Diester fumarate, method for producing the same, diester fumarate resin, and film using the same

Abstract

The present invention provides fumarate diesters containing fluorine atoms, methods for producing the same, and high molecular weight resins and films obtained from these fumarate diesters. [Solution] For example, a method for producing a fumarate diester represented by the following formula, and a fumarate diester resin containing fumarate diester residue units obtained by polymerizing the obtained fumarate diester. JPEG2026137166000028.jpg33150

Description

[Technical Field]

[0001] This disclosure relates to diester fumarate, a method for producing the same, a diester fumarate resin containing diester fumarate residue units, and a film containing the same. More specifically, it relates to diester fumarate and a diester fumarate resin containing diester fumarate residue units that exhibit excellent polymerizability and enable high molecular weight production. [Background technology]

[0002] Resins obtained from fumarate diesters, which consist of alkyl esters including diisopropyl fumarate, are known to exhibit higher polymerizability and heat resistance compared to general thermoplastic vinyl polymers, and are also known to be highly transparent (Patent Documents 1 and 2). Among fumarate diesters, resins obtained from fumarate diesters containing a fluorine atom in the alkyl ester moiety are expected to have low refractive index, high transparency, solvent resistance, corrosion resistance, and abrasion resistance due to the introduction of the fluorine atom. In particular, resins with a low refractive index and high transparency can be used in optical films such as low-reflection films and anti-reflective coatings. On the other hand, the introduction of a fluorine atom reduces polymerizability. This is thought to be because the fluorine atom has a high electronegativity, which reduces the electron density of the double bond site, which is the polymerizable group. Therefore, high molecular weight resins obtained from fumarate diesters containing a fluorine atom were not known. High molecular weight resins are needed to improve processability during film molding and to improve the mechanical strength of films. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2006-193616 [Patent Document 2] Patent No. 2816699 [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention has been made in view of the above problems, and its object is to provide a fumarate diester containing a fluorine atom, and a high molecular weight fumarate diester resin and film obtained from a fumarate diester containing a fluorine atom. [Means for solving the problem]

[0005] As a result of diligent research to solve the above problems, the inventors discovered that the polymerizability of the -(CH2)n-CR2R3R4 group of the fumarate diester represented by formula (1) below can be improved and its molecular weight increased by having a methylene chain with a specific number of carbon atoms n, thus completing the present invention.

[0006] In other words, this disclosure has the following gist: [1] A fumarate diester represented by the following formula (1).

[0007] [ka]

[0008] (In the formula, R1 represents one selected from the group consisting of linear alkyl groups having 1 to 4 carbon atoms, branched alkyl groups having 3 to 5 carbon atoms, and cyclic alkyl groups having 3 to 12 carbon atoms. R2 to R4 each independently represent a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 5 carbon atoms, except when R2 to R4 are simultaneously hydrogen atoms. n represents an integer from 2 to 4.) [2] The fumarate diester according to [1], wherein R1 of formula (1) is selected from the group consisting of 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, a tert-pentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, and a 4-tert-butylcyclohexyl group. [3] The fumarate diester according to any one of the following [1] to [2], wherein n in formula (1) is 2. [4] In the formula (1), the -(CH2)n-CR2R3R4 group (where n has the same meaning as described above) is one selected from the group consisting of a 3,3-difluoropropyl group, a 3,3,3-trifluoropropyl group, a 3,3,4,4,4-pentafluorobutyl group, a 3,3,4,4,5,5,5-heptafluoropentyl group, a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, a 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl group, a 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, a 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl group, and a 4,4,4-trifluoro-3-(trifluoromethyl)butyl group. The diester of fumaric acid according to any one of [1] to [3]. [5] The following formula (3)

[0009]

Chemical formula

[0010] (In the formula, R1 has the same meaning as R1 in the general formula (1). X represents a halogen atom.) The fumaric acid halide represented by the following general formula (4)

[0011]

Chemical formula

[0012] (In the formula, R2 to R4 and n have the same meaning as R1 in the general formula (1).) Reacting with a fluorinated alcohol represented by the following formula (1)

[0013]

Chemical formula

[0014] (In the formula, R1 represents one selected from the group consisting of a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, and a cyclic alkyl group having 3 to 12 carbon atoms. R2 to R4 each independently represent a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 5 carbon atoms, excluding the case where R2 to R4 are simultaneously hydrogen atoms. n represents an integer of 2 to 4.) A method for producing a diester fumarate represented by the formula. [6] A diester fumarate resin containing a diester fumarate residue unit represented by the following formula (2).

[0015]

Chemical formula

[0016] (In the formula, R1 to R4 and n have the same meanings as R2 to R4 and n in the general formula (1).) [7] The diester fumarate resin according to [6], containing 60 mol% or more of the diester fumarate residue unit represented by the formula (2). [8] The diester fumarate resin according to any one of [6] to [7], wherein the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate obtained from the elution curve measured by gel permeation chromatography (GPC) is 220,000 to 450,000. [9] The diester fumarate resin according to any one of [6] to [8], wherein the polydispersity Mw / Mn of the molecular weight in terms of standard polymethyl methacrylate obtained from the elution curve measured by gel permeation chromatography (GPC) is 1.5 to 2.3.

[10] The diester fumarate resin according to any one of [6] to [9], wherein R1 in the formula (2) is one selected from the group consisting of 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, a tert-pentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, and a 4-tert-butylcyclohexyl group.

[11] The diester fumarate resin according to any one of [6] to

[10] , wherein n in the formula (2) is 2.

[12] A fumarate diester resin according to any one of the claims [6] to

[11] , wherein R2 in formula (2) is selected from the group consisting of a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoroisopropyl group, R3 is selected from the group consisting of a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoroisopropyl group, and R4 is selected from the group consisting of a hydrogen atom, a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoroisopropyl group. A film containing a fumarate diester resin as described in any one of items

[13] [6] to

[12] .

[14] The film according to

[13] , characterized in that the refractive index is 1.46 or less.

[15] A film according to any one of the following items

[13] to

[14] , characterized in that it has a light transmittance of 93.5% or more and a haze of 1% or less. [Effects of the Invention]

[0017] According to this disclosure, although the fumarate diesters and fumarate diester resins of this disclosure contain fluorine atoms that reduce polymerizability, they have high polymerizability due to their unique molecular structure, and therefore can provide high molecular weight resins and films with excellent optical properties. [Modes for carrying out the invention]

[0018] A diester fumarate, which is one aspect of this disclosure (hereinafter also referred to as "the diester fumarate of this disclosure"), will be described in detail below.

[0019] The fumarate diester of this disclosure is a fumarate diester represented by the following formula (1).

[0020] [ka]

[0021] (In the formula, R1 represents one selected from the group consisting of linear alkyl groups having 1 to 4 carbon atoms, branched alkyl groups having 3 to 5 carbon atoms, and cyclic alkyl groups having 3 to 12 carbon atoms. R2 to R4 each independently represent a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 5 carbon atoms, except when R2 to R4 are simultaneously hydrogen atoms. n represents an integer from 2 to 4.) The fumarate diester of this disclosure contains fluorine atoms at R2, R3, and R4, and has a hydrocarbon group with 2 to 4 carbon atoms between it and the ester group. This suppresses the decrease in electron density of the polymerizable double bond site, thus enabling the production of a high molecular weight resin during polymerization.

[0022] Examples of linear alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl groups; examples of branched alkyl groups having 3 to 5 carbon atoms include isopropyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, and tert-pentyl groups; and examples of cyclic alkyl groups having 3 to 12 carbon atoms include cyclopropyl, cyclobutyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, 4-sec-butylcyclohexyl, and 4-tert-butylcyclohexyl groups. Among these, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, isobutyl group, sec-butyl group, sec-pentyl group, tert-pentyl group, cyclohexyl group, 4-methylcyclohexyl group, and 4-tert-butylcyclohexyl group are preferred due to their good polymerizability, and isopropyl group, tert-butyl group, isobutyl group, sec-butyl group, methylcyclohexyl group, and tert-butylcyclohexyl group are particularly preferred.

[0023] Each of R2 to R4 independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 5 carbon atoms, except in cases where R2 to R4 are simultaneously hydrogen atoms.

[0024] Examples of fluoroalkyl groups having 1 to 5 carbon atoms include trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, heptafluorobutyl, nonafluorotert-butyl, octafluoroisobutyl, and undecafluoropentyl groups. Fluorine atoms, trifluoromethyl, pentafluoroethyl, and heptafluoroisopropyl groups are preferred due to their good polymerizability.

[0025] n represents an integer between 2 and 4, and 2 is preferred in terms of the ease of obtaining raw materials.

[0026] In formula (1), it is preferable that the -(CH2)n-CR2R3R4 group (wherein n has the same meaning as above) is a 3,3-difluoropropyl group, a 3,3,3-trifluoropropyl group, a 3,3,4,4,4-pentafluorobutyl group, a 3,3,4,4,5,5,5-heptafluoropentyl group, a 3,3,4,4,5,5,6,6,6-nonanafluorohexyl group, a 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl group, a 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, a 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl group, or a 4,4,4-trifluoro-3-(trifluoromethyl)butyl group, from the standpoint of good polymerizability.

[0027] Specific examples of the fumarate diester (1) of this disclosure include the following structures, among which (1-1) to (1-10) and (1-21) to (1-30) are preferred, (1-1) to (1-5) and (1-21) to (1-25) are more preferred, and (1-1) to (1-5) are particularly preferred.

[0028] [ka]

[0029] [ka]

[0030] A method for producing diester fumarate, which is one aspect of this disclosure, will be described in detail below.

[0031] The fumarate diesters of this disclosure can be produced by esterifying a fumarate halide represented by general formula (3) with a fluorine-containing alcohol represented by general formula (4) in the presence of a base.

[0032] [ka]

[0033] (In the formula, R1, R2, R 3、 R4 and n have the same meanings as above, and X represents a halogen atom. Examples of X in the fumarate halide represented by general formula (3) include fluorine, chlorine, bromine, and iodine atoms, and chlorine atoms are preferred because they are easy to handle. Fumarate chloride can be produced from maleic acid monoester by known methods, for example, the method described in Japanese Patent No. 5728313.

[0034] In the method for producing fumarate diesters according to this disclosure, the fluorine-containing alcohol represented by general formula (4) that can be used is not particularly limited in type, but it is preferably a fluorine-containing alcohol having 3 to 11 carbon atoms and containing one or more fluorine atoms. It is more preferably a fluorine-containing alcohol having 3 to 8 carbon atoms due to its ease of synthesis, availability, and the possibility that asymmetric fluorine-containing fumarate diesters may be homopolymerizable. Examples include 3,3-difluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 3,3,4,4,4-pentafluoro-1-butanol, 3,3,4,4,5,5,5-heptafluoro-1-pentanol, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol, 3,3,4,4,5,5,6,6,7,7,7-undecafluoro-1-heptanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol, 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butanol, and 4,4,4-trifluoro-3-(trifluoromethyl)-1-butanol.

[0035] In the method for producing fumarate diesters according to the present disclosure, by using a base, the hydrogen halide produced as a by-product is made in a reaction-inert form in the form of a salt, and the addition of hydrogen halide to the multiple bond groups of the target product can be suppressed. The types of bases that can be used are not particularly limited, but examples include organic bases such as pyridine, 2,6-lutidine, 4-dimethylaminopyridine, diazabicycloundecene, 1,4-diazabicyclo[2.2.2]octane, hexamethylenetetramine, pyrrolidine, piperidine, triethylamine, ethyldiisopropylamine, cyclohexyldimethylamine, and tetramethylethylenediamine; metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; metal acetates such as potassium acetate and sodium acetate; metal phosphates such as potassium phosphate and sodium phosphate; metal fluoride salts such as sodium fluoride, potassium fluoride, and cesium fluoride; and metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium isopropyl oxide, potassium tert-butoxide, and sodium tert-butoxide. Of these, organic bases are preferred due to their availability and good salt solubility, and pyridine, triethylamine, or cyclohexyldimethylamine are more preferred. The amount of base used is preferably 1 to 20 equivalents, more preferably 1 to 5 equivalents, and most preferably equal amounts, per 1 equivalent of fumaric acid monoester halide.

[0036] In the method for producing fumarate diesters according to this disclosure, a solvent other than the above-mentioned compound may be added during the reaction. The solvent is not particularly limited as long as it is inert to the reaction, but an aprotic polar solvent is preferred because it provides good solubility of the salt. Examples of aprotic polar solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dichloromethane, chloroform, acetonitrile, dimethyl sulfoxide, and tetrahydrofuran.

[0037] In the method for producing fumarate diesters according to this disclosure, the purification of the fluorinated fumarate diester can be carried out by commonly used methods. Examples include solvent extraction, recrystallization, silica gel chromatography, thin-layer preparative chromatography, preparative liquid chromatography, or distillation. Among these, recrystallization or distillation is preferred because it allows for the purification of large quantities at once.

[0038] A fumarate diester resin (hereinafter also referred to as "the resin of this disclosure"), which is one aspect of this disclosure, will be described in detail below.

[0039] The resin of this disclosure is a resin containing a fumarate diester residue unit represented by the following formula (2).

[0040] [ka]

[0041] (In equation (2), R1 to R4 and n are equivalent to R1 to R4 and n in general equation (1).) Specifically, the following structures are possible for the fumarate diester residue unit represented by formula (2), among which (2-1)~(2-10) and (2-21)~(2-30) are preferred, (2-1)~(2-5) and (2-21)~(2-25) are more preferred, and (2-1)~(2-5) is particularly preferred.

[0042] [ka]

[0043] [ka]

[0044] The resins of this disclosure may be copolymers containing monomer residue units other than the residue unit represented by formula (2), as long as they do not exceed the scope of the present invention. Examples of other monomer residue units include one or more selected from acrylic acid residue units; acrylic acid ester residue units such as methyl acrylate residue units, ethyl acrylate residue units, and butyl acrylate residue units; hydroxy acrylate residue units such as 2-hydroxymethyl acrylate residue units; and fumarate ester residue units such as diethyl fumarate residue units, dipropyl fumarate residue units, diisopropyl fumarate residue units, dibutyl fumarate residue units, and di-tert-butyl fumarate residue units.

[0045] Furthermore, a fumarate diester resin containing the fumarate diester residue unit shown in formula (2) only needs to contain the fumarate diester residue unit shown in formula (2), and may also contain other monomer residue units other than the residue unit shown in formula (2). Among these, a fumarate diester resin consisting of the fumarate diester residue unit shown in formula (2) is particularly preferred.

[0046] In order to exhibit a good low refractive index, the resin of this disclosure preferably contains 60 mol% or more of the fumarate diester residue unit represented by formula (2), more preferably 75 mol% or more, and particularly preferably 90 mol% or more.

[0047] The weight-average molecular weight of the resin disclosed herein is preferably 220,000 to 450,000 in order to exhibit good mechanical strength. For even better mechanical strength, 250,000 to 400,000 is more preferable, and 300,000 to 380,000 is particularly preferable. Here, the weight-average molecular weight Mw can be expressed in terms of standard polymethyl methacrylate measured by gel permeation chromatography.

[0048] Furthermore, the polydispersity of the molecular weight Mw / Mn is preferably 1.5 to 2.3, as a smaller molecular weight distribution results in better mechanical strength. To achieve even better mechanical strength, 1.5 to 2.1 is more preferable, and 1.5 to 2.0 is particularly preferable. This results in films obtained from the resin of this disclosure exhibiting better mechanical strength. Here, the number-average molecular weight Mn can be expressed in terms of standard polymethyl methacrylate measured by gel permeation chromatography.

[0049] The resin of this disclosure may be manufactured by any method as long as the resin can be obtained. For example, it can be manufactured by radical polymerization of the monomer represented by formula (1) in the presence of a polymerization initiator. As a method of radical polymerization, any of the following methods can be used, such as bulk polymerization, solution polymerization, suspension polymerization, precipitation polymerization, or emulsion polymerization.

[0050] Examples of polymerization initiators used in radical polymerization include organic peroxides such as benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane; and azo-based initiators such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-butyronitrile), 2,2'-azobisisobutyronitrile, dimethyl-2'-azobisisobutyrate, and 1,1'-azobis(cyclohexane-1-carbonitride).

[0051] Furthermore, when employing solution polymerization, suspension polymerization, precipitation polymerization, or emulsion polymerization, there are no particular restrictions on the solvents that can be used. Examples include aromatic solvents such as benzene, toluene, and xylene; alcoholic solvents such as methanol, ethanol, propanol, and butanol; cyclohexane; dioxane; tetrahydrofuran; acetone; methyl ethyl ketone; N,N-dimethylformamide; dimethyl sulfoxide; isopropyl acetate; water, and mixed solvents of these are also acceptable.

[0052] Furthermore, the polymerization temperature during radical polymerization can be appropriately set according to the decomposition temperature of the polymerization initiator, and since the reaction can be easily controlled, it is generally preferable to carry out the polymerization in the range of 30 to 150°C.

[0053] A film containing the resin, which is one aspect of this disclosure (hereinafter also referred to as "the film of this disclosure"), will be described in detail below.

[0054] The film disclosed herein can be suitably used as a film for optical components. In particular, because it exhibits good polymerizability and good mechanical strength, it can be used as an optical film with excellent moldability. Furthermore, because it has a low refractive index and high light transmittance, it can be used as an optical film such as a low-reflection film or an anti-reflective coating.

[0055] In the film of this disclosure, the thickness is preferably 200.0 μm or less, more preferably 0.1 to 80.0 μm, and particularly preferably 0.1 to 30.0 μm, from the viewpoint of suitability for thinning of optical components.

[0056] The film of this disclosure preferably has a refractive index of 1.46 or less, more preferably 1.43 or less, and particularly preferably 1.41 or less, in order to avoid a decrease in the light intensity of the image display device. Here, the refractive index is the value measured at a wavelength of 589 nm.

[0057] The film disclosed herein has a light transmittance of preferably 93.5% or higher, more preferably 94.0% or higher, and particularly preferably 94.5% to 96.0%, in order to reduce the amount of reflected light at the interface of an image display device. Here, the light transmittance represents the total light transmittance and is the value measured at a wavelength of 380 to 780 nm using a transmittance measuring device equipped with a white light source, in accordance with JIS K 7361-1 (1997 edition).

[0058] The haze of the film disclosed herein is preferably 1.0% or less, and more preferably 0.5% or less. By controlling the haze within this range, a high-contrast image can be obtained when the optical film is incorporated into a display device. Here, the haze is a value measured at a wavelength of 380 to 780 nm using a general haze meter equipped with a white light source, in accordance with JIS-K 7136 (2000 edition).

[0059] The film of this disclosure may contain antioxidants to improve thermal stability when used as an optical film. Examples of antioxidants include hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants, amine antioxidants, hydroxylamine antioxidants, vitamin E antioxidants, and other antioxidants. These antioxidants may be used individually or in combination of two or more.

[0060] The film disclosed herein may contain hindered amine-based light stabilizers or ultraviolet absorbers to enhance its weather resistance when used as an optical film. Examples of ultraviolet absorbers include benzotriazole, benzophenone, triazine, and benzoate.

[0061] The film disclosed herein may contain compounds known as plasticizers for purposes such as improving mechanical properties, imparting flexibility, providing water resistance, reducing water vapor transmission, and adjusting retardation when forming an optical film. Examples of plasticizers include phosphate esters and carboxylic acid esters. Acrylic polymers may also be used.

[0062] Examples of phosphate esters include triphenyl phosphate, tricresyl phosphate, and phenyldiphenyl phosphate.

[0063] Examples of carboxylic acid esters include phthalate esters, citrate esters, fatty acid esters, glycerol esters, and alkylphthalyl alkyl glycolates. Examples of phthalate esters include dimethyl phthalate, diethyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, and diethylhexyl phthalate, while examples of citrate esters include acetyl triethyl citrate and acetyl tributyl citrate. Examples of fatty acid esters include butyl oleate, methylacetyl ricinoleate, and dibutyl sebatate; examples of glycerol esters include triacetin and trimethylolpropane tribenzoate; and examples of alkylphthalyl alkyl glycolates include methylphthalylmethyl glycolate, ethylphthalylethyl glycolate, propylphthalylpropyl glycolate, butylphthalylbutyl glycolate, octylphthalyloctyl glycolate, methylphthalylethyl glycolate, ethylphthalylmethyl glycolate, ethylphthalylpropyl glycolate, propylphthalylethyl glycolate, methylphthalylpropyl glycolate, methylphthalylbutyl glycolate, ethylphthalylbutyl glycolate, butylphthalylmethyl glycolate, butylphthalylethyl glycolate, propylphthalylbutyl glycolate, butylphthalylpropyl glycolate, methylphthalyloctyl glycolate, ethylphthalyloctyl glycolate, octylphthalylmethyl glycolate, and octylphthalylethyl glycolate. These plasticizers may be used individually or in combination of two or more.

[0064] The film of this disclosure may contain other polymers, surfactants, polymer electrolytes, conductive complexes, pigments, dyes, antistatic agents, antiblocking agents, lubricants, etc., to the extent that it does not exceed the spirit of the invention.

[0065] There are no particular limitations on the method for manufacturing the film of this disclosure, and examples include the solution casting method.

[0066] The solution casting method is a method for obtaining a film by casting a solution (hereinafter referred to as "dope") obtained by dissolving the resin of the present disclosure in a solvent onto a support substrate, and then removing the solvent by heating or other means.

[0067] In the solution casting method, any solvent capable of dissolving resins and the like can be used as the solvent for the resin solution. To minimize residual solvent when obtaining the film, the boiling point of the solvent is preferably 200°C or lower, and more preferably 170°C or lower.

[0068] Examples of such solvents include halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, and dichlorobenzene; phenols such as phenol and chlorophenol; aromatic hydrocarbons such as benzene, toluene, xylene, methoxybenzene, mesitylene, and dimethoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, and N-methyl-2-pyrrolidone; ester solvents such as ethyl acetate and butyl acetate; and t-butyl alcohol, glycerin, and ethylene glycol. Examples of solvents include alcohol-based solvents such as lycopropyl alcohol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, and 2-methyl-2,4-pentanediol; amide-based solvents such as dimethylformamide and dimethylacetamide; nitrile-based solvents such as acetonitrile and butyronitrile; ether-based solvents such as diethyl ether, dibutyl ether, and tetrahydrofuran; fluorine-based solvents such as trifluoroethyl alcohol, hexafluoroisopropanol, and hexafluorobenzene; and solvents such as carbon disulfide, ethyl cellosolve, and butyl cellosolve, either alone or in combination.

[0069] The viscosity of the resin solution can be adjusted by the molecular weight, concentration, and type of solvent of each component. There are no particular restrictions on the viscosity of the resin solution, but to facilitate film casting, it is preferably 100 to 30,000 cps, more preferably 300 to 20,000 cps, and most preferably 300 to 15,000 cps.

[0070] In the films of this disclosure, the concentration of the raw material resin relative to the dope is not particularly limited as long as dissolution and film formation are possible. The dissolution method may be carried out by dissolving the resin to a predetermined concentration at the dissolution stage, or by preparing a low-concentration solution in advance and then adjusting it to a predetermined high-concentration solution in a concentration step. Furthermore, a predetermined low-concentration resin solution may be obtained by adding various additives to a high-concentration resin solution in advance.

[0071] Furthermore, there are no particular restrictions on the supporting substrate used, and examples include polymer substrates made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonates, polystyrene, polyethylene, polypropylene, polyacrylic, polyvinyl chloride and polyvinylidene chloride, cellulose such as cellulose acetate and cellulose ether, polyvinyl alcohol, polyamide, polyimide, polyarylate, polysulfone and polyethersulfone, polyetherketone, phenolic resin, epoxy resin, aliphatic cyclic polyolefin, norbornene-based thermoplastic transparent resin, etc., glass substrates such as glass plates and quartz substrates, metal substrates such as aluminum, stainless steel and ferrotype, and inorganic substrates such as ceramic substrates. Preferably, the above substrates are polymer substrates such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, polyacrylic, cellulose such as cellulose acetate and cellulose ether, polyimide, aliphatic cyclic polyolefin, norbornene-based thermoplastic transparent resin. Particularly preferred are polymer substrates such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, polyimide, aliphatic cyclic polyolefin, norbornene-based thermoplastic transparent resin.

[0072] The casting method is not particularly limited, and any conventional method can be used. Examples include the T-die method, doctor blade method, bar coater method, slot die method, lip coater method, reverse gravure coating method, microgravure method, spin coating method, brush coating method, roll coating method, and flexographic printing method.

[0073] The drying method in the drying process is not particularly limited, and conventional heating methods can be used. Examples include hot air blowers, heating rollers, and far-infrared heaters.

[0074] The drying temperature is preferably 30 to 200°C, and particularly preferably 40 to 160°C. It is also acceptable to use a single drying stage, or to maintain appearance and shorten drying time, a multi-stage drying method is used, where the first stage is dried at a low temperature and subsequent stages at high temperatures.

[0075] The film peeling speed 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, considering factors such as productivity, mechanical precision, and stability.

[0076] The film of this disclosure can be laminated with a film containing other resins as needed. Examples of other resins include polyethersulfone, polyarylate, polyethylene terephthalate, polynaphthalene terephthalate, polycarbonate, cyclic polyolefin, maleimide resin, polyimide, and fluororesin. It is also possible to laminate a hard coat layer or a gas barrier layer.

[0077] The film disclosed herein has excellent optical properties and is suitably used as a transparent film such as a low-reflection film or an anti-reflective coating. [Examples]

[0078] The present disclosure will be described below with reference to examples, but the present disclosure is not limited to these examples. The physical properties shown in the examples were measured by the following methods.

[0079] <Analysis of monomers and polymers> Nuclear magnetic resonance (NMU) spectrometer (JEOL, product name JNM-ECZ400S / L1 or Bruker, product name Ultrasield) TM Using the plus Avance III 400MHz NMR, proton nuclear magnetic resonance spectroscopy ( 1 The result was obtained from 1H-NMR spectral analysis.

[0080] <Measurement of average molecular weight> Using a gel permeation chromatography (GPC) apparatus (Tosoh Corporation, product name HLC8320GPC (equipped with column GMHHR-H)), measurements were taken at 40°C with hexafluoroisopropanol as the solvent, and the values ​​were determined as equivalent to standard polymethyl methacrylate. <Measuring Thickness> The film thickness was measured using a high-resolution linear gauge sensor (manufactured by Ono Sokki, product name: GS-3813B). <Measuring refractive index> The refractive index at a wavelength of 589 nm was measured using an Abbe refractometer (ATAGO DR-M2 multi-wavelength Abbe refractometer). <Measurement of light transmittance> Light transmittance was measured using a spectrophotometer (manufactured by Nippon Denshoku Industries, product name: SH7000) in accordance with JIS-K 7361. <Measurement of haze> Haze was measured using a spectroscopic haze meter (manufactured by Nippon Denshoku Industries, product name: SH7000) in accordance with JIS-K 7136.

[0081] Example 1

[0082] [ka]

[0083] In a 500 mL two-necked round-bottom flask, 9.0 g (57.0 mmol) of monoisopropyl fumarate was dissolved in 250 mL of methylene chloride under an Ar atmosphere, and 450 μL (5.81 mmol, 0.10 eq.) of DMF was added. 5.00 mL (68.9 mmol, 1.21 eq.) of thionyl chloride was added dropwise to this solution while cooling with ice. The mixture was stirred at 35 °C for 3 hours, and the solvent and excess thionyl chloride were removed by distillation under reduced pressure. 250 mL of methylene chloride was added to the residue, and 25.6 mL (171 mmol, 3.00 eq.) of N,N-dimethylcyclohexylamine and 5.37 g (47.0 mmol, 0.82 eq.) of 3,3,3-trifluoro-1-propanol were added dropwise, respectively, while cooling with ice, and the mixture was stirred at room temperature for 2 hours. 1 M HCl solution was added until the reaction solution became acidic, and the mixture was extracted with methylene chloride. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then the solvent was removed by vacuum distillation. The resulting brown viscous liquid was purified by silica gel column chromatography (chloroform = 100 (Vol%)). The resulting colorless viscous liquid was distilled under reduced pressure at 120-150°C to obtain 4.57 g (18.0 mmol, yield 39%) of isopropyl (3,3,3-trifluoropropyl) fumarate (hereinafter also referred to as iPPrF-F3). 1 H-NMR (400MHz, CDCl3): δ(ppm)6.86(d,1H,C=CH,J=15.8Hz),6.82(d,1H,C=CH,J=15.8Hz),5.12(sep,1H,CH(CH3) 2,J=6.26Hz),4.43(t,2H,COOCH2,J=6.31Hz),4.43(tq,2H,CH2CF3,J=6.31,10.4Hz),1.30(d,6H,CH3,J=6.26Hz). 19 F-NMR (376.4MHz, CDCl3): δ(ppm)-65.3(s,3F). Example 2

[0084] [ka]

[0085] In a 500 mL two-necked round-bottom flask, 8.7 g (55.0 mmol) of monoisopropyl fumarate was dissolved in 250 mL of methylene chloride under an Ar atmosphere. 500 μL (6.46 mmol, 0.12 eq.) of DMF was added, and 5.00 mL (68.9 mmol, 1.21 eq.) of thionyl chloride was added dropwise while cooling on ice. The mixture was stirred at 35°C for 3 hours, and the solvent and excess thionyl chloride were removed by distillation under reduced pressure. 250 mL of methylene chloride was added, and 25.0 mL (171 mmol, 3.00 eq.) of N,N-dimethylcyclohexylamine and 4.85 g (29.5 mmol, 0.54 eq.) of 3,3,4,4,4-pentafluoro-1-butanol were added dropwise in sequence while cooling on ice. The mixture was stirred at 35°C for 2 hours, and then stirred at room temperature for 19 hours. A 1M HCl solution was added to the reaction solution until it became acidic, and the mixture was extracted with methylene chloride. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then the solvent was removed by vacuum distillation. The resulting brown viscous liquid was purified by silica gel column chromatography (chloroform = 100 (Vol%)). The resulting colorless viscous liquid was distilled under reduced pressure at 120-150°C to obtain 5.59 g (18.4 mmol, yield 62%) of isopropyl (3,3,4,4,4-pentafluorobutyl) fumarate (hereinafter also referred to as iPBuF-F5). 1 H-NMR (400MHz, CDCl3): δ(ppm)6.86(d,1H,C=CH,J=15.8Hz),6.82(d,1H,C=CH,J=15.8Hz),5.12(sep,1H,CH(CH3)2, J=6.26Hz),4.49(t,2H,COOCH2,J=6.49Hz),2.49(tt,2H,COOCH2CH2,J=6.49,17.5Hz),1.30(d,6H,CH3,J=6.26Hz). 19 F-NMR (376.4MHz, CDCl3): δ(ppm)-85.9(s,3F),-117.7(s,2F). Example 3

[0086] [ka]

[0087] In a 500 mL two-neck eggplant flask, 10.0 g (63.2 mmol) of monoisopropyl fumarate was dissolved in 250 mL of methylene chloride under an Ar atmosphere. 500 μL (6.46 mmol, 0.10 eq.) of DMF was added, and 7.00 mL (96.5 mmol, 1.53 eq.) of thionyl chloride was added dropwise while cooling with ice. The mixture was stirred at room temperature for 3 hours, and the solvent and excess thionyl chloride were distilled off under reduced pressure. 250 mL of methylene chloride was added thereto, and while cooling with ice, 20.0 mL (134 mmol, 2.11 eq.) of N,N-dimethylcyclohexylamine and 8.82 g (41.2 mmol, 0.65 eq.) of 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butanol were added dropwise in sequence, and the mixture was stirred at room temperature for 18 hours. The 1M HCl solution was added until the reaction solution became acidic, and the mixture was extracted with methylene chloride. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained brown viscous liquid was purified by silica gel column chromatography (chloroform = 100 (Vol%)). The obtained colorless viscous liquid was distilled under reduced pressure at 120 to 150 °C to obtain 7.99 g (22.6 mmol, yield 55%) of isopropyl (3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl) fumarate (hereinafter also referred to as iPiPeF-F7). 1 1H-NMR (400 MHz, CDCl3): δ (ppm) 6.86 (d, 1H, C=CH, J = 15.8 Hz), 6.81 (d, 1H, C=CH, J = 15.8 Hz), 5.12 (sep, 1H, OCH(CH3)2, J = 6.25 Hz), 4.46 (t, 2H, OCH2, J = 7.03 Hz), 2.53 (dt, 2H, OCH2CH2, J = 7.03, 20.1 Hz), 1.30 (d, 6H, OCH(CH3)2, J = 6.25). 19 19F-NMR (376.4 MHz, CDCl3): δ (ppm) -80.0 (d, 6F, CF(CF3)2, J = 6.78 Hz), -188.3 (sep, 1F, CF(CF3)2, J = 6.78 Hz). Synthesis Example 1

[0088]

Chemical Structure

[0089] In a 500 mL two-necked round-bottom flask, 15.0 g (94.9 mmol) of monoisopropyl fumarate was dissolved in 250 mL of methylene chloride under an Ar atmosphere. 700 μL (9.04 mmol, 0.10 eq.) of DMF was added, and 10.0 mL (138 mmol, 1.45 eq.) of thionyl chloride was added dropwise while cooling on ice. The mixture was stirred at 35°C for 3 hours, and the solvent and excess thionyl chloride were removed by distillation under reduced pressure. 250 mL of methylene chloride was added, and 30.0 mL (200 mmol, 2.11 eq.) of N,N-dimethylcyclohexylamine and 10.0 mL (95.2 mmol, 1.00 eq.) of 1,1,1,3,3,3-hexafluoro-2-propanol were added dropwise in sequence while cooling on ice, and the mixture was stirred at room temperature for 2 days. 1 M HCl solution was added until the reaction solution became acidic, and the mixture was extracted with methylene chloride. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then the solvent was removed by vacuum distillation. The resulting brown viscous liquid was purified by silica gel column chromatography (chloroform = 100 (Vol%)). The resulting colorless viscous liquid was distilled under reduced pressure at 120-150°C to obtain 9.30 g (30.2 mmol, yield 32%) of isopropyl (1,1,1,3,3,3-hexafluoro-2-propanyl) fumarate (hereinafter also referred to as DiPF-F6). 1 H-NMR (400MHz, CDCl3): δ(ppm)7.03(d,1H,C=CH,J=15.8Hz),6.92(d,1H,C=CH,J=15.8Hz),5.84(sep, 1H,OCH(CF3)2,J=6.00Hz),5.15(sep,1H,OCH(CH3)2,J=6.26Hz),1.30(d,6H,OCH(CH3)2,J=6.26Hz). 19 F-NMR(376.4MHz,CDCl3):δ(ppm)-73.5(s,6F,CH(CF3)2). Example 4 1.87 g (7.34 mmol) of iPPF-F3 synthesized in Example 1 and 0.153 g (0.06 mmol) of perbutyl PV (manufactured by Nippon Oil & Fats Co., Ltd.) were placed in a 75 mL glass ampoule. After repeated nitrogen purging and pressure reduction, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 48 hours. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 20 g of tetrahydrofuran. This polymer solution was dropped dropwise into 150 mL of methanol to precipitate, and then vacuum dried at 80°C for 10 hours to obtain a resin (hereinafter referred to as "Resin 1") (yield 64%). The weight-average molecular weight of the obtained Resin 1 was 258,000, and Mw / Mn = 1.7, indicating a high weight-average molecular weight. The results are shown in Table 1.

[0090] [ka]

[0091] Example 5 1.86 g (6.12 mmol) of iPBF-F5 synthesized in Example 2 and 0.013 g (0.05 mmol) of perbutyl PV (manufactured by Nippon Oil & Fats Co., Ltd.) were placed in a 75 mL glass ampoule. After repeated nitrogen purging and pressure reduction, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 48 hours. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 20 g of tetrahydrofuran. This polymer solution was dropped dropwise into 150 mL of methanol to precipitate, and then vacuum-dried at 80°C for 10 hours to obtain a resin (hereinafter referred to as "Resin 2") (yield 69%). The weight-average molecular weight of the obtained Resin 2 was 300,000, and Mw / Mn = 1.7, indicating a high weight-average molecular weight. The results are shown in Table 1.

[0092] [ka]

[0093] Example 6 8.81 g (24.9 mmol) of iPiPeF-F7 synthesized in Example 3 and 0.051 g (0.89 mmol) of perbutyl PV (manufactured by Nippon Oil & Fats Co., Ltd.) were placed in a 75 mL glass ampoule. After repeated nitrogen purging and pressure reduction, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 48 hours. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 100 g of tetrahydrofuran. This polymer solution was dropped dropwise into 750 mL of methanol to precipitate, and then vacuum dried at 80°C for 10 hours to obtain a resin (hereinafter referred to as "resin 3") (yield 75%). The weight-average molecular weight of the obtained resin 3 was 351,000, and Mw / Mn = 1.8, indicating a high weight-average molecular weight. The results are shown in Table 1.

[0094] [ka]

[0095] Example 7 0.9 g of the resin obtained in Example 4 was dissolved in 2.1 g of methyl ethyl ketone to obtain a 30% by weight resin solution. This resin solution was poured onto a polyethylene terephthalate substrate using a coater and dried in two stages at drying temperatures of 50°C and 130°C to form a film. The formed film was peeled from the substrate, and the film thickness, refractive index, light transmittance, and haze of the film alone were measured. The results are shown in Table 2. Because the obtained film contains fluorine atoms, it has a low refractive index and high light transmittance, making it suitable as an optical film.

[0096] Example 8 0.9 g of the resin 2 obtained in Example 5 was dissolved in 2.1 g of methyl ethyl ketone to obtain a 30% by weight resin solution. This resin solution was poured onto a polyethylene terephthalate substrate using a coater and dried in two stages at drying temperatures of 50°C and 130°C to form a film. The formed film was peeled from the substrate, and the film thickness, refractive index, light transmittance, and haze of the film alone were measured. The results are shown in Table 2. Because the obtained film contains fluorine atoms, it has a low refractive index and high light transmittance, making it suitable as an optical film.

[0097] Example 9 1.0 g of resin 3 obtained in Example 6 was dissolved in 4.0 g of hexafluorobenzene to obtain a 20% by weight resin solution. This resin solution was poured onto a polyethylene terephthalate substrate using a coater and dried in two stages at drying temperatures of 50°C and 130°C to form a film. The formed film was peeled from the substrate, and the film thickness, refractive index, light transmittance, and haze of the film alone were measured. The results are shown in Table 2. Because the obtained film contains fluorine atoms, it has a low refractive index and high light transmittance, making it suitable as an optical film.

[0098] Comparative Example 1 1.88 g (6.09 mmol) of iPiPF-F6 synthesized in Synthesis Example 1 and 0.012 g (0.05 mmol) of perbutyl PV (manufactured by Nippon Oil & Fats Co., Ltd.) were placed in a 75 mL glass ampoule. After repeated nitrogen purging and pressure reduction, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 48 hours. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 20 g of tetrahydrofuran. This polymer solution was added dropwise to 150 mL of methanol to precipitate, and then vacuum dried at 80°C for 10 hours to obtain a resin (hereinafter referred to as "resin 4") (yield 39%). In the fumarate diester represented by general formula (1) of the iPiPF-F6 used, n is 0, so the electron density of the polymerizable double bond site is reduced, and the obtained resin 4 has a low weight-average molecular weight, with a weight-average molecular weight of 192,000 and Mw / Mn = 1.7.

[0099] [ka]

[0100] Comparative Example 2 39.0 g (0.19 mol) of diisopropyl fumarate (DiPF) and 0.399 g (1.6 mmol) of perbutyl PV (manufactured by Nippon Oil & Fats Co., Ltd.) were placed in a 75 mL glass ampoule. After repeated nitrogen purging and pressure release, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 50°C constant temperature bath and maintaining it for 24 hours. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 400 g of tetrahydrofuran. This polymer solution was added dropwise to 3 L of methanol to precipitate, and then vacuum dried at 80°C for 10 hours to obtain a resin (hereinafter referred to as "resin 5") (yield 85%).

[0101] Comparative Example 3 0.9 g of resin 4 obtained in Comparative Example 1 was dissolved in 2.1 g of methyl ethyl ketone to obtain a 30% by weight resin solution. This resin solution was poured onto a polyethylene terephthalate substrate using a coater, and a film was formed by two-stage drying at drying temperatures of 50°C and 130°C. When attempting to peel the formed film from the substrate, cracks occurred from the edges to the center. Due to the low weight-average molecular weight of resin 4 and insufficient strength, it was unsuitable as an optical film.

[0102] Comparative Example 4 0.8 g of resin 5 obtained in Comparative Example 2 was dissolved in a mixture of 1.7 g of toluene and 2.5 g of methyl ethyl ketone to obtain a 16% by weight resin solution. This resin solution was poured onto a polyethylene terephthalate substrate using a coater and dried in two stages at drying temperatures of 50°C and 130°C to form a film. The formed film was peeled from the substrate, and the film thickness, refractive index, light transmittance, and haze of the film alone were measured. The results are shown in Table 2. The obtained film did not contain fluorine atoms, had a high refractive index, and did not possess the desired optical properties.

[0103] [Table 1]

[0104] Table 2

Claims

1. A fumarate diester represented by the following formula (1). 【Chemistry 1】 (In the formula, R １ R represents one selected from the group consisting of linear alkyl groups having 1 to 4 carbon atoms, branched alkyl groups having 3 to 5 carbon atoms, and cyclic alkyl groups having 3 to 12 carbon atoms. ２ ~R ４ Each independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 5 carbon atoms, R ２ ~R ４ Except when both are hydrogen atoms. n represents an integer between 2 and 4.

2. R in formula (1) above １ The fumarate diester according to claim 1, wherein is one selected from the group consisting of 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, a tert-pentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, and a 4-tert-butylcyclohexyl group.

3. The fumarate diester according to claim 1, wherein n in formula (1) is 2.

4. In the formula (1), -(CH ２ )n-CR ２ R ３ R ４ group (where n represents the same meaning as described above) is a 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl group, and 4,4,4-trifluoro-3-(trifluoromethyl)butyl group, and the diester fumarate according to claim 1, which is one selected from the group consisting of.

5. The following formula (3) 【Chemistry 2】 (In the formula, R １ represents one selected from the group consisting of linear alkyl groups having 1 to 4 carbon atoms, branched alkyl groups having 3 to 5 carbon atoms, and cyclic alkyl groups having 3 to 12 carbon atoms, and X represents a halogen atom. The fumarate halide represented by ) is subjected to the following general formula (4) in the presence of a base. 【Transformation 3】 (In the formula, R ２ ~R ４ Each independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 5 carbon atoms, R ２ ~R ４ Except when both are hydrogen atoms. n represents an integer between 2 and 4. The following formula (1) is characterized by reacting with a fluorine-containing alcohol represented by (1). 【Chemistry 4】 (In the formula, R １ , R ２ , R ３、 R ４ A method for producing fumarate diester as shown above. (and n has the same meaning as above.)

6. A fumarate diester resin containing a fumarate diester residue unit represented by the following formula (2). 【Transformation 5】 (In the formula, R １ R represents one selected from the group consisting of linear alkyl groups having 1 to 4 carbon atoms, branched alkyl groups having 3 to 5 carbon atoms, and cyclic alkyl groups having 3 to 12 carbon atoms. ２ ~R ４ Each independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 5 carbon atoms, R ２ ~R ４ Except when both are hydrogen atoms. n represents an integer between 2 and 4.

7. The fumarate diester resin according to claim 6, comprising 60 mol% or more of the fumarate diester residue unit represented by formula (2) above.

8. The fumarate diester resin according to claim 6, wherein the weight-average molecular weight (Mw) on a standard polymethyl methacrylate basis, obtained from the elution curve measured by gel permeation chromatography (GPC), is 220,000 to 450,000.

9. The fumarate diester resin according to claim 6, wherein the polydispersity Mw / Mn of the molecular weight, calculated on a standard polymethyl methacrylate basis and obtained from the elution curve measured by gel permeation chromatography (GPC), is 1.5 to 2.

3.

10. R in formula (2) １ The fumarate diester resin according to claim 6, wherein is one selected from the group consisting of 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, a tert-pentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, and a 4-tert-butylcyclohexyl group.

11. The fumarate diester resin according to claim 6, wherein n in formula (2) is 2.

12. In formula (2) above, -(CH ２ ) n-CR ２ R ３ R ４ The fumarate diester resin according to claim 6, wherein the group (wherein n has the same meaning as above) is one selected from the group consisting of 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl group, and 4,4,4-trifluoro-3-(trifluoromethyl)butyl group.

13. A film comprising the fumarate diester resin described in claim 6.

14. The film according to claim 13, characterized in that its refractive index is 1.46 or less.

15. The film according to claim 13, characterized in that it has a light transmittance of 93.5% or more and a haze of 1% or less.

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