Novel polymers and photo-alignment films and retardation films using the same

Abstract

The present invention provides: a polymer which has a repeating unit represented by general formula (I); and a photo-alignment film and a retardation film, each of which contains this polymer. (In general formula (I), each of Ma-c represents a moiety that forms the main chain of a copolymer; each of l, m and n represents a molar fraction of the copolymer; each of SPCRa-c represents a spacer unit; each of rings A-C represents a specific alicyclic hydrocarbon or an aromatic ring; X represents a covalent single bond, a C1-10 alkylene chain or a C3-8 cycloalkylene chain; Y represents a covalent single bond, a specific C1-10 alkylene chain, a C3-8 cycloalkylene chain, -O-, -COO-, or a combination thereof; Z represents -O-CO-CH=CH2-; R1 represents -CW=CH2 or -V-CW=CH2; and R2 represents a hydrogen atom, a C1-6 alkyl group, or a phenyl group having a specific substituent.)

Description

[Technical Field]

[0001] The present disclosure relates to a novel polymer, a photo-alignment film, and a retardation film, and more specifically to a novel polymer having, in the molecule, a side chain having a carboxylic acid group at the end, a side chain having a polymerizable group at the end, and a side chain having an aryl acrylic acid ester moiety; a composition for a photo-alignment film containing the polymer; a photo-alignment film in which a film made of the composition is imparted with liquid crystal alignment ability; and a retardation film in which a liquid crystal compound is aligned on the photo-alignment film. [Background technology]

[0002] In recent years, retardation films (optically anisotropic films) have been used in various forms in the field of displays (such as liquid crystal displays and organic electroluminescence (EL) displays). Such retardation films are manufactured by applying liquid crystal compounds, dyes, conductive compounds, etc. to an alignment film (or substrate) that has the ability to align liquid crystals, followed by alignment. One known alignment method is photoalignment, in which the alignment film is irradiated (exposed) to light such as ultraviolet light to generate an alignment control force in the alignment film and / or change the alignment control direction of the alignment film. Alignment films used for photoalignment are called photoalignment films. Furthermore, in response to the recent trend toward higher performance and greater flexibility in displays, the diversification of laminates has progressed. For this reason, alignment films are required to have high alignment properties for a variety of laminates and adhesion to the laminated materials.

[0003] It is generally known that the alignment of a photo-alignment film can be improved by incorporating liquid crystals into the photo-alignment group. Furthermore, the introduction of cross-linking groups has been used to provide adhesion to the photo-alignment film. However, liquid crystals often result in poor adhesion due to their structure, and the cross-linking groups incorporated to provide adhesion are not liquid crystalline, so there is a trade-off between high alignment in the photo-alignment film and improved adhesion.

[0004] In an attempt to provide a photo-alignment film with photo-alignment ability and improve adhesion, for example, Patent Document 1 describes a technology that uses a layer A formed from a composition containing a photo-alignment polymer and a compound having at least two isocyanate groups, and a layer B formed from a composition containing a polymerizable liquid crystal compound, a compound having at least two isocyanate groups, and a photopolymerization initiator, to provide adhesion between the layer A and the layer B.

[0005] Furthermore, Patent Document 2 discloses a polyimide compound obtained by reacting a diamine component having a photodimerizable photoalignment group and an acrylic group in the same side chain with a tetracarboxylic acid anhydride as a liquid crystal aligning agent that can improve the response speed of a liquid crystal display element without adding a photopolymerizable compound. This polyimide compound is expected to have good adhesion because it has an acrylic group at the end of the side chain. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-148805 [Patent Document 2] International Publication No. 2013 / 099804 Summary of the Invention [Problem to be solved by the invention]

[0007] The technology of Patent Document 1 requires that both the A layer and the B layer contain an isocyanate compound, which limits the degree of freedom in materials, and the inclusion of the isocyanate compound is expected to shorten the pot life of the resist.

[0008] The material of Patent Document 2 requires a high-temperature process to form a polyimide film, which makes it difficult to apply to flexible films and the like, and has the problem of high production costs.

[0009] In view of the above problems, the present disclosure aims to provide a novel polymer that, when used in a photo-alignment film, can exhibit good alignment properties that enable the liquid crystal layer to exhibit liquid crystal alignment ability and good adhesion to the liquid crystal layer, as well as a photo-alignment film and a retardation film containing the same. [Means for solving the problem]

[0010] The present disclosure provides: [1] General formula (I): [ka] [In the formula, M a , M b and M c represents the portion of the monomer units of the copolymer that forms the backbone of the copolymer; l, m, and n represent the mole fractions of the copolymer and are in each case 0 <l<1かつ0<m<1かつ0<n<1であり; SPCRa, SPCRb, and SPCRc each independently represent a spacer unit; Ring A, ring B, and ring C are each independently an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring; X is a single covalent bond, an alkylene chain having 1 to 10 carbon atoms, or a cycloalkylene chain having 3 to 8 carbon atoms; Y is selected from the group consisting of a single covalent bond; an alkylene chain having 1 to 10 carbon atoms, which is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms; -O-; -COO-; and combinations thereof; Z is -O-CO-CH=C H- (either bond may be bonded to ring C); R 1 is -CW=CH2, or -V-CW=CH2 (wherein W is hydrogen or methyl and V is -O-CO- or -CO-); R 2is a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; a phenyl group having at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom, provided that when ring C is an alicyclic hydrocarbon, R 2 is a phenyl group having at least one substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom. A polymer having a repeating unit represented by the formula: [2] Ring A, ring B and ring C are each independently [ka] [In the formula, R 3 ~R 64 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. The polymer according to the above [1], wherein the group is represented by the following formula (either bond may be bonded to each spacer unit): [3] Ring A is [ka] [In the formula, R 3 ~R 14 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. is a group represented by Ring B is [ka] [In the formula, R 7 ~R 14 , R 33 ~R 64 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. (either bond may be bonded to the spacer unit), Ring C is [ka] [In the formula, R 3 ~R 6 , R 33 ~R 40 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. The polymer according to the above item [2], wherein the group is represented by the following formula (either bond may be bonded to the spacer unit): [4] The polymer according to any one of the above [1] to [3], wherein SPCRa, SPCRb, and SPCRc are each independently a covalent single bond; an alkylene chain having 1 to 20 carbon atoms which is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms which is unsubstituted or substituted with a hydroxyl group; a phenylene which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, -CN, -NO2, and a halogen; -O-; -COO-; or a combination thereof. [5] The polymer according to the above [4], wherein SPCRa, SPCRb, and SPCRc are each independently an alkylene chain having 1 to 20 carbon atoms which is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; -O-; -COO-; or a combination thereof. [6] The polymer according to any one of the above [1] to [5], wherein Y is a combination of an alkylene chain having 1 to 10 carbon atoms, which is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group, and -O- or -COO-. [7] A composition for a photo-alignment film, comprising the polymer according to any one of [1] to [6] above. [8] A photo-alignment film formed from the composition for a photo-alignment film according to [7] above. [9] A retardation film in which a liquid crystal compound is further aligned on the photo-alignment film according to the above [8]. Regarding. [Effects of the Invention]

[0011] When the polymer of the present disclosure is used in a photo-alignment film, it exhibits good alignment that can exert the liquid crystal alignment ability of the liquid crystal layer and good adhesion to the liquid crystal layer, and by using the photo-alignment film, it is possible to obtain a retardation film that has good photo-alignment properties and excellent adhesion to the liquid crystal compound. DETAILED DESCRIPTION OF THE INVENTION

[0012] In this specification, the terms "(meth)acrylic" and "(meth)acrylate" are general terms for "methacrylic" and "acrylic", "methacrylate" and "acrylate", respectively.

[0013] Furthermore, in this specification, dashed lines used in structural formulas mean that the structural units can be bonded to any of the dashed lines, and the polymer according to the present disclosure may be a random copolymer or a block copolymer of the structural units as long as the mole fractions are within the specified ranges.

[0014] According to a first embodiment of the present disclosure, a compound of general formula (I): [ka] [In the formula, M a , M b and M c represents the portion of the monomer units of the copolymer that forms the backbone of the copolymer; l, m, and n represent the mole fractions of the copolymer and are in each case 0 <l<1かつ0<m<1かつ0<n<1であり; SPCRa, SPCRb, and SPCRc each independently represent a spacer unit; Ring A, ring B, and ring C are each independently an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring; X is a single covalent bond, an alkylene chain having 1 to 10 carbon atoms, or a cycloalkylene chain having 3 to 8 carbon atoms; Y is selected from the group consisting of a single covalent bond; an alkylene chain having 1 to 10 carbon atoms, which is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms; -O-; -COO-; and combinations thereof; Z is -O-CO-CH=C H- (either bond may be bonded to ring C); R 1 is -CW=CH2, or -V-CW=CH2 (wherein W is hydrogen or methyl and V is -O-CO- or -CO-); R 2 is a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; a phenyl group having at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom, provided that when ring C is an alicyclic hydrocarbon, R 2 is a phenyl group having at least one substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom. There is provided a polymer (also referred to as polymer (I) in this specification) having a repeating unit represented by the following formula:

[0015] In this polymer (I), M a , M b and M c are the portions of the monomer units of the copolymer that form the main chain of the copolymer, and are not particularly limited as long as they can form a typical main chain of a copolymer in the art, but are, for example, each independently selected from the group consisting of ethylene, alkoxysilane, acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, acryloylphenylene, acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether, styrene derivative, vinyl ester, maleic acid derivative, fumaric acid derivative, siloxane, and epoxide. Among these, ethylene, acrylate, methacrylate, acrylamide, methacrylamide, etc. are preferred.

[0016] In this polymer (I), for example, a monomer unit having a carboxylic acid group at the terminal related to M a (hereinafter referred to as constitutional unit α), a monomer unit having a polymerizable group at the terminal related to M b (hereinafter referred to as constitutional unit β), and a monomer unit having an aryl acrylate moiety related to M c (hereinafter referred to as constitutional unit γ) can take the form of either a random copolymer or a block copolymer within the range of specified molar fractions. As the molar fractions, in the formula, they are represented by l, m, and n for constitutional unit α, constitutional unit β, and constitutional unit γ respectively. In any case, 0 < l < 1 and 0 < m < 1 and 0 < n < 1, and 0.1 ≦ l ≦ 0.9, 0.01 ≦ m ≦ 0.4, 0.05 ≦ n ≦ 0.5 are preferred, and 0.5 ≦ l ≦ 0.8, 0.05 ≦ m ≦ 0.1, 0.1 ≦ n ≦ 0.4 are more preferred. When l is 0.1 or more, the orientation can be enhanced more, and when l is 0.9 or less, the polymer (I) tends to be more easily dissolved in a variety of solvents. When m is 0.01 or more, the laminate can be oriented with a smaller amount of light irradiation, and when m is 0.4 or less, the orientation can be made better. When n is 0.05 or more, the adhesion to the laminate material can be made better, and when n is 0.5 or less, the orientation can be enhanced more.

[0017] In this polymer (I), SPCRa, SPCRb, and SPCRc each independently represent a spacer unit, and are preferably each independently selected from a covalent single bond; an alkylene chain having 1 to 20 carbon atoms that is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms that is unsubstituted or substituted with a hydroxyl group; a phenylene that is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, -CN, -NO2, and a halogen; -O-; -COO-; or a combination thereof, and more preferably each independently represent an alkylene chain having 1 to 20 carbon atoms that is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; -O-; -COO-; or a combination thereof.

[0018] The "alkylene chain having 1 to 20 carbon atoms" in the options for the spacer unit is not particularly limited, but is more preferably an alkylene chain having 1 to 10 carbon atoms, even more preferably an alkylene chain having 2 to 8 carbon atoms, and most preferably an alkylene chain having 4 to 6 carbon atoms.

[0019] The "cycloalkylene chain having 3 to 8 carbon atoms" in the above options for the spacer unit is not particularly limited, but is more preferably a cycloalkylene chain having 3 to 6 carbon atoms.

[0020] Specific examples of SPCRa, SPCRb and SPCRc include -(CH2)3-, -(CH2)6- and the like.

[0021] Furthermore, although SPCRa, SPCRb, and SPCRc are each independently selected, it is preferable to select them so that they all have approximately the same chain length, in terms of orientation and the like.

[0022] In this polymer (I), ring A is an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring, [ka] [In the formula, R 3 ~R 64 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group (any bond may be bonded to each spacer unit), [ka] [In the formula, R 3 ~R 14 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.

[0023] In this polymer (I), ring B is an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring, [ka] [In the formula, R 3 ~R 64 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group (either bond may be bonded to the spacer unit), [ka] [In the formula, R 7 ~R 14 , R 33 ~R 64 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. It is more preferable that the group is a group represented by the following formula (either bond may be bonded to the spacer unit):

[0024] In this polymer (I), ring C is an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring, [ka] [In the formula, R 3 ~R 64 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group (any bond may be bonded to each spacer unit), [ka] [In the formula, R 3 ~R 6 , R 33 ~R 40 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. Preferably, the group is a group represented by the following formula (either bond may be bonded to the spacer unit):

[0025] R in ring A, ring B and ring C 3 ~R 64 It is preferable that all of are hydrogen atoms.

[0026] In polymer (I), as described above, the structures of ring A, ring B, and ring C are determined independently, but ring A, ring B, and ring C are preferably selected in consideration of the fact that each monomer unit preferably has a similar length as a side chain in polymer (I). From the viewpoint of improving alignment, each monomer unit preferably has a structure that exhibits liquid crystallinity.

[0027] Therefore, specific combinations of ring A, ring B and ring C include: [ka] (Either bond may be bonded to the spacer unit) A combination of [ka] (Either bond may be bonded to the spacer unit) A combination of [ka] (Either bond may be bonded to the spacer unit) A combination of [ka] combination of, and [ka] (Each bond may be bonded to each spacer unit.) It is preferably selected from:

[0028] In this polymer (I), X is a covalent single bond, an alkylene chain having 1 to 10 carbon atoms, or a cycloalkylene chain having 3 to 8 carbon atoms, and is preferably a covalent single bond.

[0029] In this polymer (I), Y is selected from the group consisting of a covalent single bond; an alkylene chain having 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms; -O-; -COO-; and combinations thereof, and is preferably an alkylene chain having 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group and which is bonded to ring B via -O-, or an alkylene chain having 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group and which is bonded to ring B via -COO-.

[0030] The alkylene chain having 1 to 10 carbon atoms in X and Y is not particularly limited and may be a straight chain or a branched chain, more preferably an alkylene chain having 1 to 6 carbon atoms, and even more preferably a straight chain alkylene chain having 1 to 6 carbon atoms.

[0031] The cycloalkylene chain having 3 to 8 carbon atoms in X and Y is not particularly limited, but is more preferably a cycloalkylene chain having 3 to 6 carbon atoms.

[0032] In this polymer (I), Z is —O—CO—CH═C H- (either bond may be bonded to ring C), and it is preferable that the bond of the oxygen atom is bonded to ring C.

[0033] In this polymer (I), R 1 is -CW=CH2, or -V-CW=CH2 (wherein W is hydrogen or methyl, and V is -O-CO- or -CO-), with -O-CO-CH2=CH2 or -O-CO-CH(CH3)=CH2 being more preferred.

[0034] In this polymer (I), R 2 is a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; a phenyl group having at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom, provided that when ring C is an alicyclic hydrocarbon, R 2 R is a phenyl group having at least one substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom. 2 Preferred examples of include a phenyl group having an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, more preferably a phenyl group having an alkoxy group having 1 to 3 carbon atoms, even more preferably a p-alkoxyphenyl group, and most preferably a p-methoxyphenyl group.

[0035] The molecular weight of the polymer (I) is preferably 5,000 to 200,000 in terms of weight average molecular weight (Mw), and more preferably 20,000 to 120,000. A weight average molecular weight of 5,000 or more can easily prevent the photo-alignment film from dissolving in a solvent when a composition containing a laminate is applied to the photo-alignment film containing the polymer. A weight average molecular weight of 200,000 or less can further improve solubility in a solvent, thereby facilitating application of the curable resin composition to the substrate. The weight average molecular weight also affects the heating temperature during retardation film formation. The higher the weight average molecular weight, the higher the heating temperature required, and a weight average molecular weight of 200,000 or less is more preferable. In this specification, the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) as described in the Examples below, and is expressed as a polystyrene-equivalent value.

[0036] A method for producing polymer (I) of the present disclosure will be described below. Because polymer (I) has a polymerizable group at the end of structural unit β, copolymerizing structural unit α, structural unit β, and structural unit γ as monomers without modification would result in the polymerizable group at the end of structural unit β also participating in the polymerization, making it impossible to obtain the desired polymer (I) of the present disclosure. For this reason, in the production of polymer (I), a two-step reaction can be used in which a precursor of structural unit β (hereinafter referred to as structural unit β precursor) is used instead of structural unit β and copolymerized with structural unit α and structural unit γ (first reaction step), and then a polymerizable group is introduced to form structural unit β (second reaction step). In this case, for example, if the compound used to introduce the polymerizable group reacts with the carboxylic acid at the end of structural unit α during the reaction to introduce the polymerizable group into the precursor of structural unit β in the second reaction step, a structural unit α in which the carboxylic acid of structural unit α is protected with a protecting group (hereinafter referred to as structural unit α derivative) can be used as the structural unit α used in the first reaction step. In other words, the method for producing polymer (I) of the present disclosure is not particularly limited, but examples include a production method in which a structural unit α derivative, a structural unit β precursor, and a structural unit γ are copolymerized in a first reaction step, a polymerizable group is introduced into the structural unit β precursor to form the structural unit β in a second reaction step, and the structural unit α derivative is deprotected to form the structural unit α.

[0037] The first reaction step will now be described in detail. In the first reaction step, for example, the structural unit α derivative, the structural unit β precursor, and the structural unit γ are dissolved in an appropriate organic solvent together with an appropriate polymerization initiator to obtain a solution. An inert gas such as nitrogen is then bubbled through the resulting solution, and the reaction is then allowed to proceed at a temperature and for a time appropriate for completion of the reaction (for example, heated to 60°C and maintained for approximately 10 hours), and the resulting reaction solution is then cooled to room temperature.

[0038] The structural unit α is not particularly limited, but examples thereof include 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid, 4-(methacryloyloxy)benzoic acid, 4-((6-(methacryloyloxy)methyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)ethyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)propyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)butyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)pentyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)heptyl )oxy)benzoic acid, 4-((6-(methacryloyloxy)octyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)nonyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)decyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)dodecyl)oxy)benzoic acid, 4'-((6-(methacryloyloxy)hexyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid, 4'-((6-(methacryloyloxy)propyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid, 4'-(methacryloyloxy)-[1,1'-biphenyl]-4-carboxylic acid, 6-((6-(methacryloyloxy)hexyl)oxy)-2-naphthalenecarboxylic acid, 6-((6-(methacryloyloxy)propyl)oxy)-2-naphthalenecarboxylic acid, 6-(methacryloyloxy)-2-naphthalenecarboxylic acid, 2-fluoro-4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid, 4-((6-(acryloyloxy)hexyl)oxy)benzoic acid, 4-(acryloyloxy)hexyl)oxy)benzoic acid, 4-((6-(acryloyloxy)methyl)oxy)benzoic acid, 4-((6-(acryloyloxy)ethyl)oxy)benzoic acid, 4-((6-(acryloyloxy)propyl)oxy)benzoic acid, 4-((6-(acryloyloxy)butyl)oxy)benzoic acid, 4-((6-(acryloyloxy)pentyl)oxy)benzoic acid, 4-((6-(acryloyloxy)heptyl)oxy)benzoic acid, 4-((6 -(acryloyloxy)octyl)oxy)benzoic acid, 4-((6-(acryloyloxy)nonyl)oxy)benzoic acid, 4-((6-(acryloyloxy)decyl)oxy)benzoic acid, 4-((6-(acryloyloxy)dodecyl)oxy)benzoic acid, 4'-((6-(acryloyloxy)hexyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid, 4'-((6-(acryloyloxy)propyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid Examples of the structural unit α include 4'-(acryloyloxy)-[1,1'-biphenyl]-4-carboxylic acid, 4'-(acryloyloxy)-[1,1'-biphenyl]-4-carboxylic acid, 6-((6-(acryloyloxy)hexyl)oxy)-2-naphthalenecarboxylic acid, 6-((6-(acryloyloxy)propyl)oxy)-2-naphthalenecarboxylic acid, 6-(acryloyloxy)-2-naphthalenecarboxylic acid, and 2-fluoro-4-((6-(acryloyloxy)hexyl)oxy)benzoic acid. These structural units α may be used alone or in combination of two or more. As described above, the structural unit α is used as a structural unit α derivative in which the carboxylic acid of the structural unit α is protected as needed. The protecting group used to protect the carboxylic acid of the structural unit α is not particularly limited, but examples include a methoxymethyl group, a benzyl ether group, a p-methoxybenzyl group, a 3,Examples include a 4-dimethoxybenzyl group, a naphthylmethyl group, a methyl group, a tert-butyldimethylsilyl group, a triethylsilyl group, a tert-butyldiphenylsilyl group, a triisopropylsilyl group, and a tetrahydropyranyl group.

[0039] As the structural unit β precursor, a compound containing Mb-SPCRb-ring B in the above formula (I), in which a functional group such as a hydroxy group has been introduced into ring B, can be used. Specific examples include, but are not limited to, 6-(4-hydroxyphenoxy)hexyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate, 6-((4'-hydroxy-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate, 4-hydroxyphenyl methacrylate, 6-(4-hydroxyphenoxy)methyl methacrylate, 6-(4-hydroxyphenoxy)ethyl methacrylate, 6-(4-hydroxyphenoxy)propyl methacrylate, 6-(4-hydroxyphenoxy)butyl methacrylate, 6-(4-hydroxyphenoxy)pentyl methacrylate, 6-(4-hydroxyphenoxy)heptyl methacrylate, 6-(4-hydroxyphenoxy)octyl methacrylate, and 6-(4-hydroxyphenoxy)nonyl Methacrylate, 6-(4-hydroxyphenoxy)decyl methacrylate, 6-(4-hydroxyphenoxy)dodecyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)methyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)ethyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)propyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)butyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)pentyl Methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)heptyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)octyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)nonyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)decyl methacrylate, 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)dodecyl methacrylate, 6-((4'-(3-hydroxymethoxy)-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate, 6-((4'-(3-hydroxyethoxy)-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate, 6-((4'-(3-hydroxybutoxy)-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate, 6-((4'-(3-hydroxypentaoxy)-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate, 6-((4'-(3-hydroxyhexaoxy)-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate, etc. These structural unit β precursors may be used alone or in combination of two or more.

[0040] The structural unit γ is not particularly limited, but examples thereof include 4-((6-(methacryloyloxy)hexyl)oxy)phenyl (E)-3-(4-methoxyphenyl)acrylate, 4-(methacryloyloxy)phenyl (E)-3-(4-methoxyphenyl)acrylate, 4-((6-(methacryloyloxy)methyl)oxy)phenyl (E)-3-(4-methoxyphenyl)acrylate, 4-((6-(methacryloyloxy)ethyl)oxy)phenyl (E)-3-(4-methoxyphenyl)acrylate, 4-((6-(methacryloyloxy)propyl)oxy)phenyl (E)-3-(4-methoxyphenyl)acrylate, 4-((6-(methacryloyloxy)butyl)oxy)phenyl (E)-3-(4-methoxyphenyl)acrylate, and 4-((6-(methacryloyloxy)pentyl)oxy)phenyl (E)-3-(4-Methoxyphenyl)acrylate, 4-((6-(methacryloyloxy)heptyl)oxy)phenyl (E)-3-(4-Methoxyphenyl)acrylate, 4-((6-(methacryloyloxy)octyl)oxy)phenyl (E)-3-(4-Methoxyphenyl)acrylate, 4-((6-(methacryloyloxy)nonyl)oxy)phenyl (E)-3-(4-Methoxyphenyl)acrylate, 4-((6-(methacryloyloxy)decyl)oxy)phenyl (E)-3-(4-Methoxyphenyl)acrylate, 4-((6-(methacryloyloxy)dodecyl)oxy)phenyl (E)-3-(4-Methoxyphenyl)acrylate, (E)-3-(4-((6-(methacryloyloxy)hexyl)oxy)phenyl)acrylic acid, (E)-3-(4-((3-(methacryloyloxy)propyl)oxy)phenyl)acrylic acid, (E)-3-(4-(methacryloyloxy)phenyl)acrylic acid, (E)-6-(4-(3-methoxy-3-oxoprop-1-en-1-yl)phenoxy)hexyl methacrylate, (E)-6-(4-(3-methoxy-3-oxoprop-1-en-1-yl)phenoxy)propyl methacrylate, (E)-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenylMethacrylate, (E)-6-(4-(3-(4-methoxyphenoxy)-3-oxoprop-1-en-1-yl)phenoxy)hexyl Methacrylate, (E)-6-(4-(3-(4-methoxyphenoxy)-3-oxoprop-1-en-1-yl)phenoxy)propyl Methacrylate, (E)-4-(3-(4-methoxyphenoxy)-3-oxoprop-1-en-1-yl)phenyl Methacrylate, (E)-6-(4-(3-(4-butoxyphenoxy)-3-oxoprop-1-en-1-yl)phenoxy)hexyl Methacrylate, (E)-6-(4-(3-(4-hexyloxyphenoxy)-3-oxoprop-1-en-1-yl)phenoxy)hexyl Methacrylate, (E)-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl 4-((6-(methacryloyloxy)hexyl)oxy)benzoate, (E)-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl 4-((6-(methacryloyloxy)propyl)oxy)benzoate, (E)-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl 4-(methacryloyloxy)benzoate, (E)-6-(4-((3-(4-(butoxy)phenyl)acryloyl)oxy)phenoxy)hexyl Methacrylate, (E)-6-(4-((3-(4-(hexyloxy)phenyl)acryloyl)oxy)phenoxy)hexyl Methacrylate, (E)-6-(4-((3-(4-fluorophenyl)acryloyl)oxy)phenoxy)hexyl Methacrylate, (E)-6-(4-((3-(4-chlorophenyl)acryloyl)oxy)phenoxy)hexyl Methacrylate, (E)-6-(4-((3-(4-bromophenyl)acryloyl)oxy)phenoxy)hexyl Methacrylate, (E)-6-(4-((3-(4-cyanophenyl)acryloyl)oxy)phenoxy)hexyl Methacrylate, (E)-6-(4-((3-(3,4-dimethoxyphenyl)acryloyl)oxy)phenoxy)hexyl Methacrylate, 4-((6-(acryloyloxy)hexyl)oxy)phenyl(E)-3-(4-Methoxyphenyl)acrylate, (E)-3-(4-((6-(acryloyloxy)hexyl)oxy)phenyl)acrylic acid, (E)-6-(4-(3-(4-methoxyphenoxy)-3-oxoprop-1-en-1-yl)phenoxy)hexyl acrylate, (E)-6-(4-(3-methoxy-3-oxoprop-1-en-1-yl)phenoxy)hexyl acrylate, (E)-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate, (E)-2-(((4-(3-methoxy-3-oxoprop-1-en-1-yl)phenoxy)carbonyl)amino)ethyl methacrylate, 2-(((4-methyl-3-oxopent-4-en-1-yl)carbamoyl)oxy)cyclohexyl (E)-3-(4-methoxyphenyl)acrylate, etc. These structural units γ may be used either alone or in combination of two or more.

[0041] The polymerization initiator is not particularly limited, but examples thereof include azonitrile compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobiscyclohexylnitrile; diacyl peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, o-methylbenzoyl peroxide and bis-3,5,5-trimethylhexanol peroxide; dialkyl peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide and 1,3-bis-(tert-butylperoxyisopropyl)-benzene; peroxyketals such as 1,1-di-tert-butylperoxycyclohexane; and alkyl peresters such as tert-butyl peroxybenzoate.Organic peroxides such as percarbonates such as diisopropyl peroxydicarbonate, α-aminoketone photopolymerization initiators such as Irgacure 907 (manufactured by BASF Japan Ltd.) and Irgacure 369 (manufactured by BASF Japan Ltd.), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylphenyl ketone, 2-methyl ... Acetophenone-based photopolymerization initiators such as ethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide. Photopolymerization initiators, thioxanthone-based photopolymerization initiators such as 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine. triazine-based photopolymerization initiators such as 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine, carbazole-based photopolymerization initiators, and imidazole-based photopolymerization initiators;Further examples include photopolymerization initiators such as α-acyloxy ester, acylphosphine oxide, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone, and thioxanthone. These polymerization initiators may be used alone or in combination of two or more.

[0042] Suitable organic solvents include, but are not limited to, tetrahydrofuran, alcohol-based solvents such as ethanol, propanol, and butanol, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, ether-based solvents such as diethyl ether and diglyme, hydrocarbon-based solvents such as hexane, cyclohexane, methylcyclohexane, toluene, and xylene, nitrile-based solvents such as acetonitrile, and amide-based solvents such as N-methylpyrrolidone and dimethylacetamide. Any of these organic solvents may be used alone, or two or more may be used in combination.

[0043] Next, the second reaction step will be described. In the second reaction step, for example, a compound that introduces a polymerizable group into the structural unit β precursor, a carboxyl activator, and an appropriate catalyst are added to the reaction solution obtained in the first reaction step to obtain a mixture. This mixture is allowed to proceed at a temperature and for a time appropriate for completion of the reaction (for example, heated to 40°C and maintained for approximately 10 hours), and then the reaction solution is cooled. An acid catalyst is added to this reaction solution, and the reaction is allowed to proceed at a temperature and for a time appropriate for completion of deprotection (for example, heated to 70°C and maintained for approximately 12 hours), and then the reaction solution is cooled to approximately room temperature. The cooled reaction solution is added dropwise to an appropriate organic solvent to produce a precipitate, which is then collected and dried under reduced pressure to obtain polymer (I).

[0044] The compound that introduces a polymerizable group into the structural unit β precursor is not particularly limited, as long as it contains R1 in formula (I) above and is capable of reacting with the functional group introduced into the structural unit β precursor to form the structural unit β. Specifically, 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid, 4'-((6-(acryloyloxy)hexyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid, 4-(3-(methacryloyloxy)propyl)benzoic acid, 4-(3-(acryloyloxy)propyl)benzoic acid, acrylic acid, glycidyl methacrylate, methacrylic acid, 4-(methacryloyloxy)benzoic acid, 4-((6-(methacryloyloxy)methyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)ethyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)butyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)ethyl)oxy)benzoic acid, (6-(methacryloyloxy)pentyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)heptyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)octyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)nonyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)decyl)oxy)benzoic acid, 4-((6-(methacryloyloxy)dodecyl)oxy)benzoic acid, 4'-((6-(methacryloyloxy)hexyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid, 4'-((6-(methacryloyloxy)propyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid, 4'-(methacryloyloxy)-[1,1'-biphenyl]-4-carboxylic acid, 6-((6-(methacryloyloxy)hexyl)oxy)-2-naphthalenecarboxylic acid, 6-((6-(methacryloyloxy)propyl)oxy)-2-naphthalenecarboxylic acid, 6-(methacryloyloxy)-2-naphthalenecarboxylic acid, 2-fluoro-4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid, 4-((6-(acryloyloxy) 4-((6-(acryloyloxy)hexyl)oxy)benzoic acid, 4-(acryloyloxy)benzoic acid, 4-((6-(acryloyloxy)methyl)oxy)benzoic acid, 4-((6-(acryloyloxy)ethyl)oxy)benzoic acid, 4-((6-(acryloyloxy)butyl)oxy)benzoic acid, 4-((6-(acryloyloxy)pentyl)oxy)benzoic acid, 4-((6-(acryloyloxy)heptyl)oxy)benzoic acid benzoic acid, 4-((6-(acryloyloxy)octyl)oxy)benzoic acid, 4-((6-(acryloyloxy)nonyl)oxy)benzoic acid, 4-((6-(acryloyloxy)decyl)oxy)benzoic acid, 4-((6-(acryloyloxy)dodecyl)oxy)benzoic acid, 4'-((6-(acryloyloxy)propyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid, 4'-(acryloyloxy) Examples of the polymerizable group-introducing compound include 6-((6-(acryloyloxy)hexyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid, 6-((6-(acryloyloxy)propyl)oxy)-2-naphthalenecarboxylic acid, 6-((6-(acryloyloxy)propyl)oxy)-2-naphthalenecarboxylic acid, 6-(acryloyloxy)-2-naphthalenecarboxylic acid, and 2-fluoro-4-((6-(acryloyloxy)hexyl)oxy)benzoic acid. These polymerizable group-introducing compounds may be used alone or in combination of two or more.

[0045] The carboxyl activating agent is not particularly limited, but examples thereof include 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, dicyclohexylcarbodiimide, 2-ethoxy-1-ethoxycarbonyl-1-ethoxycarbonyl-1,2-dihydroquinoline, etc. These carboxyl activating agents may be used alone or in combination of two or more.

[0046] Suitable catalysts include, but are not limited to, 4-(dimethylamino)pyridine, tetraphenylphosphine, amine-based catalysts such as amine, benzylamine, dibutylamine, triethanolamine, benzylamine, and triethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium bromide, triethylbenzylammonium chloride, tetraethylammonium acetate, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, triethylbenzylammonium bromide, diphenyliodonium bromide, triphenylsulfonium bromide, tri-n-octylsulfonium bromide, triphenylsulfonium chloride, and tetraethylammonium bromide, and phosphorus-based catalysts such as trimethylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, and chlorodiphenylphosphine. These catalysts may be used alone or in combination of two or more.

[0047] Suitable acid catalysts include, but are not limited to, sulfonic acids such as methanesulfonic acid, p-phenylsulfonic acid, and sulfuric acid, carboxylic acids such as acetic acid, phosphoric acid, hydrochloric acid, photoacid generators, and thermal acid generators. These acid catalysts may be used alone or in combination of two or more.

[0048] Suitable organic solvents include, but are not limited to, alcohol solvents such as normal hexane, cyclohexanone, ethanol, propanol, and butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, ether solvents such as diethyl ether and diglyme, hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, toluene, and xylene, nitrile solvents such as acetonitrile, and amide solvents such as N-methylpyrrolidone and dimethylacetamide. Any of these solvents may be used alone, or two or more may be used in combination.

[0049] In another embodiment, in the production of polymer (I), structural unit α is used in the first reaction step, and this can also be used as a precursor to structural unit β. In this case, structural unit α is used in a molar fraction of l+m, and a compound that introduces a polymerizable group into the precursor to structural unit β is added in an amount corresponding to the molar fraction m in the second reaction step. In this embodiment, deprotection is not necessary in the second reaction step.

[0050] The polymer (I) can be dissolved in an organic solvent to form a composition for a photo-alignment film, and it is usually preferable to use the polymer (I) dissolved in an organic solvent at a concentration of about 1 to 10% by mass.

[0051] (Photo-alignment film-like composition) According to a second embodiment of the present disclosure, there is provided a composition for a photo-alignment film containing the polymer (I). In addition to the polymer (I), the composition for a photo-alignment film can contain, as appropriate, components typically contained in polymerizable compositions that undergo polymerization by light and heat, such as an organic solvent and, if necessary, a photo- or thermal polymerization initiator, a surfactant, and a crosslinking agent. The contents of these optional components are not particularly limited, but typically, the composition for a photo-alignment film contains, relative to the total weight of the polymer (I) contained in the composition, preferably about 70 to about 99% by mass of the solvent, about 1 to about 10% by mass of the photo- or thermal polymerization initiator, about 0.1 to about 5% by mass of the surfactant, and about 10 to about 40% by mass of the crosslinking agent.

[0052] As the organic solvent that can be blended in the composition for photo-alignment film, any organic solvent commonly used in this field can be used, and specific examples of such organic solvents include toluene, ethylbenzene, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, dibutyl ether, acetone, methyl ethyl ketone, ethanol, propanol, cyclohexane, cyclopentanone, methylcyclohexane, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, N-methylpyrrolidone, dimethylacetamide, etc. Any of these can be used alone, or two or more can be used in combination.

[0053] Examples of photo-thermal polymerization initiators that can be incorporated into the composition for photo-alignment films include azonitrile compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 2,2'-azobiscyclohexylnitrile; diacyl peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanol peroxide; dialkyl peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, and 1,3-bis-(tert-butylperoxyisopropyl)-benzene; peroxyketals such as 1,1-di-tert-butylperoxycyclohexane; and alkyl peresters such as tert-butyl peroxybenzoate.Organic peroxides such as percarbonates such as diisopropyl peroxydicarbonate, α-aminoketone photopolymerization initiators such as Irgacure 907 (manufactured by BASF Japan Ltd.) and Irgacure 369 (manufactured by BASF Japan Ltd.), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylphenyl ketone, 2-methyl ... Acetophenone-based photopolymerization initiators such as ethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide. Photopolymerization initiators, thioxanthone-based photopolymerization initiators such as 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine. triazine-based photopolymerization initiators such as 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine, carbazole-based photopolymerization initiators, and imidazole-based photopolymerization initiators;Further examples include photopolymerization initiators such as α-acyloxy ester, acylphosphine oxide, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone, and thioxanthone. These photo-thermal polymerization initiators may be used alone or in combination of two or more.

[0054] As the surfactant that can be blended in the photo-alignment film composition, any surfactant that is generally used to form a film of uniform thickness can be used. Specific examples include anionic surfactants such as sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl ether phosphate, sodium oleyl succinate, potassium myristate, potassium coconut oil fatty acid, and sodium lauroyl sarcosinate; nonionic surfactants such as polyethylene glycol monolaurate, sorbitan stearate, glyceryl myristate, glyceryl dioleate, sorbitan stearate, and sorbitan oleate; and stearyl trimethicone. cationic surfactants such as ammonium chloride, behenyltrimethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltrimethylammonium chloride; alkyl betaines such as lauryl betaine, alkyl sulfobetaine, cocamidopropyl betaine, and alkyl dimethylaminoacetic acid betaine, amphoteric surfactants such as alkyl imidazolines, sodium lauroyl sarcosinate, and sodium cocoamphoacetate; and surfactants such as BYK-361, BYK-306, and BYK-307 (manufactured by BYK Japan Co., Ltd.), Fluorad FC430 (manufactured by 3M Japan Co., Ltd.), Megafac F171, and R08 (manufactured by DIC Corporation). These surfactants may be used alone or in combination of two or more.

[0055] As a crosslinking agent that can be blended in the composition for a photo-alignment film, any crosslinking agent commonly used in this field can be used, and specific examples of such crosslinking agents include methylol compounds, polyfunctional thiol compounds, polyfunctional (meth)acrylates, etc. Any of these crosslinking agents may be used alone, or two or more types may be used in combination.

[0056] Specific examples of methylol compounds include: (1) alkoxymethylated glycolurils such as 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone; (2) alkoxymethylated benzoguanamines such as tetramethoxymethylbenzoguanamine and tetrabutoxymethylbenzoguanamine; and (3) alkoxymethylated melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine. These can be used alone or in combination of two or more.For example, commercially available alkoxymethylated glycoluril products include glycoluril compounds (trade names: Cymel 1170, Powder Link 1174), methylated urea resins (trade names: UFR65) and butylated urea resins (trade names: UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV) manufactured by Nippon Cytec Industries Co., Ltd., and urea / formaldehyde resins (high condensation type, trade names: Beckamine J-300S, Beckamine P-955, Beckamine N) and butylated urea resins (trade names: Beckamine P-138, Beckamine P-196-M, Beckamine G-1850) manufactured by DIC Corporation. Commercially available alkoxymethylated benzoguanamine products include those manufactured by Nippon Cytec Industries Co., Ltd. (trade name: Cymel 1123), those manufactured by Sanwa Chemical Co., Ltd. (trade names: Nikalac BX-4000, Nikalac BX-37, Nikalac BL-60, and Nikalac BX-55H), and those manufactured by DIC Corporation (trade names: Super Beckamine TD-126 and Super Beckamine 15-594).Commercially available alkoxymethylated melamines include methoxymethyl type melamine compounds (trade names: Cymel 300, Cymel 301, Cymel 303, Cymel 350) and butoxymethyl type melamine compounds (trade names: Mycoat 506, Mycoat 508) manufactured by Nippon Cytec Industries Co., Ltd., methoxymethyl type melamine compounds (trade names: Nikalac MW-30, Nikalac MW-22, Nikalac MW-11, Nikalac MS-001, Nikalac MX-002, Nikalac MX-730, Nikalac MX-750, Nikalac MX-035) manufactured by Sanwa Chemical Co., Ltd., and butoxymethyl type melamine compounds (trade names: Nikalac MW-30, Nikalac MW-22, Nikalac MW-11, Nikalac MS-001, Nikalac MX-002, Nikalac MX-730, Nikalac MX-750, Nikalac MX-035) manufactured by Sanwa Chemical Co., Ltd. Examples of suitable melamine compounds include chill-type melamine compounds (trade names Nikalac MX-45, Nikalac MX-410, and Nikalac MX-302), butylated melamine resins (Super Beckamine J-820-60, Super Beckamine L-109-65, Super Beckamine L-117-60, Super Beckamine L-127-60, Super Beckamine 13-548, Super Beckamine G-821-60, Super Beckamine L-110-60, Super Beckamine L-125-60, and Super Beckamine L-166-60B) manufactured by DIC Corporation, and methylated melamine resins (trade name Super Beckamine L-105-60). Other examples include aqueous melamine resins (trade names Watersol S-695 and S-683-IM, manufactured by DIC Corporation) and Beckamine P-198.

[0057] In addition, compounds obtained by condensing melamine compounds, urea compounds, glycoluril compounds, and benzoguanamine compounds in which the hydrogen atoms of the amino groups have been substituted with methylol groups or alkoxymethyl groups can also be used as crosslinking agents. Commercially available products of such melamine compounds include Cymel 303 (manufactured by Nippon Cytec Industries Co., Ltd.), and commercially available products of such benzoguanamine compounds include Cymel 1123 (manufactured by Nippon Cytec Industries Co., Ltd.).

[0058] The polyfunctional thiol compound means a compound having two or more thiol groups in one molecule.

[0059] Specific examples of polyfunctional thiol compounds include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis(3-mercaptobutyrate), and 1,4-bis(3-mercaptobutyryloxy)butane.

[0060] The polyfunctional (meth)acrylate means a (meth)acrylate having two or more ethylenically unsaturated bonds in one molecule.

[0061] Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetradecaethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0062] Other components typically contained in polymerizable compositions that undergo polymerization by light and heat include silane coupling agents such as alkoxysilane compounds, epoxy resins, polyfunctional isocyanates, isocyanate resins such as blocked isocyanates, hydrazides, carbodiimides, and polyfunctional compounds such as acetoacetone.

[0063] The composition for a photo-alignment film of the present disclosure obtained in this manner can be applied to a substrate, and after the solvent is distilled off as necessary, the composition can be irradiated with linearly polarized light to form a photo-alignment film.

[0064] (Photo-alignment film) According to a third embodiment of the present disclosure, there is provided a photo-alignment film comprising the composition for a photo-alignment film. The photo-alignment film can be produced, for example, by applying the composition for a photo-alignment film to a substrate, evaporating the solvent as necessary, and then irradiating the resulting composition with linearly polarized light.

[0065] Examples of the substrate include glass substrates such as quartz glass, alkali glass, and non-alkali glass; resin substrates such as polyimide, polyamide, acrylic resin, polyvinyl alcohol, triacetyl cellulose, polyethylene terephthalate, cycloolefin polymer, polyethylene, polycarbonate, polystyrene, and polytrifluorochloroethylene; and metal substrates such as iron, aluminum, and copper, with glass substrates and triacetyl cellulose being more preferred.

[0066] The composition for a photo-alignment film may be applied by any method generally known in the art, such as spin coating, bar coding, die coating, screen printing, or spray coating.

[0067] The drying step for distilling off the solvent may be carried out by any method commonly used in this field, and is not particularly limited as long as a resin layer film is formed. For example, it can be carried out by a hot air dryer, a hot plate, or a far-infrared heater.

[0068] The linearly polarized light can be irradiated onto the photo-alignment film either perpendicularly or obliquely, but is preferably irradiated from the perpendicular direction.

[0069] In this specification, linearly polarized light refers to light in which the plane containing the vibration direction of the electric field (or magnetic field) is specified. Linearly polarized light can be obtained by using a polarizing filter or a polarizing prism with light from a light source. The light to be irradiated is not particularly limited, as long as it is an irradiation light that can impart photo-alignment ability of the liquid crystal layer to the photo-alignable portion (A) upon irradiation, such as infrared light, visible light, ultraviolet light (near ultraviolet light, far ultraviolet light, etc.), X-rays, or charged particle beams (e.g., electron beams, etc.). However, the irradiation light usually has a wavelength of 200 nm to 500 nm, and from the viewpoint of efficiency, near ultraviolet light of 350 nm to 450 nm is preferred. Examples of light sources include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps. The wavelength range of the ultraviolet light or visible light obtained from such light sources may be limited using an interference filter or a color filter.

[0070] The photo-alignment film according to the third embodiment of the present disclosure can impart liquid crystal alignment ability to the alignment film with lower irradiation energy than conventional photo-alignment films. Therefore, although the irradiation energy varies depending on the film thickness, for example, at a thickness of 1 μm, it is usually about 1 mJ / cm. 2 ~500mJ / cm 2 and preferably about 1 to 100 mJ / cm 2 is.

[0071] If a photomask is used when irradiating linearly polarized light, it is possible to impart a patterned ability to align liquid crystals or the like to the photo-alignment film in two or more different directions. Specifically, after applying and drying the composition for a photo-alignment film of the present disclosure, a photomask is placed thereon and linearly polarized light is irradiated to impart an alignment ability only to the exposed portion, and by repeating this process multiple times with different directions as necessary, it is possible to impart a patterned ability to align liquid crystals or the like in multiple directions.

[0072] The thickness of the photo-alignment film of the present disclosure is preferably in the range of about 10 nm to about 500 nm, more preferably about 100 nm to about 500 nm, and even more preferably about 100 to about 200 nm.

[0073] A retardation film material is applied onto the photo-alignment film of the present disclosure obtained in this manner, and then the retardation film material is converted into a liquid crystal state by heating to the phase transition temperature of the liquid crystal, and this is photo-cured to obtain various optically anisotropic films such as retardation films, viewing angle improving films, brightness improving films, and polarizing films.

[0074] (phase contrast film) According to a fourth embodiment of the present disclosure, there is provided a retardation film in which a liquid crystalline compound is further aligned on the photo-alignment film. The retardation film is a film having different refractive indices in the X-axis direction and the Y-axis direction, which are perpendicular to the Z-axis direction (film thickness direction), and in which differences occur in the speed of waves vibrating in the X-, Y-, and Z-axis directions when light travels through the film. The retardation film can be obtained by applying a retardation film material to the photo-alignment film, heating the material to the phase transition temperature of the liquid crystal to turn the retardation film material into a liquid crystal state, and then photo-curing the liquid crystal material.

[0075] The retardation film material is not particularly limited as long as it is a polymerizable liquid crystal material, and materials containing liquid crystal monomers having polymerizable groups, particularly polyfunctional monomers having two or more ethylenically unsaturated bonds in one molecule, commonly used in the art, are preferably used. Such polymerizable liquid crystal materials include those having alignment properties such as horizontal alignment, cholesteric alignment, vertical alignment, and hybrid alignment, and can be used depending on the required retardation. The polymerizable liquid crystal materials may be used alone or in combination of two or more types as necessary.

[0076] Examples of polyfunctional monomers having two or more ethylenically unsaturated bonds in one molecule include polyfunctional (meth)acrylate monomers, polyfunctional (meth)acrylamide monomers, polyfunctional vinyl monomers, and polyfunctional allyl monomers.

[0077] Specific examples of polyfunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetradecaethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0078] Specific examples of polyfunctional (meth)acrylamide monomers include N,N'-methylenebisacrylamide and polyfunctional (meth)acrylamides synthesized from ethylenediamine, phenylenediamine, and the like.

[0079] Specific examples of polyfunctional vinyl monomers include divinylbenzene, ethylene glycol divinyl ether, divinyl adipate, and divinyl succinate.

[0080] Specific examples of polyfunctional allyl monomers include diallyl phthalate, diallyl ether, diallyl malonate, and p-allylstyrene.

[0081] The solvent, photopolymerization initiator, crosslinking agent, surfactant, etc. that can be used in the composition for retardation film can be the same as those used in the production of the above-mentioned photo-alignment film composition. In addition, in applying the composition for retardation film, the above-mentioned application method for the photo-alignment film composition can be used. [Example]

[0082] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to the following examples.

[0083] [Synthesis Example 1] 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid (Compound A', Compound β1) The corresponding monoacrylate was synthesized according to the method described in Makromol. Chem., 190, pp. 2255-2268, 1989, except that methacrylic acid chloride was used in place of acrylic acid chloride.

[0084] [Synthesis Example 2] Preparation of methoxymethyl 4-((6-(methacryloyloxy)hexyl)oxy)benzoate (Compound A) 260.0 g (849 mmol) of 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid obtained in Synthesis Example 1 and 111.6 g (1103.3 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of triethylamine were dissolved in 780 g of toluene to obtain a solution. 78.6 g (976.0 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of chlorodimethyl ether was added dropwise to this solution over 1 hour, and the mixture was then heated to 40°C and maintained at this temperature for 4 hours to allow the reaction to proceed. The reaction solution was then cooled and 260 g of water was added. 260 g (2164.9 mmol) of 50% aqueous acetic acid solution was added to the separated organic layer and stirred. The separated organic layer was concentrated to obtain 291.4 g of methoxymethyl 4-((6-(methacryloyloxy)hexyl)oxy)benzoate as a pale yellow liquid (yield: 98.0%).

[0085] [Synthesis Example 3] 4'-((6-(acryloyloxy)hexyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid (Compound β2) According to the method described in Makromol. Chem., 190, pp. 2255-2268, 1989, the corresponding monoacrylate was synthesized using 4-(4-hydroxyphenyl)benzoic acid as a starting material.

[0086] [Synthesis Example 4] Methoxymethyl 4-((6-(acryloyloxy)hexyl)oxy)-[1,1'-biphenyl]-4-carboxyate (Compound B) The compound β2 produced in Synthesis Example 3 above was used as a starting material and synthesized in the same manner as in Synthesis Example 2.

[0087] [Synthesis Example 5] 6-(4-hydroxyphenoxy)hexyl methacrylate (Compound C) 6-(4-hydroxyphenoxy)-1-bromohexane was synthesized by heating 1,4-dihydroxybenzene and 1,6-dibromohexane under alkaline conditions. This product was reacted with lithium methacrylate to synthesize 6-(4-hydroxyphenoxy)hexyl methacrylate.

[0088] [Synthesis Example 6] 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate (Compound D) 4-Hydroxy-4'-hydroxypropoxybiphenyl was synthesized by heating 4,4'-biphenyldiol and 2-chloropropanol under alkaline conditions. This product was then reacted with 1,6-dibromohexane under alkaline conditions to synthesize 4-(6-bromohexyloxy)-4'-hydroxypropoxybiphenyl. This product was then reacted with lithium methacrylate to synthesize 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate.

[0089] [Synthesis Example 7] 6-((4'-hydroxy-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate (Compound E) 6-((4'-hydroxy-[1,1'-biphenyl]-4-yl)oxy)-1-bromohexane was synthesized by heating 4,4'-biphenyldiol and 1,6-dibromohexane under alkaline conditions. 6-((4'-hydroxy-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate was synthesized by reacting this product with lithium methacrylate.

[0090] [Synthesis Example 8] 4-(3-(methacryloyloxy)propyl)benzoic acid (compound β3) The corresponding monoacrylate was synthesized according to the method described in Makromol. Chem., 190, pp. 2255-2268, 1989, using 1,3-dibromopropane instead of 6-chlorohexanol and methacrylic acid instead of acrylic acid chloride.

[0091] [Synthesis Example 9] 4-(3-(acryloyloxy)propyl)benzoic acid (compound β4) The corresponding acrylate was synthesized according to the method described in Makromol. Chem., 190, pp. 2255-2268, 1989, using 1,3-dibromopropane instead of 6-chlorohexanol and acrylic acid instead of acrylic acid chloride.

[0092] [Synthesis Example 10] 4-((6-(acryloyloxy)hexyl)oxy)benzoic acid (compound β5) The monoacrylate was synthesized according to the method described in Makromol. Chem., 190, pp. 2255-2268, 1989.

[0093] [Synthesis Example 11] 4-((6-(methacryloyloxy)hexyl)oxy)phenyl (E)-3-(4-methoxyphenyl)acrylate (Compound F) p-Methoxycinnamic acid chloride was added to 6-(4-hydroxyphenoxy)hexyl methacrylate produced in Synthesis Example 5 under basic conditions to synthesize 4-((6-(methacryloyloxy)hexyl)oxy)phenyl (E)-3-(4-methoxyphenyl)acrylate.

[0094] [Synthesis Example 12] (E)-6-(4-(3-(4-methoxyphenoxy)-3-oxoprop-1-en-1-yl)phenoxy)hexyl methacrylate (Compound G) According to the method described in Makromol. Chem., 190, pp. 2255-2268, 1989, (E)-3-(4-((6-methacryloyloxy)hexyl)oxy)phenyl)acrylic acid was synthesized using methacrylic acid instead of acrylic acid chloride and 4-hydroxycinnamic acid instead of ethyl 4-hydroxybenzoate. This product was reacted with 4-methoxyphenol in the presence of a condensing agent to synthesize (E)-6-(4-(3-(4-methoxyphenoxy)-3-oxoprop-1-en-1-yl)phenoxy)hexyl methacrylate (compound G).

[0095] [Synthesis Example 13] (E)-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl 4-((6-(methacryloyloxy)hexyl)oxy)benzoate (Compound H) Using compound β1 synthesized in Synthesis Example 1 as a starting material, (E)-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl 4-((6-(methacryloyloxy)hexyl)oxy)benzoate (compound H) was synthesized by heating methyl 4-hydroxycinnamate in the presence of a condensing agent.

[0096] 1. Polymer synthesis [Example 1] (Production of Polymer I-1) <First reaction step> 8.8 g (25.2 mmol) of methoxymethyl 4-((6-(methacryloyloxy)hexyl)oxy)benzoate (structural unit α derivative, Compound A) prepared in Synthesis Example 2, 1.0 g (3.6 mmol) of 6-(4-hydroxyphenoxy)hexyl methacrylate (structural unit β precursor, Compound C), 3.2 g (7.2 mmol) of 4-((6-(methacryloyloxy)hexyl)oxy)phenyl(E)-3-(4-methoxyphenyl)acrylate (structural unit γ, Compound F), and 0.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were dissolved in 24.7 g of tetrahydrofuran to obtain a solution. Nitrogen was bubbled through this solution for 1 hour, and then the solution was heated to 60°C and maintained at this temperature for 10 hours to allow the reaction to proceed. The reaction solution was then cooled to room temperature.

[0097] <Second reaction step> To the reaction solution obtained in the first reaction step, 1.1 g (3.6 mmol) of 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid (polymerizable group-introducing compound, compound β1) prepared in Synthesis Example 1, 0.9 g (4.7 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (carboxyl activator), and 0.1 g (0.7 mmol) of 4-(dimethylamino)pyridine (catalyst A) were added to obtain a mixture. The mixture was heated to 40 ° C and maintained for 10 hours to allow the reaction to proceed, and then the reaction solution was cooled. To this reaction solution, 1.8 g (12.6 mmol) of 70% methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.) was added at room temperature, and the mixture was heated to 70 ° C and maintained for 12 hours to allow deprotection to proceed, and then the reaction solution was cooled to around room temperature. The cooled reaction mixture was added dropwise to 130 g of normal hexane to form a precipitate, which was then collected and dried under reduced pressure to obtain polymer I-1, the structure of which is shown in Table 2.

[0098] <Measurement of weight average molecular weight (MW)> The weight average molecular weight (MW) of the polymer I-1 obtained above was measured by gel permeation chromatography (GPC), and the obtained weight average molecular weight (MW) was 43,000 in terms of polystyrene.

[0099] [Examples 2 to 18] Polymers I-2 to I-18 according to each example were produced in the same manner as in Example 1, except that the type and amount of compounds forming each structural unit were changed to the compositions shown in Table 1, and the weight average molecular weight (Mw) was measured. The structural formulas of the polymers according to each example are shown in Table 2 below. However, since polymers I-15 and I-16 have the same structure as polymer I-1, and polymers I-17 and I-18 have the same structure as polymer I-5, their descriptions are omitted.

[0100] [Example 19] <First reaction step> 9.8 g (31.9 mmol) of 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid (structural unit α, Compound A'), 6.0 g (13.7 mmol) of 4-((6-(methacryloyloxy)hexyl)oxy)phenyl(E)-3-(4-methoxyphenyl)acrylate (structural unit γ, Compound F), and 0.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were dissolved in 30.1 g of cyclohexanone to obtain a solution. Nitrogen was bubbled through this solution for 1 hour. Then, after 10 hours, the reaction solution was cooled to room temperature.

[0101] <Second reaction step> To the reaction mixture obtained in the first reaction step, 0.7 g (4.56 mmol) of glycidyl methacrylate (polymerizable group-introducing compound, compound β7) and 0.02 g (0.06 mmol) of tetraphenylphosphine (catalyst B) were added at room temperature. The mixture was then heated to 100°C and maintained for 18 hours to allow the reaction to proceed. The reaction mixture was then cooled to room temperature. The reaction mixture was added dropwise to 130 g of normal hexane to produce a precipitate, which was then collected and dried under reduced pressure to obtain polymer I-19. Its structure is shown in Table 2.

[0102] <Measurement of weight average molecular weight (MW)> The weight average molecular weight (MW) of polymer I-19 was measured in the same manner as in Example 1, and was found to be 52,000.

[0103] [Comparative Example 1] 9.8 g (31.9 mmol) of 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid (structural unit α, Compound A'), 6.0 g (13.7 mmol) of 4-((6-(methacryloyloxy)hexyl)oxy)phenyl(E)-3-(4-methoxyphenyl)acrylate (structural unit γ, Compound F), and 0.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were dissolved in 30.1 g of tetrahydrofuran, and nitrogen was bubbled through the solution for 1 hour. The solution was then heated to 60°C. After 10 hours, the reaction solution was cooled and added dropwise to 130 g (1.5 mmol) of normal hexane to obtain a precipitate. The obtained precipitate was then dried under reduced pressure to obtain Polymer II having the structure shown in Table 2 above.

[0104] The weight average molecular weight of Polymer II was measured in the same manner as in Example 1, and the weight average molecular weight (MW) was found to be 35,000.

[0105] Details of the reagents listed in Table 1 are shown below. [Structural unit α derivative] Preparation of Compound A: Methoxymethyl 4-((6-(methacryloyloxy)hexyl)oxy)benzoate (Compound prepared in Synthesis Example 2) Compound B: Methoxymethyl 4-((6-(acryloyloxy)hexyl)oxy)-[1,1'-biphenyl]-4-carboxyate (compound prepared in Synthesis Example 4) [Constituent unit α] Compound A': 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid (compound prepared in Synthesis Example 1) [Structural unit β precursor] Compound C: 6-(4-hydroxyphenoxy)hexyl methacrylate (compound prepared in Synthesis Example 5) Compound D: 6-((4'-(3-hydroxypropoxy)-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate (compound prepared in Synthesis Example 6) Compound E: 6-((4'-hydroxy-[1,1'-biphenyl]-4-yl)oxy)hexyl methacrylate (compound prepared in Synthesis Example 7) [Structural unit γ] Compound F: 4-((6-(methacryloyloxy)hexyl)oxy)phenyl(E)-3-(4-methoxyphenyl)acrylate (compound prepared in Synthesis Example 11) Compound G: (E)-6-(4-(3-(4-methoxyphenoxy)-3-oxoprop-1-en-1-yl)phenoxy)hexyl methacrylate (compound prepared in Synthesis Example 12) Compound H: (E)-4-(3-methoxy-3-oxoprop-1-en-1-yl)phenyl 4-((6-(methacryloyloxy)hexyl)oxy)benzoate (compound prepared in Synthesis Example 13) Polymerization initiator: 2,2'-azobis(2,4-dimethylvaleronitrile) (Fujifilm Wako Pure Chemical Industries, Ltd.) [Polymerizable group-introducing compound] Compound β1: 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid (compound prepared in Synthesis Example 1) Compound β2: 4'-((6-(acryloyloxy)hexyl)oxy)-[1,1'-biphenyl]-4-carboxylic acid (compound prepared in Synthesis Example 3) Compound β3: 4-(3-(methacryloyloxy)propyl)benzoic acid (compound prepared in Synthesis Example 8) Compound β4: 4-(3-(acryloyloxy)propyl)benzoic acid (compound prepared in Synthesis Example 9) Compound β5: 4-((6-(acryloyloxy)hexyl)oxy)benzoic acid (compound prepared in Synthesis Example 10) Compound β6: acrylic acid (Osaka Organic Chemical Industry Co., Ltd.) Compound β7: Glycidyl methacrylate (Osaka Organic Chemical Industry Co., Ltd.) Carboxyl activator: 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (Tokyo Chemical Industry Co., Ltd.) Catalyst A: 4-(dimethylamino)pyridine (Tokyo Chemical Industry Co., Ltd.) Catalyst B: Tetraphenylphosphine (Tokyo Chemical Industry Co., Ltd.)

[0106] [Table 1]

[0107] [Table 2] TIFF0007767283000020.tif192130 TIFF0007767283000021.tif178130 TIFF0007767283000022.tif215130 TIFF0007767283000023.tif104130

[0108] 2. Preparation of composition for photo-alignment film Each of the polymers (1.05 g each) produced in Examples 1 to 19 and Comparative Example 1 was mixed with 98.95 g of propylene glycol monomethyl ether under light shielding to prepare compositions 1 to 20 for photo-alignment films, respectively.

[0109] 3. Fabrication of photo-alignment film The compositions 1 to 20 for photo-alignment films obtained above were applied to a glass substrate using a spin coater to a thickness of about 100 nm, then dried on a hot plate at 80°C for 2 minutes, and then irradiated with linearly polarized UV light at 10 to 40 mJ / cm. 2 The photo-alignment films 1 to 20 were produced by irradiation.

[0110] 4. Fabrication of retardation film A composition for a retardation film was prepared by mixing 5.7 g of a bifunctional liquid crystal acrylate (Paliocolor LC-242, manufactured by BASF), 0.3 g of a photopolymerization initiator (Irg OXE-01 (manufactured by BASF Japan Ltd.)), and 33.8 g of toluene under a light-shielded condition.

[0111] The obtained retardation film composition was applied to each of the photo-alignment films 1 to 20 using a spin coater to a thickness of about 1 μm. After that, alignment was performed at 120° C., and then unpolarized UV light was applied at 500 mJ / cm 2 2The retardation films 1 to 20 were prepared by irradiation.

[0112] Test Example 1: Evaluation of Orientation The retardation of the retardation film substrate fabricated on the photo-alignment film was measured to evaluate the alignment. The birefringence of the fabricated retardation film was measured at a wavelength (λ) of 550 nm using a retardation measurement device (OPTIPRO-standard, manufactured by Shintech Co., Ltd.), and Δn was calculated from the obtained retardation value (Re) and film thickness using the following formula. The results are shown in Table 3. Δn=(Re / film thickness) / 1000

[0113] Test Example 2: Haze Evaluation The haze of the retardation film substrate fabricated on the photo-alignment film was measured to evaluate the alignment. The haze of the fabricated retardation film was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.). The results are shown in Table 3.

[0114] From the results of Test Examples 1 and 2, sufficient alignment was observed in all retardation films. Retardation films 4, 8, 11, and 12 (Examples 4, 8, 11, and 12), which use photo-alignment films 4, 8, 11, and 12, respectively, which use relatively rigid structural units, showed slightly lower alignment at low exposure doses, but it was found that sufficient alignment could be obtained by adjusting the exposure dose. Furthermore, retardation films 3 and 7 (Examples 3 and 7), which use photo-alignment films 3 and 7, respectively, which use relatively rigid structural units but have a high ratio of the photoreactive structural unit γ, showed sufficient alignment even in the low exposure dose range.

[0115] Test Example 3: Evaluation of Adhesion Polarized UV light 20mJ / cm 2The retardation film substrates on which the photo-alignment films 1 to 20 were prepared by irradiation were cut with a cutter knife to form cross-cuts (1 mm x 1 mm x 100 squares), and then cellophane tape was applied. The number of squares remaining on the substrate without peeling off the retardation film when the cellophane tape was peeled off was counted. The adhesion between the photo-alignment film and the retardation film was evaluated based on the number of remaining squares. The results are shown in Table 3.

[0116] In Examples 1 to 19, which used photo-alignment films 1 to 19, the adhesion between the photo-alignment film and the retardation film was good in all cases, but in Comparative Example 1, which used photo-alignment film 20, it was confirmed that the polymerizable liquid crystal layer of the retardation film had completely peeled off in all squares.

[0117] [Table 3]

Claims

1. General formula (I): 【Chemistry 1】 [In the formula, M a , M b and M c represents the portion of the monomer units of the copolymer that forms the backbone of the copolymer; l, m, and n represent the mole fractions of the copolymer, with 0.1≦l≦0.9, 0.01≦m≦0.4, and 0.05≦n≦0.5 in each case; SPCRa, SPCRb, and SPCRc each independently represent a spacer unit; Ring A, ring B and ring C are each independently an unsubstituted or substituted alicyclic hydrocarbon; 【Chemistry 2】 [wherein R 3 to R 64 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group] (either bond may be bonded to each spacer unit); X is a single covalent bond, an alkylene chain having 1 to 10 carbon atoms, or a cycloalkylene chain having 3 to 8 carbon atoms; Y is selected from the group consisting of a single covalent bond; an alkylene chain having 1 to 10 carbon atoms that is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms; -O-; -COO-; and combinations thereof; Z is —O—CO—CH═CH— (either bond may be bonded to ring C); R 1 is -CW=CH 2 , or -V-CW=CH 2 wherein W is hydrogen or methyl, and V is —O—CO— or —CO—; R 2 is an alkyl group having 1 to 6 carbon atoms; a phenyl group having at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom, provided that when ring C is an alicyclic hydrocarbon, R 2 is a phenyl group having at least one substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom. A polymer having a repeating unit represented by the formula: wherein each monomer unit has a structure exhibiting liquid crystallinity.

2. General formula (I): 【Transformation 3】 [In the formula, M a , M b and M c represent the portion of the monomer units of the copolymer that form the backbone of the copolymer; l, m, and n represent the mole fractions of the copolymer, with 0.1≦l≦0.9, 0.01≦m≦0.4, and 0.05≦n≦0.5 in each case; SPCRa, SPCRb, and SPCRc each independently represent a spacer unit; Ring A, ring B and ring C each independently represent 【Chemistry 4】 [In the formula, R 3 ~R 64 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. (either bond may be bonded to each spacer unit); X is a single covalent bond, an alkylene chain having 1 to 10 carbon atoms, or a cycloalkylene chain having 3 to 8 carbon atoms; Y is selected from the group consisting of a single covalent bond; an alkylene chain having 1 to 10 carbon atoms that is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms; -O-; -COO-; and combinations thereof; Z is —O—CO—CH═CH— (either bond may be bonded to ring C); R 1 is —CW═CH 2 or —V-CW═CH 2 (wherein W is hydrogen or methyl and V is —O—CO— or —CO—); R 2 is an alkyl group having 1 to 6 carbon atoms; a phenyl group having at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom, provided that when ring C is an alicyclic hydrocarbon, R 2 is a phenyl group having at least one substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen atom. A polymer having a repeating unit represented by the formula: wherein each monomer unit has a structure exhibiting liquid crystallinity.

3. Ring A is 【Transformation 5】 [In the formula, R 3 ~R 14 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. is a group represented by Ring B is 【Transformation 6】 [In the formula, R 7 ~R 14 , R 33 ~R 64 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. (either bond may be bonded to the spacer unit), Ring C is 【Transformation 7】 [In the formula, R 3 ~R 6 , R 33 ~R 40 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group.

3. The polymer according to claim 2, wherein the group is represented by the following formula (either bond may be bonded to the spacer unit):

4. SPCRa, SPCRb and SPCRc each independently represent a covalent single bond; an alkylene chain having 1 to 20 carbon atoms which is unsubstituted or substituted with a hydroxyl group and / or a carbonyl group; an unsubstituted or cycloalkylene chain having 3 to 8 carbon atoms which is substituted with a hydroxyl group; an unsubstituted or alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, -CN, -NO 2 4. The polymer according to claim 1, which is phenylene substituted with at least one substituent selected from the group consisting of -O-, -COO-, and halogen; -O-; -COO-; or a combination thereof.

5. 5. The polymer according to claim 4, wherein SPCRa, SPCRb, and SPCRc are each independently an unsubstituted or hydroxyl- and / or carbonyl-substituted alkylene chain having 1 to 20 carbon atoms; -O-; -COO-; or a combination thereof.

6. 6. The polymer according to claim 1, wherein Y is a combination of an unsubstituted or hydroxyl- and / or carbonyl-substituted alkylene chain having 1 to 10 carbon atoms and -O- or -COO-.

7. A composition for a photo-alignment film, comprising the polymer according to any one of claims 1 to 6.

8. A photo-alignment film formed from the composition for a photo-alignment film according to claim 7.

9. A retardation film in which a liquid crystalline compound is further aligned on the photo-alignment film according to claim 8.

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