Novel fumaric acid ester resin and film including same

Abstract

Provided is a novel fumaric acid ester resin that has an excellent storage modulus at high temperatures and a film that includes the fumaric acid ester resin. A fumaric acid ester resin according to the present invention includes a residue unit represented by formula (1) and a residue unit represented by formula (2).　In formula (1), R1 and R2 each independently represent an alkyl group that has a norbornane skeleton.　In formula (2), R3 and R4 each independently represent a C1–12 straight-chain alkyl group, a C3–12 branched alkyl group, or a C3–6 cyclic alkyl group.

Description

Novel fumaric acid ester resin and film containing same

[0001] The present disclosure relates to novel fumarate-based resins and films containing the same.

[0002] Liquid crystal displays (LCDs) are the most important display devices in our multimedia society, and are widely used in everything from mobile phones and computer monitors to laptops and televisions. Many optical films are used as polarizers in LCDs to improve display characteristics such as contrast when viewed from the front or at an angle, and color compensation.

[0003] A typical example of an optical film related to polarizing plates is a retardation film. Retardation films are used as anti-reflection layers in liquid crystal displays, touch panels, and organic EL devices. Conventional retardation films are made of polycarbonate or cyclic polyolefin, both of which are polymers with positive birefringence. Here, the positive and negative birefringence are defined as follows:

[0004] The optical anisotropy of a polymer film molecularly oriented by stretching, casting with a coater, or the like can be represented by an index ellipsoid, where nx is the refractive index in the fast axis direction (the direction with the smallest refractive index) in the film plane, ny is the refractive index in the in-plane direction of the film (slow axis) perpendicular to nx, and nz is the refractive index in the thickness direction of the film (the perpendicular direction out of the film plane). In other words, in uniaxial stretching of a polymer having negative birefringence, the refractive index in the direction of the stretching axis is small (fast axis: stretching direction), and in uniaxial stretching of a polymer having positive birefringence, the refractive index in the direction perpendicular to the stretching axis is small (fast axis: direction perpendicular to the stretching direction).

[0005] Many polymers have positive birefringence. Polymers with negative birefringence include acrylic resins and polystyrene, but acrylic resins exhibit little retardation and are insufficient in terms of their properties as retardation films. Polystyrene is not currently used due to optical property issues, such as a high wavelength dependency of retardation, practical issues such as low heat resistance, and retardation stability issues, such as a high photoelastic coefficient at room temperature that causes the retardation to change with even slight stress. There is strong market demand for such retardation films that exhibit negative birefringence. Various retardation films have been developed to meet the above-mentioned required properties. Patent Documents 1 and 2 propose fumaric acid ester-based resins as optical films that exhibit negative birefringence and have a high refractive index in the thickness direction.

[0006] JP 2008-064817 A JP 2011-107281 A

[0007] In recent years, with the diversification of display use environments, there has been a demand for highly heat-resistant retardation films that are resistant to dimensional changes even when used in high-temperature environments. Retardation films using fumaric acid ester resins obtained in Patent Documents 1 and 2 have excellent optical properties such as retardation characteristics and wavelength dependency, but are prone to stress deformation at high temperatures due to their low storage modulus at high temperatures. Therefore, there has been a demand for an improvement in the storage modulus at high temperatures, and there has been a demand for fumaric acid ester resins with higher heat resistance. Fumaric acid ester resins have a β relaxation temperature (T β ) and T β If T is low, the film containing the resin is likely to be deformed by stress at high temperatures. β In recent years, from the viewpoint of environmental protection, there has been a wide demand for materials made from environmentally friendly biomass raw materials.

[0008] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a novel fumarate ester-based resin having an excellent storage modulus at high temperatures and a film containing the same. The monomer of the fumarate ester-based resin can be synthesized from a biomass raw material, and therefore the compound can meet the requirements of the above-mentioned problems.

[0009] As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by using a specific fumaric acid ester-based resin, and have thus completed the present invention.

[0010] [1] A fumarate resin containing a residue unit represented by the following formula (1) and a residue unit represented by the following formula (2): (In the formula, R １ and R ２ each independently represents an alkyl group having a norbornane skeleton. (In the formula, R ３ and R ４ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

[0011] [2] R in formula (1) １ and R ２ The fumaric acid ester-based resin according to [1] above, wherein at least one of the above groups contains a bornyl group.

[0012] [3] The fumarate ester resin according to the above [1] or [2], wherein the residue unit represented by formula (1) is a residue unit represented by any one of the following formulae (1-1) to (1-3), or an enantiomer thereof:

[0013] [4] R in formula (2) ３ and R ４ [4] The fumarate ester-based resin according to any one of [1] to [3], wherein at least one of the groups is an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, a tert-pentyl group, a sec-hexyl group, a tert-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0014] [5] The fumarate ester resin according to any one of [1] to [4] above, which has a weight-average molecular weight (Mw) of 50,000 or more in terms of standard polystyrene obtained from an elution curve measured by gel permeation chromatography (GPC).

[0015] [6] β relaxation temperature (T β ) is not observed at 120°C or lower.

[0016] [7] The fumarate ester resin according to any one of [1] to [6] above, which contains 1 mol % to 80 mol % of residue units represented by formula (1) and 20 mol % to 99 mol % of residue units represented by formula (2).

[0017] [8] A film containing the fumaric acid ester resin according to any one of [1] to [7] above.

[0018] [9] The film according to the above [8], characterized in that the out-of-plane retardation (Rth) measured at a wavelength of 589 nm, as represented by the following formula (A), is −700 to 0 nm: Rth=[(nx+ny) / 2−nz]×d(A), where nx is the refractive index in the fast axis direction (the direction with the smallest refractive index) in the film plane, ny is the refractive index in the slow axis direction in the film plane, nz is the refractive index in the perpendicular direction out of the film plane, and d is the film thickness.

[0019]

[10] Storage modulus at 100 ° C. is 7.00 × 10 ８ The film according to the above [8] or [9], having a modulus of elasticity of 100 Pa or more.

[0020]

[11] Storage modulus at 200 ° C. is 1.40 × 10 ８ The film according to any one of the above [8] to

[10] , having a modulus of elasticity of 100 Pa or more.

[0021]

[12] The film according to any one of the above [8] to

[11] , characterized in that the linear expansion coefficient α, as expressed by the following formula (B), is 110 ppm / °C or less: α=Δl / (ΔT×l)(B), where Δl is the change in film length upon temperature change, ΔT is the change in film temperature, and l is the film length before the temperature change.

[0022] According to the present disclosure, it is possible to provide a novel fumarate ester-based resin having an excellent storage modulus at high temperatures and a film containing the same.

[0023] <Fumaric acid ester-based resin> The fumaric acid ester-based resin according to one embodiment of the present disclosure will be described in detail below. The present disclosure relates to a fumaric acid ester-based resin (hereinafter also referred to as the "resin of the present disclosure") containing a residue unit represented by the following formula (1) and a residue unit represented by the following formula (2): (In the formula, R １ and R ２ each independently represents an alkyl group having a norbornane skeleton. (In the formula, R ３ and R ４ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

[0024] β relaxation temperature (T β ) is due to the side chain movement of the resin. １ By having a residue unit represented by formula (1) in which a rigid side chain of R and R2 is introduced, the resin exhibits excellent storage modulus at high temperatures and high heat resistance. Residue units represented by formula (1) alone have a high melting point due to their rigid structure, making it difficult to increase the molecular weight by polymerization. By copolymerizing a monomer that provides a residue unit represented by formula (1) with a monomer that provides a residue unit represented by formula (2), the resulting resin can be increased in molecular weight while maintaining high heat resistance. This makes films containing the resin of the present disclosure useful as retardation films, which require high heat resistance.

[0025] [Residue unit represented by formula (1)] (In the formula, R １ and R ２ each independently represents an alkyl group having a norbornane skeleton.

[0026] R in formula (1) １ , R ２The alkyl group having a norbornane skeleton in the formula (1) is a norbornyl group which may have a substituent, and the substituent is at least one selected from the group consisting of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. The norbornyl group is represented by any of the following formulas (1-A) to (1-G), and the bond direction may be either endo-type or exo-type. Among them, formulas (1-A) and (1-E) are preferred. The substituent is preferably a linear alkyl group. R in formula (1) １ and R ２ are each independent, but preferably have the same structure. (In the formula, ** represents the position of the ester bond in formula (1).)

[0027] The number of carbon atoms in the linear alkyl group as a substituent is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. Examples of linear alkyl groups include a methyl group, an ethyl group, a propyl group, and a butyl group. The number of carbon atoms in the branched alkyl group as a substituent is preferably 3 to 12, more preferably 3 to 8, and even more preferably 3 to 5. Examples of branched alkyl groups include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, and a tert-pentyl group. The number of carbon atoms in the cyclic alkyl group as a substituent is preferably 3 to 6. Examples of cyclic alkyl groups include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0028] Since the resin of the present disclosure can be made to have a high molecular weight while maintaining high heat resistance, R １ and R ２ Preferably, at least one of the above groups contains a bornyl group. The bornyl group has one methyl group at position 1 of the norbornyl group and two methyl groups at position 7, but may have substituents at other positions. The substituents that the bornyl group may have are the same as the substituents that the norbornyl group may have. The bornyl group is represented by any of the following formulas (1-a) to (1-e), and formulas (1-a), (1-b), (1-d), and (1-e) represent groups in which the bond direction is either endo-type or exo-type. Among these, formulas (1-a) and (1-e) are preferred. (In the formula, ** represents the position of the ester bond in formula (1).)

[0029] Specific examples of the residue unit represented by formula (1) include residue units represented by any of the following formulae (1-1) to (1-46), or enantiomers thereof. Among these, a residue unit represented by any of formulas (1-1), (1-2), (1-3), (1-6), (1-8), (1-17), (1-19), (1-22), (1-26), (1-28), (1-30), (1-32), (1-33), (1-34), (1-35), (1-38), (1-39), (1-41), and (1-46) is preferred, and among these, a residue unit represented by any of formulas (1-1), (1-2), (1-3), (1-8), (1-17), (1-19), (1-26), (1-28), (1-30), and (1-38) is more preferred, and a residue unit represented by any of formulas (1-1), (1-2), and (1-3) is particularly preferred. These may be used alone or in combination of two or more, or may be in an isomeric mixture state.

[0030]

[0031]

[0032] The method for producing a fumarate ester-based resin containing a residue unit represented by formula (1) may be any method as long as it can produce the resin, and examples thereof include a method of radically polymerizing a fumarate ester monomer represented by the following formula (iv): In the present disclosure, the method for synthesizing the fumarate ester monomer represented by formula (iv) may be any method as long as it can produce the fumarate ester monomer, and examples thereof include a method represented by the following formula (a): (In formula (a), R in formula (i) １ and R of formula (ii) ２ is R in formula (1) １ and R ２ X in formula (iii) has the same meaning as １ and X ２ R in formula (iv) represents an independent leaving group. １ and R ２ is R in formula (1)１ and R ２ is synonymous with

[0033] The formula (a) is a method for synthesizing a fumaric acid ester represented by formula (iv) by reacting an alcohol represented by formula (i) or (ii) with a fumaric acid compound represented by formula (iii).

[0034] R in the alcohols of formula (i) and (ii) １ and R ２ is R in formula (1). １ and R ２The same alcohols may be used as the alcohols represented by formulas (i) and (ii). The alcohols may be used in the form of a mixture of isomers, but it is preferable to use a single alcohol. Specific alcohols include (-)-borneol, (+)-borneol, (±)-borneol, (-)-isoborneol, (+)-isoborneol, (±)-isoborneol, (-)-fenchol, (+)-fenchol, (±)-fenchol, isofenchol, 4,7,7-trimethylbicyclo[2.2.1]heptan-1-ol, 4,5,5-trimethylbicyclo[2.2.1]heptan-6-ol, 1-ethyl-7,7-dimethylbicyclo[2.2.1]heptan- 2-ol, 2,3,3-trimethylbicyclo[2.2.1]heptan-1-ol, 4,5,5-trimethylbicyclo[2.2.1]heptan-2-ol, 4,6,6-trimethylbicyclo[2.2.1]heptan-5-ol, 1,5,5-trimethylbicyclo[2.2.1]heptan-7-ol, 4,5,5-trimethylbicyclo[2.2.1]heptan-7-ol, 1,5,5-trimethylbicyclo[2.2.1]heptan-2-ol, 1,2,2-trimethylbicyclo[2.2. 1]heptan-7-ol, 1,5,5-trimethylbicyclo[2.2.1]heptan-3-ol, 7-ethyl-1,7-dimethylbicyclo[2.2.1]heptan-2-ol, 1-ethyl-3,3-dimethylbicyclo[2.2.1]heptan-2-ol, 7-ethyl-4,7-dimethylbicyclo[2.2.1]heptan-3-ol, 2,7,7-trimethylbicyclo[2.2.1]heptan-1-ol, 2,2,3-trimethylbicyclo[2.2.1]heptan-1-ol, 2-methyl Chiliisoborneol, 1,2,3,3-tetramethylbicyclo[2.2.1]heptan-2-ol, 2-ethyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, 2-(1,1-dimethylethyl)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, 1,5,5,7,7-pentamethylbicyclo[2.2.1]heptan-6-ol, 2-cyclopentyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, 1,4,5,7,7-pentamethylbicyclo[2.2.1]heptan-6-ol, 2,3,3,4-tetramethylbicyclo[2.2.1]heptan-2-ol, 5-ethyl-1,5,7,7-tetramethylbicyclo[2.2.1]heptan-6-ol, 2-cyclohexyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, 2,3,3-trimethylborneol, 1,2,4,7 ,7-pentamethylbicyclo[2.2.1]heptan-2-ol, 1,2,3,7,7-pentamethylbicyclo[2.2.1]heptan-2-ol, 3-ethyl-1,2,7,7-tetramethylbicyclo[2.2.1]heptan-2-ol, 1,2,5,5-tetramethylbicyclo[2.2.1]heptan-2-ol, 1,3,3,7-tetramethylbicyclo[2.2.1]-7-ol 3,3-diethyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 2-ethyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 2-ethyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, 2,3,3,7,7-pentamethylbicyclo[2.2.1]-2-ol, 1-cyclohexylbicyclo[2.2.1] heptan-2-ol, 2-cyclohexylbicyclo[2.2.1]heptan-7-ol, 2-cyclobutyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, 2-cyclopropyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, 2-cyclohexyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, and the like. Among them, (-)-borneol, (+)-borneol, (±)-borneol, (-)-isoborneol, (+)-isoborneol, (±)-isoborneol, 4,7,7-trimethylbicyclo[2.2.1]heptan-1-ol, 1-ethyl-7,7-dimethylbicyclo[2.2.1]heptan-2-ol, 7-ethyl-1,7-dimethylbicyclo[2.2.1]heptan-2-ol, 7-ethyl-4,7-dimethylbicyclo[2.2.1]heptan-3-ol, 2-methylisoborneol, 1,5,5,7,7-pentamethylbicyclo[2.2.1]heptan-6-ol, 1,4,5,7,7-pentamethylbicyclo[2.2.1]heptan-6-ol, 5-ethyl-1,5,7,7-tetramethylbicyclo[2.2.1]heptan-6-ol, 2,3,3-trimethylborneol, 1,2,4,7,7-pentamethylbicyclo[2.2.1]heptan-2-ol, 1,2,3,7,7-pentamethylbicyclo[2.2.1]heptan-2-ol, 3-ethyl -1,2,7,7-tetramethylbicyclo[2.2.1]heptan-2-ol, 3,3-diethyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 2-ethyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 2,3,3,7,7-pentamethylbicyclo[2.2.1]-2-ol, 2-cyclohexyl-1,7,7-trimethyl Rubicyclo[2.2.1]heptan-2-ol is preferred, and among these, (-)-borneol, (+)-borneol, (±)-borneol, (-)-isoborneol, (+)-isoborneol, (±)-isoborneol, 1-ethyl-7,7-dimethylbicyclo[2.2.1]heptan-2-ol, 7-ethyl-1,7-dimethylbicyclo[2.2.1]heptan-2-ol, and -ol, 7-ethyl-4,7-dimethylbicyclo[2.2.1]heptan-3-ol, 1,5,5,7,7-pentamethylbicyclo[2.2.1]heptan-6-ol, 1,4,5,7,7-pentamethylbicyclo[2.2.1]heptan-6-ol, 5-ethyl-1,5,7,7-tetramethylbicyclo[2.2.1]heptan-6-ol, 3,3-diethyl-1,7,7-Trimethylbicyclo[2.2.1]heptan-2-ol is more preferred, and (-)-borneol, (+)-borneol, (±)-borneol, (-)-isoborneol, (+)-isoborneol, and (±)-isoborneol are particularly preferred. Among these alcohols, for example, borneol is a natural product derived from plants, but synthetic products can be synthesized from turpentine, which contains pinene, a biomass raw material, or camphor, which is synthesized from pinene. Isoborneol can also be synthesized from camphene, which can be synthesized from pinene. Therefore, it is believed that other alcohols having a similar structure to borneol and isoborneol can also be synthesized using biomass raw materials such as pinene. In recent years, from the perspective of environmental protection, there has been a widespread demand for materials made from environmentally friendly biomass raw materials, and the fumaric acid ester monomer is a compound that can meet this demand.

[0035] X in the fumaric acid compound represented by formula (iii) １ and X ２ Each of X represents an independent leaving group, but in order to obtain a fumarate ester monomer represented by formula (iv) in high yield, １ and X ２ Specific examples of the fumaric acid compound include fumaric acid and fumaric acid dichloride, and among these, fumaric acid dichloride is preferred because of its high elimination ability.

[0036] The reaction of an alcohol with a fumaric acid compound (formula (a)) is not particularly limited as long as the reaction is possible, and a condensing agent, a catalyst, or a base may or may not be used. The reaction temperature may be selected appropriately depending on the substrate.

[0037] Condensing agents used in the reaction of alcohols and fumaric acid compounds include 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide, Examples of suitable ester bond-forming condensing agents include diimide-p-toluenesulfonate, N,N'-di-tert-butylcarbodiimide, and 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide, and among these, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride, N,N'-diisopropylcarbodiimide, and N,N'-dicyclohexylcarbodiimide are preferred. Two or more of these ester bond-forming condensing agents may be used.

[0038] An acid catalyst can be used as the catalyst for the reaction between the alcohol and the fumaric acid compound. Preferred examples of the acid catalyst include sulfuric acid, p-toluenesulfonic acid, xylenesulfonic acid, and ion exchange resins containing sulfo groups, and one or more of these can be used. Examples of ion exchange resins containing sulfo groups include Amberlite and Nafion. Of these, sulfuric acid, p-toluenesulfonic acid, and xylenesulfonic acid are more preferred.

[0039] The base used in the reaction of the alcohol with the fumaric acid compound can be either an organic base or an inorganic base. Examples of organic bases include triethylamine, tributylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, piperidine, piperazine, pyrrolidine, morpholine, N-methylmorpholine, imidazole, and N-methylimidazole. Examples of inorganic bases include potassium carbonate, sodium carbonate, and sodium hydrogencarbonate.

[0040] The solvent used in the reaction of the alcohol and the fumaric acid compound is not particularly limited as long as it is a solvent that does not harm the reaction, and examples thereof include halogenated solvents such as dichloromethane and chloroform; ether solvents such as tetrahydrofuran and diethyl ether; amide solvents such as N,N-dimethylformamide; nitrile solvents such as acetonitrile; and aromatic solvents such as benzene and toluene. These solvents may be used alone or in combination of two or more.

[0041] The reaction temperature in the reaction between the alcohol and the fumaric acid compound is preferably from -50 to 200°C, more preferably from -10 to 150°C, and particularly preferably from 0 to 90°C.

[0042] [Residue unit represented by formula (2)] (In the formula, R ３ and R ４ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

[0043] The number of carbon atoms in the linear alkyl group is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the branched alkyl group is preferably 3 to 8, more preferably 3 to 6. Specific examples of R ３ , R ４ Examples of the alkyl group include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, a tert-pentyl group, a sec-hexyl group, a tert-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Among these, an ethyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, and a cyclohexyl group are preferred because they result in an optical film having excellent heat resistance and mechanical properties, and an ethyl group and an isopropyl group are more preferred, with an isopropyl group being particularly preferred.

[0044] Here, the fumarate residue unit represented by formula (2) specifically includes a diethyl fumarate residue, a diisopropyl fumarate residue, a di-sec-butyl fumarate residue, a di-tert-butyl fumarate residue, a di-sec-pentyl fumarate residue, a di-tert-pentyl fumarate residue, a di-sec-hexyl fumarate residue, a di-tert-hexyl fumarate residue, a dicyclopropyl fumarate residue, a dicyclopentyl fumarate residue, a dicyclohexyl fumarate residue, and the residues in which R ３ or R ４ and residues in which the following has been replaced (for example, an ethyl isopropyl fumarate residue, an ethyl-sec-butyl fumarate residue, etc.). Among these, diethyl fumarate residue, diisopropyl fumarate residue, di-sec-butyl fumarate residue, di-tert-butyl fumarate residue, dicyclopentyl fumarate residue, dicyclohexyl fumarate residue, isopropylethyl fumarate residue, isopropyl-tert-butyl fumarate residue, cyclohexylethyl fumarate residue, cyclohexylisopropyl fumarate residue, cyclohexyl-sec-butyl fumarate residue, cyclohexyl-tert-butyl fumarate residue, cyclohexyl-sec-pentyl fumarate residue, and Preferred are cyclohexyl-tert-pentyl residue, cyclohexyl-sec-hexyl fumarate residue, cyclohexyl-tert-hexyl fumarate residue, cyclohexylcyclopentyl fumarate residue, etc., more preferred are diethyl fumarate residue, diisopropyl fumarate residue, di-sec-butyl fumarate residue, di-tert-butyl fumarate residue, dicyclopentyl fumarate residue, dicyclohexyl fumarate residue, further preferred are diethyl fumarate residue and diisopropyl fumarate residue, and particularly preferred is diisopropyl fumarate residue. These may be used alone or in combination of two or more.

[0045] [Resin of the Present Disclosure] The resin of the present disclosure is a fumaric acid ester-based resin containing 1 mol% to 80 mol%, preferably 3 mol% to 50 mol%, particularly preferably 5 mol% to 40 mol%, further preferably 6 mol% to 30 mol%, and extremely preferably 9 mol% to 30 mol% of residue units represented by formula (1), which results in a resin with excellent heat resistance and mechanical properties. In this specification, the content (mol%) of residue units represented by formula (1) contained in the fumaric acid ester-based resin is a value measured by the measurement method described in the composition ratio of the polymer (resin) in the Examples below.

[0046] The resin of the present disclosure is a fumaric acid ester-based resin containing 20 mol% to 99 mol%, preferably 50 mol% to 97 mol%, particularly preferably 60 mol% to 95 mol%, even more preferably 70 mol% to 94 mol%, and extremely preferably 70 mol% to 91 mol% of residue units represented by formula (2), which results in a resin with excellent heat resistance and mechanical properties. In this specification, the content (mol%) of residue units represented by formula (2) contained in the fumaric acid ester-based resin is a value measured by the measurement method described in the composition ratio of the polymer (resin) in the Examples below.

[0047] The resin of the present disclosure may contain residue units other than those represented by formulas (1) and (2). Examples of residue units other than those represented by formulas (1) and (2) include one or more of the following: styrene residues, α-methylstyrene residues, and other styrene residues; acrylic acid residues; acrylic acid ester residues, such as methyl acrylate residues, ethyl acrylate residues, butyl acrylate residues, and isobornyl acrylate residues; methacrylic acid residues; methacrylic acid ester residues, such as methyl methacrylate residues, ethyl methacrylate residues, butyl methacrylate residues, and isobornyl methacrylate residues; vinyl ester residues, such as vinyl acetate residues and vinyl propionate residues; acrylonitrile residues; methacrylonitrile residues; olefin residues, such as ethylene residues and propylene residues.

[0048] In the resin of the present disclosure, since it has particularly excellent mechanical properties, the weight average molecular weight (Mw) calculated as standard polystyrene obtained from an elution curve measured by gel permeation chromatography (GPC) is preferably 50,000 or more, more preferably 80,000 to 5,000,000, particularly preferably 100,000 to 2,000,000, even more preferably 150,000 to 1,000,000, and extremely preferably 180,000 to 800,000. In this specification, the weight average molecular weight is a value measured by the measurement method described in the Examples below.

[0049] The resin of the present disclosure has particularly excellent heat resistance, and therefore, the β relaxation temperature (T β ) is not observed at temperatures below 120°C, preferably below 130°C, more preferably below 140°C, particularly preferably below 150°C, even more preferably below 180°C, and most preferably below 200°C. β is a value measured by the measurement method in the Examples described below.

[0050] [Method for producing resin of the present disclosure] The method for producing the resin of the present disclosure may be any method as long as the resin can be produced, and examples include a method for radically polymerizing a fumarate ester monomer and a method for transesterifying a fumarate ester resin. Of these, the method for radically polymerizing a fumarate ester monomer is preferred.

[0051] As the radical polymerization method, for example, any of bulk polymerization, solution polymerization, suspension polymerization, precipitation polymerization, emulsion polymerization, etc. Among them, bulk polymerization or suspension polymerization is preferred because it can produce a high molecular weight fumarate ester-based resin.

[0052] The polymerization temperature for radical polymerization is not particularly limited as long as it is equal to or higher than the melting point of the fumaric acid ester monomer, but a lower temperature is preferred, particularly since a high molecular weight fumaric acid ester resin can be obtained. For example, a temperature of 120°C or lower is preferred, more preferably 100°C or lower, and particularly preferably 80°C or lower.

[0053] Examples of polymerization initiators for radical polymerization include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, and tert-butyl peroxypivalate. organic peroxides such as tert-butyl perhydroxyoxide and tert-butylperoxy-2-ethylhexanoate; and azo initiators such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionate)dimethyl, 2,2'-azobis(2-butyronitrile), 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate and 1,1'-azobis(cyclohexane-1-carbonitrile).

[0054] <Film> A film according to one embodiment of the present disclosure will be described in detail below. The resin according to the present disclosure can be suitably used as a film for optical components. In particular, since the resin according to the present disclosure has rigid side chains, it has an excellent storage modulus at high temperatures, and is less susceptible to deformation due to stress even in a high-temperature environment, allowing it to be used as a highly durable optical film.

[0055] In the film of the present disclosure, the out-of-plane retardation (Rth) measured at a wavelength of 589 nm, as shown in the following formula (A), is preferably −700 to 0 nm, more preferably −240 to −20 nm, and particularly preferably −160 to −30 nm, in order to obtain an optical film with excellent viewing angle characteristics. In this specification, the out-of-plane retardation of the film is a value measured, for example, by the measurement method in the Examples described later. Rth=[(nx+ny) / 2−nz]×d(A) (In the formula, nx is the refractive index in the fast axis direction (the direction with the smallest refractive index) in the film plane, ny is the refractive index in the slow axis direction in the film plane, nz is the refractive index in the perpendicular direction out of the film plane, and d is the film thickness (nm).)

[0056] In terms of adaptability to thinner optical components, the thickness of the film is preferably 200.0 μm or less, more preferably 0.1 to 80.0 μm, and particularly preferably 0.1 to 50.0 μm.

[0057] In the film of the present disclosure, deformation due to stress is small even in a high-temperature environment, so the storage modulus at 100°C is preferably 7.00 × 10 ８ Pa or more, more preferably 8.00 x 10 ８ Pa or more 3.00×10 ９ More preferably, 1.00 x 10 ９ Pa or more 2.00×10 ９ Particularly preferably, 1.30 × 10 ９ Pa or more 2.00×10 ９ In this specification, the storage modulus at 100°C is a value measured by the measurement method in the examples described later.

[0058] In the film of the present disclosure, deformation due to stress is small even in a high-temperature environment of around 200°C, so the storage modulus at 200°C is preferably 1.40 × 10 ８ Pa or more, more preferably 1.50 × 10 ８ Pa or more 3.00×10 ９ More preferably, 1.60×10 ９ Pa or more 2.00×10 ９ Below, particularly preferably 1.70 × 10 ９ Pa or more 2.00×10 ９ Below, very preferably 2.00 × 10 ９ Pa or more 2.00×10 ９ In this specification, the storage modulus at 200°C is a value measured by the measurement method in the examples described later.

[0059] The film of the present disclosure contains a resin having a rigid norbornane skeleton in its side chain, resulting in a film with a small linear expansion coefficient and excellent dimensional stability at high temperatures. In the film of the present disclosure, the linear expansion coefficient α, as shown in the following formula (B), is preferably 110 ppm / °C or less, more preferably 0 to 100 ppm / °C, even more preferably 10 to 95 ppm / °C, and particularly preferably 15 to 80 ppm / °C, since this results in a film with excellent dimensional stability at high temperatures. In this specification, the linear expansion coefficient of the film is a value measured using the measurement method described in the Examples below. α=Δl / (ΔT×l)(B) (In the formula, Δl is the change in film length with temperature change, ΔT is the change in film temperature, and l is the film length before the temperature change.)

[0060] The film may contain an antioxidant to improve thermal stability, such as a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a lactone-based antioxidant, an amine-based antioxidant, a hydroxylamine-based antioxidant, a vitamin E-based antioxidant, or other antioxidants, and these antioxidants may be used alone or in combination of two or more.

[0061] The film may contain a hindered amine light stabilizer or an ultraviolet absorber to improve weather resistance, such as benzotriazole, benzophenone, triazine, or benzoate.

[0062] The film may also contain other polymers, surfactants, polymer electrolytes, conductive complexes, pigments, dyes, antistatic agents, antiblocking agents, lubricants, etc., within the scope of the invention.

[0063] The content of the resin of the present disclosure in the film of the present disclosure is not particularly limited, but may be 50% by mass or more, 70% by mass or more, 90% by mass or more, or 95% by mass or more, or may be 100% by mass, relative to the total mass of the film of the present disclosure.

[0064] The method for producing the film is not particularly limited, and the film can be produced, for example, by forming a raw material resin into a long film by a method such as solution casting.

[0065] Here, the solution casting method is a method in which a resin solution (generally called a dope) is cast onto a supporting substrate, and then the solvent is evaporated by heating and drying, and the film is peeled off from the substrate to obtain a film.

[0066] The solvent used for the resin solution in the solution casting method may be any solvent that can dissolve the resin, etc., and the boiling point of the solvent is preferably 200°C or lower, more preferably 170°C or lower, so that residual solvent is less likely to remain when a film is obtained.

[0067] Examples of the solvent include halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, and dichlorobenzene; phenols such as phenol and chlorophenol; aromatic hydrocarbons such as benzene, toluene, xylene, methoxybenzene, mesitylene, and dimethoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, and N-methyl-2-pyrrolidone; and esters such as ethyl acetate and butyl acetate. alcohol-based solvents such as t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, and 2-methyl-2,4-pentanediol; amide-based solvents such as dimethylformamide and dimethylacetamide; nitrile-based solvents such as acetonitrile and butyronitrile; ether-based solvents such as diethyl ether, dibutyl ether and tetrahydrofuran; and solvents obtained by using carbon disulfide, ethyl cellosolve, butyl cellosolve, etc., either alone or in combination.

[0068] The viscosity of the resin solution can be adjusted by the molecular weight and concentration of each component and the type of solvent. There are no particular restrictions on the viscosity of the resin solution, but to facilitate film casting, it is preferably 100 to 30,000 cps, more preferably 300 to 20,000 cps, and particularly preferably 300 to 15,000 cps.

[0069] In the present disclosure, the concentration of the raw resin in the dope is not particularly limited as long as dissolution and film formation are possible. The dissolution method may be performed so that the desired concentration is achieved during dissolution, or a low-concentration solution may be prepared in advance and then adjusted to a desired high-concentration solution by a concentration process. Furthermore, a high-concentration resin solution may be prepared in advance, and then various additives may be added to obtain a desired low-concentration resin solution.

[0070] The support substrate used is not particularly limited, and examples thereof include polymer substrates made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonates, polystyrene, polyethylene, polypropylene, polyacrylic, polyvinyl chloride and polyvinylidene chloride, cellulose acetate, cellulose ether, polyvinyl alcohol, polyamide, polyimide, polyarylate, polysulfone, polyethersulfone, polyetherketone, phenolic resins, epoxy resins, alicyclic polyolefins, norbornene-based thermoplastic transparent resins, glass substrates such as glass plates and quartz substrates, metal substrates such as aluminum, stainless steel, and ferrotypes, and inorganic substrates such as ceramic substrates. Preferred examples of the substrate include polymer substrates such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, polyacrylic, cellulose acetate and cellulose ether, polyimides, alicyclic polyolefins, and norbornene-based thermoplastic transparent resins. Particularly preferred are polymer substrates such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, polyimides, alicyclic polyolefins, and norbornene-based thermoplastic transparent resins.

[0071] The casting method is not particularly limited, and a common method can be used, such as a T-die method, a doctor blade method, a bar coater method, a slot die method, a lip coater method, a reverse gravure coating method, a microgravure coating method, a spin coating method, a brush coating method, a roll coating method, or a flexographic printing method.

[0072] The drying method in the drying step is not particularly limited, and any ordinary heating means can be used, such as a hot air blower, a heating roll, or a far-infrared heater.

[0073] The drying temperature is preferably 30 to 200° C., and particularly preferably 40 to 160° C. The drying temperature may be a single-stage condition, or in order to maintain the appearance or shorten the drying time, multi-stage drying may be used in which the first stage is dried at a low temperature and the second and subsequent stages are dried at a high temperature.

[0074] The film peeling speed in the substrate peeling step is preferably in the range of 0.1 to 30 m / min, for example, from the viewpoint of productivity, mechanical precision, stability, etc., and more preferably in the range of 1 to 30 m / min.

[0075] The film can be further laminated with a film containing other resins as needed. Examples of other resins include polyethersulfone, polyarylate, polyethylene terephthalate, polynaphthalene terephthalate, polycarbonate, cyclic polyolefin, maleimide resin, fluorine-based resin, polyimide, etc. It is also possible to laminate a liquid crystal layer, a hard coat layer, a gas barrier layer, or a layer with a controlled refractive index (low reflection layer).

[0076] The film of the present disclosure has excellent heat resistance and optical properties, and is suitable for use as a retardation film in applications such as liquid crystal displays and organic EL displays.

[0077] Furthermore, by disposing the optical film of the present disclosure on at least one surface of a polarizer, a polarizing plate with excellent heat resistance and optical properties can be obtained, and the polarizing plate is suitably used as a polarizing plate for liquid crystal displays or an anti-reflection polarizing plate.

[0078] The present disclosure will be described below with reference to examples, but the present disclosure is not limited to these examples. Details of the reagents used are also shown in Table 1.

[0079] The physical properties shown in the examples were measured by the following methods: Next, specific examples of the production of fumaric acid ester monomers and fumaric acid ester-based resins will be described.

[0080] <Structural analysis of monomer> The structural analysis of the monomer was carried out using a nuclear magnetic resonance (NMR) analyzer (manufactured by JEOL Ltd., product name: JNM-ECZ400 / L1) by proton nuclear magnetic resonance spectroscopy ( １ H-NMR) spectral analysis.

[0081] <Composition ratio of polymer (resin)> The composition ratio of the polymer was measured by proton nuclear magnetic resonance spectroscopy ( １ H-NMR spectral analysis. １ Only when it is difficult to calculate the composition ratio of the polymer due to the overlap of peaks in the H-NMR spectrum, a nuclear magnetic resonance (NMR) measurement device (manufactured by Bruker, product name: AVANCE NEO 700) is used, and the measurement mode is reverse gated decoupling. １3 C-NMR spectral analysis.

[0082] <Measurement of Weight Average Molecular Weight> A gel permeation chromatography (GPC) apparatus (manufactured by Tosoh Corporation, trade name: HLC-8320GPC) was used, and two Tosoh Corporation TSKgel Super HM-H columns were used. The column temperature was set to 40°C, and measurements were carried out at 40°C using tetrahydrofuran as a solvent, and the weight average molecular weight was calculated as a value converted into standard polystyrene.

[0083] <β relaxation temperature (T βMeasurement of the β relaxation temperature (T) during the second scan was performed using a differential scanning calorimeter (DSC) (manufactured by Hitachi High-Tech Science, product name: DSC7000X). The temperature was raised from 25°C to 200°C at a rate of 10°C / min under a nitrogen atmosphere (first scan), held at 200°C for 10 minutes, cooled to -70°C at a rate of 10°C / min, held at -70°C for 10 minutes, and then raised to 200°C at a rate of 10°C / min. β However, in order to distinguish from noise originating from the instrument, the peaks whose corresponding heights in the DDSC curve were 8 μW / min or more were taken as T β It was decided.

[0084] <Measurement of Retardation Characteristics (Rth)> Using a polarized retardation measurement system (manufactured by Axometrics, trade name: AxoScan), the out-of-plane retardation Rth shown in formula (A) was measured at a wavelength of 589 nm.

[0085] <Measurement of Thickness> The thickness of the film was measured using a high-resolution linear gauge sensor (manufactured by Ono Sokki, trade name: GS-3813B).

[0086] <Haze Measurement> Haze was measured in accordance with JIS-K 7136 using a spectroscopic haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: SH7000).

[0087] <Measurement of storage modulus> A dynamic viscoelasticity measuring device (manufactured by UBM, product name: Rheogel-E4000) was used to measure the temperature dependency of a film in tension at a measurement frequency of 10 Hz when the temperature was raised from 40°C to 180°C at a rate of 2°C / min. The storage modulus of the film at 100°C was measured. When measuring the storage modulus at 200°C, the temperature dependency was measured at a measurement frequency of 10 Hz when the temperature was raised from 40°C to 210°C at a rate of 2°C / min when the film was in tension, and the storage modulus of the film at 200°C was measured.

[0088] <Measurement of Linear Expansion Coefficient> A 3 cm x 3 cm film was prepared and placed on a Teflon (registered trademark) sheet. The film, together with the Teflon (registered trademark) sheet, was placed in an oven and the temperature was increased. In the first measurement, the temperature was increased from an initial temperature of 30°C at a rate of 5°C / min to 120°C, after which it was maintained for 20 minutes. The temperature was then decreased from 120°C at a rate of 5°C / min to 30°C, after which it was maintained for 20 minutes. In the second measurement, the temperature was increased from an initial temperature of 30°C at a rate of 5°C / min to 120°C, after which it was maintained for 20 minutes. The temperature was then decreased from 120°C at a rate of 5°C / min to 30°C, after which it was maintained for 20 minutes. During the temperature change, the temperature near the sample was measured with a contact thermocouple, and the temperature change in the film size was measured with a CCD camera. The temperature change in the film length during the second measurement, when the temperature was decreased from 120°C to 30°C, was linearly approximated, and the change in film length was calculated. The linear expansion coefficient α was calculated from the change in film length, the change in film temperature, and the film length before the temperature change using the formula (B). The linear expansion coefficient α of the film was measured as the average value of the linear expansion coefficients of the longitudinal and transverse sides of the film.

[0089] Synthesis Example 1: 40 ml of dehydrated dichloromethane and 3.95 g (25.8 mmol) of fumarolic acid dichloride were placed in a 200 ml four-neck flask equipped with a dropping funnel at 0°C under a nitrogen atmosphere. 5.73 g (56.6 mmol) of triethylamine was added dropwise to the flask using the dropping funnel. Subsequently, 7.94 g (51.5 mmol) of (-)-borneol dissolved in 30 ml of dehydrated dichloromethane was added dropwise to the flask using the dropping funnel, and the mixture was allowed to warm to room temperature and react overnight. After completion of the reaction, the reaction solution was washed twice each with 1 N hydrochloric acid, ion-exchanged water, saturated aqueous sodium bicarbonate solution, and saturated saline. The organic layer was collected and dried over sodium sulfate, and the solvent was removed under reduced pressure to obtain a crude product as a dark brown solid. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 95 / 5 vol%) and recrystallized from methanol, and then vacuum dried to obtain dibornyl fumarate (hereinafter referred to as "DBoF"). １ H-NMR (400MHz, CDCl ３): δ6.86 (s, 2H, CH=CH), 5.02-4.99 (dt, J=9.6, 2.6Hz, 2H, O-CH), 2.45-2.37 (m, 2H, CH), 2.02-1.95 (m, 2H, CH), 1.83-1.70 (m, 4H, CH), 1.39-1.24 (m, 4H, CH), 1.03 (dd, J １ =13.7,3.2Hz,2H,CH),0.93(s,6H,CH ３ ), 0.90(s,6H,CH ３ ), 0.87(s,6H,CH ３ ))

[0090] Synthesis Example 2: 200 ml of dehydrated dichloromethane and 15.8 g (0.10 mol) of fumaroyl dichloride were placed in a 1000 ml four-neck flask at 0°C under a nitrogen atmosphere. Subsequently, 23.2 g (0.22 mol) of triethylamine and 34.9 g (0.23 mol) of (±)-isoborneol dissolved in 300 ml of dehydrated dichloromethane were added dropwise to the flask. After the addition, the mixture was heated to room temperature and reacted for 65 hours. After the reaction was completed, the resulting salt was removed by filtration, and the filtrate was washed three times with ion-exchanged water and saturated saline. The organic layer was recovered and dried over sodium sulfate, and the solvent was removed by distillation under reduced pressure to obtain a crude product as a dark brown solid. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 95 / 5 vol%) and washed with cold methanol, followed by vacuum drying to obtain diisobornyl fumarate (hereinafter referred to as "DIBF"). ( １ H-NMR (400MHz, CDCl ３ ): δ6.77 (s, 2H, CH=CH), 4.79-4.46 (dd, J=7.5, 3.4Hz, 2H, O-CH), 1.88-1. 67 (m, 8H, CH), 1.61-1.55 (m, 2H, CH), 1.21-1.07 (m, 4H, CH), 1.00 (s, 6H, CH ３ ), 0.86(s,6H,CH ３ ), 0.85(s,6H,CH ３ ))

[0091] Example 1: A 75 mL glass ampoule was charged with 0.65 g (1.68 mmol) of DBoF obtained in Synthesis Example 1, 1.36 g (6.77 mmol) of diisopropyl fumarate (hereinafter referred to as "DiPF"), and 14.7 mg (0.07 mmol) of tert-butyl(2-ethylhexanoyl) peroxide as a polymerization initiator. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 60°C and maintained for 48 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was precipitated by dropwise addition to 100 mL of a precipitant (methanol / water = 75 / 25 (wt %)), followed by vacuum drying at 80°C for 4 hours, yielding 1.56 g of a fumarate ester-based resin (yield: 78%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0092] Example 2: A 75 mL glass ampoule was charged with 0.34 g (0.86 mmol) of DBoF obtained in Synthesis Example 1, 1.56 g (7.80 mmol) of DiPF, and 16.7 mg (0.08 mmol) of the polymerization initiator tert-butyl(2-ethylhexanoyl) peroxide. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 60°C and maintained for 48 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was precipitated by dripping it into 100 mL of a precipitant (methanol / water = 75 / 25 (wt %)), followed by vacuum drying at 80°C for 4 hours, yielding 1.57 g of a fumarate ester-based resin (yield: 83%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0093] Example 3: A 75 mL glass ampoule was charged with 0.51 g (1.32 mmol) of DBoF obtained in Synthesis Example 1, 1.49 g (7.44 mmol) of DiPF, and 18.2 mg (0.07 mmol) of the polymerization initiator tert-butyl peroxypivalate. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was dropped into 100 mL of a precipitant (methanol / water = 75 / 25 (wt %)) to precipitate the polymer. The resulting polymer was then vacuum-dried at 80°C for 4 hours to obtain 1.54 g of a fumarate ester-based resin (yield: 77%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight and a high T β had the following characteristics:

[0094] Example 4: A 75 mL glass ampoule was charged with 0.35 g (0.91 mmol) of DBoF obtained in Synthesis Example 1, 1.65 g (8.25 mmol) of DiPF, and 19.0 mg (0.08 mmol) of the polymerization initiator tert-butyl peroxypivalate. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was dropped into 100 mL of a precipitant (methanol / water = 75 / 25 (wt %)) to precipitate the polymer. The resulting polymer was then vacuum-dried at 80°C for 4 hours to obtain 1.56 g of a fumarate ester-based resin (yield: 78%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0095] Example 5: A 75 mL glass ampoule was charged with 0.19 g (0.48 mmol) of DBoF obtained in Synthesis Example 1, 1.82 g (9.07 mmol) of DiPF, and 19.9 mg (0.08 mmol) of the polymerization initiator tert-butyl peroxypivalate. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 100 mL of a precipitant (methanol / water = 75 / 25 (wt %)) to precipitate the polymer. The resulting polymer was then vacuum-dried at 80°C for 4 hours to obtain 1.60 g of a fumarate ester-based resin (yield: 80%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0096] Example 6: 1.13 g (2.91 mmol) of DIBF obtained in Synthesis Example 2, 0.87 g (4.36 mmol) of DiPF, and 12.2 mg (0.05 mmol) of the polymerization initiator tert-butyl peroxypivalate were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was precipitated by dripping it into 100 mL of a precipitant (methanol / water = 75 / 25 (wt%)), followed by vacuum drying at 80°C for 4 hours, yielding 0.84 g of a fumarate ester-based resin (yield: 42%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin exhibited T β No peaks due to the above were observed, indicating excellent heat resistance.

[0097] Example 7: 0.35 g (0.91 mmol) of DIBF obtained in Synthesis Example 2, 1.65 g (8.22 mmol) of DiPF, and 18.9 mg (0.08 mmol) of the polymerization initiator tert-butyl peroxypivalate were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. This polymer solution was added dropwise to 100 mL of a precipitant (methanol / water = 75 / 25 (wt%)) to precipitate the polymer. The resulting polymer was then vacuum-dried at 80°C for 4 hours to obtain 1.54 g of a fumarate ester-based resin (yield: 77%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight and a high T β had the following characteristics:

[0098] Example 8: 0.18 g (0.47 mmol) of DIBF obtained in Synthesis Example 2, 1.82 g (9.09 mmol) of DiPF, and 19.9 mg (0.08 mmol) of the polymerization initiator tert-butyl peroxypivalate were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. This polymer solution was added dropwise to 100 mL of a precipitant (methanol / water = 75 / 25 (wt%)) to precipitate the polymer. The resulting polymer was then vacuum-dried at 80°C for 4 hours to obtain 1.61 g of a fumarate ester-based resin (yield: 80%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0099] Example 9: 0.90 g (2.32 mmol) of DIBF obtained in Synthesis Example 2, 1.09 g (5.44 mmol) of DiPF, and 16.1 mg (0.06 mmol) of the polymerization initiator tert-butyl peroxypivalate were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 48 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. This polymer solution was added dropwise to 100 mL of a precipitant (methanol / water = 75 / 25 (wt%)) to precipitate the polymer. The resulting polymer was then vacuum-dried at 80°C for 4 hours to obtain 1.18 g of a fumarate ester-based resin (yield: 59%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight and a high T β had the following characteristics:

[0100] Example 10: 0.66 g (1.69 mmol) of DIBF obtained in Synthesis Example 2, 1.34 g (6.70 mmol) of DiPF, and 17.5 mg (0.07 mmol) of the polymerization initiator tert-butyl peroxypivalate were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 48 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. This polymer solution was dropped into 100 mL of a precipitant (methanol / water = 75 / 25 (wt%)) to precipitate the polymer. The resulting polymer was then vacuum-dried at 80°C for 4 hours to obtain 1.42 g of a fumarate ester-based resin (yield: 71%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0101] Example 11: 0.61 g (1.56 mmol) of DBoF obtained in Synthesis Example 1, 1.21 g (3.11 mmol) of DIBF obtained in Synthesis Example 2, 2.19 g (10.9 mmol) of DiPF, and 31.6 mg (0.13 mmol) of the polymerization initiator tert-butyl peroxypivalate were placed in a 75 mL glass ampoule. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 48 hours to allow radical polymerization. After completion of the polymerization reaction, 40 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was precipitated by dropwise addition to 200 mL of precipitant (methanol / water = 75 / 25 (wt%)), followed by vacuum drying at 80°C for 4 hours, yielding 2.64 g of a fumarate ester-based resin (yield: 78%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. １ Since it is difficult to separate peaks in H-NMR, the total value was calculated. β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0102] Example 12: 0.36 g (0.92 mmol) of DBoF obtained in Synthesis Example 1, 1.57 g (7.8 mmol) of DiPF, 0.08 g (0.47 mmol) of diethyl fumarate (hereinafter referred to as "DEF"), and 20.4 mg (0.08 mmol) of the polymerization initiator tert-butyl peroxypivalate were added to a 75 mL glass ampoule. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a constant temperature bath at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 40 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was precipitated by dropwise addition to 200 mL of precipitant (methanol / water = 75 / 25 (wt%)), followed by vacuum drying at 80°C for 4 hours, yielding 1.62 g of a fumarate ester-based resin (yield: 81%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0103] Example 13: 0.26 g (0.66 mmol) of DBoF obtained in Synthesis Example 1, 1.57 g (7.9 mmol) of DiPF, 0.17 g (0.97 mmol) of DEF, and 21.6 mg (0.09 mmol) of the polymerization initiator tert-butyl peroxypivalate were added to a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was precipitated by dropwise addition to 200 mL of precipitant (methanol / water = 75 / 25 (wt%)), followed by vacuum drying at 80°C for 4 hours, yielding 1.58 g of a fumarate ester-based resin (yield: 79%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by H-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0104] Example 14 30.0 g of isobornyl acrylate (hereinafter referred to as "IBA") was purified by passing it through a column containing 30.1 g of activated alumina as a packing material, and the polymerization inhibitor 4-methoxyphenol was removed. 0.35 g (0.91 mmol) of DBoF obtained in Synthesis Example 1, 1.55 g (7.7 mmol) of DiPF, 0.10 g (0.46 mmol) of purified IBA, and 18.9 mg (0.08 mmol) of the polymerization initiator tert-butyl peroxypivalate were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a constant temperature bath at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. This polymer solution was dropped into 200 mL of a precipitant (methanol) to precipitate the polymer, which was then vacuum dried at 80° C. for 4 hours to obtain 1.60 g of a fumaric acid ester-based resin (yield: 80%). The weight-average molecular weight of the resulting fumaric acid ester-based resin was measured. １３ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by C-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0105] Example 15: 0.51 g (1.30 mmol) of DBoF obtained in Synthesis Example 1, 1.32 g (6.6 mmol) of DiPF, 0.18 g (0.87 mmol) of IBA purified in the same manner as in Example 14, and 18.8 mg (0.08 mmol) of the polymerization initiator tert-butyl peroxypivalate were placed in a 75 mL glass ampoule. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 200 mL of precipitant (methanol) to precipitate the polymer, which was then vacuum-dried at 80°C for 4 hours to obtain 1.53 g of a fumarate ester-based resin (yield: 76%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １３ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by C-NMR measurement. Furthermore, the T β The results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight. In addition, the obtained fumaric acid ester resin exhibited a T β No peaks due to the above were observed, indicating excellent heat resistance.

[0106] Example 16: 0.50 g (1.29 mmol) of DBoF obtained in Synthesis Example 1, 0.43 g (2.14 mmol) of DiPF, 1.07 g (5.14 mmol) of IBA purified in the same manner as in Example 14, and 15.6 mg (0.06 mmol) of the polymerization initiator tert-butyl peroxypivalate were placed in a 75 mL glass ampoule. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 50°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was dropped into 200 mL of precipitant (methanol) to precipitate the polymer, which was then vacuum-dried at 80°C for 4 hours to obtain 1.49 g of a fumarate ester-based resin (yield: 74%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. １３ The composition ratio (mol%) of each residue unit in the fumaric acid ester resin was measured by C-NMR measurement. Furthermore, the T β The results are shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight and a high T β had the following characteristics:

[0107] Comparative Example 1: 2.00 g (9.99 mmol) of DiPF and 15.1 mg (0.07 mmol) of the polymerization initiator tert-butyl(2-ethylhexanoyl) peroxide were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 60°C and maintained for 48 hours to allow radical polymerization. After completion of the polymerization reaction, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. This polymer solution was dropped into 100 mL of a precipitant (methanol / water = 75 / 25 (wt%)) to precipitate the polymer, which was then vacuum-dried at 80°C for 4 hours to obtain 1.81 g of a fumarate ester-based resin (yield: 91%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. Furthermore, the T βThe results are also shown in Table 2. The obtained fumaric acid ester resin had a high weight average molecular weight, but the T β The resin obtained from the fumaric acid ester monomer that does not have a rigid structure has a low T β was confirmed to be lower.

[0108] Comparative Example 2: A 50 mL glass tube was charged with 1.9 g (5.0 mmol) of DBoF, 46 mg (0.2 mmol) of 2,2'-azobis(isobutyrate)dimethyl (Wako Pure Chemical Industries) as a polymerization initiator, and 10 mL of benzene (Wako Pure Chemical Industries). The tube was subjected to three cycles of freezing with liquid nitrogen, decompression, nitrogen substitution, and thawing. The glass tube was placed in a constant temperature bath at 60°C and maintained for 20 hours to allow radical polymerization. After completion of the polymerization reaction, the polymerized solution was precipitated by dropping it into 200 mL of a precipitant (methanol / water = 70 / 30 (wt%)). The resulting solution was then vacuum dried at 80°C for 5 hours to obtain 0.2 g of a fumarate ester-based resin (yield: 10%). The weight-average molecular weight of the resulting fumarate ester-based resin was measured. The results are shown in Table 2. The resulting fumarate ester-based resin had a low weight-average molecular weight.

[0109] Example 17: 1.0 g of the fumaric acid ester-based resin obtained in Example 1 was dissolved in a methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare an 18 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation characteristics, haze, storage modulus at 100°C and 200°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0110] Example 18: 1.0 g of the fumaric acid ester-based resin obtained in Example 2 was dissolved in a methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare a 16 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation characteristics, haze, storage modulus at 100°C and 200°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0111] Example 19: 1.0 g of the fumaric acid ester-based resin obtained in Example 3 was dissolved in a methyl ethyl ketone-toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare a 15 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation characteristics, haze, storage modulus at 100°C and 200°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0112] Example 20: 1.0 g of the fumaric acid ester-based resin obtained in Example 5 was dissolved in a methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare a 16 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation characteristics, haze, storage modulus at 100°C and 200°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0113] Example 21: 1.0 g of the fumaric acid ester-based resin obtained in Example 7 was dissolved in a methyl ethyl ketone-toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare an 18 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation characteristics, haze, storage modulus at 100°C and 200°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0114] Example 22: 1.0 g of the fumaric acid ester-based resin obtained in Example 8 was dissolved in a methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare a 16 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation properties, haze, and storage modulus at 100°C of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0115] Example 23: 1.0 g of the fumaric acid ester-based resin obtained in Example 9 was dissolved in a methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare an 18 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation characteristics, haze, storage modulus at 100°C and 200°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0116] Example 24: 1.0 g of the fumaric acid ester-based resin obtained in Example 10 was dissolved in a methyl ethyl ketone-toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare an 18 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation properties, haze, and storage modulus at 100°C of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0117] Example 25: 1.0 g of the fumaric acid ester-based resin obtained in Example 11 was dissolved in a methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare an 18 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation characteristics, haze, storage modulus at 100°C and 200°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0118] Example 26: 1.0 g of the fumaric acid ester-based resin obtained in Example 12 was dissolved in a methyl ethyl ketone-toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare a 15 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation characteristics, haze, storage modulus at 100°C and 200°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0119] Example 27: 1.0 g of the fumaric acid ester-based resin obtained in Example 13 was dissolved in a methyl ethyl ketone-toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare a 16 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation properties, haze, and storage modulus at 100°C of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0120] Example 28: 1.0 g of the fumaric acid ester-based resin obtained in Example 14 was dissolved in a methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare a 15 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation properties, haze, storage modulus at 100°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0121] Example 29: 1.0 g of the fumaric acid ester-based resin obtained in Example 15 was dissolved in a methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare a 15 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation properties, haze, and storage modulus at 100°C and 200°C of the film alone were measured. The results are also shown in Table 3. The obtained film had excellent storage modulus at high temperatures and was suitable as an optical film.

[0122] Comparative Example 3 1.0 g of the fumaric acid ester-based resin obtained in Comparative Example 1 was dissolved in a methyl ethyl ketone-toluene mixed solution (methyl ethyl ketone / toluene = 60 wt% / 40 wt%) to prepare an 18 wt% resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray Industries, Inc.) using a coater, and a film was formed by two-stage drying at temperatures of 50°C and 130°C. The formed fumaric acid ester-based resin film was peeled from the substrate, and the film thickness, retardation characteristics, haze, storage modulus at 100°C and 200°C, and linear expansion coefficient of the film alone were measured. The results are also shown in Table 3. The obtained film had low storage modulus at 100°C and 200°C and did not have the desired storage modulus at high temperatures.

[0123] Comparative Example 4 0.4 g of the fumarate ester-based resin obtained in Comparative Example 2 was dissolved in a tetrahydrofuran solution to prepare a 30 wt % resin solution. The solution was applied to a polyethylene terephthalate substrate (Lumirror T60, manufactured by Toray) using a coater, and a film was formed by two-stage drying at drying temperatures of 50°C and 130°C. When an attempt was made to peel the formed fumarate ester-based resin film from the substrate, cracks occurred all over the surface. The fumarate ester-based resin had a low weight-average molecular weight and insufficient strength, making it unsuitable as an optical film.

[0124]

[0125]

[0126] (In Table 3, "-" in the columns for storage modulus and linear expansion coefficient at 200°C means that the data was not measured.)

Claims

A fumarate resin containing a residue unit represented by the following formula (1) and a residue unit represented by the following formula (2). (In the formula, R １ and R ２ each independently represents an alkyl group having a norbornane skeleton. (In the formula, R ３ and R ４ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. R in formula (1) １ and R ２ The fumaric acid ester-based resin according to claim 1 , wherein at least one of the above groups contains a bornyl group.

2. The fumarate resin according to claim 1, wherein the residue unit represented by formula (1) is a residue unit represented by any one of the following formulas (1-1) to (1-3), or an enantiomer thereof: R in formula (2) ３ and R ４ 2. The fumaric acid ester resin according to claim 1, wherein at least one of the groups is an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, a tert-pentyl group, a sec-hexyl group, a tert-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

2. The fumarate resin according to claim 1, which has a weight average molecular weight (Mw) of 50,000 or more in terms of standard polystyrene obtained from an elution curve measured by gel permeation chromatography (GPC). 　 The β relaxation temperature (T β 2. The fumarate resin according to claim 1, wherein the temperature difference (Tc) is not observed at or below 120°C.

2. The fumarate resin according to claim 1, comprising 1 mol % to 80 mol % of residue units represented by formula (1) and 20 mol % to 99 mol % of residue units represented by formula (2). 　 A film comprising the fumaric acid ester resin according to any one of claims 1 to 7.

9. The film according to claim 8, wherein the out-of-plane retardation (Rth) measured at a wavelength of 589 nm and represented by the following formula (A) is −700 to 0 nm: Rth=[(nx+ny) / 2-nz]×d (A) (In the formula, nx represents the refractive index in the fast axis direction (the direction with the smallest refractive index) in the film plane, ny represents the refractive index in the slow axis direction in the film plane, nz represents the refractive index in the perpendicular direction outside the film plane, and d represents the thickness of the film.) 　 Storage modulus at 100°C is 7.00 x 10 ８ The film according to claim 8, wherein the modulus is 100 Pa or more. 　 Storage modulus at 200°C is 1.40 x 10 ８ The film according to claim 8, wherein the modulus is 100 Pa or more.

9. The film according to claim 8, wherein the linear expansion coefficient α represented by the following formula (B) is 110 ppm / °C or less. α=Δl / (ΔT×l)(B) (In the formula, Δl represents the change in film length when the temperature changes, ΔT represents the change in film temperature, and l represents the film length before the temperature change.)

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