Polymer composition, composition for forming retardation film, composition for forming alignment film, and retardation material

Abstract

This polymer composition contains the following polymer (P) and compound (A).　Polymer (P): a polymer (P) having a photosensitive group (p) in a side chain. Compound (A): a compound represented by formula (a), wherein in formula (a), R1 represents -COORa, wherein Ra represents a hydrogen atom or a C1-4 alkyl group.　Sp represents a divalent linear linking group.　X represents a group with a valence of (m+n) having a cyclic group.　Y represents -O- or -N(Rb)-, wherein Rb represents a hydrogen atom or a C1-4 alkyl group.　Z represents a monovalent group having a cyclic group.　m is an integer of 0-2. n is an integer of 2-4.　When a plurality of R1, Sp, Y and Z groups are present, the respective R1, Sp, Y and Z groups may be the same or different.

Description

Polymer composition, phase difference film forming composition, orientation film forming composition and phase difference material

[0001] The present invention relates to polymer compositions (particularly compositions for forming phase difference films and compositions for forming alignment films) and phase difference materials containing specific polymer components and compound components. More specifically, the present invention relates to phase difference film forming compositions and alignment film forming compositions 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 phase difference materials obtained from these film forming compositions.

[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 to be used as optical compensation films such as polarizers and phase difference plates. These polymer films are used to change the polarization state of light and are known as films that impart birefringence (also called birefringent films or phase difference films). In the following, materials that change the polarization state of light will also be referred to as phase difference materials. To meet the above 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 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 an acrylic group 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 types of polymerizable liquid crystal compounds having 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 addition, various coating-type birefringent films have been reported, such as birefringent films using a polymerizable liquid crystal compound or its polymer without using an alignment film (Patent Documents 3 and 4), and birefringent films using a polymer containing a photocrosslinkable site (Patent Documents 5 and 6).

[0005] JP-A-62-70407 JP-A-9-208957 JP-T-2002-517605 WO2008 / 031243 JP-A-2008-164925 JP-A-11-189665

[0006] In recent years, the demand for higher quality in liquid crystal displays and organic ELs has been increasing more than ever. In particular, from the viewpoint of obtaining high display quality, a retardation material that realizes high alignment and retardation values is required. As a result of the study by the present inventors, a material that satisfies the above characteristics at a high level has not always been obtained in the prior art.

[0007] An object of the present invention is to provide a retardation material that exhibits a high degree of alignment, an alignment film, and a polymer composition that provide the retardation material.

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that a polymer composition containing a specific polymer and a specific compound is suitable for a composition for forming a retardation film that forms a retardation material typified by a birefringent film and a composition for forming an alignment film that forms an alignment film, and have completed the present invention.

[0009] Therefore, the present invention includes the following aspects. A polymer composition containing the following polymer (P) and compound (A). Polymer (P): A polymer (P) having a photosensitive group (p) in the side chain. Compound (A): A compound represented by the following formula (a) (In formula (a), R １ represents -COORa (Ra represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Sp represents a divalent chain linking group. X represents a (m + n)-valent group having a cyclic group. Y represents -O- or -N(Rb)- (Rb represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Z represents a monovalent group having a cyclic group. m is an integer of 0 to 2. n is an integer of 2 to 4. R １When there are multiple Sp, Y, and Z, each R １ , Sp, Y, and Z may be the same or different. )

[0010] According to the present invention, it is possible to provide a retardation material that exhibits high orientation, an alignment film or a polymer composition that provides the retardation material. Although the mechanism by which the above effects of the present invention are obtained is not necessarily clear, it is considered to be partly due to the following. As a result of the interaction between the functional group (for example, carboxy group) in the side chain of the polymer (P) and the compound (A), a structure that contributes to the improvement of orientation is expressed, and thus it is considered that the above effects are obtained.

[0011] Hereinafter, a polymer composition containing a specific polymer component and a compound component, an alignment film or a retardation material formed using the polymer composition will be described in detail. However, the description of the constituent requirements described below is an example as one embodiment of the present invention, and is not limited to these contents. In the following description, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Also, "tert-" meaning tertiary is also represented as "t-". Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a biphenyl group, and a naphthyl group. Examples of the arylene group include arylene groups having 6 to 20 carbon atoms such as a phenylene group, a biphenylene group, and a naphthylene group. In the present invention, the main chain of the polymer refers to the "trunk" part composed of the longest chain of atoms in the polymer. Also, the side chain of the polymer refers to the part branched from the "trunk" of the polymer.

[0012] Hereinafter, embodiments of the present invention will be described in detail. [Polymer (P)] The polymer composition of the present invention contains a polymer (polymer (P)) having a photosensitive group (p) in the side chain.

[0013] (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. Examples include cinnamic acid groups, azobenzene skeletons, cinnamoyl groups, chalcone groups, coumarin groups, benzophenone groups, phenylbenzoate skeletons, or derivatives thereof, represented by the following formulas (ca-1) to (ca-2). (In formulas (ca-1) and (ca-2), Ar represents a divalent organic group having 6 to 30 carbon atoms and an arylene group, and Ar is -C(X １ ) = Bonded with the carbon atom inside 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.

[0014] In the above formulas (ca-1) and (ca-2), Ar and COOH, or Ar and -C(=O)O-*1 may be bonded to the double bond at the cis position or at the trans position, but it is preferable that they are bonded at the trans position.

[0015] The C1-C3 alkyl group mentioned above may be linear or branched, and specific examples include the methyl group, ethyl group, n-propyl group, and isopropyl group.

[0016] The polymer (P) described above preferably has a structural unit (X) having a photosensitive group (p) in its side chain. The structural unit (X) having a photosensitive group (p) in its side chain is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a photosensitive group (p).

[0017] The polymer (P) may have other functional groups besides the photosensitive group (p). Examples of other functional groups include mesogen-forming groups (m), crosslinking groups, basic functional groups, and thermally detachable groups.

[0018] (Mesogen-forming group (m)) The mesogen-forming group (m) is not particularly limited as long as it can impart liquid crystallinity, and includes not only a mesogen group but also a hydrogen-bonding mesogen group that exhibits liquid crystallinity through intermolecular hydrogen bonds.

[0019] The polymer (P) has, for example, a mesogen-forming group (m) in its side chain. When the polymer (P) has a mesogen-forming group (m), the polymer (P) preferably has a structural unit (X ｍ ) having the mesogen-forming group (m) in its side chain. The structural unit (X ｍ ) having the mesogen-forming group (m) in its side chain is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a mesogen-forming group (m).

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

[0021] Examples of the mesogen group include -Ar １ -Y-Ar ２ -. Here, Ar １ and Ar ２represents 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 a furan ring or a pyran ring; nitrogen-containing heterocycles such as a pyrrole ring or an imidazole ring, etc.). Y represents a single bond, an alkylene group having 1 to 3 carbon atoms, -CH=CH-, -C≡C-, -O-, -COO-, -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 groups. 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 structures can also be used as hydrogen-bonding mesogenic groups: -Ar-X-Ar ３ -COOH -Ar-X-Ar ３ - (Z) ｊ -COOH Here, Ar and Ar ３ Each represents an arylene group which may have substituents, either identical or different. X 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] One preferred embodiment of the above-mentioned photosensitive group (p) is a photosensitive group (p1) represented by the following formula (a1). (In formula (a1), Cy represents a single bond or a divalent organic group represented by the following formula (Ph). L represents a single bond or -O-. R Ｍ R represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms. m is an integer from 1 to 12. R and R' each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms, and some or all of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms. The hydrogen atoms on the benzene ring in formula (a1) may be substituted with substituents selected from the group consisting of alkyl groups, alkyloxy groups, alkenyl groups, alkynyl groups, and halogen atoms. * represents a bond. (In formula (Ph), X represents a single bond, an alkylene group having 1 to 3 carbon atoms, -CH=CH-, -C≡C-, -O-, -N=N-, -COO-, or -OCO-. The hydrogen atoms on the benzene ring in formula (Ph) may be substituted with substituents selected from the group consisting of alkyl groups, alkyloxy groups, alkenyl groups, alkynyl groups, and halogen atoms. *1 represents the bond with L in formula (a1). *2 represents the bond with the benzene ring in formula (a1).)

[0027] In the above formula (a1), the phenylene group and COOR Ｍ The double bond may be bonded at the cis position or at the trans position, but it is preferable that it is bonded at the trans position.

[0028] The above R Ｍ Preferred examples of the monovalent organic group in R include alkyl groups or alkoxyalkyl groups. Alkyl groups may be linear or branched, and specific examples include methyl groups, ethyl groups, n-propyl groups, and isopropyl groups. Examples of alkoxyalkyl groups include methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, and ethoxyethyl groups. The C1-C3 alkyl groups in R and R' may be linear or branched, and specific examples include methyl groups, ethyl groups, n-propyl groups, and isopropyl groups. m is an integer from 1 to 12, preferably from 2 to 10, and more preferably from 2 to 6.

[0029] Examples of alkyl groups as substituents include C1-C3 alkyl groups such as methyl, ethyl, and propyl groups. Examples of alkyloxy groups as substituents include C1-C3 alkyloxy groups such as methoxy and ethoxy groups. Examples of alkenyl groups as substituents include C2-C4 alkenyl groups such as vinyl, allyl, and 2-butenyl groups. Examples of alkynyl groups as substituents include C2-C4 alkynyl groups such as propargyl groups.

[0030] The above-mentioned photosensitive group (p1) is preferably a photosensitive group represented by any of the following formulas (a-1) to (a-2). (In the formula, R and R' each independently represent 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. m is an integer from 1 to 12. * represents a bond.)

[0031] In the above formulas (a-1) and (a-2), the phenylene group and COOCH ３ Alternatively, the phenylene group and the COOH group 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. m is an integer from 1 to 12, preferably an integer from 2 to 10, and more preferably an integer from 2 to 6.

[0032] The following structures are examples of side chains having the above-mentioned photosensitive group (p). (In formulas (p2-1) to (p2-45) above, one or more hydrogen atoms on the benzene ring or cyclohexane ring may be substituted with a methyl group, a t-butyl group, a methoxy group, a nitrile group, an acetyl group, or a halogen atom. Sp １ is, -(CH ２ ) ｓ１ - represents Sp ２ is, -(CH ２ ) ｓ２ This represents a -. s1 and s2 are independent integers between 1 and 12. * represents a combination.

[0033] Preferred examples of side chains (bm) having a mesogenic group (m) include the following structures and vinylbenzoic acid residues. (Note, Sp １ is, -(CH ２ ) ｓ１This represents -. In the above equations (bm-1) to (bm-4), s1 is an integer between 1 and 12, independently of each other. * represents a combination.

[0034] (Crosslinkable group) A crosslinkable group may be one functional group selected from the group consisting of an oxetanyl group, an oxyranyl group, a carboxyl group, and a hydroxyl group.

[0035] 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 a polymerizable unsaturated bond and a crosslinkable group.

[0036] The above structural unit (X ＣＬ Examples of monomer compounds that give the above include glycidyl (meth)acrylate, glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxybutyl α-ethylacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 6,7-epoxyheptyl α-ethylacrylate, 4-hydroxybutyl glycidyl ether (meth)acrylate, and (3-ethyloxetan-3-yl)methyl (meth)acrylate. Among these, examples include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-methyl-3-oxetanylmethyl (meth)acrylate, 4-hydroxybutylglycidyl ether (meth)acrylate, compounds having an oxetanyl group or an oxiranil 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.

[0037] (Basic functional groups) Examples of basic functional groups include acyclic amines such as dialkylamines; 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 heterocycles such as pyridine, pyrrole, imidazole, or acridine.

[0038] Examples of basic functional groups include groups having a heterocycle with five or more members. 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.

[0039] The polymer (P) has, for example, a basic functional group in its side chain. When the polymer (P) has a basic functional group, the polymer (P) is a structural unit (X) having a basic functional group in its side chain. ｈｔ It is preferable to have a structural unit (X) having a basic functional group in its side chain. ｈｔ ) is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a basic functional group.

[0040] The above structural unit (X ｈｔ Examples of monomeric compounds that give the following are the compounds (ht-1) to (ht-2) and 2-(diethylamino)ethyl methacrylate.

[0041] (Thermally Desorbable Groups) Examples of thermally detachable groups include carbamate protecting groups such as tert-butoxycarbonyl group (Boc group), 9-fluorenylmethyloxycarbonyl group (Fmoc group), benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, allyloxycarbonyl group, or 2-(trimethylsilyl)ethoxycarbonyl group.

[0042] If the polymer (P) has a thermally detachable group, the polymer (P) has a structural unit (X) with a thermally detachable group in its side chain. ＢＬIt is preferable to have a structural unit (X) having a thermally desorbable group in the side chain. ＢＬ ) is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a thermally detachable group.

[0043] The above structural unit (X ＢＬ Examples of monomeric compounds that give the following are the compounds (BL-1) to (BL-2). (In the formula, "Boc" represents the tert-butoxycarbonyl group.)

[0044] 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.

[0045] Examples of groups or structures having the polymerizable unsaturated bond mentioned above include (meth)acryloyl groups, maleimide groups, styryl groups, vinyl groups, and α-methylene-γ-butyrolactone structures. The polymer (P) of the present invention can be obtained, for example, by polymerizing a monomer compound having at least one of the polymerizable unsaturated bonds and at least one of the functional groups mentioned above.

[0046] 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.

[0047] Furthermore, the polymer (P) of the present invention may also contain structural units derived from monomer compounds other than those described above. 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.

[0048] From the viewpoint of photoreactivity, the content of structural units (X) in the polymer (P) of the present invention is preferably 5 mol% or more, and preferably 10 mol% or more, based on 100 mol% of the total structural units of the polymer (P). It may also be 100 mol% or less, 95 mol% or less, 90 mol% or less, or 80 mol% or less.

[0049] The content of the 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 photoreactivity, the content of the other structural units and structural units derived from other monomer compounds in the polymer (P) of the present invention is preferably 5 mol% or more, and preferably 10 mol% or more, based on the total of 100 mol% of structural units in the polymer (P). It may also be 95 mol% or less, or 90 mol% or less.

[0050] (Synthesis of Polymer (P)) Polymer (P) can be obtained by a polymerization reaction using monomer compounds having polymerizable unsaturated bonds, and is preferably obtained by a radical polymerization reaction. Polymerization initiators used in the 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 initiators consisting of these peroxides and reducing agents. Among these, azo compounds are preferred, and 2,2'-azobis(isobutyronitrile) and 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.

[0051] 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-dimethylacetamide, 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.

[0052] 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).

[0053] The polymer (P) of the present invention is preferably such that, considering the strength of the resulting coating film, the workability during coating film formation, and the uniformity of the coating film, the weight-average molecular weight measured by the GPC (Gel Permeation Chromatography) method is 2,000 to 2,000,000, more preferably 2,000 to 1,000,000, and even more preferably 5,000 to 200,000.

[0054] The content of polymer (P) in the polymer composition is not particularly limited, but is preferably 1 to 30% by mass, and more preferably 1 to 20% by mass.

[0055] [Compound (A)] The polymer composition of the present invention contains a compound represented by the following formula (a) (Compound (A)). (In formula (a), R １ represents -COORa (Ra represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Sp represents a divalent chain linking group. X represents a (m+n) valent group having a cyclic group. Y represents -O- or -N(Rb)- (Rb represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Z represents a monovalent group having a cyclic group. m is an integer from 0 to 2. n is an integer from 2 to 4. R １ When there are multiple Sp, Y, and Z, each R １ Sp, Y, and Z may be the same or different.

[0056] The C1-C4 alkyl groups in Ra and Rb may be linear or branched, and specific examples include methyl, ethyl, n-propyl, isopropyl, and tert-butyl groups.

[0057] The divalent chain-linking group in Sp may be linear or branched, and may be a hydrocarbon group or a group containing heteroatoms other than carbon atoms and hydrogen atoms. Examples of heteroatoms include O, N, S, P, B, Si, halogen atoms, etc.

[0058] Preferred specific examples of divalent chain linking groups in Sp include the following groups (i) to (iii): (i): Divalent alkylene group having 1 to 16 carbon atoms (ii): Any one or more methylene groups of the alkylene group in (i) above are -O-, -S-, -CO-, -COO-, -COS-, -NR ３ -, -CO-NR ３ -, -Si(R ３ ) ２ - (However, R ３ () is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. ２- A divalent group A obtained by substituting with the above (except when two adjacent methylene groups are replaced). (iii): A divalent group B obtained by substituting at least one hydrogen atom bonded to the carbon atom of the divalent alkylene group in (i) or the divalent group A in (ii) with a halogen atom, hydroxyl group, alkoxy group, nitro group, amino group, mercapto group, nitroso group, alkylsilyl group, alkoxysilyl group, silanol group, sulfino group, phosphino group, carboxyl group, cyano group, sulfo group, or acyl group, etc.

[0059] The following are more preferred examples of divalent chain-like linking groups in Sp. In the above embodiment, p is an integer from 1 to 12, more preferably an integer from 2 to 12, and even more preferably an integer from 2 to 6. q1 and q2 are each independently integers from 0 to 4, p3 is an integer from 1 to 6, and the sum of q1, q2, and p3 is from 1 to 12. p1 and p2 are each independently integers from 1 to 6. * and *1 represent bonding bonds. *1 is preferably a bonding bond that connects to an oxygen atom or a nitrogen atom in Y in formula (a).

[0060] In formula (a), Z represents a monovalent group having a cyclic group. It is preferable that Z has at least one aromatic ring. Examples of the aromatic rings include hydrocarbon aromatic rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as pyridine rings, pyrazine rings, and pyrrole rings. The number of aromatic rings that Z has is not particularly limited, but it is preferable that it has 1 to 4. These aromatic rings may have substituents. Examples of substituents include methyl groups, t-butyl groups, methoxy groups, nitrile groups, acetyl groups, or halogen atoms. From the viewpoint of suitably obtaining the effects of the present invention, it is preferable that Z is a monovalent cyclic group selected from the following structural formulas. (In the above formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Sp ３ is, -(CH ２ ) ｓ３ This represents a -. s3 are each independent integers from 1 to 12. * represents a combination.

[0061] X represents a (m+n) valence group having a cyclic group. Examples of X include residues of (m+n) valence polycarboxylic acids having a cyclic group, such as residues of divalent dicarboxylic acids having a cyclic group, or residues of tetravalent tetracarboxylic acids having a cyclic group.

[0062] Examples of divalent dicarboxylic acid residues having the above-mentioned cyclic group include, for example, a divalent organic group obtained by removing two carboxylic acids or carboxylic acid derivatives from a dicarboxylic acid or its derivative. Examples of the above-mentioned dicarboxylic acids include cyclopropanedicarboxylic acid (preferably 1,2-cyclopropanedicarboxylic acid), cyclobutanedicarboxylic acid (preferably 1,3-cyclobutanedicarboxylic acid, etc.), cyclopentanedicarboxylic acid (1,3-cyclopentanedicarboxylic acid), cyclohexanedicarboxylic acid (preferably 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid), 1,4-(2-norbornene)dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, 1,3-adamantanedicarboxylic acid, and alicyclic polycarboxylic acids such as spiro[3.3]heptane-2,6-dicarboxylic acid; Terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-biphenyldicarboxylic acid, 2,5-biphenyldicarboxylic acid, [p-terphenyl]-4,4''-dicarboxylic acid, 4,4'-stilbenidicarboxylic acid, 4,4'-transdicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4'-isopropylidene dibenzoic acid, 4,4'-oxybis(benzoic acid), 4,4'-sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3t,3't-p-phenylenediamine Examples include aromatic polycarboxylic acids such as acrylic acid, 3,3'-(p-phenylene)dipropionic acid, 2,5-franzicarboxylic acid, naphthalenedicarboxylic acid (1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid), anthracenedicarboxylic acid (1,4-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 1,6-anthracenedicarboxylic acid), 1,5-(9-oxofluorene)dicarboxylic acid, and 1,4-anthraquinonedicarboxylic acid dichloride.

[0063] Examples of tetravalent tetracarboxylic acid residues having a cyclic group include tetravalent organic groups obtained by removing four carboxylic acid groups or carboxylic acid derivatives from a tetracarboxylic acid or its derivative. Examples of tetravalent tetracarboxylic acid residues having a cyclic group include tetravalent organic groups obtained by removing two acid anhydride groups (-C(=O)-O-C(=O)-) from an aromatic tetracarboxylic acid dianhydride, or tetravalent organic groups obtained by removing two acid anhydride groups from an alicyclic tetracarboxylic acid dianhydride. In particular, X preferably has a highly planar structure and preferably has at least one substructure selected from the group consisting of a benzene ring, a naphthalene ring, and a cyclobutane ring. Note that aromatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the aromatic ring. Alicyclic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the alicyclic structure. However, none of these four carboxyl groups are bonded to an aromatic ring. Furthermore, it is not necessary to consist solely of alicyclic structures; it may also have a chain-like hydrocarbon structure or an aromatic ring structure in part. Examples of tetracarboxylic dianhydrides that give X include alicyclic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides.Examples of alicyclic tetracarboxylic dianhydrides include tetracarboxylic dianhydrides having a cyclobutane structure (e.g., 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, or 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, etc.), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4' -Dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl) Examples include alicyclic tetracarboxylic dianhydrides such as -8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride.Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2' Examples include 3,3'-biphenyltetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)-2,2-diphenylpropane dianhydride, ethylene glycol bis-anhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-(1,4-phenylenedioxy)bis(phthalic anhydride), or 4,4'-(1,4-phenylenedimethylene)bis(phthalic anhydride).

[0064] From the viewpoint of the turbidity of the film (resin film), m in formula (a) is preferably 1 to 2, and more preferably 2.

[0065] Compound (A) is preferably a compound selected from the group consisting of the following compounds.

[0066] The content of compound (A) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.3 parts 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 compound (A) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, when the polymer component (e.g., polymer (p)) in the polymer composition is 100 parts by mass.

[0067] [(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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] The polymer composition of the present invention may additionally contain components other than the polymer (P), compound (A), and 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.

[0073] 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.

[0074] Examples of the 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 crosslinkable compound preferably has a molecular weight of 10 or more, and is preferably a low molecular weight compound of 2000 or less.

[0075] Preferred specific examples of the above crosslinkable compounds (c-1) and (c-2) include the following compounds: Compounds having an epoxy group 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. 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. 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] [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.

[0083] 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.

[0084] The polymer composition of the present invention is preferably used as a composition for forming an orientation film or a composition for forming a phase difference film.

[0085] [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)

[0086] [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 (COP) 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.

[0087] [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 can be used, 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.

[0088] [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.

[0089] 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.

[0090] [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.

[0091] 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.

[0092] 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 polarizers and phase difference plates for liquid crystal displays and organic EL displays.

[0093] 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. The monomers and additives used in the examples are shown below.

[0094] (Monomer compounds having polymerizable unsaturated bonds) M-1 to M-9: Compounds represented by the following formulas (M-1) to (M-9), respectively.

[0095] (Compound (A)) Compound (A-1): Compound represented by the following formula (A-1) Compound (A-2): Mixture of structural isomers represented by the following formulas (A-2a) and (A-2b) Compound (A-3): Mixture of structural isomers represented by the following formulas (A-3a) and (A-3b) Compound (A-4): Mixture of structural isomers represented by the following formulas (A-4a) and (A-4b)

[0096] The abbreviations for the reagents used in this example are shown below. (Organic solvents) DMF: N,N-dimethylformamide THF: Tetrahydrofuran NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve CPN: Cyclopentanone

[0097] (Polymerization initiator) V601: 2,2'-Azobis(isobutyrate)dimethyl

[0098] <Other Additives> (Surfactants) AP-001: Marproof® AP-001 (Manufactured by NOF Corporation)

[0099] (Other compounds) Compound (B-1): A mixture of structural isomers represented by the following formulas (B-1a) and (B-1b) Compound (B-2): A mixture of structural isomers represented by the following formulas (B-2a) and (B-2b)

[0100] [1] Compound (A) is synthesized. Compounds (A-1) to (A-4) are novel compounds not published in the literature, etc., and the products in the following synthesis example are １ Identification was performed by 1H-NMR analysis. The analytical conditions were as follows: Instrument: Fourier transform superconducting nuclear magnetic resonance spectrometer (FT-NMR) "AVANCE III" (BRUKER Corporation) 500 MHz; Solvent: Deuterated chloroform (CDCl ３ ) or deuterated dimethyl sulfoxide (DMSO-d ６ ) Reference substance: Tetramethylsilane (TMS) (δ 0.0 ppm for １ H)

[0101] <<Synthesis of Compound (A-1)>>

[0102] (Synthesis of A-1-1) Trans-p-coumaric acid (120 g, 731 mmol), methanol (500 mL), and sulfuric acid (15 mL) were added to a 1000 mL round-bottom flask equipped with a condenser, and the mixture was reacted at 77°C for 5 hours with stirring. After the reaction was complete, the reaction mixture was poured into pure water (4000 mL) to precipitate the solid. After stirring for 30 minutes, the precipitate was filtered off and dried under reduced pressure to obtain A-1-1 (120.7 g, 677 mmol, white solid, yield 93%). １ H-NMR (CDCl ３ ): δ (ppm) = 3.81 (s, 3H), 5.97 (s, 1H), 6.29 (d, 1H), 6.86 (d, 2H), 7.42 (d, 2H), 7.66 (d, 1H).

[0103] (Synthesis of A-1-2) In a 3000 mL round-bottom flask equipped with a condenser, A-1-1 (152 g, 850 mmol), 6-chloro-1-hexanol (122 g, 890 mmol), potassium carbonate (176 g, 1275 mmol), potassium iodide (14.1 g, 85 mmol), and DMF (1200 g) were added and the mixture was reacted at 100°C for 28 hours with stirring. After the reaction was complete, the reaction mixture was poured into pure water (6000 mL) to precipitate a solid. After stirring for 30 minutes, the precipitate was filtered off, and the obtained solid was dissolved in ethyl acetate. The mixture was separated and washed with dilute hydrochloric acid and pure water, and the organic layer was removed and dried over magnesium sulfate. Then, heptane was added to precipitate a solid. The precipitate was filtered off and dried under reduced pressure to obtain A-1-2 (206 g, 740 mmol, white solid, yield 87%). １ H-NMR (CDCl ３ ): δ (ppm) = 1.27 (s, 1H), 1.46 (m, 4H), 1.60 (m, 2H), 1.81 (m, 2H), 3.66 (t, 2H), 3 .79 (s, 3H), 3.99 (t, 2H), 6.29 (d, 1H), 6.88 (d, 2H), 7.46 (d, 2H), 7.66 (d, 1H).

[0104] (Synthesis of compound (A-1)) A-1-2 (2.78 g, 10 mmol) is mixed with triethylamine (Et ３Dissolve the terephthaloyl chloride (1.01 g, 5 mmol) together with N in 10 mL of THF and stir at room temperature. While cooling with a water bath, add dropwise over 5 minutes a solution of terephthaloyl chloride (1.01 g, 5 mmol) dissolved in 5 mL of THF. After the addition was complete, stir for 30 minutes, remove the water bath, and continue stirring for 20 hours while returning to room temperature. After the reaction was complete, pour the reaction solution into 150 mL of pure water and precipitate a solid. After stirring for 1 hour, filter off the precipitate. Dissolve this solid in ethyl acetate and add heptane to precipitate another solid. Filter off the precipitate and dry under reduced pressure to obtain compound (A-1) (2.80 g, 4.08 mmol, white solid, yield 82%). １ H-NMR (CDCl ３ ): δ (ppm) = 1.55 (m, 8H), 1.83 (m, 8H), 3.79 (s, 6H), 4.00 (t, 4H), 4.36 (t , 4H), 6.28 (m, 2H), 6.87 (m, 4H), 7.46 (m, 4H), 7.63 (m, 2H), 8.08 (s, 4H).

[0105] <<Synthesis of Compound (A-2)>>

[0106] (Synthesis of A-2-1) In a 200 mL round-bottom flask equipped with a condenser, methyl 4-hydroxybenzoate (7.61 g, 50.0 mmol), 6-chloro-1-hexanol (7.17 g, 52.5 mmol), potassium carbonate (10.36 g, 75 mmol), potassium iodide (0.83 g, 5 mmol), and DMF (55.0 g) were added and the mixture was reacted at 100°C for 7 hours with stirring. After the reaction was complete, the reaction solution was poured into 300 mL of pure water, and dilute hydrochloric acid was added to quench the mixture. The precipitate was then filtered off. This solid was dissolved in THF, and then heptane was added to precipitate the solid. The precipitate was filtered off and dried under reduced pressure to obtain A-2-1 (10.8 g, 42.8 mmol, white solid, yield 86%). １ H-NMR (CDCl ３ ): δ (ppm) = 1.33 (s, 1H), 1.49 (m, 4H), 1.60 (m, 2H), 1.82 (m, 2H), 3.66 (t, 2H), 3.88 (s, 3H), 4.01 (t, 2H), 6.89 (d, 2H), 7.97 (d, 2H).

[0107] (Synthesis of compound (A-2)) A-2-1 (5.04 g, 20.0 mmol) was dissolved in NMP (20 mL) together with pyromellitic dianhydride (2.18 g, 10.0 mmol) and stirred at room temperature, and triethylamine (2.23 g) was added dropwise. After the addition was complete, the mixture was stirred and allowed to react for 72 hours. After the reaction was complete, the reaction solution was poured into water (300 mL) and stirred at room temperature for 1 hour. Then, dilute hydrochloric acid was added dropwise until the pH was about 2, and the precipitate was filtered off and dried under reduced pressure to obtain compound (A-2) (isomer mixture, 3.40 g, 4.70 mmol, white solid, yield 47%). １ H-NMR (DMSO-d ６ ): δ (ppm) = 1.44 (m, 8H), 1.75 (m, 8H), 3.81 (s, 6H), 4.04 (t, 4H), 4.27 (t, 4H), 7.02 (m, 4H), 7.90 (m, 6H), 13.78 (s, 2H).

[0108] <<Synthesis of Compound (A-3)>>

[0109] A-1-2 (2.78 g, 10.0 mmol) was dissolved in NMP (15 g) together with 1,2,3,4-cyclobutanetetracarboxylic dianhydride (0.980 g, 5.00 mmol) and stirred at room temperature, and triethylamine (1.11 g, 11 mmol) was added dropwise. After the addition of triethylamine was complete, the mixture was stirred and allowed to react for 24 hours. After the reaction was complete, the reaction solution was poured into water (400 mL), and dilute hydrochloric acid was added dropwise until the pH was approximately 2, after which the precipitate was filtered off. The obtained solid was dissolved in tetrahydrofuran, and heptane was added to precipitate the solid. The precipitate was filtered off and dried under reduced pressure to obtain compound (A-3) (isomer mixture, 3.30 g, 4.38 mmol, white solid, yield 88%). １ H-NMR (DMSO-d ６ ): δ (ppm) = 1.37 (m, 8H), 1.57 (m, 4H), 1.71 (m, 4H), 3.55 (m, 4H), 3.70 (s, 6H), 4.00 (m, 8H), 6.45 (d, 2H), 6.96 (m, 4H), 7.64 (m, 6H), 12.73 (s, 2H).

[0110] <<Synthesis of Compound (A-4)>>

[0111] A-1-2 (13.9 g, 50.0 mmol) was dissolved in NMP (75 g) together with pyromellitic dianhydride (5.45 g, 25.0 mmol) and stirred at room temperature. Triethylamine (5.56 g, 55 mmol) was added dropwise over 10 minutes. After the addition was complete, the mixture was stirred for 72 hours. After the reaction was complete, the reaction solution was poured into water (1000 mL) and stirred at room temperature for 1 hour. Then, dilute hydrochloric acid was added dropwise until the pH was approximately 2, and the precipitate was filtered off. The obtained solid was washed with pure water (500 mL) and dried under reduced pressure to obtain compound (A-4) (isomer mixture, 19.3 g, 24.9 mmol, white solid, yield 99%). １ H-NMR (DMSO-d ６ ): δ (ppm) = 1.44 (m, 8H), 1.75 (m, 8H), 3.70 (s, 6H), 4.00 (m, 4H), 4.27 (m, 4H), 6.48 (d, 2H), 6.96 (m, 4H), 7.63 (m, 6H), 8.00 (m, 2H), 13.79 (s, 2H).

[0112] [2] Synthesis of Polymers [Synthesis Example 1] A monomer mixture solution was prepared by dissolving M-1 (2.99 g, 9.00 mmol), M-2 (15.6 g, 51.0 mmol), and V-601 (0.69 g, 3.00 mmol) in CPN (42.8 g). Under a nitrogen atmosphere, the monomer mixture solution was added dropwise to CPN (18.3 g) at 70°C over 1 hour. After addition, the mixture was reacted at 70°C for 6 hours to obtain polymer solution P1.

[0113] [Synthesis Example 2] A monomer mixture solution was prepared by dissolving M-1 (2.99 g, 9.00 mmol), M-2 (10.8 g, 35.1 mmol), M-3 (3.30 g, 7.50 mmol), M-4 (0.620 g, 3.00 mmol), M-5 (0.430 g, 3.00 mmol), M-6 (0.150 g, 1.80 mmol), M-7 (0.14 g, 0.600 mmol), and V-601 (0.69 g, 3.00 mmol) in CPN (38.0 g) and dissolving them

[0114] [Synthesis Example 3] A monomer mixture solution was prepared by dissolving M-8 (12.2 g, 57.0 mmol), M-9 (0.56 g, 3.00 mmol), and V-601 (0.69 g, 3.00 mmol) in CPN (53.8 g). The mixture was reacted at 70°C for 6 hours under a nitrogen atmosphere to obtain polymer solution P3.

[0115] [3] Preparation of polymer film-forming materials [Preparation example 1] Polymer solution T1 was obtained by adding CPN (27.1 g), compound (A-1) (0.490 g), and AP-001 (5 wt% CPN solution) (1.96 g) to polymer solution P1 (40.8 g) and stirring. This polymer solution T1 was used as is as a material for forming a phase difference film.

[0116] [Preparation Examples 2-6] As shown in Table 1 below, polymer preparations T2-T6 were obtained by performing the same procedure as in Preparation Example 1, except that the type of additive was changed. These polymer preparations T2-T6 were used as materials for forming a phase difference film.

[0117] [Preparation Example 7] Polymer solution T7 was obtained by adding polymer solution P3 (0.980 g), CPN (30.1 g), compound (A-4) (98.0 mg), and AP-001 (5 wt% CPN solution) (1.96 g) to polymer solution P2 (36.9 g) and stirring. This polymer solution T7 was used as is as a material for forming a phase difference film.

[0118] [Preparation Example 8] Polymer solution T8 was obtained by adding polymer solution P3 (0.980 g), CPN (30.1 g), and AP-001 (5 wt% CPN solution) (1.96 g) to polymer solution P2 (36.9 g) and stirring. This polymer solution T8 was used as is as a material for forming a phase difference film.

[0119]

[0120] [4] Production of polymer film [Example 1] Polymer preparation solution T1 was filtered through a filter with a pore size of 5.0 μm, then bar-coated onto a COP film and dried in an oven at 73°C for 3 minutes to form a phase difference film with a thickness of 5.1 μm. The film thickness was measured using an optical film thickness meter (Filmetrics, USA, model number F20). Next, ultraviolet light with wavelengths below 325 nm cut off was applied through a polarizing plate at a rate of 200 mJ / cm² via a wire grid. ２ The coated surface was then irradiated. Subsequently, the substrate S1 with a phase difference film was fabricated by heating it in a 135°C hot air circulating oven for 5 minutes.

[0121] [Examples 2-3, Comparative Examples 1-3] As shown in Table 2 below, substrates S2-S3 and R1-R3 with phase difference films were prepared by performing the same procedure as in Example 1, except that the type of polymer preparation solution was changed.

[0122] [Example 4] Polymer preparation solution T7 was filtered through a 5.0 μm pore size filter, then bar-coated onto a COP film and dried in a 73°C oven for 3 minutes to form a phase difference film with a thickness of 4.1 μm. The film thickness was measured using an optical film thickness meter (Filmetrics, USA, model F20). Next, ultraviolet light with wavelengths below 325 nm cut off was applied through a polarizing plate at a rate of 150 mJ / cm² via a wire grid. ２ The coated surface was then irradiated. Subsequently, the substrate S4 with a phase difference film was fabricated by heating it in a 125°C hot air circulating oven for 5 minutes.

[0123] [Comparative Example 4] As shown in Table 2 below, a substrate R4 with a phase difference film was prepared by performing the same procedure as in Example 4, except that the type of polymer preparation solution was changed.

[0124] The orientation (Δn) of the phase difference films-coated substrates S1-S4 and R1-R4 obtained above was evaluated using the following method.

[0125] [Orientation Evaluation] The linear phase difference at a wavelength of 550 nm was measured using an AxoScan from Axometrics, Inc. The obtained phase difference value (nm) was divided by the film thickness (nm) of the polymer film to calculate Δn, which is summarized in Table 2.

[0126]

[0127] The results of comparing Examples 1-3 and Comparative Examples 1-3 in Table 2, and the results of comparing Example 4 and Comparative Example 4, showed that the phase difference film obtained from the polymer composition containing compound (A) exhibited higher orientation than the phase difference film obtained from the polymer composition not containing compound (A).

Claims

1. A polymer composition containing the following polymer (P) and compound (A): Polymer (P): A polymer (P) having a photosensitive group (p) in its side chain Compound (A): A compound represented by the following formula (a) (In formula (a), R １ represents -COORa (Ra represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Sp represents a divalent chain linking group. X represents a (m+n) valent group having a cyclic group. Y represents -O- or -N(Rb)- (Rb represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Z represents a monovalent group having a cyclic group. m is an integer from 0 to 2. n is an integer from 2 to 4. R １ When there are multiple Sp, Y, and Z, each R １ Sp, Y, and Z may be the same or different.

2. The divalent chain linking group in the Sp is a divalent alkylene group having 1 to 16 carbon atoms, any one or more methylene groups of the alkylene group being replaced by -O-, -S-, -CO-, -COO-, -COS-, -NR ３ -, -CO-NR ３ -, -Si(R ３ ) ２ -(where R ３ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.), or a divalent group A formed by replacing with -SO ２ -(except when replacing two adjacent methylene groups), or at least one hydrogen atom bonded to a carbon atom of the divalent alkylene group or the divalent group A is a halogen atom, a hydroxy group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilyl group, a silanol group, a sulfino group, a phosphino group, a carboxy group, a cyano group, a sulfo group, or an acyl group, the polymer composition according to claim 1.

3. The polymer composition according to claim 1, wherein the polymer (P) has other functional groups other than the photosensitive group (p), and the other functional groups are selected from a mesogenic group (m), a crosslinking group, a basic functional group, and a thermally detachable group.

4. The polymer composition according to claim 1, wherein Z has at least one aromatic ring.

5. The polymer composition according to claim 1, wherein X is a residue of a (m+n) valent polycarboxylic acid having a cyclic group.

6. The polymer composition according to claim 1, wherein the compound (A) is selected from the group consisting of the following compounds.

7. A composition for forming a phase difference film, which is a polymer composition according to any one of claims 1 to 6.

8. A composition for forming an orientation film, which is a polymer composition according to any one of claims 1 to 6.

9. 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 6 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.

10. A resin film formed from the polymer composition described in any one of claims 1 to 6.

11. A phase difference material comprising the resin film described in claim 10.

12. A compound represented by any of the following formulas (a-1) to (a-9).

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