Fumaric acid diester-based resin, film, and polarizing plate

Abstract

The present application provides wavelength dispersion R 450 / R 550 Resin capable of improving contrast, field angle characteristics, etc. in a wide wavelength region, and a film using the same. The fumaric acid diester-based resin contains a fumaric acid diester residue unit represented by the following formula (1) and a (meth)acrylate residue unit represented by the following formula (2).

Description

Technical Field

[0001] This disclosure relates to novel fumarate diester resins, films using the resin, and polarizers having the film disposed on at least one side of a polarizer. More specifically, it relates to novel fumarate diester resins suitable for optical compensation films for displays with excellent phase difference functionality. Background Technology

[0002] LCD and OLED flat panel displays (FPDs) are widely used in mobile phones, computer monitors, laptops, and televisions as the most important display devices in the multimedia society. In order to improve display characteristics, FPDs use a large number of optical compensation films. In particular, optical compensation films are essential components for improving visual recognition when viewed from the front or at an angle.

[0003] As optical compensation films, quarter-wave plates and half-wave plates are known, using polycarbonate stretched films as materials (for example, see Patent Documents 1-3). Optical compensation films are also commonly used as anti-reflective layers in reflective liquid crystal display devices, touch panels, and organic ELs. In these applications, optical compensation films with large phase differences in the long wavelength region (hereinafter referred to as "anti-wavelength dispersion films") are particularly required.

[0004] In addition, patent document 4 describes a fumarate diester / (meth)acrylate copolymer.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent No. 2818983

[0008] Patent Document 2: Japanese Patent Application Publication No. 5-297223

[0009] Patent Document 3: Japanese Patent Application Publication No. 5-323120

[0010] Patent Document 4: Japanese Patent Application Publication No. 2017-149932 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] However, the inventors' research revealed some problems with optical compensation films formed from polycarbonate. Most polycarbonate resins contain aromatic components in their main chain, which can easily increase the wavelength dispersion of the phase difference when forming stretched films. Here, wavelength dispersion refers to the variation of the phase difference depending on the measurement wavelength; for example, the phase difference R measured at a wavelength of 450 nm can be... 450 Phase difference R measured at a wavelength of 550 nm 550The ratio is expressed as R 450 / R 550 Typically, in aromatic polymers, the presence of this R... 450 / R 550 A value greater than 1.1 tends to decrease the contrast and field-of-view characteristics in the short-wavelength region.

[0013] Furthermore, the inventors found that the wavelength dispersion of the fumarate diester / (meth)acrylate copolymer described in Patent Document 4 is not sufficient.

[0014] Therefore, wavelength dispersion R is needed to improve contrast and field-angle characteristics in the short wavelength region. 450 / R 550 Low-density membrane resin.

[0015] The purpose of this disclosure is to provide R when used as a stretch film. 450 / R 550 Small, resin capable of improving contrast and field-of-view characteristics over a wide wavelength range, film using the resin, and polarizer having the film disposed on at least one side of the polarizer.

[0016] Methods for solving problems

[0017] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that a resin containing fumarate diester and a specific (meth)acrylate as residue units, and a membrane using the resin, can solve the above-mentioned problems, thereby completing the present invention.

[0018] That is, this disclosure is a fumarate diester resin comprising fumarate diester residue units as shown in formula (1) and (meth)acrylate residue units as shown in formula (2).

[0019] [Chemical Formula 1]

[0020]

[0021] (In the formula, R1 and R2 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 12 carbon atoms, respectively.)

[0022] [Chemical Formula 2]

[0023]

[0024] (In the formula, R3 represents a hydrogen atom or a methyl group. S1, S2, and S3 each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms. The alkylene group having 1 to 12 carbon atoms may optionally contain at least one selected from ether, ester, carbonate, and amide groups, and may optionally contain at least one selected from branched structures, alicyclic rings, and aromatic rings in the chain. Ring A, ring B, and ring C each independently represent an aromatic ring or heterocycle with atoms selected from carbon, nitrogen, oxygen, and sulfur atoms as cyclic atoms. R4 to R 12 Each of the following groups independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a cyanophenyl group, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkylcarboxylic acid group with 2 to 11 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, an alkylol group with 1 to 10 carbon atoms, or an aromatic cyclic group or heterocyclic group with an atom selected from carbon, nitrogen, oxygen, and sulfur atoms as the cyclic atom. (a and b independently represent 0 or 1, respectively.)

[0025] The effects of the invention

[0026] According to this disclosure, R can be provided. 450 / R 550 Small films that can improve contrast and field-of-view characteristics over a wide wavelength range, especially resins useful as optical compensation films. Detailed Implementation

[0027] The following is a detailed description of one embodiment of the fumarate diester resin disclosed herein.

[0028] This disclosure relates to a fumarate diester resin (hereinafter referred to as "the resin of this disclosure") comprising fumarate diester residue units as shown in formula (1) above and (meth)acrylate residue units as shown in formula (2) above.

[0029] The resin disclosed herein is a resin containing fumarate diester residue units as shown in formula (1) above.

[0030] In formula (1), R1 and R2 independently represent straight-chain alkyl groups with 1 to 12 carbon atoms, branched alkyl groups with 3 to 12 carbon atoms, or cyclic alkyl groups with 3 to 12 carbon atoms, respectively.

[0031] Examples of linear alkyl groups with 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl; examples of branched alkyl groups with 3 to 12 carbon atoms include isopropyl, isobutyl, sec-butyl, and tert-butyl; and examples of cyclic alkyl groups with 3 to 12 carbon atoms include cyclopropyl, cyclobutyl, and cyclohexyl. From the perspective of good polymerizability with the residue units shown in formula (2), ethyl, isopropyl, tert-butyl, and cyclohexyl are preferred, and ethyl and isopropyl are more preferred.

[0032] Furthermore, examples of specific fumarate diester residue units represented by formula (1) include, for example, fumarate monomethyl ester residue units, fumarate monoethyl ester residue units, fumarate monopropyl ester residue units, fumarate monoisopropyl ester residue units, fumarate monopentyl ester residue units, fumarate monohexyl ester residue units, fumarate mono-n-butyl ester residue units, fumarate monoisobutyl ester residue units, fumarate mono-sec-butyl ester residue units, fumarate mono-tert-butyl ester residue units, fumarate monocyclopropyl ester residue units, and fumarate monocyclobutyl ester residue units. The residues include: monocyclohexyl fumarate residue unit, dimethyl fumarate residue unit, diethyl fumarate residue unit, dipropyl fumarate residue unit, dipentyl fumarate residue unit, dihexyl fumarate residue unit, diisopropyl fumarate residue unit, di-n-butyl fumarate residue unit, diisobutyl fumarate residue unit, di-sec-butyl fumarate residue unit, di-tert-butyl fumarate residue unit, dicyclopropyl fumarate residue unit, dicyclobutyl fumarate residue unit, and dicyclohexyl fumarate residue unit. Among these, from the perspective of good polymerizability with the residue units shown in formula (2), diethyl fumarate residue unit, diisopropyl fumarate residue unit, di-tert-butyl fumarate residue unit, and dicyclohexyl fumarate residue unit are preferred, and diethyl fumarate residue unit and diisopropyl fumarate residue unit are more preferred.

[0033] The resin disclosed herein is a resin containing (meth)acrylate residue units as shown in formula (2) above. Here, (meth)acrylate residue units refer to acrylate residue units or methacrylate residue units.

[0034] In formula (2), R3 represents a hydrogen atom or a methyl group.

[0035] In formula (2), S1, S2, and S3 independently represent single bonds or alkylene groups having 1 to 12 carbon atoms. Here, the alkylene groups having 1 to 12 carbon atoms optionally contain at least one selected from ether groups, ester groups, carbonate groups, and amide groups, and optionally contain at least one selected from branched structures, alicyclic rings, and aromatic rings in the chain. The aforementioned alkylene groups may contain one or more of the above-mentioned groups.

[0036] Examples of alicyclic rings optionally included in the aforementioned alkylene group include cyclopropane rings, cyclobutane rings, cyclopentane rings, and cyclohexane rings, with cyclohexane rings being preferred. Additionally, examples of aromatic rings optionally included in the aforementioned alkylene group include benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings, with benzene rings being preferred.

[0037] The wavelength dispersion R of the film obtained by stretching the resin of this disclosure 450 / R 550From the perspective of further reducing the number of carbon atoms, the alkylene group is preferably 2 to 8, more preferably 3 to 6. When the alkylene group contains an ester group, carbonate group, amide group, alicyclic ring, or aromatic ring, the number of carbon atoms contained therein is also included in the above calculation of the number of carbon atoms.

[0038] The wavelength dispersion R of the film obtained by stretching the resin of this disclosure 450 / R 550 From the perspective of further reduction, when the above-mentioned alkylene groups contain functional groups, it is preferable to contain ether groups and / or ester groups, and more preferably to contain ether groups.

[0039] S1 is preferably a single bond, and S2 and S3 are preferably each independently an alkylene group.

[0040] For example, the following structures can be listed as alkylene groups containing ether groups. It should be noted that the bonding directions of the divalent groups and chemical structures (e.g., ester bonds, repeating units in polymer structures) exemplified in this specification are not particularly limited within the chemically permissible range.

[0041] [Chemical Formula 3]

[0042]

[0043] [Chemical Formula 4]

[0044]

[0045] [Chemical Formula 5]

[0046]

[0047] For example, the following structures can be listed as alkylene groups containing ester groups.

[0048] [Chemical Formula 6]

[0049]

[0050] [Chemical Formula 7]

[0051]

[0052] [Chemical Formula 8]

[0053]

[0054] For example, the following structures can be listed as alkylene groups containing carbonate groups.

[0055] [Chemical Formula 9]

[0056]

[0057] [Chemical Formula 10]

[0058]

[0059] For example, the following structures can be listed as alkylene groups containing amide groups.

[0060] [Chemical Formula 11]

[0061]

[0062] [Chemical Formula 12]

[0063]

[0064] [Chemical Formula 13]

[0065]

[0066] For example, the following structures can be listed as alkylene groups containing two of the above-mentioned alkylene groups selected from ether groups, ester groups, carbonate groups and amide groups.

[0067] [Chemical Formula 14]

[0068]

[0069] [Chemical Formula 15]

[0070]

[0071] As a specific preferred example of the aforementioned alkylene group, the following structures can be listed, for example.

[0072] [Chemical Formula 16]

[0073]

[0074] In formula (2), ring A, ring B, and ring C independently represent aromatic rings or heterocycles composed of atoms selected from carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and preferably represent aromatic rings or heterocycles composed of 3 to 20 carbon atoms, which may optionally contain nitrogen atoms, oxygen atoms, and sulfur atoms.

[0075] Aromatic rings or heterocycles, whose cyclic atoms are selected from carbon, nitrogen, oxygen, and sulfur atoms, include, for example, benzene rings, naphthyl rings, anthracene rings, tetraphenyl rings, phenanthrene rings, fluorene rings, azurite rings, pentaphenyl rings, pyrene rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, quinoline rings, isoquinoline rings, indole rings, phthalimide rings, tetrahydrophthalimide rings, triazole rings, benzotriazole rings, triazine rings, pyrrole rings, thiophene rings, benzothiophene rings, and benzo[[unclear text - likely a typo, should be removed]]. azole ring, benzothiazole ring, diazole ring, dibenzo[a] The rings include azole rings, dibenzothiophene rings, tetrahydrofuran rings, tetrahydropyran rings, piperidine rings, piperidinone rings, piperazine rings, thiomorpholine rings, and morpholine rings. Preferably, the rings are benzene rings, naphthalene rings, anthracene rings, benzotriazole rings, triazine rings, and tetrahydrophthalimide rings; more preferably, they are benzene rings and benzotriazole rings.

[0076] Preferably, at least one ring selected from ring A, ring B, and ring C is any of the rings shown in structures (I) to (IX) below, more preferably at least one of ring A or ring B is any of the rings shown in structures (I) to (IX) below. Furthermore, preferably ring A is bonded to any of R4 to R6 and S1, ring B to S1 and S2, and ring C to S2 and S3 at meta, para, or amphi positions, more preferably at para positions. This further reduces the wavelength dispersion R of the film using the resin of this disclosure. 450 / R 550 .

[0077] [Chemical Formula 17]

[0078]

[0079] (where R1 and R are in the formula) m R n Independently related to R4~R in equation (2) above 12 The meaning is the same. Rings (I) to (IX) are bonded to any of S1, S2, and S3 in equation (2) above, through any carbon or nitrogen atom constituting the ring.

[0080] At least one ring selected from ring A, ring B and ring C is more preferably any one of the rings shown in the following structures (I), (IV), (V) and (VI).

[0081] [Chemical Formula 18]

[0082]

[0083] (where R1 and R are in the formula) m R n Independently related to R4~R in equation (2) above 12 They have the same meaning.

[0084] In equation (2), R4~R 12Each group independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a cyanophenyl group, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkyl carboxylic acid group with 2 to 11 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, an alkyl alcohol group with 1 to 10 carbon atoms, or an aromatic cyclic group or heterocyclic group with an atom selected from carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms as cyclic atoms, preferably a hydrogen atom, a hydroxyl group, a cyano group or an alkyl group with 1 to 10 carbon atoms.

[0085] The alkyl group having 1 to 10 carbon atoms can be any of the following: straight-chain, cyclic, or branched. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, cyclopropyl, cyclobutyl, and cyclopentyl. Among these, a straight-chain alkyl group is preferred, and methyl or ethyl is more preferred.

[0086] Examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, and propoxy.

[0087] An alkyl carboxylic acid group having 2 to 11 carbon atoms is a group in which a portion of the hydrogen atoms of an alkyl group having 1 to 10 carbon atoms is replaced by a carboxyl group. Examples include carboxymethyl (-CH2COOH), 2-carboxyethyl (-CH2CH2COOH), and 3-carboxypropyl (-CH2CH2CH2COOH).

[0088] As a haloalkyl group having 1 to 10 carbon atoms, examples include groups in which some or all of the hydrogen atoms of the aforementioned alkyl groups having 1 to 10 carbon atoms are replaced by halogen atoms. As a haloalkyl group, a fluoroalkyl group is preferred, and a perfluoroalkyl group is particularly preferred.

[0089] As an alkyl alcohol group having 1 to 10 carbon atoms, it is a group in which a hydrogen atom of the alkyl group having 1 to 10 carbon atoms is replaced by a hydroxyl group. Examples include hydroxymethyl (-CH2OH), 2-hydroxyethyl (-CH2CH2OH), and 3-hydroxypropyl (-CH2CH2CH2OH).

[0090] Examples of aromatic or heterocyclic groups that use atoms selected from carbon, nitrogen, oxygen, and sulfur atoms as cyclic atoms include phenyl, naphthyl, anthracene, tetraphenyl, phenanthryl, fluorene, azulene, pentaphenyl, pyrene, pyridinyl, pyridinyl, pyrazinyl, quinolinyl, isoquinolinyl, indole, phthalimide, tetrahydrophthalimide, triazolyl, benzotriazolyl, triazinyl, pyrroleyl, thiophene, benzothiophene, and benzo[] azole group, benzothiazolium group, diazole group, dibenzo[ Azolyl, dibenzothiophene, tetrahydrofuranyl, tetrahydropyranyl, piperidinyl, piperidinone, piperazine, thiomorpholinyl, morpholinyl (the hydrogen atoms on the cyclic groups of these rings can be replaced by any substituents. Examples of substituents include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, cyanophenyl groups, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylcarboxylic acid groups with 2 to 11 carbon atoms, haloalkyl groups with 1 to 10 carbon atoms, and alkylol groups with 1 to 10 carbon atoms).

[0091] In equation (2), for a and b, the wavelength dispersion R of the film using the resin of this disclosure is... 450 / R 550 From the perspective of further reduction, it is preferable that a is 0 or 1 and b is 1, and more preferably a is 0 and b is 1.

[0092] In the resin disclosed herein, the residue unit represented by formula (2) is preferably a structure derived from one of the monomers represented by the following formula.

[0093] [Chemical Formula 19]

[0094]

[0095] [Chemical Formula 20]

[0096]

[0097] [Chemical Formula 21]

[0098]

[0099] [Chemical Formula 22]

[0100]

[0101] [Chemical Formula 23]

[0102]

[0103] [Chemical Formula 24]

[0104]

[0105] [Chemical Formula 25]

[0106]

[0107] [Chemical Formula 26]

[0108]

[0109] [Chemical Formula 27]

[0110]

[0111] [Chemical Formula 28]

[0112]

[0113] [Chemical Formula 29]

[0114]

[0115] [Chemical Formula 30]

[0116]

[0117] [Chemical Formula 31]

[0118]

[0119] [Chemical Formula 32]

[0120]

[0121] Wherein, the residue unit shown in formula (2) is preferably a structure from one of (2-1-1) to (2-1-20), (2-2-1) to (2-2-20), (2-2-36) to (2-2-55), (2-3-1) to (2-3-20), (2-4-1) to (2-4-20), (2-4-36) to (2-4-40), (2-5-1) to (2-5-20), (2-5-36) to (2-5-40), and more preferably a structure from one of (2-4-8), (2-4-10), (2-4-37), (2-5-8), (2-5-10), and (2-5-37).

[0122] Examples of fumarate diester resins disclosed herein include the following structures.

[0123] [Chemical Formula 33]

[0124]

[0125] [Chemical Formula 34]

[0126]

[0127] [Chemical Formula 35]

[0128]

[0129] [Chemical Formula 36]

[0130]

[0131] [Chemical Formula 37]

[0132]

[0133] [Chemical Formula 38]

[0134]

[0135] [Chemical Formula 39]

[0136]

[0137] [Chemical Formula 40]

[0138]

[0139] [Chemical Formula 41]

[0140]

[0141] [Chemical Formula 42]

[0142]

[0143] [Chemical Formula 43]

[0144]

[0145] [Chemical Formula 44]

[0146]

[0147] [Chemical Formula 45]

[0148]

[0149] [Chemical Formula 46]

[0150]

[0151] The resin of this disclosure preferably comprises 50 mol% or more and 99 mol% of residue units shown in formula (1) and 1 mol% or more and 50 mol% or less of residue units shown in formula (2), more preferably 70 mol% or more and 99 mol% or less of residue units shown in formula (1) and 1 mol% or more and 30 mol% or less of residue units shown in formula (2), and particularly preferably 80 mol% or more and 99 mol% or less of residue units shown in formula (1) and 1 mol% or more and 20 mol% or less of residue units shown in formula (2). Therefore, when the resin of this disclosure is formed into a film, the wavelength dispersion R... 450 / R 550 Further reduction in size allows for higher contrast in displays when used as an optical compensation film.

[0152] From the perspective of exhibiting better mechanical strength, the weight-average molecular weight of the resin disclosed herein is preferably 150,000 or more and 450,000 or less. For even better mechanical strength, it is more preferably 200,000 or more and 450,000 or less, and particularly preferably 240,000 or more and 450,000 or less. Thus, the film obtained from the resin of this disclosure exhibits better mechanical strength. Here, the weight-average molecular weight can be expressed by conversion from standard polystyrene measured by gel permeation chromatography.

[0153] As a method for manufacturing the resin disclosed herein, it can be manufactured by any method as long as the resin can be obtained. For example, it can be manufactured by combining monomers associated with the residue units shown in formulas (1) and (2) for free radical polymerization. As a method of free radical polymerization, any method such as bulk polymerization, solution polymerization, suspension polymerization, precipitation polymerization, emulsion polymerization, etc. can be used.

[0154] Examples of polymerization initiators used in free radical polymerization include organic peroxides such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, tert-butyl cumene peroxide, diisopropylbenzene peroxide, tert-butyl peracetate, tert-butyl peroxybenzoate, and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane; and azo initiators such as 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2-butanonitrile), 2,2'-azobisisobutanonitrile, dimethyl-2'-azobisisobutanonitrile, and 1,1'-azobis(cyclohexane-1-formonitrile).

[0155] Furthermore, there are no particular limitations on the solvents that can be used in solution polymerization, suspension polymerization, precipitation polymerization, and emulsion polymerization. Examples include aromatic solvents such as benzene, toluene, and xylene; alcohol solvents such as methanol, ethanol, propanol, and butanol; and cyclohexane. Alkane; tetrahydrofuran; acetone; methyl ethyl ketone; N,N-dimethylformamide; dimethyl sulfoxide; isopropyl acetate; water, etc., or mixtures of these solvents may also be listed.

[0156] In addition, the polymerization temperature during free radical polymerization can be appropriately set according to the decomposition temperature of the polymerization initiator. From the perspective of easy reaction control, it is generally carried out in the range of 30 to 150°C.

[0157] The following describes in detail one aspect of the membrane of this disclosure.

[0158] The resin disclosed herein is preferably used as a film for optical components. In particular, by forming it into a film shape and stretching it along one or more axes, it exhibits excellent phase difference, and therefore can be used as an optical compensation film. It can be used as an optical compensation film for displays, etc., by exhibiting a desired phase difference. When the resin of this disclosure is used as an optical compensation film, the optical compensation film is characterized by exhibiting the desired phase difference characteristics. That is, the film formed from the resin of this disclosure can reduce wavelength dispersion R by stretching. 450 / R 550 Therefore, it is possible to obtain an optical compensation film with excellent phase difference characteristics.

[0159] The phase difference characteristics of the film using the resin of this disclosure have a phase difference for the purpose of optical compensation of optical components.

[0160] The film thickness of the film using the resin disclosed herein is preferably 80 μm or less, more preferably 50 μm or less, and particularly preferably 30 μm or less. By reducing the film thickness, displays and the like can be made thinner.

[0161] The wavelength dispersion of the film using the resin of this disclosure can be achieved with a phase difference R of 450 nm. 450 Phase difference R with wavelength 550nm 550 The ratio of R 450 / R 550 Let R represent the preferred condition. 450 / R 550 When the value is less than 1.015, the contrast of optical components in displays and the like can be well adjusted within the above range. Furthermore, to improve the contrast of optical components in displays and the like, since wavelength dispersion exhibits inverse wavelength dispersion, R is more preferable. 450 / R 550 <1.00, R is particularly preferred 450 / R 550 <0.90. If R is limited 450 / R 550 The lower limit is above 0.80, which is used as R. 450 / R 550 The range is preferably 0.80 or higher and less than 1.015, more preferably 0.80 or higher and less than 1.00, and particularly preferably 0.80 or higher and less than 0.90.

[0162] Since the film formed from the resin of this disclosure can adjust the in-plane phase difference of optical components such as displays for optical compensation, the in-plane phase difference (Re) is preferably 10 to 300 nm. Furthermore, for better adjustment of the contrast of displays, etc., it is more preferably 50 to 280 nm, and particularly preferably 70 to 200 nm. Regarding the out-of-plane phase difference (Rth), since it can also adjust the out-of-plane phase difference of optical components such as displays for optical compensation, an out-of-plane phase difference (Rth) of -200 to 50 nm is preferred. Furthermore, for better adjustment of the contrast of displays, etc., it is more preferably -160 to 30 nm, and particularly preferably -90 to 0 nm.

[0163] Most components constituting displays have a positive Rth, which increases the Nz coefficient of the overall display structure, leading to color shift issues in IPS-type liquid crystal displays and the like. However, when the film formed from the resin of this disclosure has a negative Rth, the overall Rth of the display structure can be adjusted. Therefore, when such a resin is used as an optical compensation film, a wider field of view of the display can be achieved.

[0164] Here, the in-plane phase difference (Re) of the membrane can be calculated using equation (a). Additionally, the out-of-plane phase difference (Rth) of the membrane can be calculated using equation (b).

[0165] Re = (nx - ny) × d (a)

[0166] Rth={(nx+ny) / 2-nz}×d (b)

[0167] (In equations (a) and (b), nx represents the refractive index along the slow axis inside the film surface. ny represents the refractive index along the fast axis inside the film surface. nz represents the refractive index outside the film surface. d represents the film thickness (nm).)

[0168] Here, the fast axis direction represents the direction of minimum refractive index, and the slow axis direction represents the direction of maximum refractive index.

[0169] Since the film formed from the resin of this disclosure can achieve wide field of view when used as an optical compensation film for optical components such as displays, the Nz coefficient is preferably -5.0 or higher and 0.9 or lower. For further wide field of view, it is more preferably -1.0 or higher and 0.7 or lower, and particularly preferably -0.5 or higher and 0.5 or lower.

[0170] Here, the Nz coefficient (Nz) of the membrane can be calculated using the following formula (c).

[0171] Nz=(nx-nz) / (nx-ny) (c)

[0172] (In equation (c), nx, ny, and nz have the same meaning as in equations (a) and (b))

[0173] To improve wavelength dispersion characteristics, the film formed from the resin of this disclosure may also contain a wavelength dispersion modifier that exhibits positive birefringence.

[0174] A wavelength dispersion modifier exhibiting positive birefringence refers to an additive with positive birefringence and high wavelength dispersion characteristics. It can be used to adjust the wavelength dispersion of resins with negative birefringence. From the perspective of high positive wavelength dispersion characteristics and excellent wavelength dispersion adjustment function, aromatic compounds are preferred. Examples of aromatic compounds include naphthalene, anthracene, ultraviolet absorbers, and liquid crystal materials. In particular, from the perspective of ease of stress orientation and high positive birefringence, ultraviolet absorbers or liquid crystal materials are preferred.

[0175] Preferred examples of ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, and benzoic acid ester compounds. In particular, from the perspective of having a large positive wavelength dispersion characteristic and excellent wavelength dispersion adjustment function, at least one of benzotriazole compounds and triazine compounds is preferred as an ultraviolet absorber.

[0176] As preferred examples of liquid crystal materials, particularly considering ease of stress alignment and high positive birefringence, nematic liquid crystals can be cited. Preferred examples of nematic liquid crystals include biphenyl compounds and terphenyl compounds. As liquid crystal materials, particularly considering high positive wavelength dispersion characteristics and excellent wavelength dispersion adjustment function, at least one of cyanobiphenyl compounds or cyanoterphenyl compounds is preferred.

[0177] As a wavelength dispersant that exhibits positive birefringence, at least one of benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, biphenyl compounds, and terphenyl compounds is particularly preferred.

[0178] Examples of wavelength dispersants exhibiting positive birefringence include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]benzotriazole. Benzotrigine compounds such as 2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol] and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol; and dibenzophenones such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-5-sulfobenzophenone. Ketone compounds; 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2,6 Triazine compounds such as diphenyl-4-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine and 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-[2-(2-ethyl)hexanoyloxy)ethoxy]phenyl)-1,3,5-triazine; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate;4-Cyano-4'-methylbiphenyl, 4-Cyano-4'-ethylbiphenyl, 4-Cyano-4'-propylbiphenyl, 4-Cyano-4'-butylbiphenyl, 4-Cyano-4'-pentylbiphenyl, 4-Cyano-4'-hexylbiphenyl, 4-Cyano-4'-heptylbiphenyl, 4-Cyano-4'-n-octylbiphenyl, 4-Cyano-4'-nonylbiphenyl, 4-Cyano-4'-decylbiphenyl, 4-Cyano-4'-undecylbiphenyl, 4-Cyano-4'-dodecylbiphenyl, 4-Cyano-4'-methoxybiphenyl, 4-Cyano-4'-ethoxybiphenyl, 4-Cyano-4'-propoxybiphenyl, 4-Cyano-4'-butoxybiphenyl, 4-Cyano-4'-pentylbiphenyl Biphenyl compounds including 4-cyano-4'-hexyloxybiphenyl, 4-cyano-4'-heptyloxybiphenyl, 4-cyano-4'-n-octyloxybiphenyl, 4-cyano-4'-nonoxybiphenyl, 4-cyano-4'-decyloxybiphenyl, 4-cyano-4'-undecyloxybiphenyl, 4-cyano-4'-dodecyloxybiphenyl, 4-4'-bis(trans-4-propylcyclohexyl)biphenyl, trans-4-cyano-4'-(4-pentylcyclohexyl)biphenyl, etc.; 4-cyano-4"-methyl-p-terphenyl, 4-cyano-4"-ethyl-p-terphenyl, 4-cyano-4"-propyl-p-terphenyl, 4-cyano-4"-butyl-p-terphenyl, 4-cyano- 4”-Pentyl-p-terphenyl, 4-Cyano-4”-Hexyl-p-terphenyl, 4-Cyano-4”-Heptyl-p-terphenyl, 4-Cyano-4”-n-Octyl-p-terphenyl, 4-Cyano-4”-Nonyl-p-terphenyl, 4-Cyano-4”-Decyl-p-terphenyl, 4-Cyano-4”-Undecyl-p-terphenyl, 4-Cyano-4”-Dodecyl-p-terphenyl, 4-Cyano-4”-Methoxy-p-terphenyl, 4-Cyano-4”-Ethoxy-p-terphenyl, 4-Cyano-4”-Propoxy-p-terphenyl, 4-Cyano-4”-Butoxy-p-triphenyl, 4-Cyano-4”-Pentyloxy-p-terphenyl, 4-Cyano-4”-Hexyloxy-p-terphenyl, 4-Cyano-4”-Heptyl- Terphenyl compounds, including 4-cyano-4”-n-octyloxy-terphenyl, 4-cyano-4”-nonoxy-terphenyl, 4-cyano-4”-decyloxy-terphenyl, 4-cyano-4”-undecyloxy-terphenyl, 4-cyano-4”-dodecyloxy-terphenyl, 4-amino-terphenyl, 4,4”-diamino-terphenyl, 4-nitro-terphenyl, 4,4”-dinitro-terphenyl, 4”-ethyl-2'-fluoro-4-propyl-terphenyl, 2'-fluoro-4-pentyl-4”-propyl-terphenyl, 2',3,4-trifluoro-4”-propyl-terphenyl, and 2',3,4,5-tetrafluoro-4”-propyl-terphenyl.

[0179] From the viewpoints of compatibility with resins, in-plane phase difference, and wavelength dispersion adjustment, the molecular weight of a wavelength dispersion modifier exhibiting positive birefringence is preferably 150 to 5000, more preferably 250 to 2000, and particularly preferably 280 to 1000. Here, regarding molecular weight, when the wavelength dispersion modifier exhibiting positive birefringence is a low molecular weight compound whose molecular weight can be calculated from its chemical structure, its molecular weight is expressed as the weight-average molecular weight converted from standard polystyrene; when it is a high molecular weight compound with repeating units, its molecular weight is expressed as the weight-average molecular weight converted from standard polystyrene.

[0180] From the viewpoint of improving mechanical properties, compatibility with resin, in-plane phase difference, and wavelength dispersion adjustment, the proportion of a wavelength dispersion modifier exhibiting positive birefringence in the composition contained in the optical film of this disclosure is preferably 0.01 to 19% by mass, more preferably 2 to 10% by mass, and particularly preferably 3 to 8% by mass.

[0181] The film formed from the resin of this disclosure may also contain antioxidants to improve the thermal stability when making optical films. Examples of antioxidants include hindered phenolic 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.

[0182] The film formed from the resin disclosed herein may also contain compounds known as plasticizers for purposes such as improving the mechanical properties when making optical films, imparting flexibility, imparting water absorption resistance, reducing water vapor transmission rate, and adjusting phase difference. Examples of plasticizers include phosphate esters and carboxylic acid esters. Additionally, acrylic polymers may also be used.

[0183] Examples of phosphate esters include triphenyl phosphate, tricresyl phosphate, and diphenyl phosphate.

[0184] Examples of carboxylic acid esters include phthalates, citrates, fatty acid esters, glycerides, and alkyl phthaloyl glycolates. Examples of phthalates include dimethyl phthalate, diethyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, and diethylhexyl phthalate. Examples of citrates include triethyl acetylacetate and tributyl acetylacetate. In addition, examples of fatty acid esters include butyl oleate, methyl acetyl castor oil, and dibutyl sebacate; examples of glyceryl esters include triacetyl glycerol and trimethylolpropane tribenzoate; and examples of alkyl phthaloyl glycolate esters include methyl methyl phthaloyl acetate, ethyl phthaloyl glycolate, propyl phthaloyl glycolate, butyl phthaloyl glycolate, octyl phthaloyl glycolate, ethyl phthaloyl glycolate, and ethyl phthaloyl glycolate. Methyl phthalate, propyl ethyl phthalate, ethyl phthalate, propyl methyl phthalate, butyl methyl phthalate, butyl ethyl phthalate, methyl butyl phthalate, ethyl butyl butyl phthalate, butyl butyl phthalate, octyl methyl phthalate, octyl ethyl phthalate, methyl octyl phthalate, ethyl phthalate, methyl octyl phthalate, ethyl phthalate, methyl octyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, ethyl phthalate, etc. These plasticizers can be used alone or in combination of two or more.

[0185] The film formed from the resin of this disclosure may contain other polymers, surfactants, high molecular weight electrolytes, conductive complexes, pigments, dyes, antistatic agents, anti-blocking agents, lubricants, etc., without departing from the scope of the invention.

[0186] The film formed from the resin of this disclosure can be laminated with films containing other resins as needed. Examples of other resins include polyethersulfone, polyarylate, polyethylene terephthalate, polynaphthalene terephthalate, polycarbonate, cyclic polyolefins, maleimide resins, fluororesins, and polyimides. Additionally, hard coatings and gas barrier layers can also be laminated.

[0187] When using a film formed from the resin of this disclosure as an optical compensation film, it is preferable that the optical compensation film is a film obtained by stretching a film formed from the resin of this disclosure along one or more axes.

[0188] There are no particular limitations on the method for manufacturing the film obtained from the resin disclosed herein, and methods such as melt casting and solution casting can be cited as examples.

[0189] The specific methods for melt film formation include melt extrusion using a T-die, calendering, hot pressing, co-extrusion, co-melting, multilayer extrusion, blow molding, etc., without particular limitations. However, from the perspective of ease of subsequent stretching processing, melt extrusion using a T-die is preferred.

[0190] In the case of forming a film by melt deposition method, in order to make the forming method more suitable for achieving uniform film thickness and for preventing film defects and coloring, the forming temperature is preferably 200 to 265°C, more preferably 210 to 260°C, and particularly preferably 220 to 258°C. Here, the forming temperature refers to the temperature during forming in the melt deposition method, and is usually a value obtained by measuring the temperature at the exit of the die through which the molten resin is extruded.

[0191] Solution casting is a method in which a solution of the resin disclosed herein dissolved in a solvent (hereinafter referred to as "coating") is cast onto a support substrate, and the solvent is removed by heating or the like to obtain a film. Methods for casting the coating onto the support substrate include T-die casting, doctor blade casting, bar coating, roller coating, and lip coating. In particular, the most common industrial method is to continuously extrude the coating from a die onto a strip or drum-shaped support substrate. Examples of support substrates used include glass substrates, metal substrates such as stainless steel or ferrotype, and films made of polyethylene terephthalate. In solution casting, the viscosity of the coating solution is an extremely important factor when forming a film with high transparency, thickness accuracy, and excellent surface smoothness; preferably 10 to 20,000 cPs, more preferably 100 to 10,000 cPs.

[0192] The film formed from the resin of this disclosure is preferably further stretched into a film by the film-forming method described above, and particularly preferably by uniaxial stretching or non-equilibrium biaxial stretching.

[0193] The stretching temperature is not particularly limited, but from the perspective of obtaining good phase difference characteristics, it is preferably 50–200°C, more preferably 90–180°C. From the perspective of obtaining good phase difference characteristics, the stretching ratio of uniaxial stretching is preferably 1.05–3.5 times, more preferably 1.1–3.0 times. From the perspective of obtaining good phase difference characteristics, the stretching ratio of unbalanced biaxial stretching is preferably 1.05–3.5 times in the length direction, more preferably 1.1–3.0 times, and preferably 1.0–1.2 times in the width direction, more preferably 1.0–1.1 times. The in-plane phase difference (Re) can be controlled by the stretching temperature and stretching ratio.

[0194] The film formed from the resin of this disclosure can be used to make a polarizer, which is disposed at least on one side of a polarizer. Here, examples of polarizer configurations include a film formed from the resin of this disclosure / polarizer, a polarizer / film formed from the resin of this disclosure, and a film formed from the resin of this disclosure / polarizer / film formed from the resin of this disclosure.

[0195] Example

[0196] The present disclosure will now be described through examples, but the present disclosure is not limited to these examples. It should be noted that the various physical properties shown in the examples were determined using the following methods.

[0197] <Analysis of Monomers and Polymers>

[0198] Using a nuclear magnetic resonance (NMR) measurement device (JNEDI, trade name JNM-ECZ400S / L1), proton nuclear magnetic resonance was used. 1 It is obtained through H-NMR spectral analysis. Additionally, for those difficult to obtain... 1 The results were obtained from H-NMR spectroscopy and determined using an elemental analysis apparatus (manufactured by Perkin Elmer, trade name 2400II) through CHN elemental analysis.

[0199] <Determination of average molecular weight>

[0200] The determination was performed using a gel permeation chromatography (GPC) apparatus (Tosoh, trade name HLC8320GPC (with column MHHR-H)) at 40°C with tetrahydrofuran or N,N-dimethylformamide as solvent, and the result was calculated as a standard polystyrene equivalent.

[0201] <Determination of Phase Difference Characteristics>

[0202] The in-plane phase difference Re, out-of-plane phase difference Rth, and Nz coefficient of the film were measured using a sample tilting automatic birefringence meter (manufactured by AXOMETRICS, trade name AxoScan) with light at a wavelength of 589 nm.

[0203] <Determination of Wavelength Dispersion Characteristics>

[0204] Using a sample-tilting automated birefringence meter (manufactured by AXOMETRICS, trade name AxoScan), the phase difference R of light at a wavelength of 450 nm was measured. 450 Phase difference R with light based on wavelength 550nm 550 The wavelength dispersion characteristics of the film were determined in the form of a ratio.

[0205] Synthesis Example 1 (Synthesis of Acrylate A)

[0206] In a 300 mL three-necked flask, 4.12 g (20.8 mmol) of biphenyl-2-carboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.254 g (2.08 mmol) of diaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 50 mL of dehydrated dichloromethane (manufactured by Fujifilm and Kogyo Pure Chemicals Co., Ltd.) at 0 °C under a nitrogen atmosphere. 4.39 g (22.9 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 30 minutes. 3.00 g of 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was allowed to react overnight at room temperature. Water was added to stop the reaction. The aqueous layer was washed three times with dichloromethane, and the organic layer was washed three times with saturated brine. The organic layer was removed and dried over anhydrous sodium sulfate, followed by vacuum distillation to remove the solvent. The oil was purified by silica gel column chromatography (hexane / ethyl acetate), and the solvent was removed by vacuum distillation to obtain 4-(acryloyloxy)butyl [1,1'-biphenyl]-2-carboxylic acid (hereinafter referred to as "acrylate A") as a pale yellow liquid. 1 H-NMR (400MHz, CDCl3): δ7.82-7.80(m,2H), 7.53-7.49(m,1H), 7.42-7.28(m,6H), 6.12-6.05(m,1H), 6.3 8(d,J=8.0Hz,1H), 5.81(d,J=8.0Hz,1H), 4.04(t,J=6.0Hz,2H), 3.99(t,J=6.0Hz,2H), 1.45-1.30(m,4H))

[0207] [Chemical Formula 47]

[0208]

[0209] Synthesis Example 2 (Synthesis of Acrylate B)

[0210] Add 4.99 g (34.6 mmol) of 4-hydroxybutyl acrylate, 35 mL of dehydrated dichloromethane, 7.0 g (69 mmol) of triethylamine (manufactured by Fujifilm and Kohden Chemical Co., Ltd.), 0.85 g (6.9 mmol) of diaminopyridine (manufactured by Fujifilm and Kohden Chemical Co., Ltd., hereinafter referred to as "DMAP"), and 7.9 g (41.5 mmol) of p-toluenesulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to a 200 mL three-necked flask and dissolve at 0 °C.

[0211] After reacting for 3 hours, 100 mL of 2N hydrochloric acid was added to stop the reaction.

[0212] The reaction mixture was transferred to a separatory funnel, extracted three times with chloroform, washed once with distilled water, and then dried with sodium sulfate. The organic layer was concentrated using an evaporator and dried under vacuum at room temperature to obtain 10.7 g of 4-toluenesulfonyloxybutyl acrylate (hereinafter referred to as "acrylate B"). 1 H-NMR (400MHz, CDCl3): δ7.80-7.78(m,2H), 7.36-7.34(m,2H), 6.40-6.35(m,1H), 6.1 2-6.05(m,1H), 5.84-5.81(m,1H), 4.13-4.05(m,4H), 2.45(s,3H), 1.75-1.70(m,4H))

[0213] [Chemical Formula 48]

[0214]

[0215] Synthesis Example 3 (Synthesis of Acrylate C)

[0216] Add 25.0 g (138 mmol) of 6-bromo-1-hexanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 16.1 g (159 mmol) of triethylamine, and 200 mL of dehydrated dichloromethane to a 500 mL three-necked flask and dissolve at 0 °C.

[0217] Add 50 mL of a dehydrated dichloromethane solution containing 9.6 g (106 mmol) acryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.). Heat to room temperature and stir for 3 hours. Add 200 mL of 2N hydrochloric acid to stop the reaction. Extract the reaction product with dichloromethane, wash the organic layer three times with deionized water and three times with brine, and dry with magnesium sulfate.

[0218] The organic layer was concentrated using an evaporator to obtain 24.5 g of 6-bromohexyl acrylate (hereinafter referred to as "acrylate C"). 1 H-NMR (400MHz, CDCl3): δ6.39(d,J=18.4Hz,1H), 6.15-6.08(m,1H), 5.82(d,J=10.8Hz,1H), 1.90-1.37(m,12H))

[0219] [Chemical Formula 49]

[0220]

[0221] Synthesis Example 4 (Synthesis of Acrylate D)

[0222] In a 300 mL three-necked flask, 4.4 g (26 mmol) of 4-phenylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.2 g (52.1 mmol) of potassium carbonate (manufactured by Fujifilm and Kohden Chemical Co., Ltd.), 10.1 g (33.9 mmol) of acrylate B obtained in Synthesis Example 2, and 50 mL of dehydrated DMF (manufactured by Fujifilm and Kohden Chemical Co., Ltd.) were added and dissolved at 50 °C. The reaction was carried out for 5 hours, and then 50 mL of deionized water was added to stop the reaction. The reaction product was extracted with ethyl acetate, and the organic layer was washed three times with deionized water, three times with brine, and dried with sodium sulfate.

[0223] The organic layer was concentrated using an evaporator and purified by medium-pressure column chromatography (chloroform / hexane = 80 vol%–20 vol%) (silica gel) to obtain 5.79 g of 4-([1,1'-biphenyl]-4-yloxy)butyl acrylate (hereinafter referred to as "acrylate D"). 1 H-NMR (400MHz, CDCl3): δ7.55-7.50(m,4H), 7.43-7.39(m,2H), 7.31-7.25(m,1H), 6.98-6.94(m,2H), 6.41(d,J= 16.0Hz,1H), 6.16-6.09(m,1H), 5.82(d,J=8.0Hz,1H), 4.26-4.24(m,2H), 4.05-4.02(m,2H), 1.95-1.85(m,4H))

[0224] [Chemical Formula 50]

[0225]

[0226] Synthesis Example 5 (Synthesis of Acrylate E)

[0227] In a 300 mL three-necked flask, 6.7 g (39.2 mmol) of 4-phenylphenol, 12.0 g (51.0 mmol) of acrylate C obtained in Synthesis Example 3, 10.9 g (78.5 mmol) of potassium carbonate, 0.065 g (0.4 mmol) of potassium iodide (manufactured by Fujifilm and Koichi Chemical Co., Ltd.), and 50 mL of dehydrated DMF were added and dissolved at 120 °C. After stirring for 3 hours, the mixture was cooled to room temperature, and 100 mL of deionized water was added to stop the reaction.

[0228] The reaction product was extracted with chloroform, and the organic layer was washed three times with deionized water, three times with brine, and dried with sodium sulfate. The organic layer was concentrated using an evaporator and purified by medium-pressure column chromatography (dichloromethane / hexane = 80 vol%–20 vol%) (silica gel) to obtain 6.02 g of 6-([1,1'-biphenyl]-4-yloxy)hexyl acrylate (hereinafter referred to as "acrylate E"). 1 H-NMR (400MHz, CDCl3): δ7.56-7.49(m,4H), 7.42-7.38(m,2H), 7.31-7.27(m,1H), 6.97-6.94(m,2H), 6.40(d,J=20.0Hz,1H), 6.15- 6.08(m,1H)、5.81(d,J=12.0Hz,1H)、4.19-4.16(m,2H)、4.01-3.98(m,2H)、1.85-1.78(m,2H)、1.75-1.68(m,2H)、1.56-1.42(m,4H))

[0229] [Chemical Formula 51]

[0230]

[0231] Synthesis Example 6 (Synthesis of Acrylate F)

[0232] In a 300 mL three-necked flask, add 18.0 g (83.2 mmol) of 2-succinoxyethyl acrylate (Kyoeisha Chemical Co., Ltd.), 11.8 g (69.3 mmol) of 4-phenylphenol, 13.3 g (69.3 mmol) of EDC hydrochloride, 0.85 g (6.9 mmol) of DMAP, and 50 mL of dehydrated dichloromethane, and dissolve at 0 °C. After returning to room temperature and stirring for 3 hours, add 200 mL of deionized water to stop the reaction.

[0233] The reaction product was extracted with dichloromethane, and the organic layer was washed three times with deionized water, three times with brine, and dried with sodium sulfate. The organic layer was concentrated using an evaporator and purified by medium-pressure column chromatography (chloroform = 100 vol%) (silica gel) to obtain 19.8 g of succinate [1,1'-biphenyl]-4-yl(2-(acryloyloxy)ethyl) ester (hereinafter referred to as "acrylate F"). 1H-NMR (400MHz, CDCl3): δ7.59-7.52(m,4H), 7.46-7.39(m,2H), 7.37-7.32(m,1H), 7.18-7.14(m,2H), 6.43(d,J= 20.0Hz,1H), 6.15-6.09(m,1H), 5.84(d,J=12.0Hz,1H), 4.42-4.34(m,4H), 2.93-2.89(m,2H), 2.80-2.77(m,2H))

[0234] [Chemical Formula 52]

[0235]

[0236] Synthesis Example 7 (Synthesis of Acrylate G)

[0237] In a 300 mL three-necked flask, 6.00 g (41.6 mmol) of ethyl 2-carboxylate acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.51 g (4.2 mmol) of diaminopyridine (manufactured by Fujifilm and Koimitsu Chemical Co., Ltd., hereinafter referred to as "DMAP") were dissolved in 150 mL of dehydrated dichloromethane under a nitrogen atmosphere at 0 °C. 8.78 g (45.8 mmol) of EDC hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 30 minutes. 6.98 g (31.0 mmol) of 2-(2-benzotriazolyl)-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was allowed to react overnight at room temperature. Water was added to stop the reaction, and the organic layer was extracted. The mixture was separated three times using water / dichloromethane and three times using saturated brine / dichloromethane. Water was removed with sodium sulfate. The organic layer was removed by vacuum distillation, yielding a pale yellow liquid. Purification was performed by silica gel column chromatography (hexane / ethyl acetate) to obtain 5.1 g of 3-(2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-methylphenoxy)-3-oxopropyl acrylate (hereinafter referred to as "acrylate G"). 1 H-NMR (400MHz, CDCl3): δ7.99-7.98(m,1H), 7.93-7.91(m,2H), 7.42-7.40(m,2H), 7.32-7.28(m,1H), 7.20-7 .18(m,1H), 6.37(d,J=16.0Hz,1H), 6.08-6.01(m,1H), 5.79(d,J=8.0Hz,1H), 4.14-4.08(m,4H), 2.41(s,3H))

[0238] [Chemical Formula 53]

[0239]

[0240] Synthesis Example 8 (Synthesis of Acrylate H)

[0241] In a 300 mL three-necked flask, 7.55 g (33.5 mmol) of 2-(2-benzotriazolyl)-p-cresol, 9.26 g (67.0 mmol) of potassium carbonate, 15.0 g (50.3 mmol) of acrylate B obtained in Synthesis Example 2, and 100 mL of dehydrated DMF were added and dissolved at 50 °C. After stirring for 5 hours, the mixture was cooled to room temperature, and 50 mL of deionized water was added to stop the reaction.

[0242] The reaction product was extracted with chloroform, and the organic layer was washed three times with deionized water, three times with brine, and dried with sodium sulfate.

[0243] The organic layer was concentrated using an evaporator and purified by medium-pressure column chromatography (chloroform / hexane = 80 vol%–20 vol%) (silica gel) to obtain 10.7 g of 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-methylphenol (hereinafter referred to as "acrylate H"). 1 H-NMR (400MHz, CDCl3): δ7.96-7.94(m,2H), 7.49-7.49(m,1H), 7.43-7.41(m,2H), 7.28-7.25(m,1H), 7.03-7.01(m,1H) , 6.32(d,J=18.8Hz,1H), 6.07-6.00(m,1H), 5.77(d,J=11.2Hz,1H), 4.09-4.03(m,4H), 2.37(s,3H), 1.77-1.67(m,4H))

[0244] [Chemical Formula 54]

[0245]

[0246] Synthesis Example 9 (Synthesis of Acrylate I)

[0247] In a 300 mL three-necked flask, 5.03 g (25.8 mmol) of 4-cyano-4'-hydroxybiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.13 g (51.6 mmol) of potassium carbonate, 10.0 g (33.5 mmol) of acrylate B obtained in Synthesis Example 2, and 50 mL of dehydrated DMF were added and dissolved at 50 °C. After stirring for 5 hours, the mixture was cooled to room temperature, and 50 mL of deionized water was added to stop the reaction.

[0248] The reaction product was extracted with chloroform, and the organic layer was washed three times with deionized water, three times with brine, and dried with sodium sulfate.

[0249] The organic layer was concentrated using an evaporator and purified by medium-pressure column chromatography (chloroform = 100 vol%) (silica gel) to obtain 2.01 g of 4-((4'-cyano-[1,1'-biphenyl]-4-yl)oxy)butyl acrylate (hereinafter referred to as "acrylate I"). 1 H-NMR (400MHz, CDCl3): δ7.70-7.61(m,4H), 7.55-7.46(m,2H), 7.00-6.98(m,2H), 6.43-6.35(m,1 H), 6.17-6.05(m,1H), 5.85-5.81(m,1H), 4.27-4.24(m,2H), 4.15-4.04(m,2H), 1.92-1.90(m,4H))

[0250] [Chemical Formula 55]

[0251]

[0252] Synthesis Example 10 (Synthesis of Acrylate J)

[0253] Add 20.0 g (64.9 mmol) of 2-(acryloyloxy)ethyl (2-hydroxyethyl) phthalate (manufactured by Kyoeisha Chemical Co., Ltd.), 200 mL of dehydrated dichloromethane, 13.1 g (130.0 mmol) of triethylamine, 1.59 g (13.0 mmol) of DMAP, and 14.8 g (77.8 mmol) of p-toluenesulfonyl chloride to a 500 mL three-necked flask and dissolve at 0 °C.

[0254] After reacting for 3 hours, 200 mL of 2N hydrochloric acid was added to stop the reaction.

[0255] The reaction mixture was transferred to a separatory funnel, extracted three times with chloroform, washed once with distilled water, and then dried with sodium sulfate. The organic layer was concentrated using an evaporator and dried under vacuum at room temperature to obtain 10.7 g of 2-(acryloyloxy)ethyl (2-(toluenesulfonyloxy)ethyl) phthalate (hereinafter referred to as "acrylate J"). 1 H-NMR (400MHz, CDCl3): δ7.92-7.64(m,4H), 7.59-7.53(m,2H), 7.41-7.25(m,2H), 6.4 7-6.34(m,1H), 6.18-6.00(m,1H), 5.88-5.82(m,1H), 4.61-4.18(m,8H), 2.34(s,3H))

[0256] [Chemical Formula 56]

[0257]

[0258] Synthesis Example 11 (Synthesis of Acrylate K)

[0259] In a 300 mL three-necked flask, 2.83 g (16.6 mmol) of 4-phenylphenol, 4.60 g (33.3 mmol) of potassium carbonate, 10.0 g (21.6 mmol) of acrylate J obtained in Synthesis Example 10, and 50 mL of dehydrated DMF were added and dissolved at 50 °C. After stirring for 5 hours, the mixture was cooled to room temperature, and 50 mL of deionized water was added to stop the reaction.

[0260] The reaction product was extracted with chloroform, and the organic layer was washed three times with deionized water, three times with brine, and dried with sodium sulfate.

[0261] The organic layer was concentrated using an evaporator and purified by medium-pressure column chromatography (dichloromethane = 100 vol%) (silica gel) to obtain 0.89 g of 2-([1,1'-biphenyl]-4-yloxy)ethyl (2-(acryloyloxy)ethyl) phthalic acid (hereinafter referred to as "acrylate K"). 1 H-NMR (400MHz, CDCl3): δ7.78-7.25(m,11H), 7.05-6.93(m,2H), 6.47-6.39(m,1H), 6.20-6.00(m,1H), 5.87-5.81(m,1H), 4.68-4.24(m,8H))

[0262] [Chemical Formula 57]

[0263]

[0264] Example 1

[0265] 38.00 g (190 mmol) of diisopropyl fumarate, 6.78 g (21.0 mmol) of 2-(2-biphenoxy)ethyl acrylate, and 0.42 g (1.7 mmol) of PERBUTYL PV (manufactured by Nippon Yushi Co., Ltd.) were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was added dropwise to 3 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "Resin 1"). The weight-average molecular weight of the obtained Resin 1 was 290,000. Furthermore, by... 1¹H-NMR analysis confirmed that the composition of resin 1 was 93 / 7 (mol%) of diisopropyl fumarate residue units / 2-(2-biphenoxy)ethyl acrylate residue units.

[0266] [Chemical Formula 58]

[0267]

[0268] Example 2

[0269] 40.00 g (200 mmol) of diisopropyl fumarate, 4.09 g (22.2 mmol) of acrylate A obtained in Synthesis Example 1, and 0.46 g (1.85 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was added dropwise to 3 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "Resin 2"). The weight-average molecular weight of the obtained Resin 2 was 203,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 2 was 93 / 7 (mol%) of diisopropyl fumarate residue units / acrylate A residue units.

[0270] [Chemical Formula 59]

[0271]

[0272] Example 3

[0273] 20.02 g (100 mmol) of diisopropyl fumarate, 1.67 g (5.2 mmol) of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd.), and 0.22 g (0.89 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and depressurization, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was added dropwise to 3 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "resin 3"). The weight-average molecular weight of the obtained resin 3 was 243,000. Furthermore, by... 11H-NMR analysis confirmed that the composition of resin 3 was 93 / 7 (mol%) of diisopropyl fumarate residue unit / 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole residue unit.

[0274] [Chemical Formula 60]

[0275]

[0276] Example 4

[0277] 9.12 g (45.5 mmol) of diisopropyl fumarate, 0.72 g (2.4 mmol) of acrylate D, and 0.106 g (0.42 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 90 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain the resin (hereinafter referred to as "Resin 4"). The weight-average molecular weight of the obtained Resin 4 was 299,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 4 was 95 / 5 (mol%) of diisopropyl fumarate residue units / acrylate D residue units.

[0278] [Chemical Formula 61]

[0279]

[0280] Example 5

[0281] 6.45 g (32.2 mmol) of diisopropyl fumarate, 0.55 g (1.7 mmol) of acrylate E obtained in Synthesis Example 5, 0.070 g (0.28 mmol) of PERBUTYL PV, and 1.24 g of toluene were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 90 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain the resin (hereinafter referred to as "Resin 5"). The weight-average molecular weight of the obtained Resin 5 was 153,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 5 was 93 / 7 (mol%) of diisopropyl fumarate residue units / acrylate E residue units.

[0282] [Chemical Formula 62]

[0283]

[0284] Example 6

[0285] 4.13 g (20.8 mmol) of diisopropyl fumarate, 0.42 g (1.1 mmol) of acrylate F obtained in Synthesis Example 6, and 0.038 g (0.15 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 90 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain the resin (hereinafter referred to as "Resin 6"). The weight-average molecular weight of the obtained Resin 6 was 367,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 6 was 94 / 6 (mol%) of diisopropyl fumarate residue units / acrylate F residue units.

[0286] [Chemical Formula 63]

[0287]

[0288] Example 7

[0289] 3.75 g (18.7 mmol) of diisopropyl fumarate, 0.60 g (1.6 mmol) of acrylate F obtained in Synthesis Example 6, and 0.041 g (0.17 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 90 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "Resin 7"). The weight-average molecular weight of the obtained Resin 7 was 330,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 7 was 91 / 9 (mol%) of diisopropyl fumarate residue units / acrylate F residue units.

[0290] [Chemical Formula 64]

[0291]

[0292] Example 8

[0293] 4.13 g (20.8 mmol) of diisopropyl fumarate, 0.42 g (1.1 mmol) of acrylate G obtained in Synthesis Example 7, and 0.038 g (0.15 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 90 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "Resin 8"). The weight-average molecular weight of the obtained Resin 8 was 367,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 8 was 94 / 6 (mol%) of diisopropyl fumarate residue units / G acrylate residue units.

[0294] [Chemical Formula 65]

[0295]

[0296] Example 9

[0297] 6.87 g (34.3 mmol) of diisopropyl fumarate, 0.37 g (1.1 mmol) of acrylate H obtained in Synthesis Example 8, and 0.068 g (0.27 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was complete, the polymer was removed from the ampoule and dissolved in 90 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "Resin 9"). The weight-average molecular weight of the obtained Resin 9 was 396,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 9 was 97 / 3 (mol%) of diisopropyl fumarate residue units / acrylate H residue units.

[0298] [Chemical Formula 66]

[0299]

[0300] Example 10

[0301] 10.21 g (51.0 mmol) of diisopropyl fumarate, 0.51 g (1.6 mmol) of acrylate I obtained in Synthesis Example 9, and 0.11 g (0.44 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 90 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "Resin 10"). The weight-average molecular weight of the obtained Resin 10 was 247,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 10 was 97 / 3 (mol%) of diisopropyl fumarate residue units / acrylate I residue units.

[0302] [Chemical Formula 67]

[0303]

[0304] Example 11

[0305] 9.83 g (49.1 mmol) of diisopropyl fumarate, 0.83 g (2.6 mmol) of acrylate I obtained in Synthesis Example 9, and 0.11 g (0.44 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 90 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "Resin 11"). The weight-average molecular weight of the obtained Resin 11 was 221,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 11 was 95 / 5 (mol%) of diisopropyl fumarate residue units / acrylate I residue units.

[0306] [Chemical Formula 68]

[0307]

[0308] Example 12

[0309] 1.55 g (7.6 mmol) of diisopropyl fumarate, 0.083 g (0.24 mmol) of 4-[(6-acryloyloxy)hexyloxy]-4'-cyanobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.016 g (0.065 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 40 g of tetrahydrofuran. The polymer solution was added dropwise to 0.3 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "Resin 12"). The weight-average molecular weight of the obtained Resin 12 was 365,000. Furthermore, by... 1 ¹H-NMR analysis confirmed that the composition of resin 12 was 97 / 3 (mol%) of diisopropyl fumarate residue unit / 4-[(6-acryloyloxy)hexyloxy]-4'-cyanobiphenyl residue unit.

[0310] [Chemical Formula 69]

[0311]

[0312] Example 13

[0313] 1.11 g (5.5 mmol) of diisopropyl fumarate, 0.22 g (0.5 mmol) of acrylate K obtained in Synthesis Example 11, and 0.015 g (0.072 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 40 g of tetrahydrofuran. The polymer solution was added dropwise to 0.3 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a resin (hereinafter referred to as "Resin 13"). The weight-average molecular weight of the obtained Resin 13 was 170,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 13 was 93 / 7 (mol%) of diisopropyl fumarate residue units / K acrylate residue units.

[0314] [Chemical Formula 70]

[0315]

[0316] Example 14

[0317] 6.99 g (34.9 mmol) of diisopropyl fumarate, 0.33 g (1.9 mmol) of diethyl fumarate, 0.43 g (1.2 mmol) of 4-[(6-acryloyloxy)hexyloxy]-4'-cyanobiphenyl, and 0.068 g (0.27 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 100 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain the resin (hereinafter referred to as "Resin 14"). The weight-average molecular weight of the obtained Resin 14 was 297,000. Furthermore, by... 1 ¹H-NMR analysis confirmed that the composition of resin 14 was 91 / 6 / 3 (mol%) of diisopropyl fumarate residue unit / diethyl fumarate residue unit / 4-[(6-acryloyloxy)hexyloxy]-4'-cyanobiphenyl residue unit.

[0318] [Chemical Formula 71]

[0319]

[0320] Example 15

[0321] 6.99 g (34.9 mmol) of diisopropyl fumarate, 0.70 g (4.1 mmol) of diethyl fumarate, 0.49 g (1.4 mmol) of 4-[(6-acryloyloxy)hexyloxy]-4'-cyanobiphenyl, and 0.084 g (0.34 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 100 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain the resin (hereinafter referred to as "Resin 15"). The weight-average molecular weight of the obtained Resin 15 was 271,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 15 was 86 / 10 / 4 (mol%) of diisopropyl fumarate residue unit / diethyl fumarate residue unit / 4-[(6-acryloyloxy)hexyloxy]-4'-cyanobiphenyl residue unit.

[0322] [Chemical Formula 72]

[0323]

[0324] Example 16

[0325] 7.01 g (35.0 mmol) of diisopropyl fumarate, 1.10 g (6.4 mmol) of diethyl fumarate, 0.54 g (1.6 mmol) of 4-[(6-acryloyloxy)hexyloxy]-4'-cyanobiphenyl, and 0.071 g (0.29 mmol) of PERBUTYL PV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 100 g of tetrahydrofuran. The polymer solution was added dropwise to 0.5 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain the resin (hereinafter referred to as "Resin 16"). The weight-average molecular weight of the obtained Resin 16 was 245,000. Furthermore, by... 1 H-NMR analysis confirmed that the composition of resin 16 was 82 / 14 / 4 (mol%) of diisopropyl fumarate residue unit / diethyl fumarate residue unit / 4-[(6-acryloyloxy)hexyloxy]-4'-cyanobiphenyl residue unit.

[0326] [Chemical Formula 73]

[0327]

[0328] Example 17

[0329] 4.0 g of resin 1 obtained in Example 1 was dissolved in 16.0 g of tetrahydrofuran (THF) to obtain a 20% by mass resin solution. This resin solution was cast onto a polyethylene terephthalate (PET) film using a coating machine and dried in a two-step process at 80°C for 4 minutes followed by 130°C for 4 minutes to obtain the film. The obtained film was cut into 50 mm squares and uniaxially stretched to 1.2 times its original length at 118°C. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1-3, the wavelength dispersion of the obtained film was reduced.

[0330]

[0331] Example 18

[0332] Except that resin 2 obtained in Example 2 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 106°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0333] Example 19

[0334] Except that resin 3 obtained in Example 3 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 151°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0335] Example 20

[0336] Except that resin 4 obtained in Example 4 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 140°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0337] Example 21

[0338] Except that resin 5 obtained in Example 5 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 101°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0339] Example 22

[0340] Except that resin 6 obtained in Example 6 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 117°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0341] Example 23

[0342] Except that resin 7 obtained in Example 7 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 117°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0343] Example 24

[0344] Except that resin 8 obtained in Example 8 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 160°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0345] Example 25

[0346] Except that resin 9 obtained in Example 9 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 140°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0347] Example 26

[0348] Except that resin 10 obtained in Example 10 was used instead of resin 1 to prepare the resin solution, the stretching temperature was changed to 159°C, and the stretching ratio was changed to 1.4 times, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0349] Example 27

[0350] Except that resin 11 obtained in Example 11 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 140°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0351] Example 28

[0352] Except that resin 12 obtained in Example 12 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 140°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0353] Example 29

[0354] Except that resin 13 obtained in Example 13 was used instead of resin 1 to prepare the resin solution and the stretching temperature was changed to 140°C, the film was prepared in the same manner as in Example 14, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0355] Example 30

[0356] Except that resin 12 obtained in Example 12 was used instead of resin 1, 4% by mass of 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol] was added as an additive to prepare the resin solution relative to 100% by mass of the total resin, and the stretching temperature was changed to 117°C, the membrane was prepared in the same manner as in Example 17, and the phase difference characteristics of the obtained membrane were measured. The phase difference characteristics of the obtained membrane are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained membrane was reduced.

[0357] Example 31

[0358] Except that resin 12 obtained in Example 12 was used instead of resin 1, 3% by mass of 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine was added as an additive to prepare the resin solution relative to 100% by mass of the total resin, and the stretching temperature was changed to 115°C, the membrane was prepared in the same manner as in Example 17, and the phase difference characteristics of the obtained membrane were measured. The phase difference characteristics of the obtained membrane are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained membrane was reduced.

[0359] Example 32

[0360] Except that resin 14 obtained in Example 14 was used instead of resin 1, methyl ethyl ketone (MEK) was used instead of THF to prepare the resin solution, and the stretching temperature was changed to 138°C, the film was prepared in the same manner as in Example 17, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0361] Example 33

[0362] Except that resin 15 obtained in Example 15 was used instead of resin 1, MEK was used instead of THF to prepare the resin solution, and the stretching temperature was changed to 124°C, the film was prepared in the same manner as in Example 17, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0363] Example 34

[0364] Except that resin 16 obtained in Example 16 was used instead of resin 1, MEK was used instead of THF to prepare the resin solution, and the stretching temperature was changed to 116°C, the film was prepared in the same manner as in Example 17, and the phase difference characteristics of the obtained film were measured. The phase difference characteristics of the obtained film are shown in Table 1. Compared with Comparative Examples 1 to 3, the wavelength dispersion of the obtained film was reduced.

[0365] Comparative Example 1

[0366] 40.02 g (200 mmol) of diisopropyl fumarate and 0.41 g (1.7 mmol) of PERBUTYL PV (manufactured by Nippon Yushi Co., Ltd.) were added to a 75 mL glass ampoule. After repeated nitrogen purging and depressurization, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was added dropwise to 3 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain a diisopropyl fumarate homopolymer. The weight-average molecular weight of the obtained diisopropyl fumarate homopolymer was 257,000.

[0367] [Chemical Formula 74]

[0368]

[0369] 4.0 g of the obtained diisopropyl fumarate homopolymer was dissolved in 16.0 g of tetrahydrofuran to obtain a 20 wt% resin solution. This resin solution was cast onto a polyethylene terephthalate (PET) film using a coating machine and dried in a two-step process at 80 °C for 4 minutes followed by 130 °C for 4 minutes to obtain the film. The resulting film was cut into 50 mm squares and uniaxially stretched to 1.2 times its original length at 140 °C. The phase difference characteristics of the obtained film are shown in Table 1.

[0370] Comparative Example 2

[0371] 40.01 g (200 mmol) of diisopropyl fumarate, 2.11 g (11.5 mmol) of n-octyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.45 g (1.81 mmol) of PERBUTY LPV were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a thermostat at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was added dropwise to 3 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain the copolymer. The weight-average molecular weight of the obtained copolymer was 351,000. Furthermore, by... 1 H-NMR analysis confirmed that the copolymer composition was 96 / 4 (mol%) of diisopropyl fumarate residue units / n-octyl acrylate residue units.

[0372] [Chemical Formula 75]

[0373]

[0374] 4.0 g of the obtained resin was dissolved in 16.0 g of tetrahydrofuran to obtain a 20 wt% resin solution. This resin solution was cast onto a polyethylene terephthalate (PET) film using a coating machine and dried in a two-step process at 80 °C for 4 minutes followed by 130 °C for 4 minutes to obtain the film. The resulting film was cut into 50 mm squares and uniaxially stretched to 1.3 times its original length at 140 °C. The phase difference characteristics of the obtained film are shown in Table 1.

[0375] Comparative Example 3

[0376] 39.04 g (195 mmol) of diisopropyl fumarate, 3.89 g (21.1 mmol) of n-octyl acrylate, and 0.43 g (1.74 mmol) of PERBUTYL PV (manufactured by Nippon Yushu Co., Ltd.) were added to a 75 mL glass ampoule. After repeated nitrogen purging and reduced pressure, the ampoule was sealed under reduced pressure. Free radical polymerization was carried out by placing the ampoule in a constant temperature bath at 50 °C for 24 hours. After the polymerization reaction was completed, the polymer was removed from the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was added dropwise to 3 L of methanol to precipitate the polymer, and then dried under vacuum at 80 °C for 10 hours to obtain copolymer B. The weight-average molecular weight of the obtained copolymer was 371,000. Furthermore, by... 1 H-NMR analysis confirmed that the copolymer composition was 91 / 9 (mol%) of diisopropyl fumarate residue units / n-octyl acrylate residue units.

[0377] [Chemical Formula 76]

[0378]

[0379] 4.0 g of the obtained resin was dissolved in 16.0 g of tetrahydrofuran to obtain a 20 wt% resin solution. This resin solution was cast onto a polyethylene terephthalate (PET) film using a coating machine and dried in a two-step process at 80 °C for 4 minutes followed by 130 °C for 4 minutes to obtain the film. The resulting film was cut into 50 mm squares and uniaxially stretched to 1.3 times its original length at 105 °C. The phase difference characteristics of the obtained film are shown in Table 1.

Claims

1. A fumarate diester resin comprising fumarate diester residue units and (meth)acrylate residue units as shown in formula (1), ， In formula (1), R1 and R2 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 12 carbon atoms, respectively. The (meth)acrylate residue unit is derived from a structure selected from one of the following: (2-4-8), (2-4-10), (2-4-37), (2-5-8), (2-5-10), and (2-5-37). 。 2. The fumarate diester resin according to claim 1, comprising 50 mol% and 99 mol% of the fumarate diester residue units of formula (1), and comprising 1 mol% and 50 mol% of the (meth)acrylate residue units.

3. The fumarate diester resin according to claim 1 or 2, wherein the weight-average molecular weight converted from standard polystyrene by gel permeation chromatography is 150,000 to 450,000.

4. A membrane using the fumarate diester resin according to any one of claims 1 to 3.

5. The membrane according to claim 4, wherein it is stretched about one or more axes.

6. The membrane according to claim 4, wherein the membrane thickness is 80 μm or less.

7. The membrane according to claim 4, wherein, The in-plane phase difference (Re) shown in equation (a) is 10~300nm, and the out-of-plane phase difference (Rth) shown in equation (b) is -200~50nm. Re = (nx - ny) × d(a) Rth={(nx+ny) / 2-nz}×d(b) In the formula, nx represents the refractive index of the slow axis in the plane, ny represents the refractive index of the fast axis in the plane, nz represents the refractive index out of the plane, and d represents the film thickness.

8. The membrane according to claim 4, wherein, In-plane phase difference (R) at a wavelength of 450 nm 450 The in-plane phase difference (R) with a wavelength of 550nm 550 The ratio of R to ) 450 / R 550 Satisfy R 450 / R 550 <1.015 conditions.

9. The membrane according to claim 4, wherein, The Nz coefficient (Nz) shown in equation (c) is -5.0 ≤ Nz ≤ 0.

9. Nz=(nx-nz) / (nx-ny)(c) In equation (c), nx represents the refractive index of the slow axis in the plane, ny represents the refractive index of the fast axis in the plane, and nz represents the refractive index out of the plane.

10. A polarizer having at least one of the films according to any one of claims 4 to 9 disposed on one side of the polarizer.

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