Novel fumarate monomers, resins and films comprising same

Abstract

Provided are a novel fumarate monomer, a resin, and a film comprising the same, the fumarate monomer providing a resin having a high T [beta]. The fumarate monomer is represented by the following formula (1). In the formula, R1 represents a linear alkyl group having 1-4 carbon atoms, or a branched alkyl group having 3-5 carbon atoms, and R2 represents a linear alkyl group having 1-4 carbon atoms, a branched alkyl group having 3-12 carbon atoms, or a cyclic alkyl group having 3-6 carbon atoms.

Description

Technical Field

[0001] This disclosure relates to novel fumarate monomers, resins, and films comprising them. Background Technology

[0002] As the most important display device in the multimedia society, LCD monitors are widely used in mobile phones, computer monitors, laptops, and televisions. In the polarizing plates used in LCD monitors, a large number of optical films are used to improve display characteristics such as contrast and color compensation when viewed from the front or at an angle.

[0003] As a representative optical film related to polarizers, phase retardation film can be cited. Phase retardation film can be used as an anti-reflective layer in liquid crystal display devices, touch panels, and organic EL.

[0004] Conventional phase retardation films have used polycarbonate and cyclic polyolefins, both of which are polymers with positive birefringence. Here, the sign of birefringence is defined as follows.

[0005] The optical anisotropy of polymer films that have undergone molecular orientation through stretching, casting with a coating machine, etc., can be represented by a refractive index ellipsoid with the refractive index of the fast axis (the direction with the lowest refractive index) in the film surface set as nx, the refractive index of the in-film direction (slow axis) orthogonal to it set as ny, and the refractive index of the thickness direction (the direction perpendicular to the film surface) set as nz.

[0006] That is, in the uniaxial stretching of a polymer with negative birefringence, the refractive index is small in the stretching axis direction (fast axis: stretching direction), and in the uniaxial stretching of a polymer with positive birefringence, the refractive index is small in the axis direction orthogonal to the stretching axis direction (fast axis: direction orthogonal to the stretching direction).

[0007] Most polymers exhibit positive birefringence. Acrylic resins and polystyrene are examples of polymers with negative birefringence, but acrylic resins exhibit poor phase retardation performance, making them unsuitable as phase retardation films. Polystyrene faces several challenges: high wavelength dependence of phase retardation, which raises concerns about optical properties; low heat resistance, which hinders practical applications; and a high photoelasticity coefficient in the room temperature region, leading to phase retardation stability issues such as changes in phase retardation due to minor stress. Therefore, it is currently not used.

[0008] There is a strong market demand for retardation films exhibiting negative birefringence. Various retardation films have been developed to meet these specific requirements.

[0009] Fumarate resins have been proposed as optical films exhibiting negative birefringence and high refractive index in the thickness direction, as described in Patent Documents 1 and 2.

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Japanese Patent Application Publication No. 2008-064817

[0013] Patent Document 2: Japanese Patent Application Publication No. 2011-107281 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] In recent years, with the diversification of display usage environments, there is a demand for phase retardation films with high heat resistance that do not easily change in size even under high temperature environments. Patent documents 1 and 2 report on fumarate resins, but require fumarate resins with even higher heat resistance.

[0016] Fumarate resins have a β-relaxation temperature (T) corresponding to the side chain movement of the resin. β When T β When the display operates within or below the ambient temperature range, the dimensional stability of the film containing this resin decreases. Therefore, to further improve heat resistance, a film with high T0 is required. β Fumarate resin.

[0017] The present invention was made in view of the above-mentioned circumstances, and its object is to provide a novel fumarate monomer, resin, and film comprising the thereof, wherein the fumarate monomer is capable of forming a film with high T β The resin.

[0018] Problem Solving Methods

[0019] The inventors conducted in-depth research and discovered that the above-mentioned problems can be solved by using specific fumarate monomers, thus completing the present invention.

[0020] That is, this disclosure has the following purpose.

[0021] [1] A fumarate monomer, which is shown in the following formula (1).

[0022] [Chemical Formula 1]

[0023]

[0024] (In the formula, R1 represents a straight-chain alkyl group with 1 to 4 carbon atoms, or a branched alkyl group with 3 to 5 carbon atoms, and R2 represents a straight-chain alkyl group with 1 to 4 carbon atoms, a branched alkyl group with 3 to 12 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms.)

[0025] [2] According to the fumarate monomer described in [1] above, wherein,

[0026] R1 is methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, sec-pentyl, or tert-pentyl.

[0027] [3] According to the fumarate monomer described in [1] or [2] above, wherein,

[0028] R2 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, sec-pentyl, tert-pentyl, sec-hexyl, tert-hexyl, cyclopropyl, cyclopentyl, or cyclohexyl.

[0029] [4] The fumarate monomer according to any one of [1] to [3] above has a melting point of 80°C or below.

[0030] [5] A resin comprising residue units as shown in the following structural formula (2).

[0031] [Chemical Formula 2]

[0032]

[0033] (In the formula, R1 represents a straight-chain alkyl group with 1 to 4 carbon atoms, or a branched alkyl group with 3 to 5 carbon atoms, and R2 represents a straight-chain alkyl group with 1 to 4 carbon atoms, a branched alkyl group with 3 to 12 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms.)

[0034] [6] The resin according to [5] above further comprises residue units as shown in the following structural formula (3).

[0035] [Chemical Formula 3]

[0036]

[0037] (In the formula, R3 and R4 each independently represent a straight-chain alkyl group with 1 to 12 carbon atoms, a branched alkyl group with 3 to 12 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms.)

[0038] [7] According to the resin described in [5] or [6] above, wherein,

[0039] The weight-average molecular weight (Mw) of standard polystyrene obtained by dissolution profile determination by gel permeation chromatography (GPC) is greater than 50,000.

[0040] [8] The resin according to any one of [5] to [7] above, wherein,

[0041] The β-relaxation temperature (T0) during the second scan heating (heating rate = 10 °C / min), determined by differential scanning calorimetry (DSC). β The temperature is above 130℃.

[0042] [9] A membrane comprising any one of the resins described in any one of [5] to [8] above.

[0043]

[10] According to the membrane described in [9] above, wherein,

[0044] The out-of-plane phase difference (Rth) measured at a wavelength of 589 nm, as shown in equation (a) below, is -700 to 0 nm.

[0045] Rth = [(nx + ny) / 2 - nz] × d (a)

[0046] (In the formula, nx represents the refractive index in the fast axis direction (the direction of minimum refractive index) within the film surface, ny represents the refractive index in the slow axis direction within the film surface, nz represents the refractive index in the perpendicular direction outside the film surface, and d represents the thickness of the film.)

[0047]

[11] According to the membrane described in [9] or

[10] above, wherein,

[0048] The linear expansion coefficient α shown by the following formula (b) is below 95 ppm / ℃.

[0049] α=Δl / (ΔT×l) (b)

[0050] (In the formula, Δl represents the change in membrane length due to temperature change, ΔT represents the change in membrane temperature, and l represents the membrane length before the temperature change.)

[0051] The effects of the invention

[0052] According to this disclosure, novel fumarate monomers, resins, and films comprising the same can be provided, wherein the fumarate monomers provide high Tg... β The resin. Detailed Implementation

[0053] <Fumarate monomers>

[0054] The fumarate monomers, which are one embodiment of this disclosure, will now be described in detail.

[0055] This disclosure pertains to fumarate monomers represented by the following formula (1) (hereinafter also referred to as "monomers of this disclosure").

[0056] [Chemical Formula 4]

[0057]

[0058] (In the formula, R1 represents a straight-chain alkyl group with 1 to 4 carbon atoms, or a branched alkyl group with 3 to 5 carbon atoms. R2 represents a straight-chain alkyl group with 1 to 4 carbon atoms, a branched alkyl group with 3 to 12 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms.)

[0059] β relaxation temperature (T) β This is caused by the movement of the resin's side chains. Because the monomers of this disclosure incorporate rigid side chains containing cyclohexane rings with R1 groups, the resulting resins exhibit high Tg. β In particular, by introducing a cyclohexane ring with an R1 group at only one end, the monomer melting point can be made suitable for polymerization, and the resulting resin retains a high Tm. β Furthermore, high molecular weight polymers can be achieved. Therefore, films containing resins obtained by polymerizing the monomers of this disclosure are useful as phase retardation films requiring high heat resistance.

[0060] Examples of linear alkyl groups having 1 to 4 carbon atoms in R1 of formula (1) include methyl, ethyl, propyl, and butyl; examples of branched alkyl groups having 3 to 5 carbon atoms include isopropyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, and tert-pentyl. The resin obtained by polymerizing the monomers of this disclosure maintains a high T... β Furthermore, from the perspective of increasing molecular weight, R1 in formula (1) is preferably methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, sec-pentyl, or tert-pentyl, more preferably methyl, ethyl, isopropyl, or tert-butyl, even more preferably isopropyl or tert-butyl, and particularly preferably tert-butyl.

[0061] Examples of linear alkyl groups having 1 to 4 carbon atoms in R2 of formula (1) include methyl, ethyl, propyl, and butyl; examples of branched alkyl groups having 3 to 12 carbon atoms include isopropyl, isobutyl, sec-butyl, sec-pentyl, tert-pentyl, sec-hexyl, and tert-hexyl; and examples of cyclic alkyl groups having 3 to 6 carbon atoms include cyclopropyl, cyclopentyl, and cyclohexyl. R2 of formula (1) is preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, sec-pentyl, tert-pentyl, sec-hexyl, tert-hexyl, cyclopropyl, cyclopentyl, and cyclohexyl, more preferably ethyl, isopropyl, sec-butyl, cyclopentyl, and cyclohexyl, and particularly preferably ethyl, isopropyl, and cyclohexyl.

[0062] Examples of specific fumarate monomers represented by formula (1) include: methyl fumarate (4-methylcyclohexyl) ester, ethyl fumarate (4-methylcyclohexyl) ester, propyl fumarate (4-methylcyclohexyl) ester, isopropyl fumarate (4-methylcyclohexyl) ester, butyl fumarate (4-methylcyclohexyl) ester, isobutyl fumarate (4-methylcyclohexyl) ester, sec-butyl fumarate (4-methylcyclohexyl) ester, sec-pentyl fumarate (4-methylcyclohexyl) ester, sec-hexyl fumarate (4-methylcyclohexyl) ester, tert-pentyl fumarate (4-methylcyclohexyl) ester, tert-hexyl fumarate (4-methylcyclohexyl) ester, cyclopropyl fumarate (4-methylcyclohexyl) ester, cyclopentyl fumarate (4-methylcyclohexyl) ester, and fumarate (4-methylcyclohexyl) cyclohexyl fumarate. 4-Ethylcyclohexyl fumarate (methyl), 4-ethylcyclohexyl fumarate (ethyl), 4-ethylcyclohexyl fumarate (propyl), 4-ethylcyclohexyl fumarate (isopropyl), 4-ethylcyclohexyl fumarate (butyl), 4-ethylcyclohexyl fumarate (isobutyl), 4-ethylcyclohexyl fumarate (sec-butyl), 4-ethylcyclohexyl fumarate (sec-pentyl), 4-ethylcyclohexyl fumarate (tert-pentyl), 4-ethylcyclohexyl fumarate (sec-hexyl), 4-ethylcyclohexyl fumarate (tert-hexyl), 4-ethylcyclohexyl fumarate (cyclopropyl), 4-ethylcyclohexyl fumarate (cyclopentyl), 4-ethylcyclohexyl fumarate (cyclohexyl), 4-propylcyclohexyl fumarate (methyl), 4-propylcyclohexyl fumarate (ethyl), fumarate (4-propylcyclohexyl)propyl ester, (4-propylcyclohexyl)isopropyl fumarate, (4-propylcyclohexyl)butyl fumarate, (4-propylcyclohexyl)isobutyl fumarate, (4-propylcyclohexyl)sec-butyl fumarate, (4-propylcyclohexyl)sec-amyl fumarate, (4-propylcyclohexyl)tert-amyl fumarate, (4-propylcyclohexyl)sec-hexyl fumarate, etc. (4-propylcyclohexyl) tert-hexyl fumarate, (4-propylcyclohexyl) cyclopropyl fumarate, (4-propylcyclohexyl) cyclopentyl fumarate, (4-propylcyclohexyl) cyclohexyl fumarate, (4-isopropylcyclohexyl) methyl fumarate, (4-isopropylcyclohexyl) ethyl fumarate, (4-isopropylcyclohexyl) propyl fumarate, (4-isopropylcyclohexyl) fumarate Isopropyl fumarate, (4-isopropylcyclohexyl) butyl fumarate, (4-isopropylcyclohexyl) isobutyl fumarate, (4-isopropylcyclohexyl) sec-butyl fumarate, (4-isopropylcyclohexyl) sec-pentyl fumarate, (4-isopropylcyclohexyl) tert-pentyl fumarate, (4-isopropylcyclohexyl) sec-hexyl fumarate, (4-isopropylcyclohexyl) tert-hexyl fumarate, fumarate 4-Isopropylcyclohexyl fumarate, 4-Isopropylcyclohexyl fumarate, 4-Isopropylcyclohexyl fumarate, 4-Butylcyclohexyl fumarate, 4-Butylcyclohexyl fumarate, 4-Butylcyclohexyl fumarate, 4-Butylcyclohexyl fumarate, 4-Butylcyclohexyl fumarate, 4-Butylcyclohexyl fumarate, 4-Butylcyclohexyl fumarate, 4-Butylcyclohexyl fumarate, 4-Butylcyclohexyl fumarate(4-Butylcyclohexyl) isobutyl fumarate, (4-Butylcyclohexyl) sec-butyl fumarate, (4-Butylcyclohexyl) sec-amyl fumarate, (4-Butylcyclohexyl) tert-amyl fumarate, (4-Butylcyclohexyl) sec-hexyl fumarate, (4-Butylcyclohexyl) tert-hexyl fumarate, (4-Butylcyclohexyl) cyclopropyl fumarate, (4-Butylcyclohexyl) Cyclopentyl fumarate, (4-butylcyclohexyl)cyclohexyl fumarate, (4-tert-butylcyclohexyl)methyl fumarate, (4-tert-butylcyclohexyl)ethyl fumarate, (4-tert-butylcyclohexyl)propyl fumarate, (4-tert-butylcyclohexyl)isopropyl fumarate, (4-tert-butylcyclohexyl)butyl fumarate, (4-tert-butylcyclohexyl)isobutyl fumarate, (4- 4-tert-butylcyclohexyl fumarate, 4-tert-butylcyclohexyl fumarate, 4-tert-butylcyclohexyl fumarate, 4-tert-butylcyclohexyl fumarate, 4-tert-butylcyclohexyl fumarate, 4-tert-butylcyclohexyl fumarate, 4-tert-butylcyclohexyl fumarate, 4-tert-butylcyclohexyl cyclopropyl fumarate, 4-tert-butylcyclohexyl fumarate, 4-tert-butylcyclohexyl fumarate (4-Isobutylcyclohexyl) cyclohexyl fumarate, (4-isobutylcyclohexyl) methyl fumarate, (4-isobutylcyclohexyl) ethyl fumarate, (4-isobutylcyclohexyl) propyl fumarate, (4-isobutylcyclohexyl) isopropyl fumarate, (4-isobutylcyclohexyl) butyl fumarate, (4-isobutylcyclohexyl) isobutyl fumarate, (4-isobutylcyclohexyl) sec-butyl fumarate, fumarate ( 4-Isobutylcyclohexyl) sec-amyl fumarate, (4-isobutylcyclohexyl) tert-amyl fumarate, (4-isobutylcyclohexyl) sec-hexyl fumarate, (4-isobutylcyclohexyl) tert-hexyl fumarate, (4-isobutylcyclohexyl) cyclopropyl fumarate, (4-isobutylcyclohexyl) cyclopentyl fumarate, (4-isobutylcyclohexyl) cyclohexyl fumarate, (4-isobutylcyclohexyl) sec-butyl fumarate 4-butylcyclohexyl fumarate (4-sec-butylcyclohexyl) methyl ester, 4-sec-butylcyclohexyl fumarate (4-sec-butylcyclohexyl) ethyl ester, 4-sec-butylcyclohexyl fumarate (4-sec-butylcyclohexyl) propyl ester, 4-sec-butylcyclohexyl fumarate (4-sec-butylcyclohexyl) isopropyl ester, 4-sec-butylcyclohexyl fumarate (4-sec-butylcyclohexyl) sec-pentyl ester, fumarate 4-sec-butylcyclohexyl fumarate, 4-sec-butylcyclohexyl fumarate, 4-sec-butylcyclohexyl fumarate, 4-sec-butylcyclohexyl fumarate, 4-sec-butylcyclohexyl fumarate, 4-sec-butylcyclohexyl fumarate, 4-sec-butylcyclohexyl fumarate, 4-sec-butylcyclohexyl fumarate, 4-sec-pentylcyclohexyl fumarate, 4-sec-pentylcyclohexyl fumarate, 4-sec-pentylcyclohexyl fumarate (4-Second-pentylcyclohexyl) ethyl fumarate, (4-sec-pentylcyclohexyl) propyl fumarate, (4-sec-pentylcyclohexyl) isopropyl fumarate, (4-sec-pentylcyclohexyl) butyl fumarate, (4-sec-pentylcyclohexyl) isobutyl fumarate, (4-sec-pentylcyclohexyl) sec-butyl fumarate, (4-sec-pentylcyclohexyl) sec-pentyl fumarate, (4-sec-pentylcyclohexyl) tert-pentyl fumarate(4-Second-pentylcyclohexyl) sec-hexyl fumarate, (4-Second-pentylcyclohexyl) tert-hexyl fumarate, (4-Second-pentylcyclohexyl) cyclopropyl fumarate, (4-Second-pentylcyclohexyl) cyclopentyl fumarate, (4-Second-pentylcyclohexyl) cyclohexyl fumarate, (4-tert-pentylcyclohexyl) methyl fumarate, (4-tert-pentylcyclohexyl) ethyl fumarate, (4-tert-pentylcyclohexyl) propyl fumarate, (4-tert-pentylcyclohexyl) isopropyl fumarate, (4-tert-pentyl) Cyclohexyl)butyl fumarate, (4-tert-pentylcyclohexyl)isobutyl fumarate, (4-tert-pentylcyclohexyl)sec-butyl fumarate, (4-tert-pentylcyclohexyl)sec-pentyl fumarate, (4-tert-pentylcyclohexyl)tert-pentyl fumarate, (4-tert-pentylcyclohexyl)sec-hexyl fumarate, (4-tert-pentylcyclohexyl)tert-hexyl fumarate, (4-tert-pentylcyclohexyl)cyclopropyl fumarate, (4-tert-pentylcyclohexyl)cyclopentyl fumarate, (4-tert-pentylcyclohexyl)cyclohexyl fumarate. The resin obtained from polymerizing the monomers disclosed herein maintains high T... βFurthermore, considering the high molecular weight aspect, the preferred formulations are ethyl fumarate (4-methylcyclohexyl), isopropyl fumarate (4-methylcyclohexyl), sec-butyl fumarate (4-methylcyclohexyl), cyclopentyl fumarate (4-methylcyclohexyl), cyclohexyl fumarate (4-methylcyclohexyl), ethyl fumarate (4-ethylcyclohexyl), isopropyl fumarate (4-ethylcyclohexyl), sec-butyl fumarate (4-ethylcyclohexyl), cyclopentyl fumarate (4-ethylcyclohexyl), and fumarate (4-ethylcyclohexyl). (4-Ethylcyclohexyl)cyclohexyl ester, (4-isopropylcyclohexyl)ethyl fumarate, (4-isopropylcyclohexyl)isopropyl fumarate, (4-isopropylcyclohexyl)sec-butyl fumarate, (4-isopropylcyclohexyl)cyclopentyl fumarate, (4-isopropylcyclohexyl)cyclohexyl fumarate, (4-tert-butylcyclohexyl)ethyl fumarate, (4-tert-butylcyclohexyl)isopropyl fumarate, (4-tert-butylcyclohexyl)sec-butyl fumarate, (4-tert-butylcyclohexyl)cyclopentyl fumarate, fumarate ( 4-tert-butylcyclohexyl)cyclohexyl ester, more preferably ethyl fumarate (4-isopropylcyclohexyl), isopropyl fumarate (4-isopropylcyclohexyl), sec-butyl fumarate (4-isopropylcyclohexyl), cyclopentyl fumarate (4-isopropylcyclohexyl), cyclohexyl fumarate (4-isopropylcyclohexyl), ethyl fumarate (4-tert-butylcyclohexyl), isopropyl fumarate (4-tert-butylcyclohexyl), sec-butyl fumarate (4-tert-butylcyclohexyl), and so on. Cyclopentyl fumarate, (4-tert-butylcyclohexyl)cyclohexyl fumarate, more preferably (4-tert-butylcyclohexyl)ethyl fumarate, (4-tert-butylcyclohexyl)isopropyl fumarate, (4-tert-butylcyclohexyl)sec-butyl fumarate, (4-tert-butylcyclohexyl)cyclopentyl fumarate, (4-tert-butylcyclohexyl)cyclohexyl fumarate, particularly preferably (4-tert-butylcyclohexyl)ethyl fumarate, (4-tert-butylcyclohexyl)isopropyl fumarate, (4-tert-butylcyclohexyl)cyclohexyl fumarate.

[0063] The monomer disclosed herein has a structure in which the carbon atoms at the 1,4-positions of the cyclohexane ring are bonded to an R1 group, etc. Therefore, in the monomer disclosed herein, cis-trans isomers exist depending on the bonding direction of the R1 group to the cyclohexane ring, but as long as a high T... β Any resin is acceptable, and there are no particular restrictions on whether it is the cis or trans form.

[0064] From the viewpoint that the polymerization process of the monomers disclosed herein is simple to construct and that the resulting resin has a high molecular weight, the melting point of the monomers is preferably below 80°C, more preferably below 70°C, and particularly preferably below 60°C. In this specification, the melting point of the monomers is a value measured by the method described in the examples below.

[0065] In this disclosure, as a method for synthesizing the fumarate monomer shown in formula (1), any method can be used to produce the fumarate monomer as long as it is available, and examples include the methods shown in formula (b) and formula (c) below.

[0066] [Chemical Formula 5]

[0067]

[0068] (R2 in equation (4) and R1 in equation (5) have the same meaning as R1 and R2 in equation (1).)

[0069] Formula (b) is the maleic anhydride monoalkylation reaction that reacts maleic anhydride with the alcohol shown in general formula (4) to synthesize maleic acid monoalkyl esters.

[0070] The R2 in the alcohol represented by general formula (4) is the same as the R2 in general formula (1). Specific alcohols that can be listed include: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, 2-pentanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, 2-methyl-2-pentanol, cyclopropanol, cyclopentanol, cyclohexanol, etc. Among these, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, 2-pentanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, 2-methyl-2-pentanol, cyclopropanol, cyclopentanol, and cyclohexanol are preferred, and ethanol, isopropanol, 2-butanol, cyclopentanol, and cyclohexanol are even more preferred, and ethanol, isopropanol, and cyclohexanol are particularly preferred.

[0071] The maleic anhydride monoalkylation reaction (formula (b)) can be carried out in any manner suitable for monoalkylation, without particular limitations. It can be conducted using either a catalyst-free reaction or an acid catalyst, and the reaction temperature can be selected appropriately based on the matrix. As an acid catalyst, ion exchange resins containing sulfuric acid, p-toluenesulfonic acid, xylenesulfonic acid, or sulfonates are preferred; one or more of these can be used. Examples of ion exchange resins containing sulfonates include Amberlite resin and Nafion resin. From the viewpoint of obtaining particularly high yields, sulfuric acid, p-toluenesulfonic acid, or xylenesulfonic acid are more preferred.

[0072] The monoalkylation reaction of maleic anhydride can be carried out in any manner that allows for monoalkylation; there are no particular restrictions. A solvent may or may not be used. As for the solvent, it is acceptable as long as it is not harmful to the reaction. Examples include: halogen solvents such as dichloromethane and chloroform; ether solvents such as dioxane, tetrahydrofuran, diisopropyl ether, and cyclopentylmethyl ether; aromatic solvents such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene; and hydrocarbon solvents such as cyclohexane and methylcyclohexane. These solvents can be used individually or in combination.

[0073] From the viewpoint that high yields of maleic acid monoalkyl esters can be obtained, the reaction temperature of maleic anhydride reacting with alcohol is preferably 20 to 180°C, more preferably 25 to 150°C, and particularly preferably 30 to 130°C.

[0074] Examples of monoalkyl maleate esters obtained by monoalkylation of maleic anhydride include: monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, monoisopropyl maleate, monoisobutyl maleate, mono-sec-butyl maleate, mono-sec-pentyl maleate, mono-tert-pentyl maleate, mono-sec-hexyl maleate, mono-tert-hexyl maleate, monocyclopropyl maleate, monocyclopentyl maleate, and monocyclohexyl maleate. Preferred ingredients include monoethyl maleate, monopropyl maleate, monoisopropyl maleate, monobutyl maleate, monoisobutyl maleate, mono-sec-butyl maleate, mono-sec-pentyl maleate, mono-tert-pentyl maleate, mono-sec-hexyl maleate, mono-tert-hexyl maleate, monocyclopropyl maleate, monocyclopentyl maleate, and monocyclohexyl maleate. Further preferred ingredients are monoethyl maleate, monoisopropyl maleate, mono-sec-butyl maleate, monocyclopentyl maleate, and monocyclohexyl maleate. Particularly preferred ingredients are monoethyl maleate, monoisopropyl maleate, and monocyclohexyl maleate.

[0075] Formula (c) is a method for synthesizing the fumarate ester shown in Formula (1) by condensing the maleic acid monoalkyl ester synthesized by Formula (b) with the alcohol shown in general Formula (5) in the presence of a catalyst and then isomerizing it.

[0076] R1 in the alcohol represented by general formula (5) is the same as R1 in general formula (1). Specific alcohols that can be listed include: 4-methylcyclohexanol, 4-ethylcyclohexanol, 4-propylcyclohexanol, 4-isopropylcyclohexanol, 4-butylcyclohexanol, 4-tert-butylcyclohexanol, 4-isobutylcyclohexanol, 4-sec-butylcyclohexanol, 4-sec-pentylcyclohexanol, 4-tert-pentylcyclohexanol, etc. Among them, 4-methylcyclohexanol, 4-ethylcyclohexanol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol, and especially 4-tert-butylcyclohexanol are preferred.

[0077] The alcohols represented by general formula (5) have a structure in which the carbon atoms at the 1,4-positions of the cyclohexane ring have a hydroxyl group bonded to an R1 group. Therefore, in the alcohols represented by general formula (5), cis-trans isomers exist depending on the bonding direction of the hydroxyl group and the R1 group relative to the cyclohexane ring, but as long as a high T isomer can be obtained, a cis-trans isomer can be formed. β Any resin is acceptable, whether it is cis or trans, there is no particular limitation.

[0078] The catalyst can be any substance that enables the condensation reaction; there are no particular restrictions. Condensing agents and acid catalysts can be used. Examples of condensing agents 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, and 1-cyclohexyl-3-(2-morpholinylethyl)carbodiimide. Carbodiimide-p-toluenesulfonate, N,N'-di-tert-butylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methyliodide, preferably 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride, N,N'-diisopropylcarbodiimide, or N,N'-dicyclohexylcarbodiimide. Two or more of these ester-forming condensing agents may be used.

[0079] As acid catalysts, ion exchange resins containing sulfuric acid, p-toluenesulfonic acid, xylenesulfonic acid, or sulfonyl groups are preferred, and one or more of these can be used. Examples of ion exchange resins containing sulfonyl groups include Amberlite resin and Nafion resin. From the viewpoint of obtaining particularly high yields, sulfuric acid, p-toluenesulfonic acid, and xylenesulfonic acid are more preferred.

[0080] In the condensation reaction of the monoalkyl maleic acid ester synthesized in formula (b) with an alcohol in the presence of a condensing agent, it is preferable to add a base to facilitate the reaction. Examples of bases that can be used include, for example, organic bases, such as triethylamine, tributylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, piperidine, piperazine, pyrrolidine, morpholine, N-methylmorpholine, imidazole, and N-methylimidazole.

[0081] Isomerization reactions can be carried out as long as isomerization is possible, without particular restrictions, and there are methods that use isomerization catalysts. Preferred isomerization catalysts include, for example, amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-sec-butylamine, di-tert-butylamine, dicyclohexylamine, aziridine, pyrrolidine, morpholine, piperazine, piperidine, and ethylenediamine, with piperidine and ethylenediamine being particularly preferred.

[0082] The solvent used to react monoalkyl maleate with alcohols is not particularly limited, as long as it is not harmful to the reaction. Examples include: halogen solvents such as dichloromethane and chloroform; ether solvents such as dioxane, tetrahydrofuran, diisopropyl ether, and cyclopentylmethyl ether; aromatic solvents such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene; and hydrocarbon solvents such as cyclohexane and methylcyclohexane. These solvents can be used alone or in combination.

[0083] Regarding the solvent used in the isomerization reaction, there are no special restrictions as long as it does not react with amines. Examples include: halogen solvents such as dichloromethane and chloroform; ether solvents such as dioxane, tetrahydrofuran, diisopropyl ether, and cyclopentylmethyl ether; and aromatic hydrocarbons such as toluene and xylene.

[0084] <Resin>

[0085] The resin used as one embodiment of this disclosure will now be described in detail.

[0086] This disclosure pertains to a resin comprising residue units of the following structural formula (2) derived from the fumarate monomer shown in formula (1) above (hereinafter also referred to as "the resin of this disclosure").

[0087] [Compound 6]

[0088]

[0089] (In the formula, R1 represents a straight-chain alkyl group with 1 to 4 carbon atoms, or a branched alkyl group with 3 to 5 carbon atoms. R2 represents a straight-chain alkyl group with 1 to 4 carbon atoms, a branched alkyl group with 3 to 12 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms.)

[0090] R1 and R2 in formula (2) can use the same groups as R1 and R2 in formula (1).

[0091] Examples of specific residue units represented by formula (2) include: methyl fumarate (4-methylcyclohexyl) ester residue, ethyl fumarate (4-methylcyclohexyl) ester residue, propyl fumarate (4-methylcyclohexyl) ester residue, isopropyl fumarate (4-methylcyclohexyl) ester residue, butyl fumarate (4-methylcyclohexyl) ester residue, isobutyl fumarate (4-methylcyclohexyl) sec-butyl fumarate residue, pentyl fumarate (4-methylcyclohexyl) ester residue, tert-pentyl fumarate (4-methylcyclohexyl) ester residue, tert-hexyl fumarate (4-methylcyclohexyl) ester residue, tert-hexyl fumarate (4-methylcyclohexyl) cyclopropyl fumarate residue, and cyclopropyl fumarate (4-methylcyclohexyl) cyclopropyl fumarate residue. 4-ethylcyclohexyl fumarate residue, 4-ethylcyclohexyl fumarate methyl ester residue, 4-ethylcyclohexyl fumarate ethyl ester residue, 4-ethylcyclohexyl fumarate propyl ester residue, 4-ethylcyclohexyl fumarate isopropyl ester residue, 4-ethylcyclohexyl fumarate butyl ester residue, 4-ethylcyclohexyl fumarate isobutyl ester residue, 4-ethylcyclohexyl fumarate sec-butyl ester residue, 4-ethylcyclohexyl fumarate sec-pentyl ester residue, 4-ethylcyclohexyl fumarate tert-pentyl ester residue, 4-ethylcyclohexyl fumarate sec-hexyl ester residue, 4-ethylcyclohexyl fumarate tert-hexyl ester residue, 4-ethylcyclohexyl fumarate cyclopropyl ester residue, 4-ethylcyclohexyl fumarate cyclohexyl Amyl ester residue, (4-ethylcyclohexyl)cyclohexyl fumarate residue, (4-propylcyclohexyl)methyl fumarate residue, (4-propylcyclohexyl)ethyl fumarate residue, (4-propylcyclohexyl)propyl fumarate residue, (4-propylcyclohexyl)isopropyl fumarate residue, (4-propylcyclohexyl)butyl fumarate residue, (4-propylcyclohexyl)isobutyl fumarate residue, (4-propylcyclohexyl)sec-butyl fumarate residue, (4-propylcyclohexyl)sec-pentyl fumarate residue, (4-propylcyclohexyl)tert-pentyl fumarate residue, (4-propylcyclohexyl)sec-hexyl fumarate residue, (4-propylcyclohexyl)tert-hexyl fumarate residue, (4-propylcyclohexyl)cyclopropyl fumarate residue, (4-propylcyclohexyl) Cyclopentyl ester residue, (4-propylcyclohexyl)cyclohexyl fumarate residue, (4-isopropylcyclohexyl)methyl fumarate residue, (4-isopropylcyclohexyl)ethyl fumarate residue, (4-isopropylcyclohexyl)propyl fumarate residue, (4-isopropylcyclohexyl)isopropyl fumarate residue, (4-isopropylcyclohexyl)butyl fumarate residue, (4-isopropylcyclohexyl)isobutyl fumarate residue, (4-isopropylcyclohexyl)sec-butyl fumarate residue, (4-isopropylcyclohexyl)sec-pentyl fumarate residue, (4-isopropylcyclohexyl)tert-pentyl fumarate residue, (4-isopropylcyclohexyl)sec-hexyl fumarate residue, (4-isopropylcyclohexyl)tert-hexyl fumarate residue, (4-isopropylcyclohexyl)cyclopropyl fumarate residue(4-Isopropylcyclohexyl)cyclopentyl fumarate residue, (4-isopropylcyclohexyl)cyclohexyl fumarate residue, (4-butylcyclohexyl)methyl fumarate residue, (4-butylcyclohexyl)ethyl fumarate residue, (4-butylcyclohexyl)propyl fumarate residue, (4-butylcyclohexyl)isopropyl fumarate residue, (4-butylcyclohexyl)butyl fumarate residue, (4-butylcyclohexyl)isobutyl fumarate residue, (4-butylcyclohexyl)sec-butyl fumarate residue, (4-butylcyclohexyl)sec-pentyl fumarate residue, (4-butylcyclohexyl)tert-pentyl fumarate residue, (4-butylcyclohexyl)sec-hexyl fumarate residue, (4-butylcyclohexyl)tert-hexyl fumarate residue, (4-butylcyclohexyl)cyclopropyl fumarate residue Fumarate (4-butylcyclohexyl)cyclopentyl ester residue, fumarate (4-butylcyclohexyl)cyclohexyl ester residue, fumarate (4-tert-butylcyclohexyl)methyl ester residue, fumarate (4-tert-butylcyclohexyl)ethyl ester residue, fumarate (4-tert-butylcyclohexyl)propyl ester residue, fumarate (4-tert-butylcyclohexyl)isopropyl ester residue, fumarate (4-tert-butylcyclohexyl)butyl ester residue, fumarate (4-tert-butylcyclohexyl)isobutyl ester residue, fumarate (4-tert-butylcyclohexyl)sec-butyl ester residue, fumarate (4-tert-butylcyclohexyl)sec-pentyl ester residue, fumarate (4-tert-butylcyclohexyl)tert-pentyl ester residue, fumarate (4-tert-butylcyclohexyl)sec-hexyl ester residue, fumarate (4-tert-butylcyclohexyl)tert ... (4-tert-butylcyclohexyl)cyclopropyl fumarate residue, (4-tert-butylcyclohexyl)cyclopentyl fumarate residue, (4-tert-butylcyclohexyl)cyclohexyl fumarate residue, (4-isobutylcyclohexyl)methyl fumarate residue, (4-isobutylcyclohexyl)ethyl fumarate residue, (4-isobutylcyclohexyl)propyl fumarate residue, (4-isobutylcyclohexyl)isopropyl fumarate residue, (4-isobutylcyclohexyl)butyl fumarate residue, (4-isobutylcyclohexyl)isobutyl fumarate residue, (4-isobutylcyclohexyl)sec-butyl fumarate residue, (4-isobutylcyclohexyl)sec-pentyl fumarate residue, (4-isobutylcyclohexyl)tert-pentyl fumarate residue, (4-isobutylcyclohexyl)sec-hexyl fumarate residue, (4-isobutylcyclohexyl) ) tert-hexyl ester residue, fumarate (4-isobutylcyclohexyl)cyclopropyl ester residue, fumarate (4-isobutylcyclohexyl)cyclopentyl ester residue, fumarate (4-isobutylcyclohexyl)cyclohexyl ester residue, fumarate (4-sec-butylcyclohexyl)methyl ester residue, fumarate (4-sec-butylcyclohexyl)ethyl ester residue, fumarate (4-sec-butylcyclohexyl)propyl ester residue, fumarate (4-sec-butylcyclohexyl)isopropyl ester residue, fumarate (4-sec-butylcyclohexyl)sec-butyl ester residue, fumarate (4-sec-butylcyclohexyl)sec-pentyl ester residue, fumarate (4-sec-butylcyclohexyl)tert-pentyl ester residue, fumarate (4-sec-butylcyclohexyl)sec-hexyl ester residue,(4-sec-butylcyclohexyl) tert-hexyl fumarate residue, (4-sec-butylcyclohexyl) cyclopropyl fumarate residue, (4-sec-butylcyclohexyl) cyclopentyl fumarate residue, (4-sec-butylcyclohexyl) cyclohexyl fumarate residue, (4-sec-pentylcyclohexyl) methyl fumarate residue, (4-sec-pentylcyclohexyl) ethyl fumarate residue, (4-sec-pentylcyclohexyl) propyl fumarate residue, (4-sec-pentylcyclohexyl) isopropyl fumarate residue, ... (4-Second-pentylcyclohexyl)butyl fumarate residue, (4-Second-pentylcyclohexyl)isobutyl fumarate residue, (4-Second-pentylcyclohexyl)sec-butyl fumarate residue, (4-Second-pentylcyclohexyl)sec-pentyl fumarate residue, (4-Second-pentylcyclohexyl)tert-pentyl fumarate residue, (4-Second-pentylcyclohexyl)sec-hexyl fumarate residue, (4-Second-pentylcyclohexyl)tert-hexyl fumarate residue, (4-Second-pentylcyclohexyl)cyclopropyl fumarate residue Fumarate (4-sec-pentylcyclohexyl)cyclopentyl ester residue, fumarate (4-sec-pentylcyclohexyl)cyclohexyl ester residue, fumarate (4-tert-pentylcyclohexyl)methyl ester residue, fumarate (4-tert-pentylcyclohexyl)ethyl ester residue, fumarate (4-tert-pentylcyclohexyl)propyl ester residue, fumarate (4-tert-pentylcyclohexyl)isopropyl ester residue, fumarate (4-tert-pentylcyclohexyl)butyl ester residue, fumarate (4-tert-pentylcyclohexyl)isobutyl ester residue, fumarate The resin obtained by polymerizing the monomers of this disclosure maintains a high T... βFurthermore, considering the high molecular weight aspect, the preferred components are (4-methylcyclohexyl) ethyl fumarate residues, (4-methylcyclohexyl) isopropyl fumarate residues, (4-methylcyclohexyl) sec-butyl fumarate residues, (4-methylcyclohexyl) cyclopentyl fumarate residues, (4-methylcyclohexyl) cyclohexyl fumarate residues, (4-ethylcyclohexyl) ethyl fumarate residues, (4-ethylcyclohexyl) isopropyl fumarate residues, (4-ethylcyclohexyl) sec-butyl fumarate residues, (4-ethylcyclohexyl) cyclopentyl fumarate residues, and fumarate (4- Ethylcyclohexyl fumarate (4-isopropylcyclohexyl) cyclohexyl ester residue, fumarate (4-isopropylcyclohexyl) isopropyl ester residue, fumarate (4-isopropylcyclohexyl) sec-butyl ester residue, fumarate (4-isopropylcyclohexyl) cyclopentyl ester residue, fumarate (4-isopropylcyclohexyl) cyclohexyl ester residue, fumarate (4-tert-butylcyclohexyl) ethyl fumarate residue, fumarate (4-tert-butylcyclohexyl) isopropyl fumarate residue, fumarate (4-tert-butylcyclohexyl) sec-butyl ester residue, fumarate (4-tert-butylcyclohexyl) cyclopentyl ester residue, fumarate ( 4-tert-butylcyclohexyl)cyclohexyl ester residues, more preferably ethyl fumarate (4-isopropylcyclohexyl) ester residues, isopropyl fumarate (4-isopropylcyclohexyl) isopropyl fumarate residues, sec-butyl fumarate (4-isopropylcyclohexyl) ester residues, cyclopentyl fumarate (4-isopropylcyclohexyl) cyclohexyl fumarate residues, ethyl fumarate (4-tert-butylcyclohexyl) ester residues, isopropyl fumarate (4-tert-butylcyclohexyl) isopropyl fumarate residues, sec-butyl fumarate (4-tert-butylcyclohexyl) cyclohexyl fumarate residues, cyclohexyl ... The residues are pentyl ester residues, fumarate (4-tert-butylcyclohexyl)cyclohexyl ester residues, more preferably fumarate (4-tert-butylcyclohexyl) ethyl ester residues, fumarate (4-tert-butylcyclohexyl) isopropyl ester residues, fumarate (4-tert-butylcyclohexyl) sec-butyl ester residues, fumarate (4-tert-butylcyclohexyl) cyclopentyl ester residues, fumarate (4-tert-butylcyclohexyl) cyclohexyl ester residues, and particularly preferably fumarate (4-tert-butylcyclohexyl) ethyl ester residues, fumarate (4-tert-butylcyclohexyl) isopropyl ester residues, and fumarate (4-tert-butylcyclohexyl) cyclohexyl ester residues.

[0092] The residue unit shown in formula (2) has a structure in which the carbon atoms at the 1,4-positions of the cyclohexane ring are bonded to the R1 group, etc. Therefore, in the residue unit shown in formula (2), cis-trans isomers exist depending on the different bonding directions of the R1 group to the cyclohexane ring, but as long as a high T isomer can be obtained, β The resin can be either cis- or trans-form, and there is no particular limitation. The resin disclosed herein may have residue units shown in the cis-form (2) and residue units shown in the trans-form (2), or may have only residue units of either one.

[0093] As examples of resins disclosed herein, fumarate resins can be cited, which are derived from high T β From the viewpoint of high heat resistance resin, it is preferred to contain 40 mol% or more of the fumarate residue units shown in formula (2), more preferably 50 mol% or more, particularly preferably 60 mol% or more, and even more preferably 80 mol% or more. In the resin disclosed herein, the upper limit of the proportion of the residue units shown in formula (2) is not particularly limited, and may be 100 mol%, or for example 95 mol% or less, or 90 mol% or less.

[0094] The resin disclosed herein has good heat resistance and polymerizability, and therefore may further contain residue units as shown in the following structural formula (3) in addition to the residue units shown in structural formula (2).

[0095] [Chemical Formula 7]

[0096]

[0097] (In the formula, R3 and R4 each independently represent a straight-chain alkyl group with 1 to 12 carbon atoms, a branched alkyl group with 3 to 12 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms.)

[0098] In formula (3), R3 and R4 each independently represent a straight-chain alkyl group with 1 to 12 carbon atoms, a branched alkyl group with 3 to 12 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms.

[0099] Specific examples of R3 and R4 include ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, sec-hexyl, tert-hexyl, cyclopropyl, cyclopentyl, and cyclohexyl. From the viewpoint of producing a film with excellent heat resistance and mechanical properties, ethyl, isopropyl, sec-butyl, tert-butyl, cyclopentyl, and cyclohexyl are preferred, and isopropyl is particularly preferred.

[0100] Here, as the fumarate residue unit shown in formula (3), specifically, examples include: diethyl fumarate residue, diisopropyl fumarate residue, disec-butyl fumarate residue, ditert-butyl fumarate residue, disec-pentyl fumarate residue, ditert-pentyl fumarate residue, disec-hexyl fumarate residue, ditert-hexyl fumarate residue, dicyclopropyl fumarate residue, dicyclopentyl fumarate residue, dicyclohexyl fumarate residue, and residues in which R3 or R4 is substituted (e.g., ethyl isopropyl fumarate residue, ethyl sec-butyl fumarate residue, etc.). Preferably, the following residues are used: diethyl fumarate residue, diisopropyl fumarate residue, disec-butyl fumarate residue, ditert-butyl fumarate residue, dicyclopentyl fumarate residue, dicyclohexyl fumarate residue, isopropyl ethyl fumarate residue, isopropyl tert-butyl fumarate residue, cyclohexyl ethyl fumarate residue, cyclohexyl isopropyl fumarate residue, cyclohexyl sec-butyl fumarate residue, cyclohexyl tert-butyl fumarate residue, and cyclohexyl fumarate. The residues include sec-amyl fumarate residues, cyclohexyl tert-amyl fumarate residues, cyclohexyl sec-hexyl fumarate residues, cyclohexyl tert-hexyl fumarate residues, and cyclohexyl cyclopentyl fumarate residues, particularly preferably diethyl fumarate residues, diisopropyl fumarate residues, disec-butyl fumarate residues, ditert-butyl fumarate residues, dicyclopentyl fumarate residues, and dicyclohexyl fumarate residues, and even more preferably diethyl fumarate residues and diisopropyl fumarate residues. These can be used alone or in combination of two or more.

[0101] In the case where the resin of this disclosure contains the residue unit shown in formula (3), the proportion is preferably 5 mol% or more, more preferably 10 mol% or more. In addition, the above proportion is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, and particularly preferably 20 mol% or less.

[0102] From the viewpoint of becoming a film with heat resistance and mechanical properties, the following fumarate resins can be cited as examples: fumarate resins comprising, for example, 40 mol% or more, preferably 50 mol% or more, particularly preferably 60 mol% or more, and even more preferably 80 mol% or more.

[0103] The aforementioned fumarate resins may contain residue units other than those shown in formulas (2) and (3). Examples of residue units other than those shown in formulas (2) and (3) include: styrene residues such as styrene residues and α-methylstyrene residues; acrylic acid residues; acrylate residues such as methyl acrylate residues, ethyl acrylate residues, and butyl acrylate residues; methacrylic acid residues; methacrylate residues such as methyl methacrylate residues, ethyl methacrylate residues, and butyl 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; and one or more of the following.

[0104] In the resins disclosed herein, particularly from the viewpoint of becoming resins with excellent heat resistance, the β relaxation temperature (T0) during the second scan heating (heating rate = 10 °C / min), measured by differential scanning calorimetry (DSC), is... β The temperature is preferably 130°C or higher, more preferably 130°C to 300°C, even more preferably 140°C to 250°C, and particularly preferably 150°C to 200°C.

[0105] In the resins disclosed herein, particularly from the viewpoint of becoming resins with excellent mechanical properties, the equivalent weight-average molecular weight (Mw) of standard polystyrene obtained by dissolution curves determined by gel permeation chromatography (GPC) is preferably 50,000 or more, more preferably 80,000 or more, further preferably 80,000 to 5,000,000, particularly preferably 200,000 to 2,000,000, further particularly preferably 300,000 to 1,000,000, and most preferably 400,000 to 800,000.

[0106] As a method for manufacturing the resin disclosed herein, any method can be used to obtain the resin, including, for example, the method of free radical polymerization of the fumarate monomer described in formula (1) and the method of transesterification of the fumarate resin, wherein the method of free radical polymerization of the fumarate monomer shown in formula (1) is preferred.

[0107] As a method for free radical polymerization, any one of the following can be used, such as bulk polymerization, solution polymerization, suspension polymerization, precipitation polymerization, emulsion polymerization, etc. Among these, from the viewpoint of obtaining high molecular weight fumarate resins, bulk polymerization or suspension polymerization is preferred.

[0108] The polymerization temperature for free radical polymerization is not particularly limited as long as it is above the melting temperature of the fumarate monomers, but a low temperature is preferred from the viewpoint of obtaining fumarate resins with particularly high molecular weights. For example, 120°C or below is preferred, 100°C or below is more preferred, and 80°C or below is particularly preferred.

[0109] Examples of polymerization initiators used in free radical polymerization include: benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, tert-butyl cumene peroxide, diisopropylbenzene peroxide, tert-butyl peracetate, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di(2-ethylhexanoate peroxide)hexane, tert-butyl peroxypentanoate, tert-butanol hydrogen peroxide, and tert-butyl peroxy-2-ethylhexanoate; azo initiators such as 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2-methylpropionic acid)dimethyl ester, 2,2'-azobis(2-butanonitrile), 2,2'-azobisisobutanonitrile, dimethyl-2'-azobisisobutyl ester, and 1,1'-azobis(cyclohexane-1-carboxynitrile).

[0110] <membrane>

[0111] The membrane, which is one aspect of this disclosure, will be described in detail below.

[0112] The resin disclosed herein can be suitably used as a film for optical components. In particular, due to the resin's T... β It has high heat resistance, so it can be used as a membrane with excellent heat resistance.

[0113] In the film disclosed herein, from the viewpoint of achieving a film with excellent viewing angle characteristics, the out-of-plane phase difference (Rth) measured at a wavelength of 589 nm as shown in formula (a) below is preferably -700 to 0 nm, more preferably -240 to -20 nm, and particularly preferably -160 to -30 nm. In this specification, the out-of-plane phase difference of the film is a value measured, for example, by the measurement method described in the embodiments below.

[0114] Rth = [(nx + ny) / 2 - nz] × d (a)

[0115] (In the formula, nx represents the refractive index along the fast axis inside the film, ny represents the refractive index along the slow axis inside the film, nz represents the refractive index perpendicular to the film outside the film, and d represents the thickness of the film (nm).)

[0116] From the viewpoint of suitability for thin-film 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.

[0117] Because the membrane of this disclosure contains high T β Fumarate-based resins can produce films with low linear expansion and excellent dimensional stability at high temperatures.

[0118] In the membrane disclosed herein, from the viewpoint of achieving excellent dimensional stability at high temperatures, the linear expansion rate α shown in formula (b) below is preferably 95 ppm / ℃ or less, more preferably 0 to 90 ppm / ℃, further preferably 10 to 85 ppm / ℃, and particularly preferably 15 to 80 ppm / ℃. In this specification, the linear expansion rate of the membrane is a value measured, for example, by the measurement method described in the embodiments below.

[0119] α=Δl / (ΔT×l) (b)

[0120] (In the formula, Δl represents the change in membrane length due to temperature change, ΔT represents the change in membrane temperature, and l represents the membrane length before the temperature change.)

[0121] The membrane may contain antioxidants to improve thermal stability. Examples of such antioxidants include hindered phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, lactone-based antioxidants, amine-based antioxidants, hydroxylamine-based antioxidants, vitamin E-based antioxidants, and other antioxidants. These antioxidants can be used individually or in combination of two or more.

[0122] The membrane may contain hindered amine light stabilizers and ultraviolet absorbers to improve weather resistance. Examples of such ultraviolet absorbers include benzotriazole, benzophenone, triazine, and benzoic acid esters.

[0123] Within the scope of the invention, the membrane may contain other polymers, surfactants, high molecular weight electrolytes, conductive complexes, pigments, dyes, antistatic agents, anti-blocking agents, lubricants, etc.

[0124] There are no particular restrictions on the method of manufacturing the membrane. For example, it can be manufactured by using a solution casting method or other methods to form a long strip of membrane.

[0125] Here, solution casting refers to a method in which a resin solution (usually called dope) is cast onto a support substrate, and then the solvent is evaporated by heating and drying, causing the substrate to peel off to obtain a film.

[0126] The solvent used in the resin solution in the solution casting method can be any solvent that can dissolve resin, etc. When obtaining the film, in order to avoid leaving residual solvent, the boiling point of the solvent is preferably below 200°C, more preferably below 170°C.

[0127] Examples of solvents that can be used 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, anisole, mesitylene, and diphenyl methyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, and N-methyl-2-pyrrolidone; and ethyl acetate. Ester solvents such as butyl acetate; alcohol solvents such as tert-butanol, glycerol, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, and 2-methyl-2,4-pentanediol; amide solvents such as dimethylformamide and dimethylacetamide; nitrile solvents such as acetonitrile and butyronitrile; ether solvents such as diethyl ether, dibutyl ether, and tetrahydrofuran; solvents used alone or in combination with carbon disulfide, ethyl cellosolve, butyl cellosolve, etc.

[0128] 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 limitations on the viscosity of the resin solution, but to facilitate film casting, a viscosity of 100 to 30,000 cps is preferred, more preferably 300 to 20,000 cps, and particularly preferably 300 to 15,000 cps is preferred.

[0129] In this disclosure, the concentration of the raw resin relative to the slurry is not particularly limited as long as it allows for dissolution and film formation. The dissolution process can be carried out during the dissolution stage to achieve a given concentration, or a low-concentration solution can be prepared in advance and then adjusted to a given high-concentration solution through a concentration process. Furthermore, a given low-concentration resin solution can be prepared by adding various additives after a high-concentration resin solution has been prepared in advance.

[0130] Furthermore, there are no particular limitations on the supporting substrate used, and examples include: polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate; polystyrene; polyethylene; polypropylene; polyacrylic acid; polyvinyl chloride; polyvinylidene chloride; cellulose acetate; cellulose ether; and other polymeric substrates; polyvinyl alcohol; polyamide; polyimide; polyarylate; polysulfone; polyethersulfone; polyetherketone; phenolic resin; epoxy resin; aliphatic cyclic polyolefin; and norbornene thermoplastic transparent resin; glass substrates such as glass plates and quartz substrates; metal substrates such as aluminum, stainless steel, and iron plates for photographic applications; and inorganic substrates such as ceramic substrates. Preferred substrates include polyesters such as polyethylene terephthalate and polyethylene naphthalate; cellulose such as polypropylene, polyacrylic acid, cellulose acetate; cellulose ether; and other polymeric substrates such as polyimide, aliphatic cyclic polyolefin, and norbornene thermoplastic transparent resin. The preferred polymer substrates are polyester, polypropylene, polyimide, aliphatic cyclic polyolefin, norbornene-based thermoplastic transparent resin, etc., such as polyethylene terephthalate and polyethylene naphthalate.

[0131] There are no particular restrictions on the casting method; common methods can be used. Examples include: T-die method, doctor blade method, bar coating method, slot die method, lip coating method, reverse gravure coating method, micro-gravure coating method, spin coating method, brush coating method, roller coating method, flexographic printing method, etc.

[0132] There are no particular restrictions on the drying method used in the drying process; common heating methods can be used. Examples include hot air blowers, heating rollers, and far-infrared heaters.

[0133] The drying temperature is preferably 30~200℃, and particularly preferably 40~160℃. It should be noted that the drying temperature can be a single-stage condition, or, in order to maintain the appearance and shorten the drying time, it can be a multi-stage drying process with low temperature in the first stage and high temperature in the second stage and thereafter.

[0134] From the perspectives of productivity, mechanical precision, and stability, the peeling speed of the film in the substrate peeling process can preferably be in the range of 0.1 to 30 m / min, and more preferably in the range of 1 to 30 m / min.

[0135] The membrane can be further laminated with other resins as needed. Examples of other resins include: polyethersulfone, polyarylate, polyethylene terephthalate, and polynaphthalene terephthalate. Materials include polycarbonate, cyclic polyolefins, maleimide resins, fluorinated resins, and polyimides. Additionally, liquid crystal layers, hard coatings, gas barrier layers, and layers with controlled refractive index (low-reflection layers) can be laminated.

[0136] The film disclosed herein has excellent heat resistance and optical properties, and can be suitable for use in phase retardation films used in applications such as liquid crystal display devices and organic EL display devices.

[0137] Furthermore, by disposing the film of this disclosure on at least one side of a polarizing mirror, a polarizing plate with excellent heat resistance and optical properties can be obtained, which can be suitable for use as a polarizing plate for liquid crystal displays and a polarizing plate for anti-reflection purposes.

[0138] Example

[0139] The present disclosure will be further described below through examples, but the present disclosure is not limited to these examples. It should be noted that the details of the reagents used are all shown in Table 1.

[0140] The various physical properties shown in the examples were determined by the following methods. Next, specific examples of the manufacture of fumarate monomers and fumarate-based resins are shown.

[0141] <Structural Analysis of Monomer Precursors and Monomers>

[0142] The precursor and structural analysis of the monomer were performed using a nuclear magnetic resonance (NMR) instrument (Bruker, Ascend NMR 400 (Nanobay)), employing proton nuclear magnetic resonance spectroscopy. 1 It is determined by H-NMR spectral analysis.

[0143] <Melting point analysis of monomers>

[0144] Using a differential scanning calorimeter (DSC) (manufactured by Shimadzu Corporation, trade name: DSC250), the melting point of the monomer was determined by setting the heating / cooling rate to 10°C / minute under a nitrogen atmosphere and the peak temperature of the endothermic reaction.

[0145] Analysis of the trans ratio of monomers relative to the cyclohexane ring

[0146] Using a gas chromatograph (Shimadzu Corporation, trade name: GC-2025), the trans ratio of the monomer relative to the cyclohexane ring was determined based on the ratio of the signal from the trans isomer relative to the cyclohexane ring to the signal from the cis isomer relative to the cyclohexane ring.

[0147] <β relaxation temperature (T) β The determination of )

[0148] Using a differential scanning calorimeter (DSC) (Hitachi High-Tech Science, trade name: DSC7000X), the temperature was increased from 25°C to 200°C at a rate of 10°C / min under a nitrogen atmosphere (first scan), and held at 200°C for 10 minutes. The temperature was then decreased to -70°C at a rate of 10°C / min and held at -70°C for 10 minutes. Finally, the temperature was increased to 200°C at a rate of 10°C / min (second scan). The β-relaxation temperature (T0) during the second scan heating was measured. β ).

[0149] <Structural Analysis of Polymers (Resins)>

[0150] The structural analysis of the polymer was performed using a nuclear magnetic resonance (NMR) spectrometer (JNEJT, trade name: JNM-ECZ400 / L1), via proton NMR spectroscopy. 1 It is determined by H-NMR spectral analysis.

[0151] <Determination of weight-average molecular weight>

[0152] A gel permeation chromatography (GPC) apparatus (Tosoh, trade name: HLC-8320GPC) was used with two Tosoh TSKgel Super HM-H columns. The column temperature was set to 40°C, and tetrahydrofuran was used as the solvent. The determination was performed at 40°C and the value was obtained as a conversion value for standard polystyrene.

[0153] <Determination of Phase Difference Characteristics (Rth)>

[0154] The out-of-plane phase difference Rth, measured at a wavelength of 589 nm as shown in Equation (a), was determined using a polarized phase difference measurement system (manufactured by Axometrics, trade name: AxoScan).

[0155] <Thickness Measurement>

[0156] The thickness of the membrane was measured using a high-resolution linear position sensor (Ono Senki, trade name: GS-3813B).

[0157] <Determination of Linear Expansion Rate>

[0158] A 3cm × 3cm membrane was fabricated and placed on a Teflon sheet. The membrane and Teflon sheet were placed together in an oven, and heating was initiated. For the first heating cycle, the temperature was increased from an initial 30°C to 120°C at a rate of 5°C / min, and held for 20 minutes. Subsequently, the temperature was decreased from 120°C to 30°C at a rate of 5°C / min, and held for 20 minutes. The second heating cycle was similar, increasing from an initial 30°C to 120°C at a rate of 5°C / min, and held for 20 minutes. Subsequently, the temperature was decreased from 120°C to 30°C at a rate of 5°C / min, and held for 20 minutes. During these temperature changes, the temperature near the sample was measured using a contact thermocouple, and the dimensional temperature change of the membrane was measured using a CCD camera. A linear fit was performed on the temperature change of the membrane length during the second cooling cycle from 120°C to 30°C to calculate the change in membrane length. The linear expansion coefficient α shown in equation (b) was calculated using the changes in membrane length, membrane temperature, and membrane length before the temperature change. The linear expansion coefficient α of the membrane was measured as the average of the linear expansion coefficients on both the longitudinal and transverse sides of the membrane.

[0159] Synthesis example 1

[0160] 5.04 g (51.4 mmol) of maleic anhydride and 12.10 g (263 mmol) of ethanol were weighed into a round-bottom flask. 20 mL of cyclohexane was added as a solvent, and the mixture was heated under reflux for 4 hours (reflux temperature: 81 °C). The water bath was set to above 70 °C, and unreacted ethanol and cyclohexane were distilled off from the evaporator to concentrate the contents, thus obtaining crude monoethyl maleate. 1 H-NMR (400MHz, CDCl3): δ6.40(m,2H,CH=CH), 4.35-4.30(q,J=8.0Hz,2H,O-CH2), 1.37-1.33(t,J=8.0Hz,3H,CH3))

[0161] [Chemical Formula 8]

[0162]

[0163] Example 1

[0164] To a flask equipped with a dropping funnel, 10.81 g (69.2 mmol) of 4-tert-butylcyclohexanol, 8.59 g (42.9 mmol) of N,N′-dicyclohexylcarbodiimide (DCC), and 0.74 g (6.06 mmol) of 4-dimethylaminopyridine (DMAP) were added and dissolved in 20 mL of dichloromethane. The crude product obtained in Synthesis Example 1 was added dropwise, and the mixture was stirred in an ice bath for 2 hours. The reaction solution was filtered, and the recovered solution was concentrated by evaporation and then purified by silica gel column chromatography (chloroform = 100 vol%). 20 mL of chloroform and 1 mL of piperidine were added to the purified product, and the mixture was refluxed for 6 hours (reflux temperature: 61 °C) to isomerize the fumarate (trans-form). The reaction solution after the isomerization reaction was separated and purified by silica gel column chromatography (hexane / ethyl acetate = 90 / 10 (Vol%)), and then dried under vacuum to obtain ethyl (4-tert-butylcyclohexyl) fumarate (BCEF). 1 H-NMR (400MHz, CDCl3): δ6.83(m,2H,CH=CH), 4.77-4.71(m,1H,O-CH), 4.28-4.23(q,J=5.3Hz, 2H,O-CH2), 2.07-0.99(m,9H,CH2,CH), 1.33-1.30(t,J=5.3Hz,3H,CH3), 0.860(s,9H,(CH3)3))

[0165] The melting point of the obtained BCEF is 59.4℃.

[0166] [Chemical Formula 9]

[0167]

[0168] Synthesis example 2

[0169] 5.01 g (51.1 mmol) of maleic anhydride and 15.09 g (251 mmol) of isopropanol were measured and added to a round-bottom flask. 20 mL of cyclohexane was added as a solvent, and the mixture was heated under reflux for 4 hours (reflux temperature: 81 °C). The water bath was set to above 80 °C, and unreacted isopropanol and cyclohexane were distilled off using an evaporator to concentrate the contents, thus obtaining crude monoisopropyl maleate. 1 H-NMR (400MHz, CDCl3): δ6.47-6.34(m,2H,CH=CH), 5.23-5.14(sep,J=6.3Hz,1H,O-CH), 1.36-1.34(d,J=6.3Hz,6H,(CH3)2))

[0170] [Chemical Formula 10]

[0171]

[0172] Example 2

[0173] To a flask equipped with a dropping funnel, 8.83 g (56.5 mmol) of 4-tert-butylcyclohexanol, 8.58 g (42.9 mmol) of N,N′-dicyclohexylcarbodiimide (DCC), and 0.84 g (6.86 mmol) of 4-dimethylaminopyridine (DMAP) were added and dissolved in 20 mL of dichloromethane. The crude product obtained in Synthesis Example 2 was added dropwise, and the mixture was stirred in an ice bath for 2 hours. The reaction solution was filtered, and the recovered solution was concentrated using an evaporator. The solution was then purified by silica gel column chromatography (hexane / ethyl acetate = 70 / 30 (Vol%)). The purified product was isomerized by adding 20 mL of chloroform and 1 mL of piperidine and heating under reflux for 6 hours (reflux temperature: 61 °C). The reaction solution after the isomerization reaction was separated and purified by silica gel column chromatography (hexane / ethyl acetate = 90 / 10 (Vol%)), and then dried under vacuum to obtain isopropyl fumarate (4-tert-butylcyclohexyl) (BCiPF). 1 H-NMR (400MHz, CDCl3): δ6.81(m,2H,CH=CH), 5.15-5.06(m,1H,O-CH), 4.78-4.70(quintet,J=6.0Hz,1H,O-CH), 2.07-1.11(m,9H,CH2,CH), 1.30-1.28(d,J=6.0 Hz,6H,(CH3)2),0.86(s,9H,(CH3)3))

[0174] The obtained BCiPF has a melting point of 43.8 °C and a trans ratio of 92.7% relative to the cyclohexane ring.

[0175] [Chemical Formula 11]

[0176]

[0177] Synthesis example 3

[0178] 6.61 g (67.4 mmol) of maleic anhydride and 6.52 g (65.2 mmol) of cyclohexanol were measured and added to a round-bottom flask. 20 mL of cyclohexane was added as a solvent, and the mixture was heated under reflux for 4 hours (reflux temperature: 81 °C). The water bath was set to above 80 °C, and unreacted isopropanol and cyclohexane were distilled off using an evaporator to concentrate the contents, thus obtaining crude monocyclohexyl maleic acid. 1H-NMR (400MHz, CDCl3): δ6.32-6.25(m,2H,CH=CH),4.95(quintet,J=4.0Hz,1H,O-CH),1.89-1.72(m,10H,CH2))

[0179] [Chemical Formula 12]

[0180]

[0181] Example 3

[0182] To a flask equipped with a dropping funnel, 11.77 g (75.4 mmol) of 4-tert-butylcyclohexanol, 11.74 g (56.9 mmol) of N,N′-dicyclohexylcarbodiimide (DCC), and 0.93 g (7.6 mmol) of 4-dimethylaminopyridine (DMAP) were added and dissolved in 20 mL of dichloromethane. The crude product obtained in Synthesis Example 3 was added dropwise, and the mixture was stirred in an ice bath for 2 hours. The reaction solution was filtered, and the recovered solution was concentrated using an evaporator. The solution was then purified by silica gel column chromatography (chloroform = 100 vol%). The purified product was isomerized by adding 20 mL of chloroform and 1 mL of piperidine and heating under reflux for 6 hours (reflux temperature: 61 °C). The reaction solution after the isomerization reaction was separated and purified by silica gel column chromatography (hexane / ethyl acetate = 90 / 10 (Vol%)), and then dried under vacuum to obtain (4-tert-butylcyclohexyl) fumarate (BCCHF). 1 H-NMR (400MHz, CDCl3): δ6.82(m,2H,CH=CH),5.13-5.11,4.77-4.71(m,1H,O-CH),4.89-4. 86(m,1H,O-CH),2.07-2.05(m,2H,CH2),1.85-1.01(m,17H,CH,CH2),0.87(s,9H,(CH3)3))

[0183] The melting point of the obtained BCHF is 58.3℃.

[0184] [Chemical Formula 13]

[0185]

[0186] Synthesis example 4

[0187] 9.02 g (90.0 mmol) of cyclohexanol, 6.01 g (67.4 mmol) of N,N′-dicyclohexylcarbodiimide (DCC), and 0.99 g (8.10 mmol) of 4-dimethylaminopyridine (DMAP) were added to a flask equipped with a dropping funnel and dissolved in 20 mL of dichloromethane. The crude product obtained in Synthesis Example 2 was added dropwise, and the mixture was stirred in an ice bath for 2 hours. The reaction solution was filtered, and the recovered solution was concentrated using an evaporator. 20 mL of chloroform and 1 mL of ethylenediamine were added, and the mixture was refluxed for 4 hours (reflux temperature: 61 °C) to induce isomerization. The reaction solution after isomerization was purified by silica gel column chromatography (hexane / ethyl acetate = 90 / 10 (Vol%)), followed by vacuum drying to obtain cyclohexyl isopropyl fumarate (CHiPF). 1 H-NMR (400MHz, CDCl3): δ6.83-6.81(m,2H,CH=CH), 5.16-5.08(m,1H,O-CH), 4.90-4.84(m,1H,O-CH), 1.88-1.29(m,16H,CH2,CH3))

[0188] The obtained CHiPF is a liquid at room temperature.

[0189] [Chemical Formula 14]

[0190]

[0191] Synthesis example 5

[0192] 2.66 g (27.9 mmol) of maleic anhydride and 10.72 g (68.6 mmol) of 4-tert-butylcyclohexanol were measured and added to a round-bottom flask. 20 mL of toluene was added as solvent, and 2 mL of concentrated sulfuric acid was added as acid catalyst. The mixture was heated under reflux for 4 hours (reflux temperature: 111 °C). The water bath was set above 80 °C, and the toluene was distilled off using an evaporator to concentrate the contents. The concentrate was then purified by silica gel column chromatography (chloroform = 100 Vol%). 20 mL of chloroform and 1 mL of piperidine were added to the purified product, and the mixture was heated under reflux for 4 hours (reflux temperature: 61 °C) to induce isomerization. The reaction solution after isomerization was purified by silica gel column chromatography (hexane / chloroform = 30 / 70 (Vol%)), and then dried under vacuum to obtain di(4-tert-butylcyclohexyl fumarate) (DBCF). 1 H-NMR (400MHz, CDCl3): δ6.81(s,2H,CH=CH), 5.13-5.11,4.77-4.70(m,2H,O-CH), 2.07-1.01(m,18H,CH,CH2), 0.87-0.86(s,18H,(CH3)3))

[0193] The melting point of the obtained DBCHF is 164.4℃.

[0194] [Chemical Formula 15]

[0195]

[0196] Example 4

[0197] The ethyl (4-tert-butylcyclohexyl) fumarate (BCEF) obtained in Example 1 was melted in a hot water bath at 70°C. Then, 1.34 g (4.74 mmol) of molten ethyl (4-tert-butylcyclohexyl) fumarate (BCEF) and 12.3 mg (0.06 mmol) of tert-butyl peroxide-2-ethylhexanoate as a polymerization initiator were added to a 75 mL glass ampoule using a glass pipette. Nitrogen replacement and vacuum evacuation were repeated, followed by sealing under reduced pressure. The ampoule was then placed in a thermostat at 60°C for 48 hours to carry out free radical polymerization. After the polymerization reaction was complete, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 100 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it, and then dried under vacuum at 80 °C for 10 hours to obtain 0.70 g of fumarate resin (yield: 52%).

[0198] The weight-average molecular weight and T of the obtained fumarate resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0199] [Chemical Formula 16]

[0200]

[0201] Example 5

[0202] The isopropyl fumarate (BCiPF) obtained in Example 2 was melted in a hot water bath at 70°C. Then, 1.93 g (6.50 mmol) of the molten isopropyl fumarate (BCiPF) and 12.8 mg (0.05 mmol) of tert-butyl peroxypentanoate as a polymerization initiator were added to a 75 mL glass ampoule using a glass pipette. Nitrogen replacement and vacuum evacuation were repeated, followed by sealing under reduced pressure. The ampoule was then placed in a thermostat at 45°C for 48 hours to carry out free radical polymerization. After the polymerization reaction was complete, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 100 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it, and then dried under vacuum at 80 °C for 10 hours to obtain 0.86 g of fumarate resin (yield: 45%).

[0203] The weight-average molecular weight and T of the obtained fumarate resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0204] [Chemical Formula 17]

[0205]

[0206] Example 6

[0207] The (4-tert-butylcyclohexyl) cyclohexyl fumarate (BCCHF) obtained in Example 3 was melted in a hot water bath at 70°C. Then, 1.07 g (3.17 mmol) of the molten (4-tert-butylcyclohexyl) fumarate (BCCHF) and 6.0 mg (0.03 mmol) of tert-butyl peroxide-2-ethylhexanoate as a polymerization initiator were added to a 75 mL glass ampoule using a glass pipette. Nitrogen replacement and vacuum evacuation were repeated, followed by sealing under reduced pressure. The ampoule was then placed in a thermostat at 60°C for 48 hours to carry out free radical polymerization. After the polymerization reaction was complete, 10 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 50 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it. After washing the precipitate with 30 mL of methanol, it was dried under vacuum at 80 °C for 10 hours to obtain 0.31 g of fumarate resin (yield: 29%).

[0208] The weight-average molecular weight and T of the obtained fumarate resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0209] [Chemical Formula 18]

[0210]

[0211] Example 7

[0212] The ethyl (4-tert-butylcyclohexyl) fumarate (BCEF) obtained in Example 1 was melted in a hot water bath at 70°C. Then, 0.76 g (2.69 mmol) of the molten ethyl (4-tert-butylcyclohexyl) fumarate (BCEF) was added to a 75 mL glass ampoule using a glass pipette. 0.32 g (1.59 mmol) of diisopropyl fumarate (DiPF) and 22.7 mg (0.10 mmol) of tert-butyl peroxide-2-ethylhexanoate as a polymerization initiator were added to a 6 mL glass sample vial to prepare an initiator DiPF solution. 0.34 g of the prepared initiator DiPF solution (DiPF (0.30 mmol), tert-butyl peroxide-2-ethylhexanoate (0.02 mmol)) was added to a glass ampoule containing BCEF, and nitrogen replacement and vacuum extraction were repeated. The ampoule was then melt-sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a constant temperature bath at 60°C for 96 hours. After the polymerization reaction was complete, 10 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was then added dropwise to 50 mL of a precipitant (methanol / water = 75 / 25 (wt%)) to precipitate the polymer, and then dried under vacuum at 80°C for 10 hours to obtain 0.31 g of fumarate resin (yield: 38%).

[0213] The resin composition, weight-average molecular weight, and T of the obtained fumarate ester resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0214] [Chemical Formula 19]

[0215]

[0216] Example 8

[0217] 1.18 g (4.32 mmol) of isopropyl fumarate (BCiPF) and 0.20 g (1.11 mmol) of diisopropyl fumarate (DiPF) obtained in Example 2 were added to a 6 mL glass sample vial and melted in a 70 °C hot water bath to prepare a monomer solution. Using a glass pipette, 1.38 g of the monomer solution (BCiPF (3.97 mmol), DiPF (1.02 mmol)) and 10.4 mg (0.04 mmol) of tert-butyl peroxypentanoate as a polymerization initiator were added to a 75 mL glass ampoule. Nitrogen replacement and vacuum evacuation were repeated, followed by sealing under reduced pressure. The ampoule was placed in a 45 °C thermostat for 48 hours to carry out free radical polymerization. After the polymerization reaction was complete, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 100 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it, and then dried under vacuum at 80 °C for 10 hours to obtain 0.90 g of fumarate resin (yield: 65%).

[0218] The resin composition, weight-average molecular weight, and T of the obtained fumarate ester resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0219] [Chemical Formula 20]

[0220]

[0221] Example 9

[0222] 0.67 g (2.27 mmol) of isopropyl fumarate (BCiPF) and 0.30 g (1.51 mmol) of diisopropyl fumarate (DiPF) obtained in Example 2 were added to a 6 mL glass sample vial and melted in a 70 °C hot water bath to prepare a monomer solution. Using a glass pipette, 0.89 g of the monomer solution (BCiPF (2.07 mmol), DiPF (1.37 mmol)) and 8.20 mg (0.03 mmol) of tert-butyl peroxypentanoate as a polymerization initiator were added to a 75 mL glass ampoule. Nitrogen replacement and vacuum evacuation were repeated, followed by sealing under reduced pressure. The ampoule was placed in a 45 °C thermostat for 48 hours to carry out free radical polymerization. After the polymerization reaction was complete, 10 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 50 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it. After washing the precipitate with 50 mL of methanol, the precipitate was dried under vacuum at 80 °C for 10 hours to obtain 0.56 g of fumarate resin (yield: 63%).

[0223] The resin composition, weight-average molecular weight, and T of the obtained fumarate ester resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0224] [Chemical Formula 21]

[0225]

[0226] Comparative Example 1

[0227] 13.01 g (65.0 mmol) of diisopropyl fumarate and 136.0 mg (0.55 mmol) of tert-butyl peroxypentanoate as a polymerization initiator were added to a 75 mL glass ampoule. Nitrogen replacement and vacuum evacuation were repeated, followed by sealing under reduced pressure. The ampoule was then placed in a constant temperature bath at 50 °C and maintained for 24 hours to carry out free radical polymerization. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 130 mL of tetrahydrofuran. The polymer solution was then added dropwise to 650 mL of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain 11.28 g of fumarate resin (yield: 43%).

[0228] The weight-average molecular weight and T of the obtained fumarate resin were determined. β The results are shown in Table 2. Although the obtained fumarate resins have high weight-average molecular weights, they are T... βLow resin content. The Tg of resins obtained from fumarate monomers without rigid structures was confirmed. β It gets lower.

[0229] [Chemical Formula 22]

[0230]

[0231] Comparative Example 2

[0232] 2.01 g (8.35 mmol) of cyclohexyl isopropyl fumarate (CHiPF) obtained in Synthesis Example 4 and 16.6 mg (0.07 mmol) of tert-butyl peroxypentanoate as a polymerization initiator were added to a 6 mL glass sample vial to adjust the polymerization solution. 1.94 g of the polymerization solution (CHiPF (8.00 mmol) and tert-butyl peroxypentanoate (0.06 mmol)) was added to a 75 mL glass ampoule using a glass pipette. Nitrogen replacement and vacuum evacuation were repeated, followed by sealing under reduced pressure. The ampoule was placed in a thermostat at 45 °C for 48 hours to carry out free radical polymerization. After the polymerization reaction was complete, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 100 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it, and then dried under vacuum at 80 °C for 10 hours to obtain 1.10 g of fumarate resin (yield: 57%).

[0233] The weight-average molecular weight and T of the obtained fumarate resin were determined. β The results are shown in Table 2. Although the obtained fumarate resins have high weight-average molecular weights, they are T... β Low resin content. The T-resin obtained from fumarate monomers having an unsubstituted cyclohexyl ring at one end was confirmed. β It gets lower.

[0234] [Chemical Formula 23]

[0235]

[0236] Comparative Example 3

[0237] 0.988 g (2.51 mmol) of di(4-tert-butylcyclohexyl fumarate) (DBCF) obtained in Synthesis Example 5 and 2.6 mg (0.013 mmol) of tert-butanol hydrogen peroxide were added to a 15 mL ground glass polymerization tube. After repeated nitrogen replacement and vacuuming, the tube was placed in a nitrogen atmosphere. Free radical polymerization was carried out by placing the tube in a thermostat at 172 °C for 6 hours. After the polymerization reaction was completed, 5 mL of chloroform was added to the tube to dissolve the polymer. 200 mL of ethanol heated to 60 °C was added dropwise to the polymer solution to precipitate it. The solution was then dried under vacuum at 80 °C for 3 hours to obtain 0.322 g of fumarate resin (yield: 32.6%).

[0238] The weight-average molecular weight and T of the obtained fumarate resin were determined. β The results are shown together in Table 2. Although the obtained fumarate resins have high T... β However, it is a resin with a low weight-average molecular weight. Because fumarate monomers with rigid substituents at both ends have high melting points, the polymerization temperature required to melt the monomers becomes higher, thus confirming that it is a resin with a low weight-average molecular weight.

[0239] [Chemical Formula 24]

[0240]

[0241] Example 10

[0242] 0.4 g of the fumarate resin obtained in Example 5 was dissolved in tetrahydrofuran solution to prepare a 10% by weight resin solution. This solution was cast onto a polyethylene terephthalate substrate (PET100-TP03 PANAC) using a coating machine and dried in two stages at 50°C and 130°C to form a film with a thickness of 19 μm. The fumarate resin film was peeled off from the substrate, and the individual linear expansion and phase difference characteristics of the film were evaluated. The results are shown in Table 3. The obtained film exhibits excellent viewing angle characteristics and dimensional stability at high temperatures, making it suitable as an optical film.

[0243] Example 11

[0244] 0.4 g of the fumarate resin obtained in Example 9 was dissolved in tetrahydrofuran solution to prepare an 11 wt% resin solution. This solution was cast onto a polyethylene terephthalate substrate (PET100-TP03 PANAC) using a coating machine and dried in two stages at 50°C and 130°C to form a film with a thickness of 20 μm. The fumarate resin film was peeled off from the substrate, and the individual linear expansion and phase difference characteristics of the film were evaluated. The results are shown in Table 3. The obtained film exhibits excellent viewing angle characteristics and dimensional stability at high temperatures, making it suitable as an optical film.

[0245] Comparative Example 4

[0246] 0.4 g of the fumarate resin obtained in Comparative Example 1 was dissolved in tetrahydrofuran solution to prepare a 15 wt% resin solution. This solution was cast onto a polyethylene terephthalate substrate (PET100-TP03 PANAC) using a coating machine and subjected to two-stage drying at 50°C and 130°C to form a film with a thickness of 21 μm. The fumarate resin film was peeled off from the substrate, and the individual linear expansion and phase difference characteristics of the film were evaluated.

[0247] The results are shown together in Table 3. Due to the T of the fumarate resin in the obtained membrane... β It has a low linear expansion rate and therefore does not possess the target heat resistance.

[0248] Comparative Example 5

[0249] 0.4 g of the fumarate resin obtained in Comparative Example 2 was dissolved in tetrahydrofuran solution to prepare a 15% by weight resin solution. This solution was cast onto a polyethylene terephthalate substrate (PET100-TP03 PANAC) using a coating machine and subjected to two-stage drying at 50°C and 130°C to form a film with a thickness of 19 μm. The fumarate resin film was peeled off from the substrate, and the individual linear expansion and phase difference characteristics of the film were evaluated.

[0250] The results are shown together in Table 3. Due to the T of the fumarate resin in the obtained membrane... β It has a low linear expansion rate and therefore does not possess the target heat resistance.

[0251] Comparative Example 6

[0252] 0.4 g of the fumarate resin obtained in Comparative Example 3 was dissolved in tetrahydrofuran solution to prepare a 30 wt% resin solution. This solution was cast onto a polyethylene terephthalate substrate (PET100-TP03 PANAC) using a coating machine and dried in two stages at 50°C and 130°C to form a film with a thickness of 20 μm. The fumarate resin film was peeled off from the substrate, but the entire surface cracked. Due to the low weight-average molecular weight and insufficient strength of the fumarate resin, it is unsuitable as an optical film.

[0253] Synthesis example 6

[0254] 10.2 g (103.98 mmol) of maleic anhydride and 13.01 g (216.47 mmol) of isopropanol were measured and added to a round-bottom flask. 20 mL of cyclohexane was added as a solvent, and the mixture was heated under reflux for 4 hours (reflux temperature: 81 °C). The water bath was set to above 80 °C, and unreacted isopropanol and cyclohexane were distilled off using an evaporator to concentrate the contents, thus obtaining crude monoisopropyl maleate. 1 H-NMR (400MHz, CDCl3): δ6.47-6.34(m,2H,CH=CH), 5.23-5.14(sep,J=6.3Hz,1H,O-CH), 1.36-1.34(d,J=6.3Hz,6H,(CH3)2))

[0255] [Chemical Formula 25]

[0256]

[0257] Synthesis Example 7

[0258] 5.01 g (51.1 mmol) of maleic anhydride and 15.09 g (251 mmol) of isopropanol were measured and added to a round-bottom flask. 20 mL of cyclohexane was added as a solvent, and the mixture was heated under reflux for 4 hours (reflux temperature: 81 °C). The water bath was set to above 80 °C, and unreacted isopropanol and cyclohexane were distilled off using an evaporator to concentrate the contents, thus obtaining crude monoisopropyl maleate. 1 H-NMR (400MHz, CDCl3): δ6.47-6.34(m,2H,CH=CH), 5.23-5.14(sep,J=6.3Hz,1H,O-CH), 1.36-1.34(d,J=6.3Hz,6H,(CH3)2))

[0259] [Chemical Formula 26]

[0260]

[0261] Example 12

[0262] To a flask equipped with a dropping funnel, 18.57 g (118.83 mmol) of 4-tert-butylcyclohexanol (cis / trans mixture), 17.16 g (110.53 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC), and 1.72 g (14.08 mmol) of 4-dimethylaminopyridine (DMAP) were added and dissolved in 20 mL of dichloromethane. The crude product obtained in Synthesis Example 6 was added dropwise, and the mixture was stirred in an ice bath for 2 hours. The reaction solution was purified by separation with saturated brine, and the recovered organic phase was concentrated using an evaporator and then dried with anhydrous sodium sulfate. The dried organic phase was separated and purified by silica gel column chromatography (chloroform = 100 vol%). 20 mL of chloroform and 1 mL of piperidine were added to the purified product, and the mixture was refluxed for 4 hours (reflux temperature: 61 °C) to perform isomerization. The reaction solution after the isomerization reaction was separated and purified by silica gel column chromatography (hexane / ethyl acetate = 80 / 20 (Vol%)), and then dried under vacuum to obtain isopropyl fumarate (4-tert-butylcyclohexyl) (BCiPF). 1 H-NMR (400MHz, CDCl3): δ6.81(m,2H,CH=CH), 5.15-5.06(m,1H,O-CH), 4.78-4.70(quintet,J=6.0Hz,1H,O-CH), 2.07-1.11(m,9H,CH2,CH), 1.30-1.28(d,J=6.0 Hz,6H,(CH3)2),0.86(s,9H,(CH3)3))

[0263] The obtained BCiPF has a melting point of 43.8 °C and a trans ratio of 90.8% relative to the cyclohexane ring.

[0264] [Chemical Formula 27]

[0265]

[0266] Example 13

[0267] 8.83 g (36.5 mmol) of 4-tert-butylcyclohexanol (cis / trans mixture), 8.58 g (42.9 mmol) of N,N-dicyclohexylcarbodiimide (DCC), and 0.84 g (6.86 mmol) of 4-dimethylaminopyridine (DMAP) were added to a flask equipped with a dropping funnel and dissolved in 20 mL of dichloromethane. The crude product obtained in Synthesis Example 7 was added dropwise, and the mixture was stirred in an ice bath for 2 hours. The reaction solution was purified by separation with saturated brine, and the recovered organic phase was concentrated using an evaporator and then dried with anhydrous sodium sulfate. The dried organic phase was separated and purified by silica gel column chromatography (hexane:ethyl acetate = 70:30 Vol%). 20 mL of chloroform and 0.5 mL of piperidine were added to the purified product, and the mixture was refluxed for 6 hours (reflux temperature: 61 °C) to perform isomerization. The reaction solution after the isomerization reaction was separated and purified by silica gel column chromatography (hexane / ethyl acetate = 80 / 20 (Vol%)), and then dried under vacuum to obtain isopropyl fumarate (4-tert-butylcyclohexyl) (BCiPF). 1 H-NMR (400MHz, CDCl3): δ6.81(m,2H,CH=CH), 5.15-5.06(m,1H,O-CH), 4.78-4.70(quintet,J=6.0Hz,1H,O-CH), 2.07-1.11(m,9H,CH2,CH), 1.30-1.28(d,J=6.0 Hz,6H,(CH3)2),0.86(s,9H,(CH3)3))

[0268] The obtained BCiPF has a melting point of 44°C and a trans ratio of 90.3% relative to the cyclohexane ring.

[0269] [Chemical Formula 28]

[0270]

[0271] Example 14

[0272] 5.08 g (32.51 mmol) of 4-tert-butylcyclohexanol (cis-solution), 5.33 g (25.83 mmol) of N,N′-dicyclohexylcarbodiimide (DCC), and 0.43 g (3.52 mmol) of 4-dimethylaminopyridine (DMAP) were added to a flask equipped with a dropping funnel and dissolved in 20 mL of dichloromethane. The crude product obtained in Synthesis Example 6 was added dropwise, and the mixture was stirred in an ice bath for 2 hours. The reaction solution was filtered, and the recovered solution was concentrated using an evaporator and purified by silica gel column chromatography (chloroform = 100 vol%). 20 mL of chloroform and 1 mL of piperidine were added to the purified product, and the mixture was refluxed for 4 hours (reflux temperature: 61 °C) to perform isomerization. The reaction solution after the isomerization reaction was separated and purified by silica gel column chromatography (hexane / ethyl acetate = 90 / 10 (Vol%)), and then dried under vacuum to obtain the cis-form fumaric acid (4-tert-butylcyclohexyl) isopropyl ester (BCiPF). 1 H-NMR (400MHz, CDCl3): δ6.83(dd',2H,CH=CH), 5.15-5.06(m,1H,O-CH), 4.78-4.70(quintet,J=6.0 Hz,1H,O-CH), 2.07-1.11(m,9H,CH2,CH),1.30-1.28(d,J=6.0Hz,6H,(CH3)2), 0.86(s,9H,(CH3)3))

[0273] The resulting BChiPF is a liquid at room temperature with a trans ratio of 0.4% relative to the cyclohexane ring.

[0274] [Chemical Formula 29]

[0275]

[0276] Example 15

[0277] 0.60 g (2.01 mmol) of isopropyl fumarate (BCiPF) and 0.61 g (3.02 mmol) of diisopropyl fumarate (DiPF) obtained in Example 12 were added to a 6 mL glass sample vial and melted in a 70 °C hot water bath to prepare a monomer solution. Using a glass pipette, 1.14 g of the monomer solution (BCiPF (1.91 mmol), DiPF (2.87 mmol)) and 11.2 mg (0.04 mmol) of tert-butyl peroxypentanoate as a polymerization initiator were added to a 75 mL glass ampoule. Nitrogen replacement and vacuum were repeated, followed by sealing under reduced pressure. The ampoule was placed in a 45 °C thermostat for 48 hours to carry out free radical polymerization. After the polymerization reaction was complete, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 100 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it. The precipitate was washed with 50 mL of methanol and then dried under vacuum at 80 °C for 10 hours to obtain 0.87 g of fumarate resin (yield: 76%).

[0278] The resin composition, weight-average molecular weight, and T of the obtained fumarate ester resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0279] [Chemical Formula 30]

[0280]

[0281] Example 16

[0282] 1.60 g (5.4 mmol) of isopropyl fumarate (4-tert-butylcyclohexyl) obtained in Example 12 was added to a 6 mL glass sample vial and melted in a 70 °C hot water bath to prepare a monomer solution. 1.47 g (5.0 mmol) of the monomer solution and 12.0 mg (0.05 mmol) of tert-butyl peroxypentanoate as a polymerization initiator were added to a 75 mL glass ampoule using a glass pipette. Nitrogen replacement and vacuum evacuation were repeated, followed by sealing under reduced pressure. The ampoule was then placed in a 50 °C thermostat and maintained for 24 hours to carry out free radical polymerization. After the polymerization reaction was complete, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 100 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it. The precipitate was washed with 50 mL of methanol and then dried under vacuum at 80 °C for 10 hours to obtain 1.00 g of fumarate resin (yield: 68%).

[0283] The resin composition, weight-average molecular weight, and T of the obtained fumarate ester resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0284] [Chemical Formula 31]

[0285]

[0286] Example 17

[0287] 1.35 g (4.6 mmol) of isopropyl fumarate (BCiPF) and 0.13 g (0.7 mmol) of diethyl fumarate (DEF) obtained in Example 13 were added to a 6 mL glass sample vial and melted in a 70 °C hot water bath to prepare a monomer solution. 1.37 g of the monomer solution (BCiPF (4.3 mmol), DEF (0.65 mmol)) and 10.2 mg (0.04 mmol) of tert-butyl peroxypentanoate as a polymerization initiator were added to a 75 mL glass ampoule using a glass pipette. Nitrogen replacement and vacuum were repeated, followed by sealing under reduced pressure. The ampoule was placed in a 50 °C thermostat for 24 hours to carry out free radical polymerization. After the polymerization reaction was complete, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 100 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it. The precipitate was washed with 50 mL of methanol and then dried under vacuum at 80 °C for 10 hours to obtain 0.57 g of fumarate resin (yield: 41%).

[0288] The resin composition, weight-average molecular weight, and T of the obtained fumarate ester resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0289] [Chemical Formula 32]

[0290]

[0291] Example 18

[0292] 1.52 g (5.1 mmol) of isopropyl fumarate (4-tert-butylcyclohexyl) obtained in Example 14 was added to a 6 mL glass sample vial and melted in a 70 °C hot water bath to prepare a monomer solution. 1.42 g (4.8 mmol) of the monomer solution and 8.8 mg (0.04 mmol) of tert-butyl peroxypentanoate as a polymerization initiator were added to a 75 mL glass ampoule using a glass pipette. Nitrogen replacement and vacuum evacuation were repeated, followed by sealing under reduced pressure. The ampoule was placed in a 50 °C thermostat for 24 hours to carry out free radical polymerization. After the polymerization reaction was complete, 20 mL of tetrahydrofuran was added to the ampoule to dissolve the polymer. The polymer solution was added dropwise to 100 mL of precipitant (methanol / water = 75 / 25 (wt%)) to precipitate it. The precipitate was washed with 50 mL of methanol and then dried under vacuum at 80 °C for 10 hours to obtain 0.26 g of fumarate resin (yield: 18%).

[0293] The resin composition, weight-average molecular weight, and T of the obtained fumarate ester resin were determined. β The results are shown in Table 2. The obtained fumarate resins have high T... β And high weight-average molecular weight.

[0294] [Chemical Formula 33]

[0295]

[0296]

[0297]

[0298]

Claims

1. A fumarate monomer represented by the following formula (1), ， in the formula, R1 represents a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 5 carbon atoms, and R2 represents a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

2. The fumarate monomer according to claim 1, wherein R1 is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, a sec-butyl group, a sec-pentyl group, or a tert-pentyl group.

3. The fumarate monomer according to claim 1 or 2, wherein R2 is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a sec-pentyl group, a tert-pentyl group, a sec-hexyl group, a tert-hexyl group, a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group.

4. The fumarate monomer according to claim 1 or 2, which has a melting point of 80°C or lower.

5. A resin comprising a residue unit represented by the following structural formula (2), in the formula, R1 represents a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 5 carbon atoms, and R2 represents a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

6. The resin according to claim 5, which further comprises a residue unit represented by the following structural formula (3), ， in the formula, R3 and R4 each independently represent 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.

7. The resin according to claim 5 or 6, wherein the weight average molecular weight (Mw) converted to a standard polystyrene by an elution curve determined by gel permeation chromatography (GPC) is 500,000 or more. ， 8. The resin according to claim 5 or 6, wherein the weight average molecular weight (Mw) converted to a standard polystyrene by an elution curve determined by gel permeation chromatography (GPC) is 1,000,000 or more.

9. A film comprising the resin according to claim 5 or 6.

10. The film according to claim 9, wherein the out-of-plane retardation (Rth) determined at a wavelength of 589 nm represented by the following formula (a) is -700 to 0 nm, Rth = 〔(nx + ny) / 2 - nz〕 x d (a) The β-relaxation temperature (Tβ) measured by a differential scanning calorimeter (DSC) at the second scanning temperature increase (temperature increase rate = 10°C / min) is 130°C or higher. β ) is 130°C or higher. in the formula, nx represents a refractive index in a fast axis direction (a direction in which a refractive index is the smallest) in a film plane, ny represents a refractive index in a slow axis direction in the film plane, nz represents a refractive index in a perpendicular direction outside the film plane, and d represents a thickness of the film.

11. The film according to claim 9, wherein the linear expansion coefficient a represented by the following formula (b) is 95 ppm / °C or less, a = Δl / (ΔT x l) (b) in the formula, Δl represents an amount of change in a film length upon a change in temperature, ΔT represents an amount of change in a film temperature, and l represents a film length before a change in temperature. ​ ​ ​ ​ ​

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