Polymer composition, composition for forming retardation film, and method for producing retardation material

Abstract

Provided is a polymer composition which contains a polymer (P) and a specific compound (A).　Polymer (P): A photoresponsive polymer liquid crystal which is obtained by polymerization through a polymerizable unsaturated bond represented by any one of formulae (m-1) to (m-5) and is a side chain polymer having a mesogenic structure in a side chain, wherein the side chain having the mesogenic structure has a photosensitive group (p) and a carboxy group on the same side chain or on different side chains.　Specific compound (A): A compound represented by formula (a-1). (In the formulae (m-1) to (m-5), R1 and R2 each independently represent a hydrogen atom or a methyl group; and an asterisk (*) represents an atomic bond.) (In the formula (a-1), X represents a carboxy group, a pyridyl group which may have a substituent R5, or a dialkylamino group; and R3 represents a hydrogen atom or a specific group.)

Description

Polymer composition, composition for forming a phase difference film, and method for manufacturing a phase difference material.

[0001] The present invention relates to polymer compositions (particularly compositions for forming phase difference films) and phase difference materials containing specific polymer components and additives. More specifically, it relates to a composition for forming a phase difference film that can be suitably used in materials having optical properties suitable for applications such as display devices and recording materials (particularly optical compensation films such as polarizers and phase difference plates for liquid crystal displays and organic EL (Electroluminescence) display devices), and to a phase difference material obtained from the above-mentioned composition for forming a phase difference film.

[0002] Due to demands for improved display quality and weight reduction in liquid crystal display devices, there is a growing need for polymer films with controlled internal molecular orientation structures as optical compensation films such as polarizers and phase difference plates. These polymer films are known as films that alter the polarization state of light and impart birefringence (also called birefringent films or phase difference films). In the following, materials that alter the polarization state of light will also be referred to as phase difference materials. To meet these demands, birefringent films utilizing the optical anisotropy of polymerizable liquid crystal compounds are being developed. The polymerizable liquid crystal compounds used here are generally liquid crystal compounds having polymerizable groups and liquid crystal structural parts (structural parts having spacer parts and mesogenic parts), and (meth)acrylic groups are widely used as these polymerizable groups.

[0003] Polymerizable liquid crystal compounds can exhibit optical anisotropy by, for example, contacting them with an alignment-treated substrate and irradiating them with radiation such as ultraviolet light. Prior art includes a method (Patent Document 1) in which a specific polymerizable liquid crystal compound having (meth)acrylic groups is supported between support structures formed on a polymer film having alignment ability (hereinafter also referred to as an alignment film), and the compound is irradiated with radiation while being kept in a liquid crystal state. Another known method (Patent Document 2) involves adding a photopolymerization initiator to a mixture of two polymerizable liquid crystal compounds having (meth)acrylic groups, or a composition of this mixture mixed with chiral liquid crystal, and then irradiating it with ultraviolet light on an alignment-treated substrate.

[0004] In optical compensation for liquid crystal displays and organic EL displays, it is known that the Nz coefficient, a parameter representing the characteristics of the phase difference material, is preferably 0.5 or close to it (Patent Document 3). Here, the Nz coefficient is given by the formula {Nz = (nx - nz) / (nx - ny)}, where nx is the refractive index of the slow axis in the plane of the phase difference material, ny is the refractive index of the fast axis, and nz is the refractive index in the thickness direction of the phase difference material.

[0005] Generally, to control the Nz coefficient to around 0.5, multiple positive A plates (nx > ny = nz), positive C plates (nz > nx = ny), and negative C plates (nx = ny > nz) are combined to achieve the desired optical properties. On the other hand, there is also active development of birefringent films (hereinafter referred to as single-layer phase difference films) that exhibit the desired optical properties with only a single layer of resin. Single-layer phase difference films do not require the combination of multiple films, making it possible to thin and lighten birefringent films. Furthermore, the film manufacturing process can be simplified, which is expected to reduce manufacturing costs and improve yield.

[0006] As an example of the development of the aforementioned single-layer phase difference film, birefringent films using polymerizable liquid crystal compounds or their polymers without using an alignment film have been reported (Patent Documents 4 and 5).

[0007] Furthermore, various single-layer phase difference films have been reported, such as birefringent films (Patent Documents 6 and 7) that utilize the axially selective photoreaction and resulting photo-orientation of photoresponsive polymer liquid crystals (liquid crystalline polymethacrylate with photoresponsive mesogens in its side chains).

[0008] Japanese Patent Publication No. Sho 62-70407, Japanese Patent Publication No. Hei 9-208957, International Publication No. 2018 / 221276, Japanese Patent Publication No. 2002-517605, International Publication No. 2008 / 031243, Japanese Patent Publication No. 2008-164925, Japanese Patent Publication No. Hei 11-189665

[0009] The applicant has filed patent applications for single-layer phase difference materials using photoresponsive side-chain polymer liquid crystals (International Publication No. 2024 / 071364, International Publication No. 2024 / 038887). These materials are composed of liquid crystalline poly(meth)acrylates containing cinnamic acid, chalcone, azobenzene, N-benzylideneaniline, phenyl ester, etc., as photoresponsive functional groups in the side-chain mesogens. Triggered by the axially selective photoreaction of the side-chain mesogens upon exposure to linearly polarized ultraviolet light, the self-organizing action derived from the liquid crystal amplifies anisotropy in directions parallel or perpendicular to the polarization direction, resulting in a large phase difference value. Challenges with these polymer liquid crystal materials include their high dependence on firing temperature due to the properties of the liquid crystal material, resulting in a narrow firing temperature margin. Additionally, since the magnitude of the phase difference value also depends heavily on the amount of ultraviolet exposure, a narrow ultraviolet exposure margin is also a challenge. Furthermore, the hydrogen-bonded polymer liquid crystal, the most well-known of the aforementioned polymer liquid crystals, is a liquid crystalline polymethacrylate that exhibits liquid crystalline properties through hydrogen bond dimerization at the mesogenic ends of its side chains. While it offers advantages in terms of coating and handling, it also has the drawback that the firing temperature required to achieve a large phase difference is equivalent to or higher than the heat resistance temperature (90°C to 140°C) of the substrate film (TAC film, COP film, PET film) (120°C to 150°C). Therefore, it is not possible to achieve a sufficient phase difference within the heat resistance temperature range of the substrate. Moreover, the process for producing phase difference films can be broadly classified into 1. substrate adhesion type and 2. transfer type. However, when producing using the transfer type, a transfer (transfer) process is required from the support substrate to a different substrate after the phase difference film has been produced. At this time, the phase difference film is subjected to transfer stress, so it needs to have a certain degree of mechanical strength and toughness. However, the polymer liquid crystal has weak mechanical strength and toughness, and there is a problem that cracks occur on the surface of the phase difference film during transfer, which leads to a decrease in the performance of optical compensation and a deterioration in the yield of phase difference film manufacturing.

[0010] Solving these technical challenges would bring significant benefits to panel manufacturers, including improved image quality for liquid crystal displays and organic EL displays, reduced manufacturing burden, and consequently lower costs.

[0011] This invention was made to solve the above-mentioned problems, and compared to conventional methods, it can produce high phase difference values ​​even at low temperatures during firing, improve the firing temperature margin as well as the UV exposure margin, and reduce cracks during transfer. Therefore, high-quality phase difference films can be manufactured easily and reproducibly. The purpose of this invention is to provide a phase difference film that has excellent optical compensation properties, can be used with substrates with low heat resistance, has a good yield during manufacturing, and offers cost advantages.

[0012] As a result of diligent research to solve the aforementioned problems, the inventors of the present invention have found that a polymer composition containing a specific polymer and a specific compound is suitable for forming a phase difference film, such as a birefringent film, and for forming an alignment film, and have completed the present invention.

[0013] Accordingly, the present invention encompasses the following embodiments: [1] A polymer composition containing the following polymer (P) and specific compound (A). Polymer (P): A photoresponsive polymeric liquid crystal obtained by polymerizing polymerizable unsaturated bonds represented by any of the following formulas (m-1) to (m-5), and which is a side-chain type polymer having a mesogenic structure in its side chains, wherein the side chain having the mesogenic structure has a photosensitive group (p) and a carboxyl group on the same side chain or on separate side chains. Specific compound (A): A compound represented by the following formula (a-1). (In formulas (m-1) to (m-5), R １ , and R ２ Each of these independently represents a hydrogen atom or a methyl group. * represents a bonding bond. (In formula (a-1), X is a carboxyl group, and substituent R ５ R represents a pyridyl group or dialkylamino group which may have one or more of these groups. ３ This is a hydrogen atom, Ar-R ４ - Represents a group, (meth)acryloyloxyalkyl group, a linear alkyl group having 1 to 20 carbon atoms, or a branched alkyl group having 2 to 20 carbon atoms, or a saturated hydrocarbon group having 3 to 20 carbon atoms including a cycloalkyl group, R ４represents a single bond or a divalent organic group. Ar represents a substituent R ５ which represents a monovalent aromatic hydrocarbon group that may have one or more of the above, and the substituent R ５ represents a monovalent group having no chain linking group. When a pyridyl group or Ar has a plurality of substituents R ５ , the plurality of substituents R ５ may be the same as or different from each other.) [2] The polymer composition according to [1], wherein the polymer (P) has at least one of a group represented by the following formula (p-1) and a group represented by the following formula (p-2) as the group having the mesogen structure. (In formulas (p-1) and (p-2), A １ and A ２ each independently represent a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)-, -N(CH ３ )-, -C(=O)NH-, -C(=O)N(CH ３ )-, -NHC(=O)-, -N(CH ３ )C(=O)-, -NH- or -NH-C(=O)-NH-. L represents a single bond or an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or a monovalent organic group. X １ represents any one of the following formulas (X1-a) to (X1-c). Y １ represents any one of the following formulas (Y1-a) to (Y1-e). *1 represents a bond to the main chain derived from any one of the above formulas (m-1) to (m-5).) (In formulas (X1-a) to (X1-c), X １ａ and X １ｂ each independently represent a single bond, an aromatic group, or an alicyclic group. X １ｃ and X １ｄ each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms. When X １ａ is a single bond, X １ｃ is an alkylene group having 1 to 6 carbon atoms. When X １ｂ is a single bond, X １ｃ is an alkylene group having 1 to 6 carbon atoms. X １ｅThese are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) Represents CO. X １ａ When it is a single bond, X １ｅ It is also a single bond. ａ and X ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. *2 is A ２ (This represents a combination of two elements.) (In formulas (Y1-a) to (Y1-e), Y １ａ These are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) Represents CO. Y １ｂ * represents a single bond or an alkylene group with 1 to 6 carbon atoms. *2 is A ２ (This represents a bonding bond with.) [3] The polymer composition according to [2] in which formula (p-1) is represented by any of the following formulas (p-1a) to (p-1g). (In formulas (p-1a) to (p-1g), A １ａ and A １ｂ Each of these independently represents a single bond, -O-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, -NHC(=O)-, or -NH-. １ｄ X represents a single bond or an alkylene group having 1 to 6 carbon atoms. ａ and X ｂ Each independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. n represents an integer from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5). [4] The polymer composition according to [2] or [3] wherein the above formula (p-2) is represented by any of the following formulas (p-2a) to (p-2f). (In formulas (p-2a) to (p-2f), A １ａ and A １ｂThese independently represent a single bond, -O-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, -NHC(=O)-, or -NH-. １ｃ R represents a single bond or an alkylene group having 1 to 6 carbon atoms. n represents an integer from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5).) [5] In the above formula (a-1), R ４ A polymer composition according to any one of [1] to [4], wherein the bond is a single bond, selected from the following formulas (b-1) and (b-2). (In formulas (b-1) to (b-2), R ６ R represents an alkylene group with 1 to 10 carbon atoms. ７ and R ８ Each of these independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a cyano group. *1 represents a bond with X, and *2 represents a bond with Ar.) [6] The polymer composition according to any one of [1] to [5], wherein Ar in formula (a-1) is the following formula (c). (In formula (c), R ９ R represents a halogen atom, a hydroxyl group, a carbon-1 to carbon-2 alkoxy group, a cyano group, a carbon-3 to carbon-6 cycloalkyl group, a pyridyl group, a dialkylamino group, or a (meth)acryloyloxy group, where m is an integer from 0 to 2 and n is an integer from 0 to 5. ９ If there are multiple instances of R, then multiple R ９ They may be the same or different from each other. *3 is R ４ (This represents a bonding bond with.) [7] The polymer composition according to any one of [1] to [6], wherein the specific compound (A) is selected from the compounds represented by the following group of compounds. (In the above formula, R １２ ~R １４ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, except R １２ , R １３ and R １４ The total number of carbon atoms is between 0 and 19. １５ R represents a hydrogen atom, a methyl group, a cyano group, or a phenyl group. １６represents a hydrogen atom, a methyl group, or a cyano group. Cy represents a cycloalkyl group having 3 to 8 carbon atoms. n3 represents an integer from 0 to 10, and n4 represents an integer from 1 to 5. Q represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic group having 3 to 6 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, an acryloyloxy group, or a methacryloyloxy group. Q ２ ) represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alicyclic group having 3 to 6 carbon atoms, an acryloyloxy group, or a methacryloyloxy group.) [8] A composition for forming a phase difference film, which is a polymer composition according to any one of [1] to [7]. [9] A composition for forming an orientation film, which is a polymer composition according to any one of [1] to [7].

[10] A method for producing a phase difference material, comprising the following steps (1) to (3): (1) A step of applying the polymer composition according to any one of [1] to [7] onto a substrate to form a coating film. (2) A step of irradiating the coating film with polarized ultraviolet light. (3) A step of heating the coating film that has been irradiated with ultraviolet light.

[11] A resin film formed from the polymer composition according to any one of [1] to [7].

[12] A phase difference material comprising the resin film according to

[11] .

[0014] This invention enables the production of high phase difference values ​​even at low temperatures compared to conventional methods, improving both the firing temperature margin and the UV exposure margin, and reducing cracks during transfer. Therefore, high-quality phase difference films can be produced easily and reliably.

[0015] The following describes in detail polymer compositions containing specific polymers and specific compounds, and orientation films or phase difference materials formed using said polymer compositions. However, the following description of constituent elements is merely an example of one embodiment of the present invention and is not limited to these. In the following description, "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. Also, "tert-" meaning tertiary is also represented as "t-". Examples of aryl groups include aryl groups having 6 to 20 carbon atoms, such as phenyl groups, biphenyl groups, and naphthyl groups. Examples of arylene groups include arylene groups having 6 to 20 carbon atoms, such as phenylene groups, biphenylene groups, and naphthylene groups. In the present invention, the main chain of a polymer refers to the "stem" part of the polymer consisting of the longest chain of atoms. Also, the side chains of a polymer refer to the parts that branch off from the "stem" of the polymer.

[0016] Embodiments of the present invention will be described in detail below. [Polymer (P)] Polymer (P) is a photoresponsive polymeric liquid crystal obtained by polymerizing a monomer containing a polymerizable unsaturated bond represented by any of the following formulas (m-1) to (m-5), and is a side-chain type polymer having a mesogenic structure in its side chains, wherein the side chain having the mesogenic structure has a photosensitive group (p) and a carboxyl group on the same side chain or on separate side chains. (In formulas (m-1) to (m-5), R １ , and R ２ Each of these independently represents a hydrogen atom or a methyl group. * represents a bonding bond.

[0017] (Photosensitive group (p)) Specific examples of the photosensitive group (p) in the polymer (P) of the present invention include functional groups capable of undergoing photocrosslinking reactions (e.g., photodimerization reactions), photoisomerization reactions, or photofleece rearrangement reactions in response to light energy. In particular, it is preferable to have a cinnamic acid group from the viewpoint of the simplicity of the photoreaction and processability. For example, cinnamic acid groups represented by the following formulas (ca-1) to (ca-2), or derivatives thereof, are included. (Ar represents a divalent organic group having 6 to 30 carbon atoms and containing an arylene group, and Ar is -C(X １) = is bonded to the carbon atom and the carbon atoms that make up the aromatic hydrocarbon ring. *1 represents a bond with an atom other than a hydrogen atom. X １ , and X ２ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or a C1-C3 alkyl group, and some or all of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms. * represents a bond.) In the above formulas (ca-1) and (ca-2), Ar and COOH or COO-*1 may be bonded to the double bond at the cis position or at the trans position, but it is preferable that they be bonded at the trans position.

[0018] (Mesogenic structure) The above mesogenic structure is not particularly limited as long as it imparts liquid crystalline properties, and includes not only mesogenic groups but also hydrogen-bonding mesogenic groups that exhibit liquid crystalline properties through intermolecular hydrogen bonding.

[0019] The polymer (P) has, for example, a mesogenic group (m) in its side chain. When the polymer (P) has a mesogenic group (m), it is preferable that the polymer (P) has a structural unit (M) having a mesogenic group (m) in its side chain. The structural unit (M) having a mesogenic group (m) in its side chain is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a mesogenic group (m).

[0020] The mesogen-forming group (m) may be in an embodiment (A) having a side chain having the photosensitive group (p), or in an embodiment (B) having a side chain without the photosensitive group (p), or a combination thereof. Embodiment (A) includes, but is not limited to, an embodiment (A1) in which the mesogen-forming group is provided in the side chain by sharing part or all of the structure of the photosensitive group (p), and an embodiment (A2) in which the mesogen-forming group is provided in the side chain independently of the structure of the photosensitive group (p). In embodiment (A2), the mesogen-forming group (m) and the photosensitive group (p) may be bonded by a single bond, or they may be bonded to each other via a linking group. Examples of the linking group include alkylene groups, -O-, -S-, -SO-, and -SO ２Examples of alkylene groups include -, -CH=CH-, -C≡C-, -N=N-, -COO-, and -OCO-. Examples of the alkylene group include alkylene groups having 1 to 20 carbon atoms, such as methylene groups, ethylene groups, and propylene groups. Preferably, the alkylene group is an alkylene group having 1 to 10 carbon atoms, and more preferably, an alkylene group having 2 to 8 carbon atoms.

[0021] Examples of the above mesogenic group include -Ar １ -Y-Ar ２ - can be cited. Here, Ar １ and Ar ２ represents an arylene group which may have substituents, an arylene group which may have substituents (e.g., a cyclopropylene group, a cyclobutane group, or a cyclohexylene group, etc.), or an arylene group which may have substituents (e.g., oxygen-containing heterocycles such as furan rings and pyran rings; nitrogen-containing heterocycles such as pyrrole rings and imidazole rings, etc.). Y represents a single bond, an alkylene group with 1 to 3 carbon atoms, -CH=CH-, -C≡C-, -O-, -COO-, or -OCO-, -CH=N-, or an arylene group.

[0022] The positions of the binding sites of the arylene group and heterocyclic residue are not particularly limited as long as they impart liquid crystalline properties, however, the phenylene group is preferably bound at the p-position, and the naphthylene group is preferably bound at the 2,6-position.

[0023] The above-mentioned arylene group, cycloalkylene group, and heterocyclic residue may have substituents. Examples of substituents include alkyl groups, formyl groups, alkyloxy groups, alkenyl groups, alkynyl groups, halogen atoms, haloalkyl groups, optionally substituted cycloalkyl groups, and optionally substituted aryl groups. Examples of alkyl groups include C1-C3 alkyl groups such as methyl, ethyl, and propyl groups. Examples of alkyloxy groups include C1-C3 alkyloxy groups such as methoxy and ethoxy groups. Examples of alkenyl groups include C2-C4 alkenyl groups such as vinyl, allyl, and 2-butenyl groups. Examples of alkynyl groups include C2-C4 alkynyl groups such as propargyl groups. Examples of haloalkyl groups include C1-C3 haloalkyl groups such as trifluoromethyl. Examples of cycloalkyl groups include C3-C6 cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl groups. The above-mentioned cycloalkyl group and aryl group may have substituents, such as a methoxy group and a halogen atom.

[0024] A more preferred specific example of the above-mentioned mesogenic group is the following structure. (* indicates a link.)

[0025] In addition to hydroxybenzoic acid residues, the following structure can also be used as a hydrogen-bonding mesogenic group: -Ar-Q-Ar ３ -COOH -Ar-Q-Ar ３ - (Z) ｊ -COOH Here, Ar and Ar ３Each represents an arylene group which may have substituents, either identical or different. Q represents a single bond, an alkylene group having 1 to 3 carbon atoms, -CH=CH-, -C≡C-, -O-, -COO-, -OCO-, or -CH=N-. Z represents -CH=CH-. j is an integer between 2 and 3, preferably 2. The above arylene group may have substituents, and examples of such substituents include alkyl groups, formyl groups, alkyloxy groups, alkenyl groups, alkynyl groups, halogen atoms, and haloalkyl groups. Specific examples of alkyl groups, alkyloxy groups, alkenyl groups, alkynyl groups, and haloalkyl groups as substituents include, for example, "-Ar １ -Y-Ar ２ Specific examples of alkyl groups, alkyloxy groups, alkenyl groups, alkynyl groups, and haloalkyl groups mentioned in the explanation of "-" can be found.

[0026] The polymer (P) preferably has at least one of the groups represented by the following formulas (p-1) and (p-2) as the mesogenic structure. (In equations (p-1) and (p-2), A １ and A ２ These are, independently, single bonds, -O-, -C(=O)-, -C(=O)O-, -OC(=O)-, and -N(CH ３ )-, -C(=O)NH-, -C(=O)N(CH ３ )-, -NHC(=O)-, -N(CH ３ ) represents C(=O)-, -NH-, or -NH-C(=O)-NH-. L represents a single bond or an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or a monovalent organic group. X １ This represents one of the following equations (X1-a) to (X1-c). Y １ This represents one of the following formulas (Y1-a) to (Y1-e). *1 represents a bond to the main chain derived from one of the above formulas (m-1) to (m-5). (In formulas (X1-a) to (X1-c), １ａ and X １ｂ Each of these independently represents a single bond, an aromatic group, or an alicyclic group.１ｃ and X １ｄ each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms. When X １ａ is a single bond, X １ｃ is an alkylene group having 1 to 6 carbon atoms. When X １ｂ is a single bond, X １ｃ is an alkylene group having 1 to 6 carbon atoms. X １ｅ represents a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-, -NHCO- or -N(CH ３ )CO-. When X １ａ is a single bond, X １ｅ is also a single bond. X ａ and X ｂ each independently represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 3 carbon atoms. *2 represents a bonding hand to A ２ ) (In formulas (Y1-a) to (Y1-e), Y １ａ represents a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-, -NHCO- or -N(CH ３ )CO-. Y １ｂ represents a single bond or an alkylene group having 1 to 6 carbon atoms. *2 represents a bonding hand to A ２ )

[0027] X １ａ and X １ｂ The aromatic ring in the aromatic group of may be a monocyclic ring or a polycyclic ring. The polycyclic ring may be a fused ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. X １ａ and X １ｂ The aliphatic ring in the alicyclic group of may be a monocyclic ring or a polycyclic ring. The polycyclic ring may be a fused ring or a bridged ring. Examples of the aliphatic ring include a cyclohexane ring.

[0028] Examples of the structure represented by formulas (p-1a) to (p-1g) below are given for formula (p-1). (In formulas (p-1a) to (p-1g), A １ａ and A １ｂ Each of these independently represents a single bond, -O-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, -NHC(=O)-, or -NH-. １ｄ X represents a single bond or an alkylene group having 1 to 6 carbon atoms. ａ and X ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. n represents an integer from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5).

[0029] Examples of the structure represented by the following equations (p-2a) to (p-2f) are given by equation (p-2). (In formulas (p-2a) to (p-2f), A １ａ and A １ｂ These independently represent a single bond, -O-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, -NHC(=O)-, or -NH-. １ｃ represents a single bond or an alkylene group having 1 to 6 carbon atoms. n represents an integer from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5).

[0030] More specifically, the structure represented by the following equations (p-1-1) to (p-1-7) is an example of the aforementioned equation (p-1).

[0031] (In formulas (p-1-1) to (p-1-7), X ａ and X ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. n is the number of methylene groups, ranging from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5).

[0032] More specifically, the structure represented by the following formulas (p-2-1) to (p-2-8) is an example of (p-2).

[0033] (In formulas (p-2-1) to (p-2-8), n is the number of methylene groups, ranging from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5).)

[0034] The polymer (P) may have mesogenic groups in its side chains that do not have terminal carboxyl groups, represented by the following formula (p-3) or (p-4). (In equations (p-3) and (p-4), A １ and A ２ These are, independently, single bonds, -O-, -C(=O)-, -C(=O)O-, -OC(=O)-, and -N(CH ３ )-, -C(=O)NH-, -C(=O)N(CH ３ )-, -NHC(=O)-, -N(CH ３ ) represents C(=O)-, -NH-, or -NH-C(=O)-NH-. L represents a single bond or an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or a monovalent organic group. X ２ This represents one of the following equations (X²-a) to (X²-b). ２ This represents one of the following formulas (Y2-a) to (Y2-e). *1 represents a bond to the main chain derived from one of the above formulas (m-1) to (m-5). (In formulas (X2-a) to (X2-b), ２ａ and X ２ｂ Each of these independently represents a single bond, an aromatic group, or an alicyclic group. ２ｃ X represents a single bond or an alkylene group having 1 to 6 carbon atoms. ２ｄ These are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) Represents CO. X ２ｅ These are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３)-,-NHCO- or-N(CH ３ ) Represents CO. X ２ｂ When it is a single bond, X ２ｄ It is a single bond. In equation (X²-a), X ２ａ When it is a single bond, X ２ｅ It is a single bond. In equation (X²-b), X ２ａ When it is a single bond, X ２ｃ X is an alkylene group having 1 to 6 carbon atoms. ａ and X ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. Q １ * represents a hydrogen atom, -CN, halogen group, C1-C5 alkyl group, (C1-C5 alkyl)carbonyl group, C3-C7 cycloalkyl group, or C1-C5 alkoxy group. *2 is A ２ (This represents a combination of two elements.) (In equations (Y2-a) to (Y2-e), Q １ * represents a hydrogen atom, -CN, halogen group, C1-C5 alkyl group, (C1-C5 alkyl)carbonyl group, C3-C7 cycloalkyl group, or C1-C5 alkoxy group. *2 is A ２ (This represents a combination of two elements.)

[0035] X ２ａ , and X ２ｂ The aromatic ring in the aromatic group may be a monocyclic or polycyclic ring. The polycyclic ring may be a fused ring. Examples of aromatic rings include benzene rings and naphthalene rings. ２ａ , and X ２ｂ The aliphatic ring in the alicyclic group may be monocyclic or polycyclic. The polycyclic ring may be fused or bridged. An example of an aliphatic ring is a cyclohexane ring.

[0036] Examples of the above formula (p-3) include structures represented by the following formulas (p-3a) to (p-3h). (In formulas (p-3a) to (p-3h), A １ａ and A １ｂEach of these independently represents a single bond, -O-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, -NHC(=O)-, or -NH-. １ｅ X represents a single bond or an alkylene group with 1 to 6 carbon atoms. ａ and X ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. n represents an integer from 2 to 10. Q １ *1 represents a hydrogen atom, -CN, halogen group, C1-C5 alkyl group, (C1-C5 alkyl)carbonyl group, C3-C7 cycloalkyl group, or C1-C5 alkoxy group.

[0037] Examples of structures represented by the formula (p-3) include those represented by (p-3-1) to (p-3-10).

[0038] (In formulas (p-3-1) to (p-3-10), X ａ and X ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. Q １ represents a hydrogen atom, -CN, halogen group, C1-C5 alkyl group, (C1-C5 alkyl)carbonyl group, C3-C7 cycloalkyl group, or C1-C5 alkoxy group. n is the number of methylene groups, ranging from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5).

[0039] More specifically, the structure represented by the following equations (p-4-1) to (p-4-5) is an example of the aforementioned (p-4). (In formulas (p-4-1) to (p-4-5), Q １ represents a hydrogen atom, -CN, halogen group, C1-C5 alkyl group, (C1-C5 alkyl)carbonyl group, C3-C7 cycloalkyl group, or C1-C5 alkoxy group. n is the number of methylene groups, ranging from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5).

[0040] Some monomers that give the above structure are commercially available, while others can be produced by methods such as those described in International Publication WO2014 / 054785.

[0041] Examples of polymers (P) used in the present invention include the following polymers: • A (co)polymer of monomers containing a monomer having a group represented by formula (p-1) • A copolymer of a monomer mixture containing a monomer having a group represented by formula (p-1) and a monomer having a group represented by formula (p-2) • A copolymer of a monomer mixture containing a monomer having a group represented by formula (p-1) and a monomer having a group represented by formula (p-4) • A copolymer of a monomer mixture containing a monomer having a group represented by formula (p-2) and a monomer having a group represented by formula (p-3)

[0042] (Other functional groups) The polymer (P) may have other functional groups other than the mesogenic group described above. Examples of other functional groups include crosslinking groups or groups having a heterocycle of five or more members for the purpose of assisting in the curing process.

[0043] Polymer (P) may have, for example, other functional groups in its side chains. Polymer (P) may also have structural units (X2) having other functional groups in their side chains. Structural units (X2) having other functional groups in their side chains are, for example, structural units derived from monomer compounds having polymerizable unsaturated bonds and other functional groups.

[0044] ((Crosslinkable Group)) A crosslinkable group is a functional group selected from the group consisting of an oxetanyl group, an oxyranyl group, a carboxyl group, and a hydroxyl group.

[0045] The polymer (P) has, for example, a crosslinkable group in its side chain. When the polymer (P) has a crosslinkable group, the polymer (P) is a structural unit (X) having a crosslinkable group in its side chain. ＣＬ It is preferable to have a structural unit (X) having a crosslinkable group in the side chain. ＣＬ ) is, for example, a structural unit derived from a monomer compound having polymerizable unsaturated bonds and crosslinkable groups.

[0046] The above structural unit (XＣＬ Examples of monomer compounds that give ) include (meth)acrylate glycidyl, α-ethylacrylate glycidyl, α-n-propylacrylate glycidyl, α-n-butylacrylate glycidyl, (meth)acrylate 3,4-epoxybutyl, α-ethylacrylate 3,4-epoxybutyl, (meth)acrylate 3,4-epoxycyclohexylmethyl, (meth)acrylate 6,7-epoxyheptyl, α-ethylacrylate 6,7-epoxyheptyl, (meth)acrylate 3-methyl-3-oxetanylmethyl, (meth)acrylate (3-ethyloxetan-3-yl) Examples include methyl, 4-hydroxybutyl glycidyl ether (meth)acrylate, and compounds having an oxetanyl group or an oxyranyl group such as those of the following formulas (G1) to (G3); carboxyl group-containing compounds such as (meth)acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and hydroxyl group-containing compounds such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0047] (Groups having heterocyclic rings of 5 or more members for the purpose of curing assistance) Examples of heterocyclic rings in groups having heterocyclic rings of 5 or more members include cyclic amines such as piperidine, piperazine, 1,2,3-triazole, purine, 1,4-diazabicyclo[2.2.2]octane (triethylenediamine), quinuclidine, morpholin, diazabicycloundecene (DBU), diazabicyclononene (DBN), and N,N-dimethyl-4-aminopyridine (DMAP); and aromatic heterocyclic rings such as pyridine, pyrrole, imidazole, or acridine.

[0048] A group having a heterocycle with five or more members is, for example, a residue obtained by removing a hydrogen atom from a heterocycle with five or more members.

[0049] The polymer (P) has, for example, a group having a heterocyclic ring of five or more members in its side chain. When the polymer (P) has a group having a heterocyclic ring of five or more members, the polymer (P) has a structural unit (X) having a group having a heterocyclic ring of five or more members in its side chain. ｈｔ It is preferable to have a structural unit (X) having a group having a heterocycle of 5 or more members in its side chain. ｈｔ ) is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a group having a heterocyclic ring of five or more members.

[0050] The above structural unit (X ｈｔ Examples of monomeric compounds that give ) include the following compounds (ht-1) to (ht-2).

[0051] The polymer (P) of the present invention may have structural units other than structural unit (X) (hereinafter also referred to as other structural units). Preferably, the other structural units are structural units derived from monomer compounds having polymerizable unsaturated bonds.

[0052] In the present invention, examples of groups or structures having polymerizable unsaturated bonds include (meth)acryloyl groups, maleimide groups, styryl groups, vinyl groups, and α-methylene-γ-butyrolactone structures.

[0053] The polymer (P) of the present invention can be obtained, for example, by polymerizing a monomer compound having at least one polymerizable unsaturated bond and at least one functional group.

[0054] Furthermore, if the polymer (P) of the present invention has the above-mentioned other structural units, it can be obtained by polymerizing a monomer compound having at least one of the above-mentioned polymerizable unsaturated bonds and at least one of the above-mentioned other functional groups. In addition, the polymer (P) of the present invention may also contain structural units derived from monomer compounds other than the above-mentioned monomer compounds. Specific examples of other monomer compounds include (meth)acrylic acid ester compounds, maleimide compounds, maleic anhydride, styrene compounds, vinyl compounds, (meth)acrylamide compounds, and the like.Methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, benzyl (meth)acrylate, naphthyl (meth)acrylate, anthryl (meth)acrylate, anthrylmethyl (meth)acrylate, phenyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 2-methoxyethyl (meth)acrylate (meth)acrylic acid ester compounds such as acrylate, methoxytriethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-propyl-2-adamantyl (meth)acrylate, 8-methyl-8-tricyclodecyl (meth)acrylate, 8-ethyl-8-tricyclodecyl (meth)acrylate, etc. Maleimide compounds such as N-benzylmaleimide, 4-maleimidobutyric acid, N-methoxycarbonylmaleimide, and N-cyclohexylmaleimide; styrene compounds such as styrene, 4-methylstyrene, 4-vinylphenylboronic acid, 4-vinylbenzoic acid, and trans-anethole; vinyl compounds such as vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether; styrene compounds such as styrene, 4-methylstyrene, 4-chlorostyrene, and 4-bromostyrene; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; (meth)acrylamide compounds such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-(hydroxymethyl)(meth)acrylamide, N-isopropyl(meth)acrylamide, N-propyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-(methoxymethyl)(meth)acrylamide, and N-(butoxymethyl)(meth)acrylamide.

[0055] In the polymer (P) of the present invention, the content of structural units derived from monomer compounds having a group represented by formula (p-1) and a polymerizable unsaturated bond is preferably 3 mol% or more, and more preferably 5 mol% or more, based on 100 mol% of the total structural units of polymer (P). In the polymer (P) of the present invention, the content of structural units derived from monomer compounds having a group represented by formula (p-2) and a polymerizable unsaturated bond is preferably 5 mol% or more, and more preferably 10 mol% or more, based on 100 mol% of the total structural units of polymer (P).

[0056] In the polymer (P) of the present invention, the content of structural units (Y) derived from monomer compounds having a carboxyl group and a polymerizable unsaturated bond is preferably 3 mol% or more, and more preferably 5 mol% or more, based on 100 mol% of the total structural units of the polymer (P), from the viewpoint of interaction with the specific compound (A) and the resulting improvement of the exposure margin. It may also be 100 mol%, but from the viewpoint of reliability, including light resistance after commercialization, it is preferably 80 mol% or less, and more preferably 60 mol% or less.

[0057] The content of the above-mentioned other structural units and structural units derived from other monomer compounds in the polymer (P) of the present invention is the remaining portion when the content of structural unit (X) is less than 100 mol%. From the viewpoint of deterioration of the phase difference value due to the introduction of non-oriented components, the content of the above-mentioned other structural units and structural units derived from other monomer compounds in the polymer (P) of the present invention is preferably 40 mol% or less, and preferably 30 mol% or less, with respect to the total of 100 mol% of structural units in the polymer (P).

[0058] (Synthesis of Polymer (P)) The polymerization method for a specific polymer does not need to be particularly limited, but for example, it can be synthesized by free radical polymerization or living radical polymerization (nitroxide-mediated radical polymerization (NMP) using nitroxide as the dormant species), atom transfer radical polymerization (ATRP) using metal complexes, reversible addition-cleavage chain transfer (RAFT) polymerization using sulfur compounds as the dormant species, reversible transfer catalytic polymerization (RTCP) using alkyl iodide compounds as the dormant species and phosphorus compounds or alcohols as catalysts, etc.), or chain transfer polymerization. In this case, when using living radical polymerization, it is preferable to use RAFT polymerization because the inclusion of metal residues or halogen compounds may adversely affect each property.

[0059] The polymer (P) can be obtained by a polymerization reaction using a monomer compound having polymerizable unsaturated bonds, and is preferably obtained by a radical polymerization reaction. Examples of polymerization initiators used in this polymerization reaction include initiators that are normally used in radical polymerization, such as azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl; organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, and 1,1'-bis(t-butylperoxy)cyclohexane; hydrogen peroxide; and redox-type initiators consisting of these peroxides and reducing agents. Among these, azo compounds are preferred, and 2,2'-azobis(isobutyronitrile) or 2,2'-azobis(isobutyric acid)dimethyl are more preferred. These can be used as polymerization initiators, either individually or in combination of two or more. The amount of polymerization initiator used is preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 40 parts by mass, per 100 parts by mass of the total monomer compound used in the reaction.

[0060] The polymerization reaction of the above polymer (P) is preferably carried out in an organic solvent. Examples of organic solvents used in this reaction include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds. Specific examples include tetrahydrofuran, cyclopentanone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, pro Pyrene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,Examples include 4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. These can be used individually or in combination of two or more as organic solvents. Furthermore, in radical polymerization reactions, oxygen in organic solvents inhibits the polymerization reaction; therefore, it is preferable to use organic solvents that have been degassed to the greatest extent possible.

[0061] In the polymerization reaction of the above polymer (P), the reaction temperature is preferably 30 to 120°C, and more preferably 60 to 110°C. The reaction time is preferably 1 to 36 hours, and more preferably 2 to 24 hours. Furthermore, the amount of organic solvent used (a) is preferably such that the total amount of monomers used in the reaction (b) is 0.1 to 50% by mass of the total amount of the reaction solution (a + b).

[0062] The polymer (P) of the present invention, considering the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film, preferably has a weight-average molecular weight of 2,000 to 2,000,000 as measured by the GPC (Gel Permeation Chromatography) method, more preferably 2,000 to 1,000,000, and even more preferably 5,000 to 500,000.

[0063] The content of polymer (P) in the polymer composition is not particularly limited, but is preferably 1 to 30% by mass, and more preferably 5 to 30% by mass.

[0064] [Specific Compound (A)] Specific compound (A) is the compound represented by the following formula (a-1). (In formula (a-1), X is a carboxyl group, and substituent R ５ R represents a pyridyl group or dialkylamino group which may have one or more of these groups. ３ This is a hydrogen atom, Ar-R ４ - Represents a group, (meth)acryloyloxyalkyl group, a linear alkyl group having 1 to 20 carbon atoms, or a branched alkyl group having 2 to 20 carbon atoms, or a saturated hydrocarbon group having 3 to 20 carbon atoms including a cycloalkyl group, R ４ represents a single bond or a divalent organic group. Ar represents a substituent R. ５ Represents a monovalent aromatic hydrocarbon group which may have one or more substituents R ５ R represents a monovalent group that does not have a chain-linking group. A pyridyl group or Ar is a substituent R. ５ If there are multiple substituents R ５ They may be the same or different from each other.

[0065] In the above formula (a-1), R ３Examples of linear or branched alkyl groups represented by include alkyl groups having 1 to 20 carbon atoms, with alkyl groups having 1 to 5 carbon atoms being preferred. Examples of such alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n Examples include butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-eicosyl group. Among these, methyl group, ethyl group, n-propyl group, n-butyl group, and isobutyl group are preferred.

[0066] In the above formula (a-1), R ３Examples of saturated hydrocarbon groups having 3 to 20 carbon atoms that include a cycloalkyl group as represented by include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, 2-cyclopropylethyl group, 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, and 2-cycloheptylethyl group. Among these, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, and 2-cyclohexylethyl group are preferred.

[0067] In the above formula (a-1), R ３ Ar-R ４ - If it is a group, R is a divalent organic group that connects X and Ar. ４ It is preferable that is a divalent group selected from the following formulas (b-1) and (b-2). (In formulas (b-1) to (b-2), R ６ R represents an alkylene group with 1 to 10 carbon atoms. ７ and R ８ Each of these independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a cyano group. (*1 represents a bond with X, and *2 represents a bond with Ar.)

[0068] R ６ The alkylene group may be branched. In formula (b-2), R ７ and R ８ The carbon-carbon double bond may be bonded at the cis position or at the trans position.

[0069] In the above formula (a-1), R ３ Ar-R ４ - If it is a group, substituent R ５ Examples of aromatic hydrocarbon groups that may have a monovalent aromatic hydrocarbon group include phenyl groups, biphenyl groups, and terphenyl groups.

[0070] substituent R ５Examples of monovalent groups that do not have a chain-like linking group include halogen atoms, hydroxyl groups, alkoxy groups having 1 to 2 carbon atoms, cyano groups, cycloalkyl groups having 3 to 6 carbon atoms, pyridyl groups, dialkylamino groups, and (meth)acryloyloxy groups. Examples of alkyl groups in dialkylamino groups include methyl groups and ethyl groups.

[0071] For example, Ar in equation (a-1) can be given by the following equation (c). (In formula (c), R ９ R represents a halogen atom, a hydroxyl group, a carbon-1 to carbon-2 alkoxy group, a cyano group, a carbon-3 to carbon-6 cycloalkyl group, a pyridyl group, a dialkylamino group, or a (meth)acryloyloxy group, where m is an integer from 0 to 2 and n is an integer from 0 to 5. ９ If there are multiple instances of R, then multiple R ９ They may be the same or different from each other. *3 is R ４ (This represents a combination of two elements.)

[0072] Examples of specific compounds (A) include those represented by the following group of compounds. (In the above formula, R １２ ~R １４ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, except R １２ , R １３ and R １４ The total number of carbon atoms is between 0 and 19. １５ R represents a hydrogen atom, a methyl group, a cyano group, or a phenyl group. １６ represents a hydrogen atom, a methyl group, or a cyano group. Cy represents a cycloalkyl group having 3 to 8 carbon atoms. n3 represents an integer from 0 to 10, and n4 represents an integer from 1 to 5. Q represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic group having 3 to 6 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, an acryloyloxy group, or a methacryloyloxy group. Q ２ (This represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alicyclic group having 3 to 6 carbon atoms, an acryloyloxy group, or a methacryloyloxy group.)

[0073] R １２~R １４ The alkyl group may be branched. １６ The hydrocarbon group may be branched.

[0074] R １６ Examples of hydrocarbon groups include alkyl groups, aromatic hydrocarbon groups which may be substituted with alkyl groups, and aralkyl groups. An example of an aromatic hydrocarbon group is the phenyl group. Examples of aralkyl groups include the benzyl group and the phenethyl group.

[0075] The content of specific compound (A) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 part by mass or more, when the polymer component (e.g., polymer (P)) in the polymer composition is 100 parts by mass. Furthermore, the content of specific compound (A) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, when the polymer component (e.g., polymer (P)) in the polymer composition is 100 parts by mass.

[0076] [(B) Organic Solvents] The polymer composition of the present invention preferably contains an organic solvent (good solvent). The organic solvent (good solvent) is not particularly limited as long as it is an organic solvent that dissolves the polymer components. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylphosphoramide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropane Examples include ionamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, cyclopentanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, tetrahydrofuran, tetrahydrofurfuryl alcohol, etc. These may be used individually or in combination of two or more.

[0077] Furthermore, the polymer composition of the present invention may contain a solvent (poor solvent) that improves the uniformity of film thickness and surface smoothness when the polymer composition is applied.

[0078] Specific examples of solvents (poor solvents) that improve the uniformity of film thickness and surface smoothness include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate Tate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, vinegar Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate,Examples of solvents with low surface tension include propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, and 2-(2-ethoxypropoxy)propanol.

[0079] The poor solvent may be used alone or as a mixture of two or more. When a poor solvent is used, its content is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass, in the solvent so as not to significantly reduce the solubility of the polymer.

[0080] The content of organic solvents in the polymer composition is not particularly limited, but is preferably 70 to 99% by mass, more preferably 75 to 99% by mass, and particularly preferably 80 to 99% by mass, based on 100% by mass of the polymer composition.

[0081] The polymer composition of the present invention may additionally contain components other than the polymer (P) and the solvent (hereinafter also referred to as additive components). Examples of such additive components include compounds that improve film thickness uniformity and surface smoothness, compounds that increase the strength of the film (hereinafter also referred to as crosslinking compounds), adhesion aids that improve the adhesion between the film and the substrate, and photosensitizers.

[0082] Compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples of these include F-Top® 301, EF303, EF352 (manufactured by Tochem Products), Megafac® F171, F173, F560, F563, R-30, R-40, R-41 (manufactured by DIC), Florard FC430, FC431 (manufactured by 3M), Asahiguard® AG710 (manufactured by AGC), Surflon® S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical), BYK-302, BYK-331, BYK-348, BYK-360N, BYK-381, BYK-3441 (manufactured by BYK), and others. The content of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component (e.g., polymer (P)) contained in the polymer composition.

[0083] Examples of the above crosslinkable compounds include at least one crosslinkable compound selected from the group consisting of a crosslinkable compound (c-1) having at least one substituent selected from epoxy groups, oxetanyl groups, oxazoline structures, cyclocarbonate groups, blocked isocyanate groups, hydroxyl groups, and alkoxy groups, and a crosslinkable compound (c-2) having a polymerizable unsaturated group. The above crosslinkable compounds preferably have a molecular weight of 10 or more, and preferably low molecular weight compounds of 2000 or less. Preferred specific examples of the above crosslinkable compounds (c-1) and (c-2) include the following compounds. Compounds containing epoxy groups include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A type epoxy resins such as Epicote 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resins such as Epicote 807 (manufactured by Mitsubishi Chemical Corporation), and hydrogenated bisphenol F epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation). Compounds in which a tertiary nitrogen atom is bonded to an aromatic carbon atom, such as phenol A type epoxy resin, biphenyl skeleton-containing epoxy resins such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), (o,m,p-) cresol novolac type epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), tetrakis(glycidyloxymethyl)methane, N,N,N',N'-tetraglycidyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis[4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane;N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-2-methyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl ) Compounds in which a tertiary nitrogen atom is bonded to an aliphatic carbon atom, such as cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, 1,3,5-tris(N,N-diglycidylaminomethyl)benzene, isocyanurate compounds such as triglycidyl isocyanurate (manufactured by Nissan Chemical Corporation), compounds described in paragraph

[0037] of Japanese Patent Publication No. 10-338880, and compounds described in WO2017 / 170483, etc. Compounds having an oxetanyl group include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (Aronoxetane OXT-121 (XDO)), bis[2-(3-oxetanyl)butyl] ether (Aronoxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), and compounds having two or more oxetanyl groups as described in paragraphs

[0170] to

[0175] of WO2011 / 132751; Compounds having an oxazoline structure include compounds such as 2,2'-bis(2-oxazoline) and 2,2'-bis(4-methyl-2-oxazoline), polymers and oligomers having an oxazoline group such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.), and compounds described in paragraph

[0115] of Japanese Patent Publication No. 2007-286597;Examples of compounds having a cyclocarbonate group include N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N',-di[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine, and the compounds described in paragraphs

[0025] to

[0030] and

[0032] of WO2011 / 155577; Compounds containing a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Tosoh Corporation), and Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals). Examples of commercially available compounds such as those listed below, compounds represented by formulas (bL-1) to (bL-3), compounds having two or more protected isocyanate groups as described in paragraphs

[0046] to

[0047] of Japanese Patent Publication No. 2014-224978, compounds having three or more protected isocyanate groups as described in paragraphs

[0119] to

[0120] of WO2015 / 141598, etc.

[0084] Compounds having a hydroxyl group and / or alkoxy group include N,N,N',N'-tetrakis(2-hydroxyethyl)adipoamide, compounds represented by the following formulas (pL-1) to (pL-4), 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, compounds described in WO2015 / 072554 and paragraph

[0058] of Japanese Patent Publication No. 2016-118753, compounds described in Japanese Patent Publication No. 2016-200798, compounds described in WO2010 / 074269, etc.

[0085] Examples of crosslinkable compounds having polymerizable unsaturated groups include glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-,1,3-mixture), glycerin tris(meth)acrylate, glycerol 1,3-diglycerolate di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, etc.

[0086] The above compounds are examples of crosslinkable compounds and are not limited thereto. For example, other components disclosed on pages 53

[0105] to 55

[0116] of WO2015 / 060357 can be cited. Furthermore, two or more crosslinkable compounds may be combined.

[0087] When using a crosslinkable compound, the content of the crosslinkable compound in the polymer composition is preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymer component (e.g., polymer (P)) contained in the polymer composition.

[0088] Specific examples of compounds that improve adhesion between the film and the substrate include functional silane-containing compounds, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane Xysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonylacetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3 - Aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Examples of compounds include p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatetopropyltriethoxysilane.

[0089] When an adhesion aid is used, the content of the adhesion aid in the polymer composition is preferably 0.1 to 30 parts by mass, and more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer component (e.g., polymer (P)) contained in the polymer composition.

[0090] Examples of the above-mentioned photosensitizers include benzophenone, benzophenone derivatives such as 2,4-dichlorobenzophenone and N,N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, and 9-hydroxymethylanthracene.

[0091] The amount of photosensitizer is not particularly limited, but is preferably 0.2 to 10 parts by mass, and more preferably 0.5 to 7 parts by mass, per 100 parts by mass of the polymer component (e.g., polymer (P)) contained in the polymer composition.

[0092] [Preparation of Polymer Composition] The polymer composition of the present invention is preferably prepared as a coating solution suitable for forming a phase difference material. That is, the polymer composition used in the present invention is preferably prepared as a solution in which polymer (P) and the above-mentioned solvent are dissolved. Here, the content of polymer (P) is preferably 1 to 30% by mass, and more preferably 1 to 20% by mass, in the polymer composition of the present invention.

[0093] The polymer composition of the present invention may contain other polymers in addition to the polymer (P) described above. In this case, the content of the other polymer in the polymer component is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass. Examples of the other polymers include polymers that are not photosensitive side-chain polymers capable of exhibiting liquid crystalline properties, such as poly(meth)acrylates, polyamic acids, and polyimides.

[0094] The polymer composition of the present invention is preferably used as a composition for forming orientation films and a composition for forming phase difference films.

[0095] [Resin film, phase difference material, method for manufacturing phase difference material] The resin film of the present invention is formed from the polymer composition of the present invention. The resin film can be obtained, for example, by step (1) described later. The phase difference material of the present invention has the resin film of the present invention. The phase difference material of the present invention can be manufactured, for example, by a method including the following steps (1) to (3) (hereinafter, manufacturing method (A)). Furthermore, when the polymer composition of the present invention is used as a composition for forming an orientation film, in addition to the above steps (1) to (3), step (4) described later may be added (hereinafter, manufacturing method (B)). Step (1): A step of applying the polymer composition of the present invention onto a substrate to form a coating film (coating film formation step), Step (2): A step of irradiating the coating film with polarized ultraviolet light (light irradiation step), and Step (3): A step of heating the coating film irradiated with ultraviolet light (heating step)

[0096] [Step (1): Coating Film Formation Step] Step (1) is a step of forming a coating film by applying the polymer composition of the present invention onto a substrate. More specifically, the polymer composition of the present invention is applied to a substrate such as a substrate (e.g., silicon / silicon dioxide coated substrate, silicon nitride substrate, glass substrate coated with metal (e.g., aluminum, molybdenum, chromium, etc.), glass substrate, quartz substrate, ITO substrate, etc.) or a film (e.g., triacetylcellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film) by methods such as bar coating, spin coating, flow coating, roll coating, slit coating, spin coating following slit coating, inkjet method, or printing method. After application, the solvent can be evaporated at 50 to 200°C, preferably 50 to 150°C, using a heating means such as a hot plate, a hot air circulation oven, or an IR (infrared) oven to obtain a coating film.

[0097] [Step (2): Light Irradiation Step] In Step (2), polarized ultraviolet light is irradiated onto the coating film obtained in Step (1). When irradiating the film surface of the coating film with polarized ultraviolet light, the polarized ultraviolet light is irradiated onto the substrate from a certain direction via a polarizing plate. As the ultraviolet light, ultraviolet light in the wavelength range of 100 to 400 nm can be used. For example, ultraviolet light in the wavelength range of 290 to 400 nm can be selected and used so as to selectively induce a photocrosslinking reaction. Preferably, the optimal wavelength is selected via a filter or the like depending on the type of coating film used. For example, a bandpass filter (BPF) with a central wavelength of 365 nm or a long-wavepass filter (LWPF) that transmits wavelengths longer than 313 nm can be used to reduce light with a wavelength of 313 nm. As a light source for illumination, for example, low-pressure mercury lamps, high-pressure mercury lamps, deep UV lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury xenon lamps, excimer lasers (e.g., KrF excimer lasers), fluorescent lamps, LED lamps, halogen lamps (e.g., sodium lamps), microwave-excited electrodeless lamps, etc., can be used.

[0098] [Step (3): Heating Step] In step (3), the coating film that was irradiated with polarized ultraviolet light in step (2) is heated. Heating can impart orientation control ability to the coating film. Heating can be performed using heating means such as a hot plate, a hot air circulation oven, or an IR (infrared) oven. The heating temperature can be determined considering the temperature at which the liquid crystalline properties of the coating film used will be exhibited. Preferably, the heating temperature is within the temperature range of the temperature at which the polymer (P) contained in the polymer composition of the present invention exhibits liquid crystalline properties (hereinafter referred to as the liquid crystal expression temperature). Preferably, the temperature range of the heating temperature after irradiation with polarized ultraviolet light is a temperature range with the lower limit of the liquid crystal expression temperature range of the polymer (P) as the lower limit and the upper limit being 10°C lower than the upper limit of that liquid crystal expression temperature range. Note that the liquid crystal expression temperature is a temperature above the liquid crystal transition temperature at which a phase transition occurs from the solid phase to the liquid crystal phase on the surface of the polymer or coating film, and below the isotropic phase transition temperature (Tiso) at which a phase transition occurs from the liquid crystal phase to the isotropic phase. For example, exhibiting liquid crystalline properties at 130°C or below means that the liquid crystal transition temperature at which the phase transition from the solid phase to the liquid crystal phase occurs is 130°C or below. The thickness of the coating film formed after heating can be appropriately selected considering the steps and optical properties of the substrate used, and for example, 0.5 to 10 μm is preferred.

[0099] The phase difference material of the present invention may also be manufactured by using the above polymer composition as an orientation film forming composition, and by a method that includes the following step (4) in addition to the above steps (1) to (3). In this manufacturing method, the thickness of the coating film (orientation film) formed after heating in step (3) can be appropriately selected considering the step height and optical properties of the substrate used, for example, 5 to 300 nm is preferred, and 10 to 200 nm is more preferred.

[0100] [Step (4): Step to form a liquid crystal layer] Step (4) is a step to form a liquid crystal layer by applying a polymerizable liquid crystal to the alignment film obtained in step (3) and curing it. This forms a coating film (liquid crystal layer) containing polymerizable liquid crystal. The polymerizable liquid crystal used here is a polymerizable liquid crystal compound or liquid crystal composition that polymerizes by at least one of the following treatments: heating and light irradiation. Conventionally known polymerizable liquid crystals can be used, and nematic liquid crystal compounds can be mentioned. Cholesteric liquid crystals; discotic liquid crystals; twisted nematic alignment liquid crystals with chiral agents added may also be used. The polymerizable liquid crystal compound preferably has polymerizable functional groups that can be three-dimensionally crosslinked within the molecule. Examples of such polymerizable functional groups include polymerizable functional groups that polymerize by the action of ultraviolet light, ionizing radiation such as electron beams, or heat. Representative examples of these polymerizable functional groups include radical polymerizable functional groups and cationic polymerizable functional groups. Typical examples of radically polymerizable functional groups include functional groups having at least one addition polymerizable ethylenically unsaturated double bond. Specific examples include substituted or unsubstituted vinyl groups, acrylate groups (a general term encompassing acryloyl groups, methacryloyl groups, acryloyloxy groups, and methacryloyloxy groups), etc. Specific examples of cationically polymerizable functional groups include epoxy groups. Other polymerizable functional groups include, for example, isocyanate groups and unsaturated triple bonds. Among these, functional groups having ethylenically unsaturated double bonds are preferred from a process standpoint. Furthermore, liquid crystal compounds having polymerizable functional groups at their terminals are particularly preferred. The polymerizable liquid crystal may be a mixture of multiple liquid crystal compounds, and may be a composition containing other liquid crystal compounds (excluding polymerizable liquid crystal compounds), other polymerizable compounds (excluding polymerizable liquid crystal compounds), known polymerization initiators, surfactants, photosensitizers, chain transfer agents, antioxidants, ultraviolet absorbers, radical scavengers, light stabilizers, optically active compounds, silane coupling agents, solvents, etc. Examples of commercially available polymerizable liquid crystals include RMS03-013C and RMS16-089 manufactured by Merck.

[0101] To coat the polymerizable liquid crystal as described above onto the alignment film formed in step (3), an appropriate coating method such as a bar coater, roll coater, spinner, printing method, or inkjet method can be used. Next, the polymerizable liquid crystal coating film formed as described above is subjected to one or more treatments selected from heating and light irradiation to cure the coating film and form a liquid crystal layer. It is preferable to perform these treatments in superposition, as this yields good alignment. The heating temperature of the coating film should be appropriately selected depending on the type of polymerizable liquid crystal used. For example, it may be heated to a temperature in the range of 40 to 80°C, and the heating time can be, for example, 0.5 to 5 minutes. Unpolarized ultraviolet light having a wavelength in the range of 200 to 500 nm can preferably be used as the irradiation light. The amount of light irradiation is 50 to 10,000 mJ / cm². ２ Preferably, the concentration is 100 to 5,000 mJ / cm². ２ It is preferable to do so.

[0102] The phase difference material of the present invention obtained by the above manufacturing method (A) or (B) is a material having optical properties suitable for applications such as display devices and recording materials, and is particularly suitable as an optical compensation film such as a polarizer and phase difference plate for liquid crystal displays and organic EL displays.

[0103] The present invention will be described in more detail below with reference to synthesis examples, preparation examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0104] The monomers used in the examples are shown below. The side chains derived from MA-1 to MA-5 have the structure represented by formula (p-1), and the side chains derived from MB-1 to MB-8 have the structure represented by formula (p-2).

[0105]

[0106] (Specific compound) (Me represents a methyl group.)

[0107]

[0108] (Chain transfer agent)

[0109] The abbreviations for the reagents used in this example are as follows: (Organic solvent) CPN: Cyclopentanone NMP: N-methyl-2-pyrrolidone (Polymerization initiator) AIBN: 2,2'-azobisisobutyronitrile

[0110] [1] Synthesis of Polymers <Synthesis Example 1> MA-1 (4.00 g, 12.0 mmol), MB-1 (20.9 g, 68.2 mmol), R-1 (32.4 mg, 0.0803 mmol), AIBN (6.59 mg, 0.0401 mmol), and NMP (37.4 g) were weighed into a 100 ml two-necked flask and stirred at room temperature for 20 minutes to dissolve. The reaction solution was purged with nitrogen by nitrogen bubbling and then heated and stirred in an oil bath set to 60°C for 24 hours. After heating and stirring, the reaction solution was added to methanol (300 g) and the polymer was reprecipitated. Subsequently, the polymer was washed by filtration and methanol washing three times and dried to obtain polymer powder P-1. The weight-average molecular weight (hereinafter also referred to as "Mw") of the obtained polymer was 192,300, and the polydispersity (hereinafter also referred to as "PDI") obtained from weight-average molecular weight / number-average molecular weight was 1.8.

[0111] <Synthesis Examples 2-10> As shown in Table 1 below, polymer powders P-2 to P-10 were obtained by performing the same procedure as in Synthesis Example 1, except that the type and amount (g) of polymerization control agent used and the amount of AIBN were changed.

[0112]

[0113] [2] Preparation of phase difference film forming material <Preparation example 1> CPN (8.60 g) was added to polymer powder P-1 (1.40 g) obtained in synthesis example 1 and stirred. This was filtered through a 5.0 μm pore size filter to obtain polymer preparation solution PD-1. This polymer preparation solution PD-1 was used as is as a coating solution for forming a phase difference film.

[0114] <Preparation Example 2> Polymer powders P-1 (1.26 g) and AM-1 (0.14 g) obtained in Synthesis Example 1 were mixed with CPN (8.60 g) and stirred. This was filtered through a 5.0 μm pore size filter to obtain polymer preparation solution PD-1. This polymer preparation solution PD-2 was used as a coating solution to form a phase difference film.

[0115] <Preparation Examples 3-54> As shown in Table 2 below, polymer preparation solutions PD-3 to 54 were obtained by performing the same procedure as in Preparation Example 2, except that the type and amount (g) of polymer powder used and the type and amount (g) of additives (specific compound, MA-1 or MB-1) were changed.

[0116]

[0117]

[0118] [3] Manufacturing of a single-layer phase difference film <Example 1> Polymer preparation solution PD-1 was applied to a COP (cycloolefin polymer) film substrate using a bar coater to a thickness of approximately 3.6 μm. This substrate was dried in a hot air circulating oven at 50°C for 3 minutes (first drying), and then exposed to ultraviolet light at a wavelength of 365 nm at a rate of 100-300 mJ / cm² from a high-pressure mercury lamp via a cut filter (325 nm low-cut filter) and a polarizing plate. ２ The substrate was irradiated with [a specific light source]. Subsequently, it was heated in an IR oven at 120-140°C for 5 minutes (second drying) to produce the phase difference film-coated substrate PDF-1.

[0119] <Examples 2-30, 91-104, Comparative Examples 1-3, 10-16> As shown in Tables 3-1, 3-2, and 3-3 below, the same procedure as in Example 1 was performed except for changing the type of polymer preparation solution to obtain the phase difference film substrates PDF-2 to 54.

[0120]

[0121]

[0122]

[0123] For each of the phase difference film-coated substrates PDF-1 to PDF-54, the phase difference and Nz coefficient under each exposure and firing condition were evaluated using the method described below, and the results are summarized in Tables 4-1, 4-2, and 4-3.

[0124] [Phase Difference Evaluation] The linear phase difference, Nz coefficient, and refractive index in the N-axis direction (nz') at a wavelength of 550 nm were measured using an AxoScan from Axometrics, and the results are summarized in Tables 4-1 and 4-2. The Nz coefficient is calculated using the following formula (eq1), where nx' is the refractive index in the slow phase axis direction, ny' is the refractive index in the fast phase axis direction, nz' is the refractive index in the polar angle direction, and d represents the phase difference film thickness.

[0125]

[0126]

[0127]

[0128] From Examples 1-30 and 105-118 in Tables 4-1 to 4-3, it can be seen that phase difference films prepared using the specific compound tend to have a higher phase difference value compared to phase difference films that do not use the specific compound (Comparative Example 1). This is thought to be due to the fact that the specific compound interacts with the mesogens constituting the polymer liquid crystal in the phase difference film via hydrogen bonding, increasing the apparent refractive index of the mesogens, and that these interact cooperatively with the mesogens that are not compounded, resulting in reorientation.

[0129] When comparing the phase difference values ​​at low-temperature firing (120°C) and high-temperature firing (140°C) for phase difference films made using a specific compound (Examples 1-30) and for phase difference films without the specific compound (Comparative Example 1), it can be seen that the phase difference films made using the specific compound consistently show higher phase difference values ​​at low-temperature firing (120°C). This is thought to be because the thermal mobility of the mesogen improved when the specific compound was used. By using the specific compound, a large phase difference value can be achieved even at low-temperature firing, thus suppressing deterioration of the substrate due to heat and making it possible to use substrates with low heat resistance. Therefore, it becomes possible to produce phase difference films that are not restricted by substrate type or process.

[0130] While the phase difference value at low-temperature firing (120°C) increases with the use of specific compounds, there is a certain degree of variation in the extent of this increase. This indicates that the phase difference increase effect at low-temperature firing depends on the intrinsic structure of the specific compound used, and is thought to be derived from the physical properties of the specific compound. Preferred conditions for the specific compound include high compatibility with the polymer (P), exhibiting liquid crystalline properties when compounded, and being a compounded mesogen that is easily reoriented. Specific examples of preferred specific compounds include the group of specific compounds that do not have chain-like linking groups, as can be seen from the phase difference values ​​at low-temperature firing in Examples 1-30, Examples 105-118, Comparative Examples 2-3, and Comparative Examples 17-23.

[0131] Examples 1 to 30 show that even when specific compounds are used, the Nz coefficient is always in the range of 0.4 to 0.6. As described in the background art, an Nz coefficient of around 0.5 is most desirable due to optical compensation, but it can be seen that the desirable refractive index ellipsoid shape can be maintained even when specific compounds are used.

[0132] Examples 5, 27, and 28 showed that the phase difference value increased as the content of the specific compound increased, and remained constant beyond a certain amount. This indicates that the optical properties change depending on the content of the specific compound, and it is preferable to use an amount that maximizes the effect of each agent. If the content of the specific compound is low, the effect of increasing the phase difference value is small, and if the content is high, the characteristic compound does not disperse in the polymer (P) and precipitates on the film surface. The preferred range for the content of the specific compound is 0.1 to 50 parts by mass per 100 parts by mass of polymer, more preferably 0.5 to 30 parts by mass, and even more preferably 1.0 to 20 parts by mass.

[0133] Examples 5, 29, and 30 confirm that the phase difference enhancement effect of using a specific compound can be confirmed even when the type of polymer is changed. From this, it can be seen that the phase difference enhancement effect of using a specific compound does not depend on the synthesis method or type of polymer (P). Polymer (P) may be polymerized by free radical polymerization, chain transfer polymerization, or living radical polymerization.

[0134] [Evaluation of Process Influence] Using the results from Tables 4-1, 4-2, and 4-3, the degree of process influence was evaluated based on the phase difference values ​​when phase difference films were produced under each condition (conditions with different firing temperatures and exposure amounts). The influence of exposure amount and the influence of firing temperature were calculated using the following formulas. The results are shown in Tables 5-1, 5-2, and 5-3 below. Note that the smaller the value, the smaller the variation in phase difference values ​​in response to process variations. Influence of exposure amount (%) = [(R Ｅ３００ -R Ｅ１００ ) / R Ｅ３００ ] x 100 R Ｅ３００ : 130℃, 300mJ / cm ２ Phase difference value R Ｅ１００ :130℃, 100mJ / cm ２ Influence of firing temperature on the phase difference value (%) = [(R Ｔ１４０ -R Ｔ１３０ ) / R Ｔ１４０ ] x 100 R Ｔ１４０ :140℃, 100mJ / cm ２ Phase difference value R Ｔ１３０ :130℃, 100mJ / cm ２ Phase difference value

[0135]

[0136]

[0137]

[0138] Examples 31-60 and 119-132 show that the single-layer phase difference materials of the present invention all exhibited lower process influence compared to Comparative Example 4, which did not use the specific compound. This indicates that when the specific compound is used, the variation in phase difference values ​​due to differences in exposure amount and firing temperature is small (the steepness of the phase difference value is suppressed), and the UV exposure margin and firing temperature margin are expanded. As mentioned above, the polymer (P) contained in the single-layer phase difference material of the present invention has a large phase difference variation due to firing temperature and exposure amount, and narrow process margins have been a major challenge. However, by using the specific compound, this can be mitigated, leading to improvements in manufacturing reproducibility and yield.

[0139] Examples 31-60, Examples 119-132, Comparative Examples 5-6, and Comparative Examples 24-30 show that the variation in phase difference values ​​uniformly decreases when specific compounds are used, but the degree of this decrease varies depending on the specific compound, and the process margin also shows structural dependence on the specific compound. As mentioned above, the degree of this is related to the preferred intrinsic structure of the specific compound and the associated physical properties, and by selecting the specific compound defined in the present invention, it is possible to benefit from improved process margins.

[0140] Examples 36 and 59-60 all show that the variation in phase difference values ​​is lower and the process margin is expanded compared to Comparative Example 4. This indicates that the expansion of the process margin due to the use of a specific compound does not depend on the synthesis method or type of the base polymer (P).

[0141] [Evaluation of crack resistance during transfer] The crack resistance was evaluated by counting the number of cracks that occurred on the surface of the phase difference film when the single-layer phase difference film prepared by the above method was transferred to another substrate. More specifically, the phase difference film prepared on the COP substrate was attached to a glass substrate with an adhesive on its surface, and the single-layer phase difference film was transferred from the COP substrate to the glass substrate by peeling off the COP substrate. The single-layer phase difference film was exposed to ultraviolet light at 100 mJ / cm². ２ The products were manufactured at a firing temperature of 130°C. The results are shown in Tables 6-1, 6-2, and 6-3 below.

[0142]

[0143]

[0144]

[0145] Examples 61-90, 133-146, Comparative Examples 7-9, and Comparative Examples 31-37 show that the single-layer phase difference material of the present invention exhibits fewer cracks during transfer and improved crack resistance. Cracks occur due to the weak mechanical strength of the phase difference material itself and the accumulated stress during the orientation of the phase difference material. However, by using the specific compound of the present invention, it is thought that the specific compound interacts with the photosensitive groups (e.g., mesogenic groups) constituting the polymer (P), thereby imparting toughness to the polymer (P).

Claims

1. A polymer composition comprising the following polymer (P) and specific compound (A). Polymer (P): a photoresponsive polymer liquid crystal that is a side-chain polymer obtained by polymerizing a polymerizable unsaturated bond represented by any of the following formulas (m-1) to (m-5) and has a mesogen structure in the side chain, wherein the side chain having the mesogen structure has a photosensitive group (p) and a carboxy group on the same side chain or on different side chains. Specific compound (A): a compound represented by the following formula (a-1). (In formulas (m-1) to (m-5), R １ and R ２ each independently represent a hydrogen atom or a methyl group. * represents a bond.) (In formula (a-1), X represents a carboxy group, a pyridyl group which may have one or more substituents R ５ , or a dialkylamino group; R ３ represents a hydrogen atom, an Ar-R ４ - group, a (meth)acryloyloxyalkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 2 to 20 carbon atoms, or a saturated hydrocarbon group having 3 to 20 carbon atoms containing a cycloalkyl group; R ４ represents a single bond or a divalent organic group. Ar represents a monovalent aromatic hydrocarbon group which may have one or more substituents R ５ ; the substituent R ５ represents a monovalent group that does not have a chain linking group. When the pyridyl group or Ar has a plurality of substituents R ５ , the plurality of substituents R ５ may be the same as or different from each other.) 2. The polymer composition according to claim 1, wherein the polymer (P) has at least one of the following groups having the mesogenic structure: a group represented by formula (p-1) and a group represented by formula (p-2). (In equations (p-1) and (p-2), A １ and A ２ These are, independently, single bonds, -O-, -C(=O)-, -C(=O)O-, -OC(=O)-, and -N(CH ３ )-, -C(=O)NH-, -C(=O)N(CH ３ )-, -NHC(=O)-, -N(CH ３ ) represents C(=O)-, -NH-, or -NH-C(=O)-NH-. L represents a single bond or an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or a monovalent organic group. X １ This represents one of the following equations (X1-a) to (X1-c). Y １ This represents one of the following formulas (Y1-a) to (Y1-e). *1 represents a bond to the main chain derived from one of the above formulas (m-1) to (m-5). (In formulas (X1-a) to (X1-c), １ａ and X １ｂ Each of these independently represents a single bond, an aromatic group, or an alicyclic group. １ｃ and X １ｄ Each of these independently represents a single bond or an alkylene group having 1 to 6 carbon atoms. １ａ When it is a single bond, X １ｃ X is an alkylene group having 1 to 6 carbon atoms. １ｂ When it is a single bond, X １ｃ X is an alkylene group having 1 to 6 carbon atoms. １ｅ These are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) Represents CO. X １ａ When it is a single bond, X １ｅ It is also a single bond. ａ and X ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. *2 is A ２ (This represents a combination of two elements.) (In formulas (Y1-a) to (Y1-e), Y １ａ These are single bonds, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ３ )-, -CONH-, -CON(CH ３ )-,-NHCO- or-N(CH ３ ) Represents CO. Y １ｂ * represents a single bond or an alkylene group with 1 to 6 carbon atoms. *2 is A ２ (This represents a combination of two elements.) 3. The polymer composition according to claim 2, wherein the formula (p-1) is represented by any of the following formulas (p-1a) to (p-1g). (In formulas (p-1a) to (p-1g), A １ａ and A １ｂ Each of these independently represents a single bond, -O-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, -NHC(=O)-, or -NH-. １ｄ X represents a single bond or an alkylene group having 1 to 6 carbon atoms. ａ and X ｂ Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. n represents an integer from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5).

4. The polymer composition according to claim 2, wherein the formula (p-2) is represented by any of the following formulas (p-2a) to (p-2f). (In formulas (p-2a) to (p-2f), A １ａ and A １ｂ These independently represent a single bond, -O-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, -NHC(=O)-, or -NH-. １ｃ represents a single bond or an alkylene group having 1 to 6 carbon atoms. n represents an integer from 2 to 10. *1 represents a bond to the main chain derived from any of the above formulas (m-1) to (m-5).

5. In the above formula (a-1), R ４ The polymer composition according to claim 1, wherein the single bond is selected from the following formulas (b-1) and (b-2). (In formulas (b-1) to (b-2), R ６ R represents an alkylene group with 1 to 10 carbon atoms. ７ and R ８ Each of these independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a cyano group. (*1 represents a bond with X, and *2 represents a bond with Ar.) 6. The polymer composition according to claim 1, wherein Ar in formula (a-1) is the following formula (c). (In formula (c), R ９ R represents a halogen atom, a hydroxyl group, a carbon-1 to carbon-2 alkoxy group, a cyano group, a carbon-3 to carbon-6 cycloalkyl group, a pyridyl group, a dialkylamino group, or a (meth)acryloyloxy group, where m is an integer from 0 to 2 and n is an integer from 0 to 5. ９ If there are multiple instances of R, then multiple R ９ They may be the same or different from each other. *3 is R ４ (This represents a combination of two elements.) 7. The polymer composition according to claim 1, wherein the specific compound (A) is selected from the compounds represented by the following group of compounds. (In the above formula, R １２ ~R １４ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, except R １２ , R １３ and R １４ The total number of carbon atoms is between 0 and 19. １５ R represents a hydrogen atom, a methyl group, a cyano group, or a phenyl group. １６ represents a hydrogen atom, a methyl group, or a cyano group. Cy represents a cycloalkyl group having 3 to 8 carbon atoms. n3 represents an integer from 0 to 10, and n4 represents an integer from 1 to 5. Q represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic group having 3 to 6 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, an acryloyloxy group, or a methacryloyloxy group. Q ２ (This represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alicyclic group having 3 to 6 carbon atoms, an acryloyloxy group, or a methacryloyloxy group.) 8. A composition for forming a phase difference film, which is a polymer composition according to any one of claims 1 to 7.

9. A composition for forming an orientation film, which is a polymer composition according to any one of claims 1 to 7.

10. A method for producing a phase difference material, comprising the following steps (1) to (3): (1) Applying a polymer composition according to any one of claims 1 to 7 onto a substrate to form a coating film; (2) Irradiating the coating film with polarized ultraviolet light; (3) Heating the coating film that has been irradiated with ultraviolet light.

11. A resin film formed from the polymer composition according to any one of claims 1 to 7.

12. A phase difference material comprising the resin film described in claim 11.

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