue unit, 4-phenylcinnamic acid isopropyl residue unit, 4-phenylcinnamic acid n-propyl residue unit, 4-phenylcinnamic acid n-butyl residue unit, 4-phenylcinnamic acid sec- Examples thereof include a butyl residue unit, a 4-phenylcinnamic acid tert-butyl residue unit, and a 4-phenylcinnamic acid 2-ethylhexyl residue unit.

  The fumaric acid ester copolymer of the present invention is particularly excellent in polymerizability and compatibility. Therefore, the fumaric acid diester residue unit is 20 to 90 mol%, and the p-position substituted silica represented by the general formula (3) is used. A fumaric acid ester copolymer containing 5 to 75 mol% of a cinnamate residue unit and 5 to 30 mol% of a fumaric acid monoester residue unit represented by the following general formula (4) is preferable. Here, when the fumaric acid monoester residue unit is 30 mol% or more, it may be difficult to develop retardation characteristics.

(In the formula, R ₇ represents an alkyl group having 1 to 12 carbon atoms.)
In addition, when the fumarate diester residue unit is a diethyl fumarate residue, the fumaric acid ester copolymer of the present invention is fumaric acid if the p-position cinnamate residue unit is 75 mol% or less. Even if it does not contain a monoester residue unit, it will be particularly excellent in polymerizability and compatibility, so that a diethyl fumarate residue unit of 20 to 95 mol%, p-position substituted cinnamon represented by the general formula (3) It is preferable that it is 5-75 mol% of acid ester residue units and 0-30 mol% of fumaric acid monoester residue units represented by the general formula (4). In addition, when the fumarate diester residue unit is a diethyl fumarate residue unit, a fumaric acid ester polymer having excellent compatibility is obtained, so that the diethyl fumarate residue unit is 20 to 90 mol%, the general formula ( The p-substituted cinnamate residue units represented by 3) are more preferably 5 to 75 mol%, and the fumaric acid monoester residue units represented by formula (4) are more preferably 5 to 30 mol%.

R ₇ which is an ester substituent of a fumaric acid monoester residue unit in the fumaric acid ester copolymer is an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, s- Examples thereof include a butyl group, a t-butyl group, an s-pentyl group, a t-pentyl group, an s-hexyl group, a t-hexyl group, a 2-ethylhexyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group, which are ester groups having 1 to 4 carbon atoms, are preferable from the viewpoint of compatibility with cellulose ether. As the fumarate monoester residue unit represented by the general formula (4), for example, monomethyl fumarate residue, monoethyl fumarate residue, mono-n-propyl fumarate residue, monoisopropyl fumarate residue, fumarate Acid mono-n-butyl residue, mono-s-butyl fumarate residue, mono-t-butyl fumarate residue, mono-n-pentyl fumarate residue, mono-s-pentyl fumarate residue, fumarate Acid mono-t-pentyl residue, mono-n-hexyl fumarate residue, mono-s-hexyl fumarate residue, mono-t-hexyl fumarate residue, mono-2-ethylhexyl fumarate, mono fumarate A cyclopropyl residue, a monocyclopentyl fumarate residue, a monocyclohexyl fumarate residue, etc. are mentioned. Among these, since the compatibility with cellulose ether is good, the unit is monomethyl fumarate residue, monoethyl fumarate residue, monoisopropyl fumarate residue, mono-n-propyl fumarate residue, fumaric acid A fumaric acid monoester residue unit selected from a mono-n-butyl residue unit, a mono-s-butyl fumarate residue unit, and a mono-t-butyl fumarate residue unit is preferred.

  Further, in terms of phase difference characteristics and compatibility, the fumaric acid ester polymer of the present invention is 20 to 94.5 mol% of a fumaric acid diester residue unit represented by the general formula (2). 5 to 75 mol% of p-substituted cinnamate residue units shown, and an acrylate residue unit shown by the following general formula (5), a methacrylic acid ester residue unit shown by the following general formula (6) And 0.5-30 mol% of a residue unit selected from the group consisting of an acrylic amide residue unit represented by the following general formula (7) and a methacrylic acid amide residue unit represented by the following general formula (8) A fumarate polymer is also preferably used.

(In formula, R < ₈ >, R < ₉ >, R < ₁₀ >, R < ₁₁ > shows a C1-C12 alkyl group, an alkylene group, or an ether group each independently.)
The fumaric acid ester copolymer can be copolymerized with fumaric acid diesters and p-position substituted cinnamic acid esters, with the total amount of monomers including the fumaric acid diester and p-position substituted cinnamic acid ester being 100 mol%. 0 to 20 mol% of the monomer residue unit may be included.

  Examples of the residue units of other monomers copolymerizable with the fumaric acid diesters and p-substituted cinnamate esters include styrene residues such as styrene residues and α-methylstyrene residues; Acrylic acid residue; Acrylic acid ester residue such as methyl acrylate residue, ethyl acrylate residue, butyl acrylate residue; methacrylic acid residue; methyl methacrylate residue, ethyl methacrylate residue, methacrylic acid Methacrylic acid ester residues such as butyl residue; vinyl ester residues such as vinyl acetate residue and vinyl propionate residue; vinyl ether residues such as methyl vinyl ether residue, ethyl vinyl ether residue and butyl vinyl ether residue; N- such as N-methylmaleimide residue, N-cyclohexylmaleimide residue, N-phenylmaleimide residue Substituted maleimide residues; acrylonitrile residues; methacrylonitrile residues; cinnamic acid residues; methyl cinnamate residues, ethyl cinnamate residues, isopropyl cinnamate residues, n-propyl cinnamate residues Cinnamate residues such as n-butyl cinnamate residue, s-butyl cinnamate residue, t-butyl cinnamate residue, 2-ethylhexyl cinnamate residue; ethylene residue, propylene Examples thereof include one or more of olefin residues such as residues; vinyl pyrrolidone residues; vinyl pyridine residues and the like.

The fumaric acid ester copolymer is particularly excellent in mechanical properties and excellent in moldability during film formation. Therefore, a standard obtained from an elution curve measured by gel permeation chromatography (GPC). The number average molecular weight (Mn) in terms of polystyrene is preferably 1 × 10 ^{3 to} 5 × 10 ⁶ , and more preferably 5 × 10 ³ to 2 × 10 ⁵ .

  The ratio of the composition of the cellulose resin and the fumarate copolymer in the resin composition of the present invention is 30 to 99% by weight of the cellulose resin and 1 to 70% by weight of the fumarate copolymer. When the cellulosic resin is less than 30% by weight (when the fumaric acid ester copolymer exceeds 70% by weight), or when the cellulosic resin exceeds 99% by weight (the fumaric acid ester copolymer is less than 1% by weight) In the case), it is difficult to control the phase difference. Preferably, the cellulose-based resin is 30 to 90% by weight and the fumaric acid ester copolymer is 10 to 70% by weight, more preferably the cellulose-based resin is 40 to 80% by weight and the fumaric acid ester copolymer is 20 to 60% by weight. is there.

  The fumarate ester copolymer may be produced by any method as long as the fumarate ester copolymer is obtained. For example, fumaric acid diesters and p-substituted cinnamate esters, Some of them can be produced by carrying out radical polymerization using a monomer copolymerizable with fumaric acid diesters and p-substituted cinnamate esters. Examples of the p-substituted cinnamates include methyl 4-nitrocinnamate, ethyl 4-nitrocinnamate, isopropyl 4-nitrocinnamate, 4-nitronitrocinnamate, 4-nitrocinnamic acid n, and the like. -Butyl, 4-nitrocinnamic acid sec-butyl, 4-nitrocinnamic acid tert-butyl, 4-nitrocinnamic acid 2-ethylhexyl, 4-bromocinnamic acid ethyl, 4-bromocinnamic acid ethyl, 4-bromocinnamic acid isopropyl 4-bromocinnamic acid n-propyl, 4-bromocinnamic acid n-butyl, 4-bromocinnamic acid sec-butyl, 4-bromocinnamic acid tert-butyl, 4-bromocinnamic acid 2-ethylhexyl, 4-iodocinnamic 4-methyl iodocinnamate 4-methyl iodocinnamate, 4-isopropyl iodocinnamate, 4-iodocinnamate n-propyl, 4-iodocinnamate n-butyl 4-tert-butyl 4-iodocinnamate, 4-tert-butyl 4-iodocinnamate, 4-ethylhexyl 4-iodocinnamate, methyl 4-cyanocinnamate, 4-cyanocyanocinnamate, 4-isopropyl cyanocyanocinnamate, 4-cyanocinnamic acid n-propyl, 4-cyanocinnamic acid n-butyl, 4-cyanocinnamic acid sec-butyl, 4-cyanocinnamic acid tert-butyl, 4-cyanocinnamic acid 2-ethylhexyl, 4-sulfonic acid silicic acid Methyl cinnamate, 4-sulfonic acid ethyl cinnamate, 4-sulfonic acid isopropyl cinnamate, 4-sulfonic acid n-propyl cinnamate, 4-sulfonic acid n-butyl cinnamate, 4-sulfonic acid cinnamon Sec-Butyl acid, tert-Butyl 4-sulfonate cinnamate, 2-ethylhexyl 4-sulfonate cinnamate, ethyl 4-carboxylate cinnamate, 4-carbo Isopropyl cinnamate, 4-carboxylate n-propyl cinnamate, 4-carboxylate n-butyl cinnamate, 4-carboxylate cinnamate sec-butyl, 4-carboxylate cinnamate tert-butyl, 2-ethylhexyl 4-carboxylate cinnamate, methyl 4-phenylcinnamate, ethyl 4-phenylcinnamate, isopropyl 4-phenylcinnamate, n-propyl 4-phenylcinnamate, 4-phenylcinnamate Examples include n-butyl acid, sec-butyl 4-phenylcinnamate, tert-butyl 4-phenylcinnamate, 2-ethylhexyl 4-phenylcinnamate, and the like. When fumaric acid monoesters are used as the copolymerizable monomer, examples of the fumaric acid monoesters include monomethyl fumarate, monoethyl fumarate, mono-n-propyl fumarate, and monofumarate. Isopropyl, mono-n-butyl fumarate, mono-s-butyl fumarate, mono-t-butyl fumarate, mono-n-pentyl fumarate, mono-s-pentyl fumarate, mono-t-pentyl fumarate, Examples include mono-n-hexyl fumarate, mono-s-hexyl fumarate, mono-t-hexyl fumarate, mono-2-ethylhexyl fumarate, monocyclopropyl fumarate, monocyclopentyl fumarate, monocyclohexyl fumarate, etc. It is done.

  In the present invention, examples of other copolymerizable monomers used in radical polymerization include styrenes such as styrene and α-methylstyrene; acrylic acid; methyl acrylate, ethyl acrylate, butyl acrylate, and the like. Acrylic acid esters; Methacrylic acid; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; Vinyl esters such as vinyl acetate and vinyl propionate; Acrylonitrile; Methacrylonitrile; Methyl cinnamate; Cinnamic acid esters such as ethyl cinnamate and propyl cinnamate; cinnamic acid; olefins such as ethylene and propylene; vinyl pyrrolidone; one or more of vinyl pyridine and the like.

  As the radical polymerization method, for example, any of a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a precipitation polymerization method, an emulsion polymerization method and the like can be employed.

  Examples of the polymerization initiator used for radical polymerization include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, and dicumyl peroxide. , Organic peroxides such as 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane; 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′- Azo series such as azobis (2-butyronitrile), 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (cyclohexane-1-carbonitrile) An initiator etc. are mentioned.

  And there is no restriction | limiting in particular as a solvent which can be used in solution polymerization method or precipitation polymerization method, For example, aromatic solvents, such as benzene, toluene, xylene; Alcohol solvents, such as methanol, ethanol, propyl alcohol, and butyl alcohol; Examples thereof include dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, isopropyl acetate, and a mixed solvent thereof.

  Moreover, the polymerization temperature at the time of performing radical polymerization can be suitably set according to the decomposition temperature of a polymerization initiator, and generally it is preferable to carry out in the range of 30-150 degreeC.

  The resin composition of the present invention may contain an antioxidant in order to improve the thermal stability. Antioxidants include, for example, hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants, amine antioxidants, hydroxylamine antioxidants, vitamin E series Antioxidants and other antioxidants may be mentioned, and these antioxidants may be used alone or in combination of two or more.

  The resin composition of the present invention may contain a hindered amine light stabilizer or an ultraviolet absorber in order to improve the weather resistance. Examples of the ultraviolet absorber include benzotriazole, benzophenone, triazine, benzoate and the like.

  In the resin composition of the present invention, a compound known as a so-called plasticizer may be added for the purpose of improving mechanical properties, imparting flexibility, imparting water absorption resistance, reducing water vapor transmission rate, adjusting retardation, etc. Examples of the plasticizer include phosphate esters and carboxylic acid esters. Acrylic polymers are also used. Examples of phosphate esters include triphenyl phosphate, tricresyl phosphate, phenyl diphenyl phosphate, and the like. Examples of the carboxylic acid ester include phthalic acid ester and citric acid ester. Examples of the phthalic acid ester include dimethyl phthalate, diethyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, and diethyl hexyl phthalate. Examples include triethyl and acetyl tributyl citrate. In addition, butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, triacetin, trimethylolpropane tribenzoate and the like can also be mentioned. Alkylphthalylalkyl glycolates are also used for this purpose. The alkyl in the alkylphthalylalkyl glycolate is an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl phthalyl alkyl glycolate include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl glycolate Ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, propyl phthalyl ethyl glycolate, methyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, Butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl Rikoreto, octyl phthalyl methyl glycolate, octyl phthalyl ethyl glycolate, and the like. Two or more of these plasticizers may be mixed and used.

  The resin composition of the present invention may contain an additive having an aromatic hydrocarbon ring or an aromatic heterocycle for the purpose of adjusting the phase difference. The birefringence Δn represented by the following formula (A) of the additive used for the purpose of adjusting the phase difference is not particularly limited. However, since it is an optical compensation film having excellent optical characteristics, it is preferably 0.00. It is 05 or more, More preferably, it is 0.05-0.5, Most preferably, it is 0.1-0.5. The Δn of the additive can be obtained by molecular orbital calculation.

Δn = ny−nx (A)
(In the formula, nx represents the refractive index in the fast axis direction of the additive molecule, and ny represents the refractive index in the slow axis direction of the additive molecule.)
When the resin composition of the present invention contains an additive having an aromatic hydrocarbon ring or aromatic heterocycle, the additive having an aromatic hydrocarbon ring or aromatic heterocycle in the resin composition of the present invention Is not particularly limited as to the number of aromatic hydrocarbon rings or aromatic heterocycles in the molecule, but it is preferably 1 to 12 in order to provide an optical compensation film having excellent optical properties. Preferably 1-8. Examples of the aromatic hydrocarbon ring include a 5-membered ring, a 6-membered ring, a 7-membered ring, or a condensed ring composed of two or more aromatic rings. Examples of the aromatic heterocycle include a furan ring. Thiophene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring, 1,3,5-triazine ring and the like.

  The aromatic hydrocarbon ring or aromatic heterocycle may have a substituent. Examples of the substituent include a hydroxyl group, an ether group, a carbonyl group, an ester group, a carboxylic acid residue, an amino group, and an imino group. Amide group, imide group, cyano group, nitro group, sulfonyl group, sulfonic acid residue, phosphonyl group, phosphonic acid residue and the like.

  Examples of the additive having an aromatic hydrocarbon ring or aromatic heterocycle used in the present invention include tricresyl phosphate, trixylenyl phosphate, triphenyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, Phosphate ester compounds such as bisphenol A bis (diphenyl phosphate); dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dinormal octyl phthalate, 2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl Phthalate compounds such as phthalate, didecyl phthalate, diisodecyl phthalate; tributyl trimellitate, tri-normal hex Trimellitic acid ester-based compounds such as rutrimellitate, tri (2-ethylhexyl) trimellitate, tri-normal octyl trimellitate, tri-isoctyl trimellitate, tri-isodecyl trimellitate; tri (2-ethylhexyl) pyromellitate, Pyromellitic acid such as tetrabutyl pyromellitate, tetra-normal hexyl pyromellitate, tetra (2-ethylhexyl) pyromellitate, tetra-normal octyl pyromellitate, tetra-isooctyl pyromellitate, tetra-isodecyl pyromellitate Ester compounds; benzoic acid ester compounds such as ethyl benzoate, isopropyl benzoate, ethyl paraoxybenzoate; phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenol Salicylic acid ester compounds such as rusalicylate; Glycolic acid ester compounds such as methylphthalylethyl glycolate, ethylphthalylethyl glycolate, butylphthalylbutyl glycolate; 2- (2′-hydroxy-5′-t- Benzotriazole compounds such as butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole; 2-hydroxy-4-methoxybenzophenone, 2,2′- Benzophenone compounds such as dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, N-benzenesulfone Sulfons such as amides Mido compounds, 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl)- 1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-butoxyphenyl)- Examples thereof include triazine compounds such as 1,3,5-triazine, preferably tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, 2-hydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetra Examples thereof include hydroxybenzophenone, and these can be used alone or in combination of two or more as required.

  When an additive having an aromatic hydrocarbon ring or an aromatic heterocycle is contained in the resin composition of the present invention, the aromatic carbonization in the resin composition of the present invention is preferable from the viewpoint of optical properties and mechanical properties. The ratio of the additive having a hydrogen ring or an aromatic heterocycle is 0.01 to 30% by weight (the above resin component: 70 to 99.99% by weight), more preferably 0.01 to 20% by weight, Most preferably, it is 0.01 to 15 weight%.

  The resin composition of the present invention contains other polymers, surfactants, polymer electrolytes, conductive complexes, pigments, dyes, antistatic agents, antiblocking agents, lubricants and the like within the scope of the invention. May be.

  The resin composition of the present invention can be obtained by blending a cellulose resin and a fumarate ester copolymer.

  As a blending method, methods such as melt blending and solution blending can be used. The melt blending method in the case where an additive having an aromatic hydrocarbon ring or an aromatic heterocycle is contained in the resin composition of the present invention is a method in which a resin and an aromatic hydrocarbon ring or an aromatic heterocycle are formed by heating. In this method, the additive is melted and kneaded. The solution blending method is a method in which a resin and an additive having an aromatic hydrocarbon ring or aromatic heterocycle are dissolved in a solvent and blended. Solvents used for solution blending include, for example, chlorinated solvents such as methylene chloride and chloroform; aromatic solvents such as toluene and xylene; alcohol solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol and propanol; dioxane and tetrahydrofuran An ether solvent such as dimethylformamide, N-methylpyrrolidone or the like can be used. It is also possible to blend after dissolving each resin and an additive having an aromatic hydrocarbon ring or aromatic heterocycle in a solvent, and it is also possible to dissolve each resin powder, pellets, etc. in a solvent after kneading. Is possible. The obtained blended resin solution can be poured into a poor solvent to precipitate the resin composition, or it can be used in the production of an optical compensation film as it is.

  The optical compensation film using the resin composition of the present invention preferably has a thickness of 5 to 200 μm, more preferably 10 to 100 μm, from the viewpoints of handleability of the film and suitability for thinning of the optical member. 20-80 micrometers is especially preferable and 20-60 micrometers is the most preferable.

  The retardation characteristics of the optical compensation film using the resin composition of the present invention vary depending on the target optical compensation film. For example, 1) In-plane retardation (Re) represented by the following formula (1) is Preferably it is 80-300 nm, More preferably, it is 100-300 nm, Most preferably, it is 100-280 nm, Comprising: Nz coefficient shown by following formula (2) becomes like this. Preferably it is 0.35-0.65, More preferably, it is 0.45. 2) The in-plane retardation (Re) is preferably 50 to 200 nm, more preferably 80 to 160 nm, and the Nz coefficient is preferably −0.2 to 0.2, more preferably. Is -0.1 to 0.1, 3) The in-plane retardation (Re) is preferably 0 to 20 nm, more preferably 0 to 5 nm, and the out-of-plane retardation (Rt) represented by the following formula (3) ) Is preferably -150～20Nm, more preferably -150～10Nm, particularly preferably include such things is -120～0Nm. The phase difference characteristics at this time are measured using a fully automatic birefringence meter (manufactured by Oji Scientific Instruments Co., Ltd., trade name KOBRA-21ADH) under a measurement wavelength of 589 nm.

  These have retardation characteristics that are difficult to develop with conventional optical compensation films made of cellulose resin.

Re = (ny−nx) × d (1)
Nz = (ny−nz) / (ny−nx) (2)
Rth = [(nx + ny) / 2−nz] × d (3)
(Where nx represents the refractive index in the fast axis direction in the film plane, ny represents the refractive index in the slow axis direction in the film plane, nz represents the refractive index outside the film plane, and d represents the film. Indicates thickness.)
The wavelength dispersion characteristic of the optical film of the present invention is preferably 0.60 <Re (450) / Re (550) <1.05, and more preferably 0.61 <Re (450) in order to suppress color misregistration. ) / Re (550) <1.02, particularly preferably 0.61 <Re (450) / Re (550) <1.00.

  When cellulose ether is used as the cellulose resin of the present invention, an optical film having a low wavelength dispersion can be provided alone. A resin composition obtained by blending this film with a fumaric acid ester copolymer exhibiting negative birefringence in the stretching direction can generally provide an optical film exhibiting reverse wavelength dispersion. .

  Satisfying these retardation characteristics and chromatic dispersion characteristics at the same time is difficult to express in a conventional optical compensation film using a cellulose-based resin. However, when cellulose ether is used in the present invention, the invention relates to the present invention. An optical compensation film using the resin composition satisfies these characteristics at the same time.

  In order to reduce the required film thickness, the optical compensation film of the present invention has a ratio Re (589) (nm) / film thickness (μm) of retardation to film thickness at 589 nm of 4.0 nm / μm or more. Is preferred.

  The optical compensation film of the present invention has a light transmittance of preferably 85% or more, and more preferably 90% or more, for improving luminance.

  The optical compensation film of the present invention has a haze of preferably 1% or less, more preferably 0.5% or less, for improving contrast.

  As a method for producing an optical compensation film using the resin composition of the present invention, any method may be used as long as the optical compensation film of the present invention can be produced. Since an excellent optical compensation film can be obtained, it is preferably produced by a solution casting method. Here, the solution casting method is a method of obtaining an optical compensation film by casting a resin solution (generally referred to as a dope) on a support substrate and then evaporating the solvent by heating. As a casting method, for example, a T-die method, a doctor blade method, a bar coater method, a roll coater method, a lip coater method or the like is used. In general, a method of continuously extruding is used. Examples of the support substrate used include a glass substrate, a metal substrate such as stainless steel and ferrotype, and a plastic substrate such as polyethylene terephthalate. In order to industrially continuously form a substrate having high surface properties and optical homogeneity, a metal substrate having a mirror-finished surface is preferably used. In the solution casting method, the viscosity of the resin solution is an extremely important factor when producing an optical compensation film with excellent thickness accuracy and surface smoothness. The viscosity of the resin solution is the resin concentration, molecular weight, and type of solvent. It depends on.

  A resin solution for producing an optical compensation film using the resin composition of the present invention is prepared by dissolving a cellulose resin and a fumaric acid ester copolymer in a solvent. The viscosity of the resin solution can be adjusted by the molecular weight of the polymer, the concentration of the polymer, and the type of solvent. Although there is no restriction | limiting in particular as a viscosity of a resin solution, In order to make film coating property easier, Preferably it is 100-10000 cps, More preferably, it is 300-5000 cps, Most preferably, it is 500-3000 cps.

  Examples of the method for producing an optical compensation film using the resin composition of the present invention include 30 to 99% by weight of a cellulose-based resin represented by the general formula (1) and a fumaric acid diester residue represented by the general formula (2). A resin composition containing 1 to 70% by weight of a fumaric acid ester copolymer containing 20 mol% or more of base units and 5 mol% or more of a p-substituted cinnamate residue represented by the general formula (3) is used as a solvent. And the resulting resin solution is cast on a substrate, dried and then peeled off from the substrate.

  The optical compensation film obtained using the resin composition of the present invention is preferably uniaxially stretched or unbalanced biaxially stretched in order to develop in-plane retardation (Re). As a method for stretching the optical compensation film, it is possible to use a longitudinal uniaxial stretching method by roll stretching, a transverse uniaxial stretching method by tenter stretching, an unbalanced sequential biaxial stretching method or an unbalanced simultaneous biaxial stretching method by a combination thereof. it can. Moreover, in this invention, a phase difference characteristic can be expressed, without using the special extending | stretching method which extends | stretches under the effect | action of the shrinkage force of a heat-shrinkable film.

  The thickness of the optical compensation film at the time of stretching is preferably from 10 to 200 μm, more preferably from 30 to 150 μm, particularly preferably from 30 to 100 μm, from the viewpoint of easiness of stretching treatment and compatibility with thinning of the optical member. .

  The stretching temperature is not particularly limited, but is preferably 50 to 200 ° C., more preferably 100 to 180 ° C., because good retardation characteristics can be obtained. Although there is no restriction | limiting in particular in the draw ratio of uniaxial stretching, since favorable phase difference characteristics are acquired, 1.05-4.0 times are preferable and 1.1-3.5 times are more preferable. Although there is no restriction | limiting in particular in the draw ratio of unbalance biaxial stretching, since it becomes an optical compensation film excellent in the optical characteristic, 1.05-4.0 times are preferable in a length direction, and 1.1-3.5 Is more preferably 1.0 to 1.2 times, and more preferably 1.05 to 1.1 times in the width direction, since an optical compensation film having excellent optical characteristics is obtained. The in-plane retardation (Re) can be controlled by the stretching temperature and the stretching ratio.

  The optical compensation film using the resin composition of the present invention can be laminated with a film containing another resin as necessary. Examples of other resins include polyether sulfone, polyarylate, polyethylene terephthalate, polynaphthalene terephthalate, polycarbonate, cyclic polyolefin, maleimide resin, fluorine resin, polyimide, and the like. It is also possible to laminate a hard coat layer or a gas barrier layer.

  An optical compensation film using the resin composition of the present invention is useful as an optical compensation film for liquid crystal displays or an antireflection film because it is a thin film and exhibits specific retardation characteristics.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

  In addition, the various physical properties shown by an Example were measured with the following method.

<Analysis of polymer>
The structural analysis of the polymer was determined by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR) spectrum analysis using a nuclear magnetic resonance measuring apparatus (manufactured by JEOL, trade name: JNM-GX270).

In the case where the fumaric acid ester copolymer contains a fumaric acid monoester residue unit, when the composition ratio analysis is more difficult than the ¹ H-NMR spectrum analysis, JIS K 2501 (2003 edition) petroleum product and lubricating oil-neutralization value The concentration of fumaric acid monoester was determined according to the test method.

<Measurement of number average molecular weight>
Using a gel permeation chromatography (GPC) apparatus (manufactured by Tosoh Corporation, trade name: C0-8011 (equipped with column GMH _HR- H)), measurement was performed at 40 ° C. using tetrahydrofuran or dimethylformamide as a solvent, It calculated | required as a standard polystyrene conversion value.

<Measurement of light transmittance and haze of optical compensation film>
The light transmittance and haze of the prepared film were measured using a haze meter (trade name: NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.). The light transmittance was measured according to JIS K 7361-1 (1997 edition). Measurements were made in accordance with JIS-K 7136 (2000 version).

<Measurement of phase difference characteristics>
The retardation characteristics of the optical compensation film were measured using light having a wavelength of 589 nm using a sample tilt type automatic birefringence meter (manufactured by Oji Scientific Instruments, trade name: KOBRA-WR).

<Measurement of wavelength dispersion characteristics>
Using a sample tilt type automatic birefringence meter (manufactured by Oji Scientific Instruments, trade name: KOBRA-WR), optical as a ratio of phase difference Re (450) due to light having a wavelength of 450 nm and phase difference Re (550) due to light having a wavelength of 550 nm The wavelength dispersion characteristic of the compensation film was measured.

Synthesis Example 1 (Synthesis 1 of fumarate ester copolymer (diisopropyl fumarate / monoethyl fumarate / 4-nitroethylcinnamate copolymer))
In a glass ampule with a capacity of 75 mL, 57 g of diisopropyl fumarate, 5.1 g of monoethyl fumarate, 3.9 g of ethyl 4-nitrocinnamate, and 2,5-dimethyl-2,5-di (2-ethylhexanoyl) as a polymerization initiator Peroxy) hexane 1.46 g was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 62 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 22 g of acid monoethyl / 4-nitrocinnamic acid ethyl copolymer was obtained. The number average molecular weight of the obtained polymer was 18,000, diisopropyl fumarate residue unit 78 mol%, monoethyl fumarate residue unit 12 mol%, and ethyl 4-nitrocinnamate residue unit 10 mol%.

Synthesis Example 2 (Synthesis 2 of fumarate ester copolymer (diisopropyl fumarate / monoisopropyl fumarate / 4-nitroethylcinnamate copolymer))
A glass ampule with a capacity of 75 mL was charged with 53 g of diisopropyl fumarate, 5.8 g of monoisopropyl fumarate, 6.0 g of ethyl 4-nitrocinnamate, and 2,5-dimethyl-2,5-di (2-ethylhexahexayl) as a polymerization initiator. Noylperoxy) hexane (1.91 g) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 120 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 31 g of acid monoisopropyl-4-nitrocinnamate ethyl copolymer was obtained. The number average molecular weight of the obtained polymer was 16,000, diisopropyl fumarate residue unit 68 mol%, monoisopropyl fumarate residue unit 15 mol%, and ethyl 4-nitrocinnamate residue unit 17 mol%. .

Synthesis Example 3 (Synthesis 3 of Fumarate Ester Copolymer (Diisopropyl Fumarate / Monoisopropyl Fumarate / 4-Nitrocinnamate Ethyl Copolymer) 3)
A glass ampule with a capacity of 75 mL was charged with 48 g of diisopropyl fumarate, 5.7 g of monoisopropyl fumarate, 11.0 g of ethyl 4-nitrocinnamate, and 1,1′-azobis (cyclohexane-1-carbonitrile) as a polymerization initiator. 567 g was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was put into a thermostat at 80 ° C. and held for 144 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 10 g of acid monoisopropyl-4-nitrocinnamic acid ethyl copolymer was obtained. The number average molecular weight of the obtained polymer was 13,000, diisopropyl fumarate residue unit 51 mol%, monoisopropyl fumarate residue unit 16 mol%, and ethyl 4-nitrocinnamate residue unit 33 mol%. .

Synthesis Example 4 (Synthesis 4 of fumarate ester copolymer (diisopropyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer))
In a glass ampoule with a capacity of 75 mL, 40 g of diisopropyl fumarate, 4.9 g of monoethyl fumarate, 5.2 g of ethyl 4-cyanocinnamate, and 2,5-dimethyl-2,5-di (2-ethylhexanoyl) as a polymerization initiator Peroxy) hexane 1.49 g was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 17 g of acid monoethyl / 4-cyanocyanocinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 25,000, diisopropyl fumarate residue unit 78 mol%, monoethyl fumarate residue unit 9 mol%, and ethyl 4-cyanocinnamate residue unit 13 mol%.

Synthesis Example 5 (Synthesis 5 of fumarate ester copolymer (diisopropyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer))
In a 75 mL glass ampule, 45 g of diisopropyl fumarate, 6.0 g of monoethyl fumarate, 12.9 g of ethyl 4-cyanocinnamate and 2,5-dimethyl-2,5-di (2-ethylhexanoyl) as a polymerization initiator Peroxy) hexane 1.929 g was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 120 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 14 g of acid monoethyl / 4-cyanoethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 17,000, diisopropyl fumarate residue unit 58 mol%, monoethyl fumarate residue unit mol 10%, 4-cyanocinnamate ethyl residue unit mol 32%.

Synthesis Example 6 (Synthesis 6 of Fumarate Ester Copolymer (Diisopropyl Fumarate / Monoethyl Fumarate / 4-Bromocinnamate Ethyl Copolymer) 6)
In a glass ampoule with a capacity of 75 mL, 47 g of diisopropyl fumarate, 7.2 g of monoethyl fumarate, 11.0 g of ethyl 4-bromocinnamate and 2,5-dimethyl-2,5-di (2-ethylhexanoyl) as a polymerization initiator Peroxy) hexane (1.91 g) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 33 g of acid monoethyl / 4-bromoethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 25,000, diisopropyl fumarate residue unit mol 73%, monoethyl fumarate residue unit mol 12%, and ethyl 4-bromocinnamate residue unit mol 15%.

Synthesis Example 7 (Synthesis 7 of Fumarate Ester Copolymer (Diisopropyl Fumarate / Monoethyl Fumarate / 4-Nitrocinnamate Ethyl Copolymer) 7)
In a glass ampule with a capacity of 75 mL, 59 g of diisopropyl fumarate, 2.5 g of monoethyl fumarate, 3.8 g of ethyl 4-nitrocinnamate, and 2,5-dimethyl-2,5-di (2-ethylhexanoyl) as a polymerization initiator Peroxy) hexane (1.99 g) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 62 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 30 g of acid monoethyl / 4-nitrocinnamic acid ethyl copolymer was obtained. The number average molecular weight of the obtained polymer was 24,000, diisopropyl fumarate residue unit 87 mol%, monoethyl fumarate residue unit 4 mol%, and 4-nitrocinnamic acid ethyl residue unit 9 mol%.

Synthesis Example 8 (Synthesis of fumarate ester copolymer (diisopropyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer 8))
In a glass ampoule with a capacity of 75 mL, 58 g of diisopropyl fumarate, 3.0 g of monoethyl fumarate, 7.0 g of ethyl 4-cyanocinnamate, and 2,5-dimethyl-2,5-di (2-ethylhexanoyl) as a polymerization initiator Peroxy) hexane (1.90 g) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 62 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 16 g of acid monoethyl / 4-cyanocyanocinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 21,000, diisopropyl fumarate residue unit 81 mol%, monoethyl fumarate residue unit 4 mol%, and ethyl 4-cyanocinnamate residue unit 15 mol%.

Synthesis Example 9 (Synthesis 9 of fumarate ester copolymer (diethyl fumarate / monoethyl fumarate / 4-nitroethylcinnamate copolymer))
In a glass ampule with a capacity of 75 mL, 58 g of diethyl fumarate, 2.7 g of monoethyl fumarate, 4.1 g of ethyl 4-nitrocinnamate, and 2,5-dimethyl-2,5-di (2-ethylhexanoyl) as a polymerization initiator Peroxy) hexane (17.17 g) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diethyl fumarate / fumarate. 27 g of acid monoethyl / 4-nitrocinnamic acid ethyl copolymer was obtained. The number average molecular weight of the obtained polymer was 16,000, diethyl fumarate residue unit 84 mol%, monoethyl fumarate residue unit 6 mol%, and 4-nitrocinnamate ethyl residue unit 10 mol%.

Synthesis Example 10 (Synthesis 10 of fumarate ester copolymer (diethyl fumarate / 4-nitrocinnamate ethyl copolymer) 10)
A glass ampule with a capacity of 75 mL was charged with 53 g of diethyl fumarate, 12 g of ethyl 4-nitrocinnamate, and 0.567 g of 1,1′-azobis (cyclohexane-1-carbonitrile), which is a polymerization initiator, to replace nitrogen and release pressure. After repeating, sealing was performed under reduced pressure. This ampoule was put into a thermostat at 80 ° C. and held for 144 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours, whereby diethyl fumarate / 4 -13 g of ethyl nitrocinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 13,000, diethyl fumarate residue unit 69 mol%, and 4-nitrocinnamic acid ethyl residue unit 31 mol%.

Synthesis Example 11 (Synthesis 11 of fumarate ester copolymer (diethyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer 11))
In a glass ampule with a capacity of 75 mL, 57 g of diethyl fumarate, 2.7 g of monoethyl fumarate, 5.2 g of ethyl 4-cyanocinnamate and 2,5-dimethyl-2,5-di (2-ethylhexanoyl) as a polymerization initiator Peroxy) hexane (17.17 g) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diethyl fumarate / fumarate. 33 g of acid monoethyl / 4-cyanocyanocinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 21,000, diethyl fumarate residue unit 85 mol%, monoethyl fumarate residue unit 5 mol%, and ethyl 4-cyanocinnamate residue unit 10 mol%.

Synthesis Example 12 (Synthesis 12 of fumarate ester copolymer (diethyl fumarate / 4-cyanoethylcinnamate copolymer))
In a glass ampule with a capacity of 75 mL, 54 g of diethyl fumarate, 11.0 g of ethyl 4-cyanocinnamate and 2.12 g of 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane as a polymerization initiator After repeating nitrogen substitution and depressurization, it was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 120 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours, whereby diethyl fumarate / 4 -15 g of ethyl cyanocinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 15,000, diethyl fumarate residue unit 68 mol%, and ethyl 4-cyanocinnamate residue unit mol 32%.

Synthesis Example 13 (Synthesis 13 of Fumarate Ester Copolymer (Diethyl Fumarate / Monoethyl Fumarate / 4-Bromocinnamate Ethyl Copolymer) 13)
A glass ampoule with a capacity of 75 mL was charged with 52 g of diethyl fumarate, 3.2 g of monoethyl fumarate, 9.8 g of ethyl 4-bromocinnamate, and 2,5-dimethyl-2,5-di (2-ethylhexanoyl) as a polymerization initiator. Peroxy) hexane (17.17 g) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diethyl fumarate / fumarate. 34 g of acid monoethyl / 4-bromoethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 23,000, diethyl fumarate residue unit mol 83%, monoethyl fumarate residue unit mol 5%, 4-bromocinnamic acid ethyl residue unit mol 12%.

Synthesis Example 14 (Synthesis of di-t-butyl fumarate)
A 300 mL autoclave equipped with a stirrer and a thermometer was charged with 60 mL of ethylene glycol dimethyl ether, 20 g of maleic acid and 4 g of sulfuric acid, and then 51 g of 2-methylpropylene was injected and reacted at 40 ° C. for 2 hours with stirring.

  80 mL of ethylene glycol dimethyl ether solution of di-t-butyl maleate and 0.3 g of piperidine obtained by neutralizing and washing the reaction solution obtained in the above reaction with 150 mL of a stirrer, a cooler and a thermometer. The mixture was charged into three necks and reacted at 110 ° C. for 2 hours with stirring. As a result of GC analysis of the obtained reaction liquid, the isomerization rate to di-t-butyl fumarate was 99%. After distilling off the solvent of the obtained reaction solution, sublimation was performed to obtain 22 g of 99% pure di-t-butyl fumarate.

Synthesis Example 15 (Synthesis 14 of fumarate ester copolymer (di-t-butyl fumarate / monoethyl fumarate / 4-nitroethylcinnamate copolymer) 14)
A glass ampule with a capacity of 75 mL was charged with 57 g of di-t-butyl fumarate, 5.7 g of monoethyl fumarate, 3.4 g of ethyl 4-nitrocinnamate, and 2,5-dimethyl-2,5-di (2 -Ethylhexanoyl peroxy) hexane 1.75g was put, and after nitrogen substitution and depressurization were repeated, it was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 62 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain di-tuma fumarate. 26 g of butyl / monoethyl fumarate / 4-nitroethylcinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 22,000, di-t-butyl fumarate residue unit 77 mol%, monoethyl fumarate residue unit 13 mol%, 4-nitrocinnamate ethyl residue unit 10 mol%. Met.

Synthesis Example 16 (Synthesis 15 of fumarate ester copolymer (di-t-butyl fumarate / monoisopropyl fumarate / 4-nitroethylcinnamate copolymer 15))
A glass ampule with a capacity of 75 mL was charged with 53 g of di-t-butyl fumarate, 5.8 g of monoisopropyl fumarate, 5.5 g of ethyl 4-nitrocinnamate, and 2,5-dimethyl-2,5-di ( 2-ethylhexanoylperoxy) hexane 1.75 g was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 120 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain di-tuma fumarate. -33 g of butyl / monoisopropyl fumarate / 4-nitroethylcinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 18,000, fumardi-t-butyl residue unit 69 mol%, monoisopropyl fumarate residue unit 15 mol%, ethyl 4-nitrocinnamate residue unit 16 mol%. there were.

Synthesis Example 17 (Synthesis 16 of fumarate ester copolymer (di-t-butyl fumarate / monoisopropyl fumarate / 4-nitroethylcinnamate copolymer 16))
Glass ampule fumarate -t- butyl 48g capacity 75 mL, fumaric acid monoisopropyl 5.3 g, 4-nitrocinnamic acid ethyl 10.1g and the polymerization initiator 1,1 '- azobis (cyclohexane-1-carbonitrile (Nitrile) 0.823 g was added, and after nitrogen substitution and depressurization were repeated, it was sealed under reduced pressure. This ampoule was put into a thermostat at 80 ° C. and held for 144 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain di-tuma fumarate. 13 g of butyl / monoisopropyl fumarate / 4-nitroethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 15,000, di-t-butyl fumarate residue unit 53 mol%, monoisopropyl fumarate residue unit 15 mol%, ethyl 4-nitrocinnamate residue unit 32 mol. %Met.

Synthesis Example 18 (Synthesis 17 of fumarate ester copolymer (di-t-butyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer) 17)
A glass ampule with a capacity of 75 mL was charged with 40 g of di-t-butyl fumarate, 4.0 g of monoethyl fumarate, 4.7 g of ethyl 4-cyanocinnamate, and 2,5-dimethyl-2,5-di (2 -Ethylhexanoyl peroxy) hexane 1.49g was put, and after nitrogen substitution and depressurization were repeated, it was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain di-tuma fumarate. 21 g of butyl / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 28,000, di-t-butyl fumarate residue unit 77 mol%, monoethyl fumarate residue unit 10 mol%, ethyl 4-cyanocinnamate residue unit 13 mol%. Met.

Synthesis Example 19 (Synthesis 18 of fumarate ester copolymer (di-t-butyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer 18))
A glass ampule with a capacity of 75 mL was charged with 45 g of di-t-butyl fumarate, 5.1 g of monoethyl fumarate, 11.0 g of ethyl 4-cyanocinnamate, and 2,5-dimethyl-2,5-di (2 -Ethylhexanoylperoxy) hexane 1.696g was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 120 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain di-tuma fumarate. 15 g of butyl / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 19,000, di-t-butyl fumarate residue unit 58 mol%, monoethyl fumarate residue unit mol 9%, ethyl 4-cyanocinnamate residue unit mol 33% Met.

Synthesis Example 20 (Synthesis 19 of fumarate ester copolymer (di-t-butyl fumarate / monoethyl fumarate / 4-bromoethyl cinnamate copolymer 19))
A glass ampule with a capacity of 75 mL was charged with 47 g of di-t-butyl fumarate, 6.0 g of monoethyl fumarate, 9.6 g of ethyl 4-bromocinnamate, and 2,5-dimethyl-2,5-di (2 -Ethylhexanoylperoxy) 1.70 g of hexane was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain di-tuma fumarate. 38 g of butyl / monoethyl fumarate / 4-bromoethylcinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 30,000, di-t-butyl fumarate residue unit 74 mol%, monoethyl fumarate residue unit 11 mol%, 4-bromocinnamic acid ethyl residue unit 15 mol% Met.

Synthesis Example 21 (Synthesis of fumarate ester copolymer (di-t-butyl fumarate / monoethyl fumarate / 4-nitroethylcinnamate copolymer 20))
In a glass ampule with a capacity of 75 mL, 59 g of di-t-butyl fumarate, 2.1 g of monoethyl fumarate, 3.2 g of ethyl 4-nitrocinnamate and 2,5-dimethyl-2,5-di (2 -Ethylhexanoylperoxy) hexane 1.68g was put, and after nitrogen substitution and depressurization were repeated, it was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 62 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain di-tuma fumarate. 35 g of butyl / monoethyl fumarate / 4-nitroethylcinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 29,000, di-t-butyl fumarate residue unit 87 mol%, monoethyl fumarate residue unit 4 mol%, 4-nitrocinnamic acid ester residue unit 9 mol% Met.

Synthesis Example 22 (Synthesis of fumarate ester copolymer (diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-nitroethyl cinnamate copolymer 21))
In a glass ampule with a capacity of 75 mL, 49 g of diisopropyl fumarate, 6.7 g of diethyl fumarate, 4.0 g of 2-hydroxyethyl acrylate, 4.9 g of ethyl 4-nitrocinnamate, and 2,5-dimethyl-2 which is a polymerization initiator , 5-di (2-ethylhexanoylperoxy) hexane (1.97 g) was added, nitrogen substitution and depressurization were repeated, and the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 27 g of diethyl acid / 2-hydroxyethyl acrylate / 4-nitroethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 21,000, diisopropyl fumarate residue unit 69 mol%, diethyl fumarate residue unit 10 mol%, 2-hydroxyethyl acrylate residue unit 10 mol%, 4-nitrosilicate. The ethyl cinnamate residue unit was 11 mol%.

Synthesis Example 23 (Synthesis 22 of fumarate ester copolymer (diisopropyl fumarate / N- (n-butoxymethyl) acrylamide / 4-nitroethylcinnamate copolymer 22))
A glass ampoule with a capacity of 75 mL was charged with 50 g of diisopropyl fumarate, 8.0 g of N- (n-butoxymethyl) acrylamide, 6.8 g of ethyl 4-nitrocinnamate, and 2,5-dimethyl-2,5-di-polymerization initiator. (2-Ethylhexanoylperoxy) hexane (1.91 g) was added, nitrogen substitution and depressurization were repeated, and the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 120 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / N 28 g of-(n-butoxymethyl) acrylamide / 4-nitroethylcinnamic acid copolymer was obtained. The number average molecular weight of the obtained polymer was 15,000, diisopropyl fumarate residue unit 70 mol%, N- (n-butoxymethyl) acrylamide residue unit 15 mol%, 4-nitrocinnamic acid ethyl residue unit 15 Mol%.

Synthesis Example 24 (Synthesis 23 of fumarate ester copolymer (diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-nitroethylcinnamate copolymer 23))
A glass ampule with a capacity of 75 mL was charged with 42 g of diisopropyl fumarate, 6.3 g of diethyl fumarate, 4.0 g of 2-hydroxyethyl acrylate, 11.0 g of ethyl 4-nitrocinnamate and 1,1′-azobis ( (Cyclohexane-1-carbonitrile) 0.918 g was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was put into a thermostat at 80 ° C. and held for 144 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 10 g of diethyl acrylate / 2-hydroxyethyl acrylate / 4-nitroethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 11,000, diisopropyl fumarate residue unit 47 mol%, diethyl fumarate residue unit 10 mol%, 2-hydroxyethyl acrylate residue unit 9 mol%, 4-nitrosilicate. The ethyl cinnamate residue unit was 34 mol%.

Synthesis Example 25 (Synthesis of fumarate ester copolymer (diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-cyanoethyl cinnamate copolymer 24))
In a glass ampule with a capacity of 75 mL, 41 g of diisopropyl fumarate, 6.7 g of diethyl fumarate, 4.0 g of 2-hydroxyethyl acrylate, 13.0 g of ethyl 4-cyanocinnamate, and 2,5-dimethyl-2 which is a polymerization initiator , 5-di (2-ethylhexanoylperoxy) hexane (1.97 g) was added, nitrogen substitution and depressurization were repeated, and the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 120 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / fumarate. 12 g of diethyl acrylate / 2-hydroxyethyl acrylate / 4-cyanoethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 15,000, diisopropyl fumarate residue unit 45 mol%, diethyl fumarate residue unit 11 mol%, 2-hydroxyethyl acrylate residue unit 11 mol%, 4-cyanosilicate. The ethyl cinnamate residue unit was 33% mol.

Synthesis Example 26 (Synthesis of fumarate ester copolymer (diisopropyl fumarate / N- (n-butoxymethyl) acrylamide / 4-bromoethyl ethyl cinnamate copolymer 25))
A glass ampoule with a capacity of 75 mL was charged with 47 g of diisopropyl fumarate, 7.1 g of N- (n-butoxymethyl) acrylamide, 10.7 g of ethyl 4-bromocinnamate, and 2,5-dimethyl-2,5-di-polymerization initiator. 1.85 g of (2-ethylhexanoylperoxy) hexane was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 65 ° C. and held for 72 hours for radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampule and dissolved in 50 g of tetrahydrofuran. This polymer solution was dropped into 2 kg of hexane, precipitated, washed with 2 kg of methanol / water = 60/40 (wt% / wt%), and then vacuum-dried at 80 ° C. for 10 hours to obtain diisopropyl fumarate / N 31 g of-(n-butoxymethyl) acrylamide / 4-bromo ethyl cinnamate copolymer was obtained. The number average molecular weight of the obtained polymer was 21,000, diisopropyl fumarate residue unit 72 mol%, N- (n-butoxymethyl) acrylamide residue unit 13 mol%, 4-bromocinnamic acid ethyl residue unit 15 Mol%.

Example 1
Ethylcellulose as a cellulose resin (ETHOCEL standard 100 manufactured by Dow Chemical Co., Ltd., molecular weight Mn = 55,000, molecular weight Mw = 176,000, Mw / Mn = 3.2, total substitution degree DS = 2.5) 80 g, 70 g of diisopropyl fumarate / monoethyl fumarate / 4-nitroethyl cinnamate copolymer obtained in Synthesis Example 1 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio) to obtain an 18 wt% resin solution. And an optical compensation film (resin composition) having a width of 150 mm was obtained (ethylcellulose: 53% by weight, diisopropyl fumarate / monoethyl fumarate) after flowing on a polyethylene terephthalate film with a coater and drying at a drying temperature of 25 ° C. / 4 ethyl nitrocinnamate copolymer: 47 wt. ). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm).

  The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 2
90 g of ethyl cellulose used in Example 1 and 60 g of diisopropyl fumarate / monoisopropyl fumarate / 4-nitrocinnamate copolymer obtained in Synthesis Example 2 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resulting solution was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 60% by weight). , Diisopropyl fumarate / monoisopropyl fumarate / 4-nitroethylcinnamate copolymer: 40% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 3
105 g of ethylcellulose used in Example 1 and 45 g of diisopropyl fumarate / monoisopropyl fumarate / 4-nitroethylcinnamate copolymer obtained in Synthesis Example 3 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resulting solution was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 70% by weight). , Diisopropyl fumarate / monoisopropyl fumarate / 4-nitroethylcinnamate copolymer: 30% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 4
75 g of ethylcellulose used in Example 1 and 75 g of diisopropyl fumarate / monoethyl fumarate / 4-cyanoethylcinnamate copolymer obtained in Synthesis Example 4 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resulting solution was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 50% by weight, Diisopropyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer: 50% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 5
90 g of ethylcellulose used in Example 1 and 60 g of diisopropyl fumarate / monoethyl fumarate / 4-cyanoethylcinnamate copolymer obtained in Synthesis Example 5 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resulting solution was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 60% by weight, Diisopropyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer: 40% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 6
75 g of ethyl cellulose used in Example 1 and 75 g of diisopropyl fumarate / monoethyl fumarate / 4-bromoethyl cinnamate copolymer obtained in Synthesis Example 6 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resulting solution was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 50% by weight, Diisopropyl fumarate / monoethyl fumarate / 4-bromoethyl cinnamate copolymer: 50% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 7
75 g of ethylcellulose used in Example 1 and 75 g of diisopropyl fumarate / monoethyl fumarate / 4-nitrocinnamate copolymer obtained in Synthesis Example 7 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resin solution was 18% by weight, cast on a support of a solution casting apparatus by the T-die method, dried at a drying temperature of 25 ° C., and then an optical compensation film (resin composition) having a width of 150 mm was obtained ( Ethyl cellulose: 50% by weight, diisopropyl fumarate / monoethyl fumarate / 4-nitroethyl cinnamate: 50% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film had the desired optical characteristics of in-plane retardation (Re) and Nz coefficient, and had a large Re (589) / film thickness.

Example 8
75 g of ethylcellulose used in Example 1 and 75 g of diisopropyl fumarate / monoethyl fumarate / 4-cyanoethylcinnamate copolymer obtained in Synthesis Example 8 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resin solution was 18% by weight, cast on a support of a solution casting apparatus by the T-die method, dried at a drying temperature of 25 ° C., and then an optical compensation film (resin composition) having a width of 150 mm was obtained ( Ethyl cellulose: 50% by weight, diisopropyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer: 50% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film had the desired optical characteristics of in-plane retardation (Re) and Nz coefficient, and had a large Re (589) / film thickness.

Example 9
Ethylcellulose as a cellulose resin (ETHOCEL standard 100 manufactured by Dow Chemical Co., Ltd., molecular weight Mn = 55,000, molecular weight Mw = 176,000, Mw / Mn = 3.2, total substitution degree DS = 2.5) 80 g, 70 g of diethyl fumarate / monoethyl fumarate / 4-nitrocinnamate copolymer obtained in Synthesis Example 9 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio) to obtain an 18 wt% resin solution. And an optical compensation film (resin composition) having a width of 150 mm was obtained (ethylcellulose: 53% by weight, diethyl fumarate / monoethyl fumarate) after flowing on a polyethylene terephthalate film with a coater and drying at a drying temperature of 25 ° C. / 4 ethyl nitrocinnamate copolymer: 47% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm).

  The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 10
90% of ethyl cellulose used in Example 1 and 60 g of diethyl fumarate / 4-nitrocinnamate copolymer obtained in Synthesis Example 10 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio) to obtain 18% by weight. After being poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C., an optical compensation film (resin composition) having a width of 150 mm was obtained (ethylcellulose: 60% by weight, diethyl fumarate / 4-Nitrocinnamic acid ethyl copolymer: 40% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 11
75 g of ethyl cellulose used in Example 1 and 75 g of diethyl fumarate / monoethyl fumarate / 4-cyanoethylcinnamate copolymer obtained in Synthesis Example 11 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resulting solution was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 50% by weight, Diethyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer: 50% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 12
18% by weight of 85 g of ethyl cellulose used in Example 1 and 65 g of diethyl 4-cyanocinnamate copolymer obtained in Synthesis Example 12 in methylene chloride: acetone = 8: 2 (weight ratio) After being poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C., an optical compensation film (resin composition) having a width of 150 mm was obtained (ethyl cellulose: 57% by weight, diethyl fumarate / 4-ethyl cyanocinnamate copolymer: 43% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 13
75 g of ethyl cellulose used in Example 1 and 75 g of diethyl fumarate / monoethyl fumarate / 4-bromocinnamate copolymer obtained in Synthesis Example 13 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resulting solution was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 50% by weight, Diethyl fumarate / monoethyl fumarate / 4-bromoethyl cinnamate copolymer: 50% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 14
Ethylcellulose as a cellulose resin (ETHOCEL standard 100 manufactured by Dow Chemical Co., Ltd., molecular weight Mn = 55,000, molecular weight Mw = 176,000, Mw / Mn = 3.2, total substitution degree DS = 2.5) 80 g, 70 g of di-t-butyl fumarate / monoethyl fumarate / 4-nitrocinnamate copolymer obtained in Synthesis Example 15 was dissolved in methylene chloride: acetone = 8: 2 (weight ratio) and 18 wt. % Resin solution, poured on a polyethylene terephthalate film with a coater, and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 53% by weight, difumarate diacid). -T-butyl / monoethyl fumarate / 4-nitroethyl cinnamate copolymer: 47 layers %). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm).

  The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 15
90 g of ethyl cellulose used in Example 1 and 60 g of di-t-butyl fumarate / monoisopropyl fumarate / 4-nitroethyl cinnamate copolymer obtained in Synthesis Example 16 were mixed with methylene chloride: acetone = 8: 2 (weight). Ratio) to obtain a 18% by weight resin solution, which was poured onto a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethylcellulose). : 60 wt%, di-t-butyl fumarate / monoisopropyl fumarate / 4-nitroethylcinnamate copolymer: 40 wt%). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 16
105 g of ethyl cellulose used in Example 1 and 45 g of di-t-butyl fumarate / monoisopropyl fumarate / 4-nitrocinnamate copolymer obtained in Synthesis Example 17 were mixed with methylene chloride: acetone = 8: 2 (weight). Ratio) to obtain a 18% by weight resin solution, which was poured onto a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethylcellulose). : 70% by weight, di-t-butyl fumarate / monoisopropyl fumarate / 4-nitroethylcinnamate copolymer: 30% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 17
75 g of ethylcellulose used in Example 1 and 75 g of di-t-butyl fumarate / monoethyl fumarate / 4-cyanoethylcinnamate copolymer obtained in Synthesis Example 18 were mixed with methylene chloride: acetone = 8: 2 (weight ratio). ) To give a 18% by weight resin solution, which was poured onto a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C., to obtain an optical compensation film (resin composition) having a width of 150 mm (ethylcellulose: 50 wt%, di-t-butyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer: 50 wt%). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 18
90 g of ethyl cellulose used in Example 1 and 60 g of di-t-butyl fumarate / monoethyl fumarate / 4-cyanocyanocinnamate copolymer obtained in Synthesis Example 19 were mixed with methylene chloride: acetone = 8: 2 (weight ratio). ) To give a 18% by weight resin solution, which was poured onto a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C., to obtain an optical compensation film (resin composition) having a width of 150 mm (ethylcellulose: 60 wt%, di-t-butyl fumarate / monoethyl fumarate / 4-cyanoethyl cinnamate copolymer: 40 wt%). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 19
75 g of ethylcellulose used in Example 1 and 75 g of di-t-butyl fumarate / monoethyl fumarate / 4-bromoethylcinnamate copolymer obtained in Synthesis Example 20 were mixed with methylene chloride: acetone = 8: 2 (weight ratio). ) To give a 18% by weight resin solution, which was poured onto a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C., to obtain an optical compensation film (resin composition) having a width of 150 mm (ethylcellulose: 50 wt%, di-t-butyl fumarate / monoethyl fumarate / 4-bromoethyl cinnamate copolymer: 50 wt%). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 20
75 g of ethyl cellulose used in Example 1 and 75 g of di-t-butyl fumarate / monoethyl fumarate / 4-nitroethylcinnamate copolymer obtained in Synthesis Example 21 were mixed with methylene chloride: acetone = 8: 2 (weight ratio). ) To give an 18% by weight resin solution, cast on a support of a solution casting apparatus by a T-die method, dried at a drying temperature of 25 ° C., and then an optical compensation film (resin composition) having a width of 150 mm. (Ethyl cellulose: 50% by weight, di-t-butyl fumarate / monoethyl fumarate / 4-nitroethyl cinnamate: 50% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film had the desired optical characteristics of in-plane retardation (Re) and Nz coefficient, and had a large Re (589) / film thickness.

Example 21
Ethylcellulose as a cellulose resin (ETHOCEL standard 100 manufactured by Dow Chemical Co., Ltd., molecular weight Mn = 55,000, molecular weight Mw = 176,000, Mw / Mn = 3.2, total substitution degree DS = 2.5) 78 g, 72 g of diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-nitroethyl cinnamate copolymer obtained in Synthesis Example 22 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resulting solution was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 52% by weight, Diisopropyl fumarate / diethyl fumarate / acrylic acid 2 Hydroxyethyl / 4-nitrocinnamic acid ethyl copolymer: 48 wt%). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm).

  The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 22
88 g of ethyl cellulose used in Example 1 and 62 g of diisopropyl fumarate / N- (n-butoxymethyl) acrylamide / 4-nitroethyl cinnamate copolymer obtained in Synthesis Example 23 were mixed with methylene chloride: acetone = 8: 2 ( (Weight ratio) to obtain an 18% by weight resin solution, which was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C., and an optical compensation film (resin composition) having a width of 150 mm was obtained ( Ethylcellulose: 59% by weight, diisopropyl fumarate / N- (n-butoxymethyl) acrylamide / 4-nitroethylcinnamic acid copolymer: 41% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 23
102 g of ethylcellulose used in Example 1 and 48 g of diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-nitroethylcinnamate copolymer obtained in Synthesis Example 24 were mixed with methylene chloride: acetone = 8: 2. It was dissolved in (weight ratio) to give a resin solution of 18% by weight, poured on a polyethylene terephthalate film with a coater, dried at a drying temperature of 25 ° C., and then an optical compensation film (resin composition) having a width of 150 mm was obtained. (Ethylcellulose: 68 wt%, diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-nitroethylcinnamate copolymer: 32 wt%). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 24
88 g of ethylcellulose used in Example 1 and 62 g of diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-cyanoethylcinnamate copolymer obtained in Synthesis Example 25 were mixed with methylene chloride: acetone = 8: 2. It was dissolved in (weight ratio) to give a resin solution of 18% by weight, poured on a polyethylene terephthalate film with a coater, dried at a drying temperature of 25 ° C., and then an optical compensation film (resin composition) having a width of 150 mm was obtained. (Ethylcellulose: 59 wt%, diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-cyanoethylcinnamate copolymer: 41 wt%). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Example 25
75 g of ethyl cellulose used in Example 1 and 75 g of diisopropyl fumarate / N- (n-butoxymethyl) acrylamide / 4-bromocinnamic acid ethyl copolymer obtained in Synthesis Example 26 were mixed with methylene chloride: acetone = 8: 2 ( (Weight ratio) to obtain an 18% by weight resin solution, which was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25 ° C., and an optical compensation film (resin composition) having a width of 150 mm was obtained ( Ethyl cellulose: 50% by weight, diisopropyl fumarate / N- (n-butoxymethyl) acrylamide / 4-bromoethyl cinnamate copolymer: 50% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 1.

  The obtained optical compensation film has high light transmittance, excellent transparency, small haze, in-plane retardation (Re) and Nz coefficient, and has the desired optical characteristics, and Re (589). / The film thickness was large.

Comparative Example 1
150 g of ethyl cellulose used in Example 1 was dissolved in methylene chloride: acetone = 8: 2 (weight ratio) to obtain an 18 wt% resin solution, which was cast on a support of a solution casting apparatus by the T-die method and dried. After drying at a temperature of 25 ° C., a film having a width of 150 mm was obtained. The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 1.4 times at 150 ° C. (thickness after stretching 30 μm). The resulting film was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are shown in Table 2.

  The obtained film had a large out-of-plane retardation (Rth) in the thickness direction and did not have the desired optical characteristics.

Comparative Example 2
180 g of diisopropyl fumarate / monoethyl fumarate / 4-nitrocinnamate copolymer used in Example 1 was dissolved in methylene chloride: acetone = 8: 2 (weight ratio) to obtain an 18 wt% resin solution. After casting on a support of a solution casting apparatus by a die method and drying at a drying temperature of 25 ° C., a film (resin composition) having a width of 150 mm and a thickness of 40 μm was obtained. The resulting film was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 2.

  The obtained film had a small out-of-plane retardation (Rth) in the thickness direction and did not have the desired optical characteristics, and had a small Re (589) / film thickness.

Comparative Example 3
30 g of ethyl cellulose used in Example 1 and 120 g of diisopropyl fumarate / monoethyl fumarate / 4-nitrocinnamate copolymer obtained in Synthesis Example 1 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resin solution was 18% by weight, cast on a support of a solution casting apparatus by the T-die method, dried at a drying temperature of 25 ° C., and then an optical compensation film (resin composition) having a width of 150 mm was obtained ( Ethyl cellulose: 20% by weight, diisopropyl fumarate / monoethyl fumarate / 4-nitroethylcinnamate copolymer: 80% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 2.

  The obtained film did not have the optical characteristics of which the Nz coefficient was intended, and the Re (589) / film thickness was small.

Comparative Example 4
180 g of diethyl fumarate / monoethyl fumarate / 4-nitrocinnamate copolymer used in Example 9 was dissolved in methylene chloride: acetone = 8: 2 (weight ratio) to obtain an 18 wt% resin solution. After casting on a support of a solution casting apparatus by a die method and drying at a drying temperature of 25 ° C., a film (resin composition) having a width of 150 mm and a thickness of 40 μm was obtained. The resulting film was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 2.

  The resulting film had a small out-of-plane retardation (Rth) in the thickness direction and did not have the desired optical characteristics, and had a small Re (589) / film thickness.

Comparative Example 5
30 g of ethylcellulose used in Example 1 and 120 g of diethyl fumarate / monoethyl fumarate / 4-nitrocinnamate copolymer obtained in Synthesis Example 9 were dissolved in methylene chloride: acetone = 8: 2 (weight ratio). The resin solution was 18% by weight, cast on a support of a solution casting apparatus by the T-die method, dried at a drying temperature of 25 ° C., and then an optical compensation film (resin composition) having a width of 150 mm was obtained ( Ethyl cellulose: 20% by weight, diethyl fumarate / monoethyl fumarate / 4-nitroethylcinnamate copolymer: 80% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 2.

  The obtained film did not have the optical characteristics of which the Nz coefficient was intended, and the Re (589) / film thickness was small.

Comparative Example 6
180% of a resin prepared by dissolving 180 g of di-t-butyl fumarate / monoethyl fumarate / 4-nitroethyl cinnamate copolymer used in Example 14 in methylene chloride: acetone = 8: 2 (weight ratio). The solution was cast on a support of a solution casting apparatus by the T-die method and dried at a drying temperature of 25 ° C., and then a film (resin composition) having a width of 150 mm and a thickness of 40 μm was obtained. The resulting film was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 2.

  The resulting film had a small out-of-plane retardation (Rth) in the thickness direction and did not have the desired optical characteristics, and had a small Re (589) / film thickness.

Comparative Example 7
30 g of ethyl cellulose used in Example 1 and 120 g of di-t-butyl fumarate / monoethyl fumarate / 4-nitroethyl cinnamate copolymer obtained in Synthesis Example 15 were mixed with methylene chloride: acetone = 8: 2 (weight ratio). ) To give an 18% by weight resin solution, cast on a support of a solution casting apparatus by a T-die method, dried at a drying temperature of 25 ° C., and then an optical compensation film (resin composition) having a width of 150 mm. (Ethyl cellulose: 20% by weight, di-t-butyl fumarate / monoethyl fumarate / 4-nitroethylcinnamate copolymer: 80% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 2.

  The obtained film did not have the optical characteristics of which the Nz coefficient was intended, and the Re (589) / film thickness was small.

Comparative Example 8
18 weight% of 180 g of diisopropyl fumarate / diethyl fumarate / ethyl 2-hydroxyethyl acrylate / 4-nitrocinnamate copolymer used in Example 21 dissolved in methylene chloride: acetone = 8: 2 (weight ratio). % Resin solution, cast on a support of a solution casting apparatus by T-die method and dried at a drying temperature of 25 ° C., and then a film (resin composition) having a width of 150 mm and a thickness of 40 μm was obtained. The resulting film was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 2.

  The resulting film had a small out-of-plane retardation (Rth) in the thickness direction and did not have the desired optical characteristics, and had a small Re (589) / film thickness.

Comparative Example 9
30 g of ethyl cellulose used in Example 1 and 120 g of diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-nitroethylcinnamate copolymer obtained in Synthesis Example 22 were added to methylene chloride: acetone = 8: 2. It is dissolved in (weight ratio) to give a resin solution of 18% by weight, cast onto a support of a solution casting apparatus by a T-die method, dried at a drying temperature of 25 ° C., and then an optical compensation film (resin having a width of 150 mm) Composition) was obtained (ethyl cellulose: 20% by weight, diisopropyl fumarate / diethyl fumarate / 2-hydroxyethyl acrylate / 4-nitroethyl cinnamate copolymer: 80% by weight). The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 150 ° C. (thickness after stretching: 30 μm). The optical compensation film thus obtained was measured for light transmittance, haze, retardation characteristics, and wavelength dispersion characteristics. The results are also shown in Table 2.

  The obtained film did not have the optical characteristics of which the Nz coefficient was intended, and the Re (589) / film thickness was small.

Claims (22)

30 to 99% by weight of a cellulose resin represented by the following general formula (1), 20 mol% or more of a fumaric acid diester residue unit represented by the following general formula (2), and p represented by the following general formula (3) A resin composition comprising 1 to 70% by weight of a fumaric acid ester copolymer containing 5 mol% or more of a position-substituted cinnamate residue unit.
_{(Wherein, R 1, R 2, R} 3 each independently represent hydrogen or a substituent having 1 to 12 carbon atoms.)
(In formula, R < ₄ >, R < ₅ > shows a C1-C12 alkyl group.)
(In the formula, R ₆ represents an alkyl group having 1 to 12 carbon atoms. X represents a nitro group, a bromo group, an iodo group, a cyano group, a chloro group, a sulfonic acid group, a carboxylic acid group, or a phenyl group.) The resin compound according to claim 1, wherein the cellulose resin represented by the general formula (1) is a cellulose ether. The resin composition according to claim 2, wherein the degree of etherification (substitution degree) of the cellulose ether is 1.5 to 3.0. The fumaric acid ester copolymer is a fumaric acid diester residue unit of 20 to 90 mol%, a p-position substituted cinnamic acid ester residue unit of 5 to 75 mol% represented by the general formula (3), and the following general formula (4 The resin composition according to any one of claims 1 to 3, wherein the resin composition is a fumaric acid ester copolymer containing 5 to 30 mol% of a fumaric acid monoester residue unit represented by formula (1).
(In the formula, R ₇ represents an alkyl group having 1 to 12 carbon atoms.) Fumaric acid ester copolymer, diethyl fumarate residue unit 20 to 95 mol%, the general formula p-position-substituted cinnamic acid ester residue unit 5-75 mol% represented by (3), the following general formula (4 Fumarate ester copolymer containing 0-30 mol% of fumaric acid monoester residue units, 20-90 mol% of diisopropyl fumarate residue units, p-position substituted cinnamon represented by general formula (3) ester residue unit 5-75 mol%, and fumaric acid ester copolymer containing 5 to 30 mol% of fumaric acid monomethyl ester residue unit represented by the following general formula (4), fumarate -t- butyl residues group units 20 to 90 mol%, the general formula (3) p-position-substituted cinnamic acid ester residue unit 5-75 mol% represented by, and fumaric acid monoester residue unit 5 represented by the following general formula (4) Contains ~ 30 mol% The resin composition according to any one of claims 1 to claim 3, characterized in that the fumaric acid ester copolymer selected from the group consisting of fumaric acid ester copolymers.
(In the formula, R ₇ represents an alkyl group having 1 to 12 carbon atoms.) The fumaric acid monoester residue unit according to claim 4 or 5, wherein the monomethyl fumarate residue unit, the monoethyl fumarate residue unit, the monoisopropyl fumarate residue unit, the mono-n-propyl fumarate residue Selected from the group consisting of units, mono-n-butyl fumarate residue units, mono-s-butyl fumarate residue units, mono-t-butyl fumarate residue units, mono-2-ethylhexyl fumarate residue units The resin composition according to claim 4, wherein the resin composition is a fumaric acid monoester residue unit. The fumaric acid ester copolymer is 20 to 94.5 mol% of a fumaric acid diester residue unit represented by the general formula (2), and a p-substituted cinnamate ester unit of 5 to 5 represented by the general formula (3). 75 mol%, and an acrylate residue unit represented by the following general formula (5), a methacrylic ester residue unit represented by the following general formula (6), and an acrylic amide residue represented by the following general formula (7) A fumaric acid ester copolymer comprising a base unit and a residue unit of 0.5 to 30 mol% selected from the group consisting of methacrylic acid amide residue units represented by the following general formula (8): The resin composition according to any one of claims 1 to 3.
(In the formula, R ₈ represents an alkylene group having 1 to 12 carbon atoms.)
(In the formula, R ₉ represents an alkylene group having 1 to 12 carbon atoms.)
(In the formula, R ₁₀ represents an alkyl group having 1 to 12 carbon atoms.)
(In the formula, R ₁₁ represents an alkyl group having 1 to 12 carbon atoms.) p-substituted cinnamate residue unit is 4-nitrocinnamate methyl residue unit, 4-nitrocinnamic acid ethyl residue unit, 4-nitrocinnamic acid isopropyl residue unit, 4-nitrocinnamic acid n-propyl Residue unit, 4-nitrocinnamic acid n-butyl residue unit, 4-nitrocinnamic acid sec-butyl residue unit, 4-nitrocinnamic acid tert-butyl residue unit, 4-nitrocinnamic acid 2-ethylhexyl residue Unit: 4-bromocinnamic acid methyl residue unit, 4-bromocinnamic acid ethyl residue unit, 4-bromocinnamic acid isopropyl residue unit, 4-bromocinnamic acid n-propyl residue unit, 4-bromocinnamic acid n -Butyl residue unit, 4-bromocinnamic acid sec-butyl residue unit, 4-bromocinnamic acid tert-butyl residue unit, 4-bromocinnamic acid 2-ethylhexyl residue Position, 4-iodocinnamate methyl residue unit, 4-iodocinnamate ethyl residue unit, 4-iodocinnamate isopropyl residue unit, 4-iodocinnamate n-propyl residue unit, 4-iodocinnamate n -Butyl residue unit, 4-iodocinnamic acid sec-butyl residue unit, 4-iodocinnamic acid tert-butyl residue unit, 4-iodocinnamic acid 2-ethylhexyl residue unit, 4-cyanocinnamic acid methyl residue Units: 4-cyanocinnamic acid ethyl residue unit, 4-cyanocinnamic acid isopropyl residue unit, 4-cyanocinnamic acid n-propyl residue unit, 4-cyanocinnamic acid n-butyl residue unit, 4-cyanocinnamic leather unit Acid sec-butyl residue unit, 4-cyanocinnamic acid tert-butyl residue unit, 4-cyanocinnamic acid 2-ethylhexyl residue unit, 4-sulfonic acid cinnamic acid Residue unit, 4-sulfonic acid ethyl cinnamate residue unit, 4-sulfonic acid cinnamate isopropyl residue unit, 4-sulfonic acid cinnamic acid n-propyl residue unit, 4-sulfonic acid cinnamic acid n-butyl residue unit, 4-sulfonic acid cinnamic acid sec-butyl residue unit, 4-sulfonic acid cinnamic acid tert-butyl residue unit, 4-sulfonic acid cinnamic acid 2-ethylhexyl residue unit, 4 -Carboxylic acid ethyl cinnamate residue unit, 4-carboxylic acid cinnamate isopropyl residue unit, 4-carboxylic acid cinnamate n-propyl residue unit, 4-carboxylic acid cinnamate n-butyl residue unit 4-carboxylic cinnamate sec-butyl residue unit, 4-carboxylic cinnamate tert-butyl residue unit, 4-carboxylic cinnamate 2-ethylhexyl residue unit, methyl 4-phenylcinnamate residue Units, 4-phenylcinnamic acid ethyl residue unit, 4-phenylcinnamic acid isopropyl residue unit, 4-phenylcinnamic acid n-propyl residue unit, 4-phenylcinnamic acid n-butyl residue unit, It is selected from the group consisting of a 4-phenylcinnamic acid sec-butyl residue unit, a 4-phenylcinnamic acid tert-butyl residue unit, and a 4-phenylcinnamic acid 2-ethylhexyl residue unit. The resin composition according to any one of claims 1 to 7. An optical compensation film comprising the resin composition according to any one of claims 1 to 8, and having a thickness of 5 to 200 µm. An optical compensation film comprising the resin composition according to any one of claims 1 to 8, and having a thickness of 20 to 60 µm. The in-plane retardation (Re) represented by the following formula (1) is 80 to 300 nm, and the Nz coefficient represented by the following formula (2) is 0.35 to 0.65, or The optical compensation film according to claim 10.
Re = (ny−nx) × d (1)
Nz = (ny−nz) / (ny−nx) (2)
(Where nx represents the refractive index in the fast axis direction in the film plane, ny represents the refractive index in the slow axis direction in the film plane, nz represents the refractive index outside the film plane, and d represents the film. Indicates thickness.) Plane retardation represented by the following formula (1) (Re) is 50 to 300 nm, claim 9 Nz coefficient represented by the following formula (2) is characterized in that it is a -0.2～0.2 Or the optical compensation film of Claim 10.
Re = (ny−nx) × d (1)
Nz = (ny−nz) / (ny−nx) (2)
(Where nx represents the refractive index in the fast axis direction in the film plane, ny represents the refractive index in the slow axis direction in the film plane, nz represents the refractive index outside the film plane, and d represents the film. Indicates thickness.) The in- plane retardation (Re) represented by the following formula (1) is 0 to 20 nm, and the out-of-plane retardation (Rth) represented by the following formula (3) is −150 to 20 nm. Item 11. The optical compensation film according to Item 9 or Item 10.
Re = (ny−nx) × d (1)
Rth = [(nx + ny) / 2−nz] × d (3)
(Where nx represents the refractive index in the fast axis direction in the film plane, ny represents the refractive index in the slow axis direction in the film plane, nz represents the refractive index outside the film plane, and d represents the film. Indicates thickness.) The optical compensation film according to any one of claims 9 to 13, wherein the light transmittance is 85% or more. The optical compensation film according to any one of claims 9 to 14, wherein the haze is 1% or less. The ratio Re (450) / Re (550) of retardation at 450 nm to retardation at 550 nm is 0.60 <Re (450) / Re (550) <1.05. Item 16. The optical compensation film according to any one of Items 15. The ratio Re (589) (nm) / film thickness (μm) of retardation at 589 nm and film thickness is 4.0 nm / μm or more, wherein the ratio is at least 4.0 nm / μm. The optical compensation film described in 1. 30-99% by weight of a cellulose-based resin represented by the general formula (1), 20 mol% or more of a fumaric acid diester residue unit represented by the general formula (2), and a p-position substituted silicon represented by the general formula (3) A resin composition containing 1 to 70% by weight of a fumaric acid ester copolymer containing 5 mol% or more of a cinnamate residue unit is dissolved in a solvent, and the resulting resin solution is cast on a substrate, dried, It peels from a base material, The manufacturing method of the optical compensation film of any one of Claims 9-17 characterized by the above-mentioned. 19. The method for producing an optical compensation film according to claim 18, wherein the degree of etherification when the cellulose resin represented by the general formula (1) is cellulose ether is 1.5 to 3.0. The method for producing an optical compensation film according to claim 18, wherein the resin composition according to claim 6 or 7 is used. 19. The method for producing an optical compensation film according to claim 18 , wherein a film having a thickness of 10 to 200 [mu] m obtained by casting is uniaxially stretched or unbalanced biaxially stretched. 19. The method for producing an optical compensation film according to claim 18 , wherein a film having a thickness of 30 to 100 [mu] m obtained by casting is uniaxially stretched or unbalanced biaxially stretched.