Copolymers, liquid crystal compositions, liquid crystal cured layers, optical films, polarizing plates, image display devices, and lithographic printing plates.

Abstract

The present invention aims to provide a copolymer capable of forming a layer in which unevenness and repulsion are suppressed and adhesion to the roll is also suppressed, as well as a liquid crystal composition, a liquid crystal cured layer, an optical film, a polarizing plate, an image display device, and a lithographic printing plate. [Solution] A copolymer having repeating units A derived from hydrophobic monomers and repeating units B represented by a predetermined formula (1), wherein the number-average molecular weight of the monomers constituting the repeating unit B is 500 or more and 20000 or less.

Description

[Technical Field]

[0001] The present invention relates to copolymers, liquid crystal compositions, liquid crystal cured layers, optical films, polarizing plates, image display devices, and lithographic printing plates. [Background technology]

[0002] Leveling agents are added to smooth coating films obtained by applying coating compositions such as paint compositions, resist compositions, liquid crystal compositions, and image recording layer forming compositions. Specifically, by adding a leveling agent to the coating composition, the leveling agent is directed onto the surface of the coating film, reducing the surface tension of the coating film and resulting in a smoother coating. Furthermore, a smoother coating film can suppress the occurrence of unevenness and paint repellency.

[0003] Examples of such leveling agents include, for example, -Si[OSi(R)3], as described in Patent Document 1. n [R'] 3-n A leveling agent is described which includes a polymer containing polymer blocks (A1) of polymerizable monomers (a1) having a functional group represented by (n is an integer from 1 to 3; R is independently an alkyl group having 1 to 3 carbon atoms; R' is independently an alkyl group having 1 to 3 carbon atoms) in a predetermined mass ratio ([Claim 1]). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 7151909 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present inventors investigated the leveling agent described in Patent Document 1 and found that there is room for improvement in its effect of suppressing unevenness and repellency in the layer containing the leveling agent, and that there is a problem in that when the layer containing the leveling agent comes into contact with the conveyor roll, a part of the coating film adheres to the roll and peels off.

[0006] Therefore, the object of the present invention is to provide a copolymer that can form a layer in which the occurrence of unevenness and repulsion is suppressed and adhesion to the roll is also suppressed, as well as a liquid crystal composition, a liquid crystal cured layer, an optical film, a polarizing plate, an image display device, and a lithographic printing plate. [Means for solving the problem]

[0007] As a result of diligent research to achieve the above objectives, the present inventors have discovered that by using a copolymer having repeating units A derived from a hydrophobic monomer and repeating units B derived from a monomer satisfying a predetermined number-average molecular weight and represented by formula (1) described later, as a leveling agent, it is possible to form a layer in which unevenness and repulsion are suppressed and adhesion to the roll is also suppressed, thus completing the present invention. In other words, the inventors have found that the above problem can be solved by the following configuration.

[0008] [1] A copolymer having repeating units A derived from hydrophobic monomers and repeating units B represented by formula (1) described later, wherein the number-average molecular weight of the monomers constituting repeating unit B is 500 or more and 20000 or less. [2] The copolymer according to [1], wherein the content of repeating unit A is 40 to 85% by mass relative to the total mass of repeating unit A and repeating unit B. [3] The copolymer according to [1] or [2], wherein the monomer constituting the repeating unit B is crystalline. [4] The copolymer according to any one of [1] to [3], wherein Rk in formula (1), described later, represents an optionally substituted monovalent aromatic group, an optionally substituted monovalent heterocyclic group, or an alkyl group. Here, one or more non-adjacent -CH2- groups that constitute part of the alkyl group may be substituted with -O- or -CO-. [5] A copolymer according to any one of [1] to [4], which does not have a photo-directing group. [6] A copolymer according to any of [1] to [5], wherein the repeating unit A is represented by any of the formulas (2) to (4) described later. [7] A copolymer according to any of [1] to [6], wherein the weight-average molecular weight is 5,000 or more and 80,000 or less. A liquid crystal composition comprising a copolymer described in any of [8] [1] to [7] and a liquid crystal compound. [9] The liquid crystal composition according to [8], wherein the liquid crystal compound is a polymerizable liquid crystal compound.

[10] The liquid crystal composition according to [9], wherein the polymerizable liquid crystal compound is at least one polymerizable liquid crystal compound selected from the group consisting of polymerizable rod-shaped liquid crystal compounds and polymerizable disc-shaped liquid crystal compounds.

[11] A liquid crystal cured layer obtained by fixing the orientation state of the liquid crystal composition described in [8] or [9]. An optical film having the liquid crystal curing layer described in

[12]

[11] . A polarizing plate having the optical film described in

[13]

[12] and a polarizer.

[14] An image display device having the optical film described in

[12] .

[15] A lithographic printing plate comprising a support and an image recording layer provided on the support, wherein the image recording layer contains a copolymer according to any of [1] to [7]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a copolymer that can form a layer in which the occurrence of unevenness and repulsion is suppressed and adhesion to the roll is also suppressed, as well as a liquid crystal composition, a liquid crystal cured layer, an optical film, a polarizing plate, an image display device, and a lithographic printing plate. [Modes for carrying out the invention]

[0010] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In addition, in this specification, the upper limit value or the lower limit value described in a certain numerical range in a numerically described stepwise range may be replaced with the upper limit value or the lower limit value of another stepwise numerical range. Also, the upper limit value or the lower limit value described in a certain numerical range in the numerical range described in this specification may be replaced with the value shown in the examples. In this specification, each component may be used alone as one kind of substance corresponding to each component, or two or more kinds may be used in combination. Here, when two or more kinds of substances are used in combination for each component, the content of that component refers to the total content of the combined substances, unless otherwise specified. In addition, the bonding direction of the divalent group (for example, -O-CO-) described in this specification is not particularly limited. For example, in the bond of "L 1 -L 2 -L 3 ", when L 2 is -O-CO-, if the position bonded to the L 1 side is *1 and the position bonded to the L 3 side is *2, then L 2 may be *1-O-CO-*2 or *1-CO-O-*2.

[0011] In this specification, Re(λ) and Rth(λ) represent in-plane retardation and thickness-direction retardation at wavelength λ, respectively. When there is no particular description, the wavelength λ is 550 nm. In addition, in this specification, Re(λ) and Rth(λ) are values measured at wavelength λ using AxoScan OPMF-1 (manufactured by OptoSciences). Specifically, by inputting the average refractive index ((nx+ny+nz) / 3) and film thickness (d) into AxoScan OPMF-1, Slow axis direction (°) Re(λ)=R0(λ) Rth(λ)=((nx+ny) / 2-nz)×d This is calculated. Note that R0(λ) is a value displayed by the AxoScan OPMF-1, and it means Re(λ).

[0012] In this specification, examples of substituents (monovalent substituents) include the substituents listed in substituent group A below. In this specification, "may have substituents" includes not only embodiments without substituents but also embodiments having one or more substituents. <Substituent group A> Examples of substituents include, Halogen atoms (e.g., fluorine, chlorine, bromine atoms); Alkyl groups (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and particularly preferably 1 to 8 carbon atoms, for example, linear alkyl groups having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), branched alkyl groups having 3 to 6 carbon atoms (e.g., isopropyl group, isobutyl group, tert-butyl group, sec-butyl group, neopentyl group, isohexyl group, 3-methylpentyl group), and cyclic alkyl groups having 3 to 12 carbon atoms (e.g., cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group)); Alkenyl groups (preferably alkenyl groups having 2 to 48 carbon atoms, more preferably alkenyl groups having 2 to 18 carbon atoms, such as vinyl groups, allyl groups, 1-butenyl groups, and 2-butenyl groups); Alkynyl group (preferably an alkynyl group having 2 to 6 carbon atoms, more preferably an alkynyl group having 2 to 4 carbon atoms, for example, an ethynyl group, a 1-propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group); Aryl groups (preferably aryl groups having 6 to 48 carbon atoms, more preferably aryl groups having 6 to 24 carbon atoms, for example, phenyl group, oligoaryl group (naphthyl group, anthryl group), phenanthrenyl group, fluorenyl group, pyrenyl group, triphenylenyl group, biphenyl group); Heteroaryl groups (preferably heterocyclic groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazole-1-yl group); Arylalkyl groups (preferably arylalkyl groups having 7 to 15 carbon atoms, for example, benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1-methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, tetrahydronaphthyl group, naphthylmethyl group, naphthylethyl group, indenyl group, fluorenyl group, anthracenylmethyl group (anthrylmethyl group), phenantrenylmethyl group (phenanthrylmethyl group)); Silyl groups (preferably silyl groups having 3 to 38 carbon atoms, more preferably silyl groups having 3 to 18 carbon atoms, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group); Hydroxyl group; cyano group; nitro group; morpholino group; Alkoxy groups (preferably alkoxy groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group, cycloalkyloxy group (for example, cyclopentyloxy group, cyclohexyloxy group)); Aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms, for example, a phenoxy group or a 1-naphthoxy group); Alkenyloxy groups (preferably alkenyloxy groups having 2 to 6 carbon atoms, for example, vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, prenyloxy group); Heterocyclic oxy groups (preferably heterocyclic oxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group); Silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably a silyloxy group having 1 to 18 carbon atoms, for example, trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group); Acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably an acyloxy group having 2 to 24 carbon atoms, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group, an acryloyloxy group, a methacryloyloxy group); Hydroxyalkylene oxy group (preferably a hydroxyalkylene oxy group having 2 to 10 carbon atoms, for example, a hydroxyethylene oxy group); Alkoxycarbonyloxy groups (preferably alkoxycarbonyloxy groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, ethoxycarbonyloxy groups, t-butoxycarbonyloxy groups, cycloalkyloxycarbonyloxy groups (for example, cyclohexyloxycarbonyloxy groups)); An aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, a phenoxycarbonyloxy group); Carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably a carbamoyloxy group having 1 to 24 carbon atoms, for example, N,N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group); Sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably a sulfamoyloxy group having 1 to 24 carbon atoms, for example, N,N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group); Alkylsulfonyloxy groups (preferably alkylsulfonyloxy groups having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylsulfonyloxy groups, hexadecylsulfonyloxy groups, cyclohexylsulfonyloxy groups); Aryl sulfonyloxy group (preferably an aryl sulfonyloxy group having 6 to 32 carbon atoms, more preferably an aryl sulfonyloxy group having 6 to 24 carbon atoms, for example, a phenyl sulfonyloxy group); Acyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, formyl group, acetyl group, acryloyl group, methacryloyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group); Alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group); An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, a phenoxycarbonyl group); Carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably a carbamoyl group having 1 to 24 carbon atoms, for example, carbamoyl group, N,N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N,N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N,N-dicyclohexylcarbamoyl group); Amino groups (preferably with 32 or fewer carbon atoms, more preferably with 24 or fewer carbon atoms, for example, amino groups, methylamino groups, N,N-dimethylamino groups, N,N-dibutylamino groups, tetradecylamino groups, 2-ethylhexylamino groups, cyclohexylamino groups); Anilino group (preferably anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, anilino group, N-methylanilino group); Heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, a 4-pyridylamino group); Carbonamide group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamide group, benzamide group, tetradecaneamide group, pivaloylamide group, cyclohexaneamide group); Ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably a ureido group having 1 to 24 carbon atoms, for example, a ureido group, an N,N-dimethylureido group, or an N-phenylureido group); Imide group (preferably an imide group having 36 or fewer carbon atoms, more preferably an imide group having 24 or fewer carbon atoms, for example, N-succinimide group, N-phthalimide group); Alkoxycarbonylamino groups (preferably alkoxycarbonylamino groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group); Aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms, for example, a phenoxycarbonylamino group); Sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably a sulfonamide group having 1 to 24 carbon atoms, for example, methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group); Sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably a sulfamoylamino group having 1 to 24 carbon atoms, for example, N,N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group); Azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably an azo group having 1 to 24 carbon atoms, for example, a phenylazo group or a 3-pyrazolylazo group); Alkylthio groups (preferably alkylthio groups having 1 to 48 carbon atoms, more preferably alkylthio groups having 1 to 24 carbon atoms, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group); An arylthio group (preferably with 6 to 48 carbon atoms, more preferably an arylthio group with 6 to 24 carbon atoms, for example, a phenylthio group); Heterocyclic thio groups (preferably heterocyclic thio groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group); Alkyl sulfinyl group (preferably an alkyl sulfinyl group having 1 to 32 carbon atoms, more preferably an alkyl sulfinyl group having 1 to 24 carbon atoms, for example, a dodecane sulfinyl group); Aryl sulfinyl group (preferably an aryl sulfinyl group having 6 to 32 carbon atoms, more preferably an aryl sulfinyl group having 6 to 24 carbon atoms, for example, a phenyl sulfinyl group); Alkyl sulfonyl groups (preferably alkyl sulfonyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methyl sulfonyl group, ethyl sulfonyl group, propyl sulfonyl group, butyl sulfonyl group, isopropyl sulfonyl group, 2-ethylhexyl sulfonyl group, hexadecyl sulfonyl group, octyl sulfonyl group, cyclohexyl sulfonyl group); Arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 48 carbon atoms, more preferably arylsulfonyl groups having 6 to 24 carbon atoms, for example, phenylsulfonyl groups and 1-naphthylsulfonyl groups); Sulfamoyl group (preferably a sulfamoyl group having 32 or fewer carbon atoms, more preferably a sulfamoyl group having 24 or fewer carbon atoms, for example, sulfamoyl group, N,N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group); Phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably a phosphonyl group having 1 to 24 carbon atoms, for example, a phenoxyphosphonyl group, an octyloxyphosphonyl group, or a phenylphosphonyl group); A phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group); Epoxy group;-NHCOCH3;-SO2NHC2H4OCH3;-NHSO2CH3; These are some examples, and you may combine two or more of them. These substituents may be further substituted by other substituents. Furthermore, if there are two or more substituents, they may be identical or different. They may also be bonded to each other to form a ring where possible.

[0013] [Copolymer] The copolymer of the present invention is a copolymer having repeating units A derived from hydrophobic monomers and repeating units B represented by formula (1) described later, wherein the number-average molecular weight of the monomers constituting repeating unit B is 500 or more and 20000 or less. Here, since the repeating unit B is a repeating unit that does not correspond to the repeating unit A, the copolymer of the present invention is a copolymer having the repeating unit A and the repeating unit B separately. Furthermore, for the effects of the present invention to become apparent, it is preferable that the repeating unit A of the copolymer does not contain fluorine atoms, and more preferably that the copolymer does not contain fluorine atoms. Furthermore, it is preferable that the copolymer of the present invention is a copolymer that does not have photo-orienting groups. A photo-orienting group is a group that has a photo-orienting function that induces rearrangement or an anisotropic chemical reaction upon irradiation with anisotropic light (for example, plane-polarized light).

[0014] As described above, in the present invention, when the copolymer of the present invention is used as a leveling agent, the occurrence of unevenness and repellency is suppressed, and a layer can be formed in which adhesion to the roll is also suppressed. The details of this reason are still unclear, but the inventors speculate that it is due to the following reasons. First, because the copolymer of the present invention has repeating units A, it is unevenly distributed on the surface of the layer containing the copolymer, thereby suppressing the occurrence of unevenness and repulsion. Furthermore, the copolymer of the present invention is as shown in formula (1) described later, L 12 L via (divalent linking group) 13 The introduction of (urethane bonds, amide bonds, or urea bonds), that is, the presence of hydrogen bonding groups located away from the main chain, is thought to increase the surface strength of the copolymer-containing layer, thereby suppressing adhesion to the roll. The following describes in detail each repeating unit of the copolymer of the present invention.

[0015] [Repeating Unit A] The repeating unit A of the copolymer of the present invention is a repeating unit derived from a hydrophobic monomer. Here, hydrophobic monomers are defined as monomers whose CLogP value, calculated by ChemDraw, is greater than 4. As hydrophobic monomers, monomers having both hydrophobic and polymerizable groups are preferred. The hydrophobic group is preferably a C1-C50 alkyl group or a C2-C50 alkenyl group having at least one (preferably 2 to 60, more preferably 4 to 20) silicon atoms as substituents, or a C4 or more alkyl group (preferably C5 to 50, more preferably C5 to 40) having two or more (preferably 3 or more, more preferably 4 to 10) terminal methyl groups. The polymerizable groups are preferably known radical polymerizable groups or cationic polymerizable groups, and more preferably acryloyl groups or methacryloyl groups.

[0016] In the present invention, it is preferable that the repeating unit A is a repeating unit represented by any of the following formulas (2) to (4) in order to further suppress the occurrence of unevenness and repellency and to form a layer in which adhesion to the roll is further suppressed.

[0017] [ka]

[0018] In equations (2) to (4) above, m represents an integer from 2 to 16, n represents an integer from 2 to 10000, and p represents an integer from 1 to 8. R 11 and R 12 Each of these independently represents either a hydrogen atom or an alkyl group. R 13 represents a hydrogen atom or substituent. L 11 is -O- or -NR Z - represents R Z represents a hydrogen atom or substituent. L 21 This represents a linking group with m+1 valence. L 22 This represents a single bond or a divalent linking group. L 23 This represents a single bond or a p+1 valent linking group. R 21 ~R 25 Each of these independently represents an alkyl group, alkenyl group, aryl group, or alkylenearyl group, which may have substituents. However, in formula (2) above, multiple R 21 These may be the same or different, and there may be multiple R 22 These may be the same or different, and there may be multiple R 23 These may be the same or different. Also, in equation (3) above, multiple R 24 These may be the same or different, and there may be multiple R 25 These may be the same or different. X represents an alkyl group with 4 to 40 carbon atoms having two or more terminal methyl groups. However, if p is an integer between 2 and 8, multiple X values ​​may be the same or different.

[0019] <Repeating unit represented by equation (2)> [ka]

[0020] As stated above, m in formula (2) represents an integer from 2 to 16, but is preferably an integer from 3 to 15, more preferably an integer from 3 to 10, and even more preferably an integer from 3 to 6.

[0021] R in equation (2) above 11 and R 12 As mentioned above, each of these independently represents either a hydrogen atom or an alkyl group. Examples of alkyl groups include linear alkyl groups with 1 to 18 carbon atoms, branched alkyl groups with 3 to 18 carbon atoms, or cyclic alkyl groups. Specifically, examples include methyl groups, ethyl groups, propyl groups, butyl groups, isopropyl groups, tert-butyl groups, and cyclohexyl groups. In this invention, R 11 and R 12 Preferably, it is a hydrogen atom.

[0022] R in equation (2) above 13 As mentioned above, represents a hydrogen atom or substituent. Examples of substituents include those listed in substituent group A above (particularly alkyl groups, alkenyl groups, and aryl groups). In this invention, R 13 Preferably, the group is a hydrogen atom or an alkyl group; more preferably, a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; even more preferably, a hydrogen atom, a methyl group, or an ethyl group; and particularly preferably, a hydrogen atom or a methyl group.

[0023] In equation (2) above, L 11 As mentioned above, -O- or -NR Z - represents R Z represents a hydrogen atom or substituent. R ZExamples of substituents represented by the above-mentioned substituent group A include the substituents listed above, among which alkyl groups are preferred, linear alkyl groups having 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred. In the present invention, L 1 -O- or -NH- is preferred, and -O- is more preferred.

[0024] In equation (2) above, L 21 As mentioned above, this represents an m+1 valent linking group. Examples of the above-mentioned m+1 valent linking group include, for example, a hydrocarbon group having 1 to 50 carbon atoms that may have substituents, in which some of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms. Examples of substituents that the hydrocarbon group may have include those listed in substituent group A above, among which alkyl groups are preferred, linear alkyl groups having 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred. Examples of heteroatoms in which some of the carbon atoms may be substituted include silicon atoms, oxygen atoms, and nitrogen atoms. L 21 Examples include the groups represented by the following structural formulas K-1-L to K-6-L. In the substructure formulas, * represents L in formula (2). 11 This represents the bond position with -SiR in equation (2), where ** is -SiR 21 R 22 R 23 This represents the bonding position with the group represented by . Of these, L 21 The group represented by the following structural formula K-1-L is preferred.

[0025] [ka]

[0026] R in equation (2) above 21 ~R 23As described above, each independently represents an alkyl group, alkenyl group, aryl group, or alkylenearyl group, which may have substituents. However, multiple R 21 These may be the same or different, and there may be multiple R 22 These may be the same or different, and there may be multiple R 23 These may be the same or different. Examples of the alkyl groups mentioned above include linear alkyl groups having 1 to 18 carbon atoms, and branched or cyclic alkyl groups having 3 to 18 carbon atoms. Examples of the above-mentioned alkenyl groups include alkenyl groups having 2 to 12 carbon atoms. Examples of the aryl group mentioned above include aryl groups having 6 to 12 carbon atoms. Examples of the alkylenearyl group mentioned above include alkylenearyl groups having 7 to 30 carbon atoms. Specifically, this includes groups that combine an alkylene group having 1 to 4 carbon atoms with an aryl group having 6 to 12 carbon atoms. Furthermore, examples of substituents that the alkyl group may have include those listed in substituent group A above, among which alkyl groups, alkylcarbonyl groups, alkyloxycarbonyl groups, alkylcarbonyloxy groups, or alkoxy groups are preferred. In this invention, R 21 ~R 23 It is preferable that both of these are alkyl groups, as this further suppresses the occurrence of unevenness.

[0027] <Repeating unit represented by formula (3)> [ka]

[0028] R in equation (3) above 11 , R 12 , R 13 , L 11 , R 21 , R 22 , and, R 23This is the same as that described in formula (2) above, and the preferred embodiment is also the same.

[0029] As stated above, n in formula (3) represents an integer from 2 to 10000, but is preferably an integer from 5 to 5000, more preferably from 10 to 1000, even more preferably from 12 to 500, and particularly preferably from 15 to 300.

[0030] In equation (3) above, L 22 As mentioned above, this represents a single bond or a divalent linking group. Here, L 22 One example of a divalent linking group represented by this embodiment is a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. As the above aliphatic hydrocarbon group, an alkylene group having 1 to 15 carbon atoms is preferred, and an alkylene group having 2 to 8 carbon atoms is more preferred. Furthermore, one or more of the -CH2- groups constituting part of the above aliphatic hydrocarbon group may be independently substituted with a group selected from -O-, -S-, -CO-, and -N(Q)-. Note that these substitutions may involve two or more -CH2- groups, as long as no adjacent groups are substituted with the same group. That is, for example, -CH2-CH2- may be substituted with -O-CO-, but not with -OO-. Q represents a hydrogen atom or substituent. L 22 Preferably, the alkylene group has 2 to 8 carbon atoms and may have substituents.

[0031] Also, L 22 Regarding the divalent linking group represented by one aspect of Q, substituents that may be present include divalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and substituents represented by one aspect of Q include those listed in substituent group A above, among which, for example, are hydroxyl groups, halogen atoms, amino groups, alkyl groups, alkoxy groups, acyl groups, aryl groups, nitro groups, cyano groups, alkylcarbonyl groups, and sulfonyl groups.

[0032] R in equation (3) above 24 and R 25 As described above, each of these independently represents an alkyl group, alkenyl group, aryl group, or alkylenearyl group, which may have substituents. These specific examples are R in equation (2) above. 21 ~R 23 The following are examples of what was explained in [the previous section]. In this invention, R 24 and R 25 It is preferable that the element be an alkyl group because it further suppresses the occurrence of unevenness.

[0033] <Repeating unit represented by formula (4)> [ka]

[0034] R in equation (4) above 11 , R 12 , R 13 , and, L 11 This is the same as that described in formula (2) above, and the preferred embodiment is also the same.

[0035] As mentioned above, p in equation (4) represents an integer from 1 to 8, but is preferably an integer from 1 to 5, and more preferably an integer from 1 to 4.

[0036] In the above equation (4), L 23 As mentioned above, this represents a single bond or a p+1 valent linking group. Examples of the above-mentioned p+1 valent linking group include, for example, a p+1 valent hydrocarbon group having 1 to 50 carbon atoms, which may have substituents, and in which some of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms. Examples of substituents that the hydrocarbon group may have include those listed in substituent group A above, among which alkyl groups are preferred, linear alkyl groups having 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred. Examples of heteroatoms in which some of the carbon atoms may be substituted include silicon atoms, oxygen atoms, and nitrogen atoms. L 23 Examples include the group represented by the following structural formulas K-7-L to K-9-L. In the substructure formulas, * represents L in formula (3). 11 This represents the bonding position with , and ** represents the bonding position with X in equation (3). In the present invention, L 23 Preferably, the group consists of a single bond or a group represented by the following structural formula K-8-L.

[0037] [ka]

[0038] As described above, X in formula (4) represents an alkyl group having 4 to 40 carbon atoms and having two or more terminal methyl groups. However, if p is an integer from 2 to 8, the multiple Xs may be the same or different. Here, "terminal methyl group" refers to a methyl group that constitutes the end of a linear or side chain of a hydrocarbon group. For example, linear alkyl groups such as n-propyl and n-butyl groups are alkyl groups having one terminal methyl group, isopropyl groups are alkyl groups having two terminal methyl groups, and t-butyl groups are alkyl groups having three terminal methyl groups. Therefore, for example, an n-hexyl group is an alkyl group with 6 carbon atoms and one terminal methyl group, but any of the groups represented by formulas (a-1) to (a-3) below all have 4 to 40 carbon atoms and have two or more terminal methyl groups (methyl groups enclosed by dotted lines in the formulas below). The number of terminal methyl groups is two or more, preferably three or more, and more preferably four to ten.

[0039] [ka]

[0040] A concrete example of repeating unit A is the repeating unit represented by the following formulas K-1 to K-26. In the repeating units exemplified below, n represents a value between 2 and 10000. [ka] JPEG2026122741000009.jpg28160JPEG2026122741000010.jpg32159JPEG2026122741 000011.jpg24157JPEG2026122741000012.jpg37157JPEG2026122741000013.jpg43153

[0041] Repeating unit A may be used alone or in combination of two or more types. In the present invention, it is preferable that the content of the repeating unit A is 40 to 85% by mass relative to the total mass of the repeating unit A and the repeating unit B described later, in order to form a layer in which the occurrence of unevenness is further suppressed. Furthermore, the lower limit of the content of the repeating unit A is preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more. Furthermore, the upper limit of the content of the repeating unit A is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 72% by mass or less.

[0042] [Repeating Unit B] The repeating unit B of the copolymer of the present invention is a repeating unit represented by the following formula (1), and the number-average molecular weight of the monomers constituting the repeating unit B is 500 or more and 20000 or less. Here, the number-average molecular weight of the monomers constituting the repeating unit B is the number-average molecular weight of the copolymer. 1 It can be calculated from the ratio of chemical shifts (peaks) in H-NMR (Nuclear Magnetic Resonance). For example, L in equation (1) below 13 The peaks that belong to L 12It can be calculated from the ratio to the peak attributed to

[0043]

Chemical formula

[0044] In the above formula (1), R 11 and R 12 each independently represents a hydrogen atom or an alkyl group. R 13 represents a hydrogen atom or a substituent. L 11 represents -O- or -NR Z -. R Z represents a hydrogen atom or a substituent. L 12 represents a divalent linking group. L 13 represents a urethane bond, an amide bond, or a urea bond. Rk represents a substituent.

[0045] R 11 、R<000009​​​​​​​​​​​​​​​Furthermore, one or more of the -CH2- groups constituting part of the above aliphatic hydrocarbon group may be independently substituted with a group selected from -O-, -S-, -CO-, and -N(Q)-. Note that these substitutions may involve two or more -CH2- groups, as long as no adjacent groups are substituted with the same group. That is, for example, -CH2-CH2- may be substituted with -O-CO-, but not with -OO-. Q represents a hydrogen atom or substituent. Furthermore, examples of substituents that may be present in aliphatic hydrocarbon groups, etc., and substituents represented by one aspect of Q include the substituents listed in the substituent group A described above, among which are, for example, hydroxyl groups, halogen atoms, amino groups, alkyl groups, alkoxy groups, acyl groups, aryl groups, nitro groups, cyano groups, alkylcarbonyl groups, and sulfonyl groups.

[0047] In the present invention, L 12 The following linking groups are preferred. * indicates the bond position. *-(LO)q-* *-(LO)q-(LO)r-* *-L-NH-CO-O-(L-CO-O)qL-* *-L-NH-CO-(OL-CO-OL-CO)qOL-* *-LO-(CO-LO)q-* Here, q and r are not particularly limited as long as they are integers that independently satisfy the condition that the number-average molecular weight of the monomers constituting the repeating unit B is between 500 and 20000, for example, 1 to 500. Furthermore, L represents an alkylene group having 1 to 12 carbon atoms, which may have substituents, and an alkylene group having 1 to 6 carbon atoms, which may have substituents, is preferred. Note that multiple Ls may be the same or different.

[0048] As mentioned above, Rk in formula (1) represents a substituent. In the present invention, it is preferable that Rk represents a monovalent aromatic group which may have substituents, a monovalent heterocyclic group which may have substituents, or an alkyl group, because this allows for the formation of a layer in which adhesion to the roll is more suppressed. Furthermore, one or more non-adjacent -CH2- groups among the -CH2- groups constituting part of the alkyl group may be substituted with -O- or -CO-. Examples of monovalent aromatic groups include monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, specifically phenyl groups, 2,6-diethylphenyl groups, naphthyl groups, and biphenyl groups. Examples of monovalent heterocyclic groups include monovalent aromatic heterocyclic groups having 6 to 20 carbon atoms, specifically the 4-pyridyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of alkyl groups include linear alkyl groups with 1 to 18 carbon atoms, branched alkyl groups with 3 to 18 carbon atoms, or cyclic alkyl groups. Specifically, examples include methyl groups, ethyl groups, propyl groups, butyl groups, isopropyl groups, tert-butyl groups, and cyclohexyl groups.

[0049] In the present invention, it is preferable that the monomer constituting the repeating unit B exhibits crystalline properties, as this allows for the formation of a layer in which adhesion to the roll is more suppressed. Here, the presence or absence of crystalline properties of a monomer can be determined by whether or not its melting point is observed using a differential scanning calorimetry (DSC).

[0050] A concrete example of repeating unit B is the repeating unit represented by the following equations H-1 to H-17. [ka] JPEG2026122741000016.jpg36119JPEG2026122741000017.jpg64130

[0051] Repeating unit B may be used alone or in combination of two or more types. In the present invention, the content of the repeating unit B is preferably 20 to 70% by mass relative to the total mass of the repeating unit A and the repeating unit B described above. Furthermore, the lower limit of the content of the repeating unit B is preferably 25% by mass or more, and more preferably 30% by mass or more. Furthermore, the upper limit of the content of the repeating unit B is preferably 65% ​​by mass or less, and more preferably 60% by mass or less.

[0052] [Other repeating units C] The copolymer of the present invention may have other repeating units C besides those described above. Other repeating units C include, for example, L in equation (1) above. 13 Examples include repeating units that do not have a repeating property. Furthermore, other repeating units C are preferably repeating units derived from (meth)acrylate having a polyalkylene oxide or repeating units derived from (meth)acrylate having an aromatic group, and more preferably repeating units derived from (meth)acrylate having a polyalkylene oxide.

[0053] The weight-average molecular weight of the copolymer of the present invention is preferably 5,000 to 80,000, and more preferably 10,000 to 50,000. When the weight-average molecular weight is 5000 or higher, the occurrence of unevenness is further suppressed, and a layer with further suppression of adhesion to the roll can be formed. When the weight-average molecular weight is 80000 or lower, a layer with further suppression of repulsion can be formed. Here, the weight-average molecular weight in this invention is the value measured by gel permeation chromatography (GPC) under the following conditions. • Solvent (eluent): Tetrahydrofuran • Device name: EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation) • Columns: Three columns of TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (all manufactured by Tosoh Corporation) are connected together for use. Column temperature: 40°C • Sample concentration: 0.1% by mass ·Flow rate: 0.35ml / min • Calibration curve: A calibration curve was used based on six samples of TOSOH TSK standard polystyrene with Mw=706000~1013 (Mw / Mn=1.03~1.06).

[0054] [Liquid crystal composition] The liquid crystal composition of the present invention is a liquid crystal composition containing the copolymer of the present invention described above and a liquid crystal compound. The components of the liquid crystal composition of the present invention, other than the copolymer of the present invention, will be described in detail below.

[0055] [Liquid crystal compound] The liquid crystal compound contained in the liquid crystal composition of the present invention is not particularly limited. Furthermore, while there are no particular limitations on the types of liquid crystal compounds, they can generally be classified into rod-shaped and disc-shaped types based on their shape. Each of these further has low-molecular-weight and high-molecular-weight types. High-molecular-weight compounds generally refer to those with a degree of polymerization of 100 or more (Polymer Physics and Phase Transition Dynamics, by Masao Doi, p. 2, Iwanami Shoten, 1992).

[0056] In this invention, any liquid crystal compound can be used, but it is preferable to use a rod-shaped liquid crystal compound or a disc-shaped liquid crystal compound (discotic liquid crystal compound). Two or more rod-shaped liquid crystal compounds, two or more disc-shaped liquid crystal compounds, or a mixture of rod-shaped and disc-shaped liquid crystal compounds may also be used.

[0057] As the rod-shaped liquid crystal compound, for example, the one described in claim 1 of Japanese Patent Publication No. 11-513019 or paragraphs

[0026] to

[0098] of Japanese Patent Application Publication No. 2005-289980 is preferred, and as the disc-shaped liquid crystal compound, for example, the one described in paragraphs

[0020] to

[0067] of Japanese Patent Application Publication No. 2007-108732 or paragraphs

[0013] to

[0108] of Japanese Patent Application Publication No. 2010-244038 is preferred.

[0058] In the present invention, the liquid crystal compound is preferably a liquid crystal compound having polymerizable groups (i.e., a polymerizable liquid crystal compound). The polymerizable liquid crystal compound is preferably at least one polymerizable liquid crystal compound selected from the group consisting of polymerizable rod-shaped liquid crystal compounds and polymerizable disc-shaped liquid crystal compounds. The orientation of a polymerizable liquid crystal compound can be fixed by polymerization. Furthermore, after the liquid crystal compound has been fixed by polymerization, it no longer needs to exhibit liquid crystalline properties.

[0059] The polymerizable groups of the polymerizable liquid crystal compound are not particularly limited, but polymerizable groups capable of radical polymerization or cationic polymerization are preferred. As the radical polymerizable group, known radical polymerizable groups can be used, and preferred examples include the acryloyloxy group or the methacryloyloxy group. In this case, the polymerization rate is generally known to be faster with the acryloyloxy group, and from the viewpoint of improving productivity, the acryloyloxy group is preferred, but the methacryloyloxy group can also be used as a polymerizable group in the same way. Known cationic polymerizable groups can be used as the cationic polymerizable group, specifically including alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and vinyloxy groups. Among these, alicyclic ether groups or vinyloxy groups are preferred, and epoxy groups, oxetanyl groups, or vinyloxy groups are particularly preferred.

[0060] Furthermore, in the present invention, a liquid crystal compound exhibiting inverse wavelength dispersion may be used as the liquid crystal compound. Herein, in this specification, a "reverse wavelength dispersive" liquid crystal compound refers to a compound in which, when the in-plane retardation (Re) value of a phase difference film made using the same is measured at a specific wavelength (visible light range), the Re value becomes equivalent or higher as the measured wavelength increases.

[0061] In this invention, the liquid crystal compound may be used alone or in combination of two or more types. The liquid crystal compound content is preferably 10 to 99% by mass, and more preferably 50 to 95% by mass, relative to the total solid content (100% by mass) of the liquid crystal composition.

[0062] 〔solvent〕 The liquid crystal composition of the present invention preferably contains a solvent. Examples of solvents include ketones [e.g., acetone, 2-butanone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, cyclopentanone (CPO), etc.], ethers [e.g., dioxane, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate (PGMEA), etc.], aliphatic hydrocarbons [e.g., hexane, etc.], alicyclic hydrocarbons [e.g., cyclohexane, etc.], aromatic hydrocarbons [e.g., toluene, xylene, trimethylbenzene, etc.], and halogenated carbons [e.g., di Examples include chloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc., esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (e.g., methanol (MeOH), ethanol, isopropyl alcohol (IPA), butanol, cyclohexanol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), and amides (e.g., dimethylformamide, dimethylacetamide, etc.). These solvents may be used individually or in combination of two or more.

[0063] [Polymerization initiator] The liquid crystal composition of the present invention preferably contains a polymerization initiator. As a polymerization initiator, a photopolymerization initiator that can initiate the polymerization reaction by ultraviolet irradiation is preferred. Examples of photopolymerization initiators include α-carbonyl compounds, acyloin ethers, α-hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, combinations of triarylimidazole dimers and p-aminophenyl ketones, acridine and phenazine compounds and oxadiazole compounds, and acylphosphine oxide compounds. Oxime-type polymerization initiators are also preferred as polymerization initiators. Specific examples include the initiators described in paragraphs

[0049] to

[0052] of International Publication No. 2017 / 170443.

[0064] [Other ingredients] The liquid crystal composition of the present invention may contain other components besides those described above. Examples of other components include tilt angle control agents, plasticizers, and crosslinking agents.

[0065] [Liquid crystal hardening layer] The liquid crystal curing layer of the present invention is a liquid crystal curing layer obtained by fixing the orientation state of the liquid crystal composition of the present invention as described above. Examples of methods for forming a liquid crystal hardened layer include using the liquid crystal composition of the present invention described above to achieve a desired orientation state, and then fixing it by polymerization. Here, the conditions for achieving the desired orientation state are not particularly limited, but it is preferable to perform a heat treatment, and it is more preferable to perform a cooling treatment after the heat treatment. The heating temperature in the heat treatment is preferably 10 to 250°C, more preferably 50 to 200°C, and even more preferably 70 to 150°C, from the viewpoint of machinability. The heating time in the heat treatment is preferably 1 to 300 seconds, and more preferably 1 to 60 seconds. The temperature in the cooling treatment after the heat treatment is not particularly limited as long as it is lower than the heating temperature in the heat treatment, but it is preferably room temperature (23°C) to 80°C. In addition, the conditions for the above polymerization are not particularly limited. However, in the case of polymerization by light irradiation, it is preferable to use ultraviolet light. The irradiation amount is preferably 10 mJ / cm 2 ~50 J / cm 2 preferably, 20 mJ / cm 2 ~5 J / cm 2 more preferably, 30 mJ / cm 2 ~3 J / cm 2 even more preferably, 50~1000 mJ / cm 2 particularly preferably. Further, in order to accelerate the polymerization reaction, it may be carried out under heating conditions.

[0066] As the alignment state of the liquid crystal compound in the liquid crystal cured layer of the present invention, any of horizontal alignment, vertical alignment, tilted alignment, and twisted alignment may be used.

[0067] The thickness of the liquid crystal cured layer of the present invention is not particularly limited, but is preferably 0.1~10 μm, more preferably 0.5~5 μm.

[0068] [Optical film] The optical film of the present invention is an optical film having the liquid crystal cured layer of the present invention.

[0069] [Substrate] The optical film of the present invention may have a substrate for supporting the liquid crystal cured layer of the present invention. Such a substrate is preferably transparent. In the present invention, "transparent" means that the transmittance of visible light is 60% or more, preferably 80% or more, and more preferably 90% or more.

[0070] Examples of the above substrate include a glass substrate and a polymer film. Examples of polymer film materials include cellulose polymers; acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene polymers; polycarbonate polymers; polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin); polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymer; vinyl chloride polymers; amide polymers such as nylon and aromatic polyamides; imide polymers; sulfone polymers; polyethersulfone polymers; polyetheretherketone polymers; polyphenylene sulfide polymers; vinylidene chloride polymers; vinyl alcohol polymers; vinyl butyral polymers; arylate polymers; polyoxymethylene polymers; epoxy polymers; and polymers obtained by mixing these polymers. The thickness of the above-mentioned substrate is not particularly limited, but is preferably 1 to 200 μm, and more preferably 2 to 100 μm. The substrate is preferably peelable.

[0071] Furthermore, in the present invention, the substrate may be a liquid crystal curing layer 2 (particularly an optically anisotropic layer) different from the liquid crystal curing layer of the present invention.

[0072] [Orientation film] The liquid crystal cured layer and any other liquid crystal cured layer in the optical film of the present invention may be formed on the surface of an alignment film (in particular, a photo-alignment film described later).

[0073] The alignment film can be any film that has the function of aligning the liquid crystal compounds contained in the composition. Alignment films are generally composed primarily of polymers. Numerous polymer materials for alignment films are described in various publications, and many commercially available products are available. As polymer materials for alignment films, polyvinyl alcohol, polyimide, or derivatives thereof are preferred, with modified or unmodified polyvinyl alcohol being more preferred. Examples of alignment films that an optical film may have include the alignment film described on page 43, line 24 to page 49, line 8 of International Publication No. 01 / 88574; the alignment film made of modified polyvinyl alcohol described in paragraphs

[0071] to

[0095] of Japanese Patent Publication No. 3907735; and the liquid crystal alignment film formed by the liquid crystal alignment agent described in Japanese Patent Application Publication No. 2012-155308.

[0074] It is also preferable to use a photo-alignment film as the alignment film, as this prevents objects from coming into contact with the surface of the alignment film during its formation, thus preventing deterioration of the surface quality. The photo-alignment film is not particularly limited, but can be an alignment film formed from polymer materials such as polyamide compounds and polyimide compounds as described in paragraphs

[0024] to

[0043] of International Publication No. 2005 / 096041; a liquid crystal alignment film formed from a liquid crystal alignment agent having photo-aligning groups as described in Japanese Patent Application Publication No. 2012-155308; or Rolic Technologies' trade name LPP-JP265CP, etc.

[0075] The thickness of the orientation film is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm, and even more preferably 0.01 to 0.5 μm.

[0076] [Polarizing plate] The polarizing plate of the present invention is preferably a polarizing plate having the optical film of the present invention described above and a polarizer.

[0077] [Polarizer] The polarizer in the polarizing plate of the present invention is not particularly limited as long as it is a material that has the function of converting light into a specific linear polarization, and conventionally known absorpting polarizers and reflective polarizers can be used. Absorbing polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. Iodine-based and dye-based polarizers include coated polarizers and stretched polarizers, both of which are applicable, but polarizers made by adsorbing iodine or a dichroic dye onto polyvinyl alcohol and then stretching it are preferred. Furthermore, as a method for obtaining a polarizer by stretching and dyeing a laminated film in which a polyvinyl alcohol layer is formed on a substrate, examples include those described in Japanese Patent Publication No. 5048120, Japanese Patent Publication No. 5143918, Japanese Patent Publication No. 4691205, Japanese Patent Publication No. 4751481, and Japanese Patent Publication No. 4751486, and these known technologies related to polarizers can also be preferably utilized. Reflective polarizers include polarizers made by stacking thin films with different birefringences, wire grid polarizers, and polarizers that combine a cholesteric liquid crystal with a selective reflection range and a quarter-wave plate. In particular, polarizers containing polyvinyl alcohol-based resin (polymers containing -CH2-CHOH- as repeating units; at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers) are preferred because they offer superior adhesion.

[0078] In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 5 to 40 μm, more preferably 5 to 30 μm, and even more preferably 5 to 20 μm. With the above thickness, it is possible to make the display device thinner.

[0079] [Image display device] The image display device of the present invention is an image display device having the optical film or polarizing plate of the present invention (hereinafter collectively referred to as "the optical film, etc." of the present invention). The display elements used in the image display device are not particularly limited, and examples include liquid crystal cells, organic electroluminescent (hereinafter abbreviated as "EL (Electro Luminescence)") display panels, and plasma display panels. Of these, liquid crystal cells and organic EL display panels are preferred, and organic EL display panels are more preferred. In other words, as the image display device, a liquid crystal display device using a liquid crystal cell as the display element, or an organic EL display device using an organic EL display panel as the display element is preferred, and an organic EL display device is more preferred.

[0080] [Liquid crystal display device] An example of an image display device is a liquid crystal display device having an optical film or the like of the present invention and a liquid crystal cell. Furthermore, it is preferable to use the optical film of the present invention as the front polarizing plate among the polarizing plates provided on both sides of the liquid crystal cell, and it is more preferable to use the optical film of the present invention as both the front and rear polarizing plates.

[0081] [Organic EL display device] An example of an image display device is an organic EL display device, which includes, for instance, a polarizing plate of the present invention (a polarizing plate with a polarizer positioned on the viewing side) and an organic EL display panel, in that order from the viewing side. Furthermore, an organic EL display panel is a display panel constructed using an organic EL element in which an organic light-emitting layer (organic electroluminescent layer) is sandwiched between electrodes (between the cathode and the anode). The configuration of the organic EL display panel is not particularly limited, and known configurations can be adopted.

[0082] [Lithographic printing plate original plate] The lithographic printing plate of the present invention comprises a support and an image recording layer provided on the support, wherein the image recording layer contains the copolymer of the present invention described above. Hereinafter, the support and the components of the image recording layer other than the copolymer of the present invention, as well as other layers (e.g., undercoat layer, backcoat layer, etc.), can be those described in paragraphs

[0079] to

[0304] of International Publication No. 2024 / 117242. These descriptions are incorporated herein by reference. [Examples]

[0083] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0084] [Example 1] [Preparation of alkali-saponified cellulose acylate film] A cellulose acylate film (TG40, manufactured by Fujifilm Corporation) was prepared as the base material. The cellulose acylate film was passed through a dielectric heating roll at a temperature of 60°C to raise the film surface temperature to 40°C. Then, an alkaline solution with the composition shown below was applied to the band surface of the film using a bar coater at a rate of 14 ml / m². 2 The material was coated and then transported for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Co., Limited, heated to 110°C. Subsequently, 3 ml / m2 of pure water was applied using a bar coater. After that, the material was washed with water using a fountain coater and dewatered with an air knife three times, and then transported to a 70°C drying zone for 10 seconds to dry, thereby producing an alkaline saponified cellulose acylate film.

[0085] ------------------------------------------------------------------ Alkaline solution ------------------------------------------------------------------ • Potassium hydroxide 4.7 parts by mass ·Water 15.8 parts by mass Isopropanol 63.7 parts by mass • Surfactant SF-1:C 14 H 29 O(CH2CH 2O ) 20 H 1.0 parts by mass • Propylene glycol 14.8 parts by mass ------------------------------------------------------------------

[0086] [Formation of orientation film] An orientation film coating solution with the following composition was continuously applied to the surface of a cellulose acylate film that had undergone alkali saponification using a #14 wire bar. It was dried with 60°C hot air for 60 seconds, and then with 100°C hot air for 120 seconds. The degree of saponification of the modified polyvinyl alcohol used was 96.8%.

[0087] ------------------------------------------------------------------ Orientation film coating solution ------------------------------------------------------------------ • 10 parts by mass of the following modified polyvinyl alcohol-1 ·Water 170 parts by mass • Methanol 57 parts by mass ------------------------------------------------------------------

[0088] Modified polyvinyl alcohol-1 [In the formula, the numerical values ​​listed for each repeating unit represent the content (mol%) of each repeat relative to the total number of repeating units.] [ka]

[0089] [Formation of a liquid crystal hardened layer (fabrication of an optical film)] The cellulose acylate film prepared as described above was continuously rubbed on the orientation side. At this time, the longitudinal direction of the long film and the transport direction were parallel, and the angle between the longitudinal direction of the film (transport direction) and the rotation axis of the rubbing roller was set to 77.0°. If the longitudinal direction of the film (transport direction) is set to 90°, and observing from the film side, with the film width direction as the reference (0°) and counterclockwise rotation represented as a positive value, the rotation axis of the rubbing roller is at 13.0°. In other words, the position of the rotation axis of the rubbing roller is the position obtained by rotating 77.0° clockwise with respect to the longitudinal direction of the film.

[0090] Using the cellulose acylate film treated with the above rubbing process as a substrate, a liquid crystal composition (1) containing a rod-shaped liquid crystal compound of the following composition was applied using a Gieser coating machine to form a composition layer. The absolute value of the weighted average helical induced force of the chiral agent in the composition layer in step 1 was 0.0 μm-1. Next, the resulting composition layer was heated at 80°C for 60 seconds. This heating caused the rod-shaped liquid crystal compounds in the composition layer to be oriented in a predetermined direction. Subsequently, under oxygen-containing air (oxygen concentration: approximately 20 vol%) at 30°C, ultraviolet light was irradiated onto the composition layer using a 365 nm LED lamp (manufactured by Acroedge Co., Ltd.) (irradiation dose: 70 mJ / cm²). 2 ). Next, the resulting composition layer was heated at 80°C for 10 seconds. Subsequently, nitrogen purging was performed to achieve an oxygen concentration of 100 ppm by volume, and ultraviolet light was irradiated onto the composition layer at 75°C using a metal halide lamp (manufactured by iGraphics Co., Ltd.) (irradiation dose: 500 mJ / cm²). 2 A liquid crystal cured layer (optically anisotropic layer) was formed with a fixed orientation state of the liquid crystal compound. An optical film was then fabricated.

[0091] ------------------------------------------------------------------ Liquid crystal composition (1) ------------------------------------------------------------------ • 80 parts by mass of the following rod-shaped liquid crystal compound (A) • 17 parts by mass of the following precipitation-inhibiting compound (A) • 3 parts by mass of the following precipitation-inhibiting compound (B) • Ethylene oxide-modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) 4 parts by mass • Photopolymerization initiator (Ominirad.819) IGM Resins BV) 3 parts by mass • 0.48 parts by mass of the following left-handed chiral agent (L1) • 0.43 parts by mass of the following right-handed chiral agent (R1) • 0.08 parts by mass of copolymer B-1 as described in Table 1 below. • Methyl isobutyl ketone 72 parts by mass • Ethyl propionate 72 parts by mass ------------------------------------------------------------------

[0092] Rod-shaped liquid crystal compound (A) [A mixture of the following liquid crystal compounds (RA), (RB), and (RC) in a mass ratio of 84:14:2] [ka]

[0093] Precipitation-inhibiting compound (A) [In the following formula, Me represents a methyl group.] [ka]

[0094] Precipitation inhibiting compound (B) [ka]

[0095] Left-hand torsional chiral agent (L1) [In the formula below, Bu represents a methyl group.] [ka]

[0096] Right-handed chiral agent (R1) [ka]

[0097] The optical film prepared as described above was cut parallel to the rubbing direction, and the liquid crystal hardened layer was observed from the cross-sectional direction using a polarizing microscope. The thickness of the liquid crystal hardened layer was 2.6 μm. The region on the substrate side of the liquid crystal hardened layer with a thickness (d2) of 1.3 μm (second region) showed homogeneous orientation with no twist angle, while the region on the air side (opposite the substrate) of the liquid crystal hardened layer with a thickness (d1) of 1.3 μm (first region) showed twisted orientation of the liquid crystal compound. Furthermore, the optical properties of the optical film were determined using Axometrics' Axoscan and its analysis software (Multi-Layer Analysis). The product of Δn2 and thickness d2 (nm) at a wavelength of 550 nm in the second region (Δn2d2) was 178 nm, the torsion angle of the liquid crystal compound was 0°, and the orientation axis angle of the liquid crystal compound with respect to the long longitudinal direction was -11.0° on the side in contact with the substrate and -11.0° on the side in contact with the first region. Furthermore, the product of Δn1 and thickness d1 (nm) at a wavelength of 550 nm in the first region (Δn1d1) was 180 nm, the torsion angle of the liquid crystal compound was 88°, and the orientation axis angle of the liquid crystal compound with respect to the longitudinal direction was -11.0° on the side in contact with the second region and -91.0° on the air side. The orientation axis angle of the liquid crystal compound contained in the liquid crystal curing layer is expressed by observing the substrate from the surface side of the liquid crystal curing layer, with the longitudinal direction of the substrate being the reference 0°, and clockwise (rightward) rotation being negative and counterclockwise (leftward) rotation being positive. Furthermore, the torsional structure of the liquid crystal compound is expressed here by observing the substrate from the surface side of the liquid crystal hardened layer, and using the orientation axis direction of the liquid crystal compound on the surface side (front side) as a reference, a clockwise (rightward) orientation axis direction of the liquid crystal compound on the substrate side (backward side) is represented as negative, and a counterclockwise (leftward) orientation axis direction is represented as positive.

[0098] [Fabrication of polarizers] A polyvinyl alcohol (PVA) film with a thickness of 80 μm was stained by immersion in an iodine aqueous solution with an iodine concentration of 0.05 mass% at 30°C for 60 seconds. Next, the obtained film was stretched longitudinally to five times its original length while immersed in a boric acid aqueous solution with a boric acid concentration of 4 mass% for 60 seconds, and then dried at 50°C for 4 minutes to obtain a polarizer with a thickness of 20 μm.

[0099] [Fabrication of polarizer protective film] A commercially available cellulose acylate film, Fujitac TG40UL (manufactured by Fujifilm Corporation), was prepared and immersed in a 1.5 mol / liter sodium hydroxide aqueous solution at 55°C. After that, the sodium hydroxide was thoroughly rinsed off with water. Subsequently, the resulting film was immersed in a 0.005 mol / liter dilute sulfuric acid aqueous solution at 35°C for 1 minute, and then immersed in water to thoroughly rinse off the dilute sulfuric acid solution. Finally, the resulting film was thoroughly dried at 120°C to produce a polarizer protective film with a saponified surface.

[0100] [Fabrication of circular polarizing plates] The optical film prepared as described above was subjected to saponification treatment in the same manner as the preparation of the polarizer protective film described above. Subsequently, the polarizer and polarizer protective film described above were continuously bonded to the substrate surface contained in the optical film using a polyvinyl alcohol-based adhesive to produce a long circular polarizer. In other words, the circular polarizer consisted of a polarizer protective film, a polarizer, a substrate, and a liquid crystal curing layer, in that order. Furthermore, the absorption axis of the polarizer coincided with the longitudinal direction of the circular polarizer, the rotation angle of the in-plane slow axis of the second region with respect to the absorption axis of the polarizer was 11.0°, and the rotation angle of the in-plane slow axis of the surface of the first region opposite to the second region with respect to the absorption axis of the polarizer was 91.0°. The rotation angle of the in-plane slow axis described above is determined by observing the liquid crystal hardened layer from the polarizer side, with the longitudinal direction of the substrate set as the reference 0°, and expressing the angle as positive for counterclockwise rotation and negative for clockwise rotation.

[0101] [Examples 2-17] An optical film and a circular polarizer are prepared in the same manner as in Example 1, except that the copolymer shown in Table 1 below is used instead of copolymer B-1. Note that the types of repeating units A and B listed in Table 1 below are the same as the repeating units exemplified above for each repeating unit.

[0102] [Comparative Example 1] An optical film and a circular polarizer are prepared in the same manner as in Example 1, except that copolymer C-1 shown in Table 1 below is used instead of copolymer B-1. Comparative Example 1 is an example corresponding to Patent Document 1 (Patent No. 7151909).

[0103] 〔evaluation〕 (1) On an 18 x 30 cm substrate that has not undergone rubbing treatment, the liquid crystal composition used for forming the liquid crystal curing layer in each example and comparative example is applied, and a wind of 1.0 m / min is applied for 30 seconds from 10 to 40 seconds after application in a direction parallel to the substrate and consistent with the application direction. Next, the above film is sandwiched between two polarizing plates arranged in crossed nicols, and light is transmitted from bottom to top (towards the observer). After 80 seconds, the unevenness of color and brightness is observed and evaluated according to the following criteria. The results are shown in Table 1 below. A: No unevenness is visible across the entire surface. B: Slight unevenness is visible in some areas. C: Slight unevenness is visible across the entire surface. D: Significant unevenness is visible across the entire surface.

[0104] (2) Hajiki Five 18 x 30 cm films are randomly cut from each optical film prepared in each example and comparative example. The number of "rejects" in the liquid crystal curing layer is counted, and the average number of rejects is calculated. Rejects refer to areas where the liquid crystal curing layer has not been formed. Rejects are areas that remain dark even when the sample is rotated, when a sample consisting of an optical film containing a liquid crystal curing layer and a support without a liquid crystal curing layer is laminated with a 90° offset, and observed under crossed nicol conditions using a polarizing microscope in transmission mode. Based on these results, the following criteria are used for evaluation. The results are shown in Table 1 below. A: 0 shots B: 1 or more but less than 20 C: 20 or more but less than 60 D: More than 60 bullets

[0105] (3) Adhesion to the roll The optical films prepared in each example and comparative example were sandwiched between SUS (stainless steel) plates, roll-pressed at a linear pressure of 5 MPa, and evaluated according to the following evaluation criteria. The results are shown in Table 1 below. Furthermore, the optical film after roll pressing is observed using a polarizing microscope, with the liquid crystal coated surface of the optical film facing the objective lens, and the longitudinal direction of the optical film set to 0°, the upper polarizer to 20°, and the lower polarizer to 315°. When observed, the absence of localized brightness and color differences is evaluated as the liquid crystal director being uniformly oriented (excellent orientation). <Evaluation Method> The results observed using the above observation method were classified according to the following criteria. The results are shown in Table 1 below. A: Visual inspection revealed no deposits on the SUS plate, and the orientation was not disordered. B: No deposits were visible on the SUS plate, but the orientation was disordered. C: Visual inspection revealed that some deposits were present on the SUS plate, and its orientation was disordered. D: Visual inspection revealed deposits on the entire surface of the SUS plate, and the orientation was disordered.

[0106] [Table 1]

[0107] The results shown in Table 1 indicate that when a copolymer without repeating unit B represented by formula (1) is used, there is room for improvement in the effect of suppressing unevenness and repellency, and there is also a problem of it sticking to the roll side (Comparative Example 1). In contrast, when a copolymer having repeating units A and B, wherein the number-average molecular weight of the monomers constituting repeating unit B is 500 or more and 20,000 or less is used, it can be seen that a layer can be formed in which unevenness and repulsion are suppressed, and adhesion to the roll is also suppressed (Examples 1 to 17). In particular, a comparison between Examples 1 and 6-9 shows that when the content of repeating unit A is 40-85% by mass relative to the total mass of repeating unit A and repeating unit B (described later), a layer with more suppressed unevenness can be formed. Furthermore, a comparison between Example 1 and Example 11 reveals that when the monomer constituting the repeating unit B exhibits crystalline properties, it is possible to form a layer in which adhesion to the roll is more suppressed. Furthermore, a comparison between Example 1 and Example 17 shows that when Rk in formula (1) represents a potentially substituted monovalent aromatic group, a potentially substituted monovalent heterocyclic group, or an alkyl group, it is possible to form a layer in which adhesion to the roll is more suppressed. Furthermore, a comparison of Examples 1, 4, and 5 shows that when a copolymer with a weight-average molecular weight of 5000 or more is used, a layer with more suppressed adhesion to the roll can be formed. Furthermore, a comparison of Examples 1 to 3 shows that when a copolymer with a weight-average molecular weight of 80,000 or less is used, a layer with more suppressed repulsion can be formed.

[0108] [Creation of lithographic printing plates] Except for using polymer B-1 as the polymer used to form image recording layer A, the lithographic printing plate was prepared in the same manner as described in paragraphs

[0334] to

[0364] of International Publication No. 2024 / 117242.

[0109] 〔evaluation〕 (1) The lithographic printing plate to be produced is processed to 40cm x 62cm. The outermost surface of the resulting sample is visually observed under white light illumination of 750-1500 Lux, and the uniformity is evaluated according to the following criteria. -standard- A: No unevenness is visible across the entire surface. B: Slight unevenness is visible in some areas. C: Slight unevenness is visible across the entire surface. D: Significant unevenness is visible across the entire surface.

[0110] (2) Hajiki The lithographic printing plate to be produced is processed to 40cm x 62cm. The outermost surface of the resulting sample is visually observed under white light illumination of 750-1500 Lux, and the repellency is evaluated according to the following criteria. A: 0 shots B: 1 or more but less than 40 C: There are 40 or more but less than 100 bullets. C: More than 100 bullets

[0111] (3) Adhesion to the roll The lithographic printing plates to be produced will be sandwiched between SUS (stainless steel) plates, roll-pressed at a linear pressure of 5 MPa, and evaluated according to the following evaluation criteria. <Evaluation Method> The results of observations made using the above observation method will be classified according to the following criteria. A: No deposits are visible on the SUS plate. B: Some deposits are visible on the SUS plate. C: Visually, a thin layer of deposits is visible across the entire surface of the SUS plate. D: Visible to the naked eye, deposits are clearly visible all over the SUS plate.

[0112] The evaluation results for all the lithographic printing plates produced were "A," indicating that it is possible to form an image recording layer with suppressed unevenness and bleed, as well as reduced adhesion to the roll.

Claims

1. A copolymer having repeating units A derived from hydrophobic monomers and repeating units B represented by the following formula (1), wherein the number-average molecular weight of the monomers constituting the repeating unit B is 500 or more and 20,000 or less. 【Chemistry 1】 Here, in equation (1) above, R １１ and R １２ Each of these independently represents either a hydrogen atom or an alkyl group. R １３ represents a hydrogen atom or substituent. L １１ is -O- or -NR Ｚ Represents -. R Ｚ represents a hydrogen atom or substituent. L １２ This represents a divalent linking group. L １３ This represents a urethane bond, amide bond, or urea bond. Rk represents a substituent.

2. The copolymer according to claim 1, wherein the content of the repeating unit A is 40 to 85% by mass relative to the total mass of the repeating unit A and the repeating unit B.

3. The copolymer according to claim 1, wherein the monomer constituting the repeating unit B exhibits crystalline properties.

4. The copolymer according to claim 1, wherein Rk in formula (1) represents a substituted monovalent aromatic group, a substituted monovalent heterocyclic group, or an alkyl group. Here, among -CH that constitutes a part of the alkyl group ２ -, one or two or more non-adjacent -CH ２ - may be substituted with -O- or -CO-.

5. The copolymer according to claim 1, which does not have a photo-orienting group.

6. The copolymer according to claim 1, wherein the repeating unit A is represented by any of the following formulas (2) to (4). 【Chemistry 2】 Here, in equations (2) to (4) above, m represents an integer from 2 to 16, n represents an integer from 2 to 10000, and p represents an integer from 1 to 8. R １１ and R １２ Each of these independently represents either a hydrogen atom or an alkyl group. R １３ represents a hydrogen atom or substituent. L １１ is -O- or -NR Ｚ Represents -. R Ｚ represents a hydrogen atom or substituent. L ２１ This represents an m+1 valent linking group. L ２２ This represents a single bond or a divalent linking group. L ２３ This represents a single bond or a p+1 valent linking group. R ２１ ~R ２５ Each of these independently represents an alkyl group, alkenyl group, aryl group, or alkylenearyl group, which may have substituents. However, in formula (2) above, multiple R ２１ These may be the same or different, and there may be multiple R ２２ These may be the same or different, and there may be multiple R ２３ These may be the same or different. Also, in formula (3) above, multiple R ２４ These may be the same or different, and there may be multiple R ２５ These may be the same or different. X represents an alkyl group having 4 to 40 carbon atoms and having two or more terminal methyl groups. However, if p is an integer from 2 to 8, multiple Xs may be the same or different.

7. The copolymer according to claim 1, wherein the weight-average molecular weight is 5,000 or more and 80,000 or less.

8. A liquid crystal composition comprising a copolymer according to any one of claims 1 to 7 and a liquid crystal compound.

9. The liquid crystal composition according to claim 8, wherein the liquid crystal compound is a polymerizable liquid crystal compound.

10. The liquid crystal composition according to claim 9, wherein the polymerizable liquid crystal compound is at least one polymerizable liquid crystal compound selected from the group consisting of polymerizable rod-shaped liquid crystal compounds and polymerizable disc-shaped liquid crystal compounds.

11. A liquid crystal cured layer having the orientation state of the liquid crystal composition described in claim 8 fixed.

12. An optical film having the liquid crystal curing layer described in claim 11.

13. A polarizing plate comprising the optical film described in claim 12 and a polarizer.

14. An image display device having the optical film described in claim 12.

15. A lithographic printing plate comprising a support and an image recording layer provided on the support, wherein the image recording layer contains the copolymer described in any one of claims 1 to 7.

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