Polymer composition and single-layer retardation material

Abstract

Provided is a polymer composition which contains a polymer (P) and a compound (A), and also contains a base, a thermal base generator, or a photo base generator.　Polymer (P): a re-orientable polymer which has a photosensitive group (p) in a side chain, and additionally has a nucleophilic group X in a side chain Compound (A): a compound represented by formula (a-1) (In the formula (a-1), Z represents a divalent group; Qa represents -Cl, -Br, -I, -OCOR or -OSO2R; and R represents an alkyl group having 1-5 carbon atoms, a phenyl group, or a p-methylphenyl group. The two Qa moieties may be the same as or different from each other.)

Description

Polymer composition and single-layer phase difference material

[0001] The present invention relates to a composition containing a polymer and a single-layer phase difference material. More specifically, it relates to a composition containing a liquid crystalline polymer that has optical properties suitable for applications such as display devices and recording materials, and in particular can be suitably used in optical compensation films such as polarizers and phase difference plates for liquid crystal displays and organic EL (Electroluminescence) display devices, and a single-layer phase difference material obtained from said composition.

[0002] Due to demands for improved display quality and weight reduction in liquid crystal displays and organic EL displays, 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. To meet this demand, 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] Such polymerizable liquid crystal compounds are generally polymerized (formed into films) by irradiation with radiation such as ultraviolet light. For example, a method is known in which a specific polymerizable liquid crystal compound having an acrylic group is supported between oriented supports, and a polymer is obtained by irradiating the compound with radiation while maintaining it in a liquid crystal state (Patent Document 1), or a method is known in which a photopolymerization initiator is added to a mixture of two types of polymerizable liquid crystal compounds having an acrylic group, or a composition in which chiral liquid crystal is mixed with this mixture, and a polymer is obtained by irradiating it with ultraviolet light (Patent Document 2).

[0004] Furthermore, various single-layer coated orientation films have been reported, including orientation films using polymerizable liquid crystal compounds or polymers that do not require a liquid crystal alignment film (Patent Documents 3 and 4), and orientation films using polymers containing photocrosslinking sites (Patent Documents 5 and 6).

[0005] On the other hand, in some cases, such single-layer coated films are more efficient when peeled from the substrate and transferred to an adhesive film or the like. Therefore, depending on the process, there is a need for a film that can withstand transfer, but it has become clear that cracks may occur during the transfer process.

[0006] Japanese Patent Publication No. Sho 62-70407, Japanese Patent Publication No. Hei 9-208957, European Patent Application Publication No. 1090325, Specification International Publication No. 2008 / 031243, Japanese Patent Publication No. 2008-164925, Japanese Patent Publication No. Hei 11-189665

[0007] The present invention has been made in view of the above problems, and aims to provide a polymer composition that enables the production of a single-layer phase difference material with fewer cracks occurring during transfer by a simpler process, and a single-layer phase difference material obtained from the composition.

[0008] The inventors of the present invention have conducted extensive research to solve the above problems and have found that by using a composition containing a specific polymer, a specific crosslinking agent, and a basic compound, a single-layer phase difference material with fewer cracks occurring during transfer can be obtained, thus completing the present invention.

[0009] Accordingly, the present invention encompasses the following embodiments: [1] A polymer composition containing the following polymer (P) and the following compound (A), as well as a base, a thermobase generator, or a photobase generator. Polymer (P): A reorienting polymer having a photosensitive group (p) in its side chain, and further having a nucleophilic group X in its side chain. Polymer compound (A): A compound represented by the following formula (a-1). (In formula (a-1), Z represents a divalent group, and Qa is -Cl, -Br, -I, -OCOR, or -OSO) ２ [1] R represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a p-methylphenyl group. The two Qa may be the same or different. [2] The polymer composition according to [1], wherein the nucleophilic group X is a carboxyl group. [3] The polymer composition according to [1] or [2], wherein Qa in formula (a-1) is -Cl, -Br, or -OCOR. [4] The polymer composition according to [1] or [2], wherein the compound (A) is selected from the group consisting of the following compounds. [5] A composition for forming a phase difference film, wherein the polymer composition is described in any one of the above items [1] to [4]. [6] A composition for forming an orientation film, wherein the polymer composition is described in any one of the above items [1] to [4]. [7] A method for producing a phase difference material, comprising the following steps (1) to (3): (1) Applying the polymer composition described in any one of the above items [1] to [4] 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. [8] A resin film formed from the polymer composition described in any one of the above items [1] to [4]. [9] A phase difference material comprising the resin film described in [8].

[0010] The present invention provides a phase difference material that produces fewer cracks during transfer, as well as an orientation film and polymer composition that provide the phase difference material. The mechanism by which the above effects of the present invention are obtained is not entirely clear, but the following is considered to be one of the contributing factors. It is thought that the above effects are obtained because a substitution reaction occurs between the nucleophilic group X on the side chain of polymer (P) and the leaving group Y of compound (A), resulting in the emergence of a structure that contributes to improving the mechanical properties of the film.

[0011] The following describes in detail polymer compositions containing specific polymer components and compound components, 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 "trunk" 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 "trunk" of the polymer. In the present invention, reorientation refers to the property that even in the state of a coating film after the solvent has evaporated, it can be fluidized by heating and its shape can be changed.

[0012] Embodiments of the present invention will be described in detail below. [Polymer (P)] The polymer composition of the present invention is a reorienting polymer having a photosensitive group (p) in its side chain, and further contains a polymer (polymer (P)) having a nucleophilic group X in its side chain. The photosensitive group (p) and the nucleophilic group X may be present in the same side chain or in separate side chains. For example, the nucleophilic group X may be part of the photosensitive group (p), in which case it is preferable that the nucleophilic group X is located at the end of the photosensitive group.

[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). (Ar represents a divalent organic group having 6 to 30 carbon atoms and containing an arylene group, and Ar is -C(X１ ) = 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.

[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 structural units (P) having a photosensitive group (p) in its side chain. The structural units (P) having a photosensitive group (p) in its side chain are, for example, structural units derived from monomer compounds 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 above mesogen-forming group (m) is not particularly limited as long as it imparts liquid crystalline properties, and includes not only mesogen groups but also hydrogen-bonding mesogen 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 the mesogenic group (m) in its side chain. The structural unit (M) having the mesogenic group (m) in its side chain is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and the mesogenic group (m).

[0020] The mesogenic group (m) may be in mode (A) having a side chain containing the photosensitive group (p), or mode (B) having a side chain not containing the photosensitive group (p), or a combination of these. In the above-mentioned mode (A), examples include, but are not limited to, mode (A1) in which the mesogenic group is provided in the side chain by sharing part or all of the structure of the photosensitive group (p), and mode (A2) in which the mesogenic group is provided in the side chain independently of the structure of the photosensitive group (p). In the above-mentioned mode (A2), the mesogenic group (m) and the photosensitive group (p) may be bonded via a single bond or may be bonded to each other via a linking group. Examples of the linking group include alkylene groups, -O-, -S-, -SO-, -SO ２ -, -CH=CH-, -C≡C-, -N=N-, -COO-, and -OCO-. Examples of the alkylene group include C1-C20 alkylene groups such as methylene group, ethylene group and propylene group. The alkylene group is preferably a C1-C10 alkylene group, and more preferably a C1-C10 alkylene group.

[0021] Examples of the mesogenic group include -Ar １ -Y-Ar ２ -. Here, Ar １ and Ar ２each, independently, represent an arylene group which may have a substituent, a cycloalkylene group which may have a substituent (e.g., cyclopropylene group, cyclobutylene group, cyclohexylene group, etc.), and a divalent heterocyclic residue which may have a substituent (e.g., oxygen-containing heterocycles such as furan ring and pyran ring; nitrogen-containing heterocycles such as pyrrole ring and 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 bonding positions of the arylene group and the heterocyclic residue are not particularly limited as long as liquid crystallinity is imparted, but a phenylene group is preferably bonded at the p-position, and a naphthylene group is preferably bonded at the 2,6-position.

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

[0024] More preferable specific examples of the mesogenic group include the following structures. (* 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 ３ Each 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] 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), E 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 include alkyl groups or alkoxyalkyl groups. The C1-C4 alkyl group may be linear or branched, and specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, and tert-butyl group. m is an integer from 1 to 12, preferably an integer from 2 to 10, and more preferably an integer 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).

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041] (In formulas (p2-1) to (p2-47) 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 ) ｓ２This represents a -. s1 and s2 are independent integers between 1 and 12. * represents a combination.

[0042] Preferred examples of side chains (bm) having a mesogenic group (m) include the following structures and vinylbenzoic acid residues. (Sp in the above equations (bm-1) to (bm-4) １ Each is independently - (CH ２ ) ｓ１ This represents a minus sign. s1 is an integer between 1 and 12. * represents a combination.

[0043] (Nucleophilic group X) Examples of nucleophilic group X include functional groups selected from the group consisting of carboxyl groups, hydroxyl groups, amino groups, and mercapto groups.

[0044] Examples of monomer compounds that give the above-mentioned nucleophilic group X include 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, 4-hydroxystyrene, and N-(4-hydroxyphenyl)maleimide.

[0045] The nucleophilic group X may be a group possessed by the photosensitive group (p). That is, the photosensitive group (p) may contain the nucleophilic group X. In that case, it is preferable that the photosensitive group (p) contains the nucleophilic group X at its terminal end.

[0046] Furthermore, when the nucleophilic group X is a carboxyl group, it is preferable to introduce a side chain from among the example formulas (p2-1) to (p2-47) that have a COOH group at the terminal end.

[0047] The nucleophilic group X may be a group possessed by the mesogenic group (m). That is, the mesogenic group (m) may contain the nucleophilic group X. In that case, it is preferable that the mesogenic group (m) contains the nucleophilic group X at its terminal end.

[0048] The polymer (P) of the present invention may have structural units other than those described above (hereinafter also referred to as other structural units). Preferably, the other structural units are structural units derived from monomer compounds having polymerizable unsaturated bonds.

[0049] 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.

[0050] 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.

[0051] 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 the following: (meth)acrylic acid ester compounds, maleimide compounds, maleic anhydride, styrene compounds, vinyl compounds, (meth)acrylamide compounds, etc. 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) (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 maleimide, N-methylmaleimide, N-phenylmaleimide, N-benzylmaleimide, 4-maleimide butyric acid, N-methoxycarbonylmaleimide, and N-cyclohexylmaleimide; styrene compounds such as styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene, 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; and (meth)acrylamide compounds such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-propyl(meth)acrylamide, and N-tert-butyl(meth)acrylamide.

[0052] From the viewpoint of photoreactivity, the content of structural units (P) in the polymer (P) of the present invention is preferably 3 mol% or more, relative to 100 mol% of the total structural units of the polymer (P). Furthermore, if the structural unit (P) contains both a photosensitive group (p) and a nucleophilic group X, the content of structural units (P) in the polymer (P) may be 100 mol% or less, 95 mol% or less, 90 mol% or less, or 80 mol% or less. If the structural unit (P) does not contain a nucleophilic group X, the content of structural units (P) in the polymer (P) may be 95 mol% or less, 90 mol% or less, or 80 mol% or less.

[0053] The content of structural units containing nucleophilic groups X in the polymer (P) of the present invention is preferably 5 mol% or more, and more preferably 10 mol% or more, based on 100 mol% of the total structural units of the polymer (P), from the viewpoint of the mechanical properties of the film. It may also be 95 mol% or less, 90 mol% or less, or 80 mol% or less.

[0054] The content of the other structural units and structural units derived from other monomeric compounds in the polymer (P) of the present invention is the remaining portion when the total content of structural unit (P) and structural units having a nucleophilic group X is less than 100 mol%.

[0055] (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.

[0056] 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.

[0057] 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).

[0058] 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.

[0059] 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.

[0060] [Compound (A)] The polymer composition of the present invention contains a compound represented by the following formula (a-1) (Compound (A)). In formula (a-1), the Qa portion is a leaving group Y. (In formula (a-1), Z represents a divalent group, and Qa is -Cl, -Br, -I, -OCOR, or -OSO) ２ R represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a p-methylphenyl group. The two Qa may be the same or different.

[0061] In formula (a-1), Z is a linear or branched alkylene group having 2 to 12 carbon atoms, -(CH ２ CH ２ O) ｎ -CH ２ CH ２ The groups with n being 1 to 13, cyclohexylene groups and phenylene groups are preferred, as are ethylene groups, 1,3-propanediyl groups, 1,4-butanediyl groups, 1,5-pentanediyl groups, 1,6-hexanediyl groups, 1,7-heptanediyl groups, 1,8-octanediyl groups, 1,10-decanediyl groups, 1,12-dodecanediyl groups, and -CH ２ C (CH ２ ) ２ CH ２ - group or - CH ２ CH ２ OCH ２ CH ２ - A group is even more preferred, and a 1,4-butanediyl group or a 1,6-hexanediyl group is particularly preferred from the viewpoint of raw material availability and the crack resistance of the resulting phase difference material.

[0062] The following compounds are examples of compounds represented by formula (a-1).

[0063] The content of compound (A) in the polymer composition 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.

[0064] [Base, thermal base generator, or photobase generator] A base, thermal base generator, or photobase generator is added to facilitate the reaction between the nucleophilic group of polymer (P) and the leaving group of compound (A).

[0065] Examples of usable bases include organic bases such as pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, trinormalpropylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, 2-(dimethylamino)ethyl(meth)acrylate, and 2-(diethylamino)ethyl(meth)acrylate; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium hydride, sodium bicarbonate, potassium carbonate, cesium carbonate, and potassium phosphate; and metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide.

[0066] However, if a base is added directly to the composition, a reaction may occur between the nucleophilic group X of the polymer (P) and the leaving group of compound (A), potentially resulting in gelation of the composition. For this reason, the base may be added immediately before forming the coating film, or a thermobase generator or photobase generator may be used as described below. Thermobase generators and photobase generators do not promote the reaction between the nucleophilic group X of the polymer (P) and the leaving group of compound (A) in the composition state because, at room temperature, the base is protected by a protecting group or latent due to salt formation.

[0067] Preferred thermal base generators are compounds having a basic site (e.g., a primary amino group, an aliphatic heterocycle (e.g., a pyrrolidine skeleton), an aromatic heterocycle (e.g., an imidazole ring, an indole ring), or a guanidino group), where the basic site is generated during calcination. Preferred specific examples include amino acids in which some or all of the basic site is protected, and compounds in which the NH of a nitrogen-containing aromatic heterocycle is protected. Examples of protecting groups for the basic site of the above amino acids or nitrogen-containing aromatic heterocycles include carbamate protecting groups such as tert-butoxycarbonyl groups and 9-fluorenylmethoxycarbonyl groups. Specific examples of the above amino acids include glycine, alanine, cysteine, methionine, asparagine, glutamine, valine, leucine, phenylalanine, tyrosine, tryptophan, proline, hydroxyproline, arginine, histidine, lysine, and ornithine.

[0068] Furthermore, examples of thermal base generating agents include carbamates such as 1-methyl-1-(4-biphenylyl)ethyl carbamate and 2-cyano-1,1-dimethylethyl carbamate; ureas such as urea and N,N-dimethyl-N'-methylurea; guanidines such as guanidine trichloroacetate, guanidine phenylsulfonylacetate, and guanidine phenylpropiolate; dihydropyridines such as 1,4-dihydronicotinamide; dimethylpiperidines such as N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,6-dimethylpiperidine, and N-(benzyloxycarbonyl)-2,6-dimethylpiperidine; quaternary ammonium salts such as tetramethylammonium phenylsulfonylacetate and tetramethylammonium phenylpropiolate; and dicyandiamides. Other examples include U-CAT® 18X, an organic acid salt of tetramethylammonium, and U-CAT® SA810, SA831, SA841, and SA851 [all manufactured by Sunapro Co., Ltd.], which are salts of U-CAT® 1102,1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), an organic acid salt of DBN.

[0069] The molecular weight of the above-mentioned thermobase generating agent may be 2000 or less, 1000 or less, or 500 or less.

[0070] Examples of photobase generators include alkylamine-based photobase generators such as 9-anthrylmethyl-N,N-diethylcarbamate; cycloalkylamine-based photobase generators such as 9-anthryl-N,N-dicyclohexylcarbamate, 1-(9,10-anthraquinone-2-yl)ethyl-N,N-dicyclohexylcarbamate, dicyclohexylammonium-2-(3-benzoylphenyl)propionate, 9-anthryl-N-cyclohexylcarbamate, 1-(9,10-anthraquinone-2-yl)ethyl-N-cyclohexylcarbamate, cyclohexylammonium-2-(3-benzoylphenyl)propionate, and (E)-N-cyclohexyl-3-(2-hydroxyphenyl)acrylamide; and 9-anthrylmethyl=piperidine-1-carboxylate and (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propene Piperidine-based photobase generators such as -1-one, (2-nitrophenyl)methyl-4-hydroxypiperidine-1-carboxylate, (2-nitrophenyl)methyl-4-(methacryloyloxy)piperidine-1-carboxylate; guanidinium-2-(3-benzoylphenyl)propionate, 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidinium-2-(3-benzoylphenyl)propionate Examples include guanidine-based photobase generators such as onate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium-n-butyltriphenyl borate, and 1,5,7-triazabicyclo[4.4.0]deca-5-enium-2-(9-oxoxanthene-2-yl)propionate; and imidazole-based photobase generators such as 1-(9,10-anthraquinone-2-yl)ethyl-imidazole-1-carboxylate.

[0071] The content of the above-mentioned base, thermal base generator, or photobase generator in the polymer composition is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polymer component (e.g., polymer (p)) in the polymer composition.

[0072] [Organic solvent] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] The polymer composition of the present invention may additionally contain components other than the polymer (P), compound (A), base or thermal base generator (photobase generator), and solvent (hereinafter also referred to as additive components). Examples of such additive components include compounds that improve film thickness uniformity and surface smoothness, adhesion aids that enhance adhesion between the film and the substrate, and photosensitizers.

[0078] Compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples 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, SC1 Examples include 03, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), BYK-302, BYK-331, BYK-348, BYK-350, BYK-361N, BYK-381, BYK-399, BYK-3441 (manufactured by BYK Corporation), Disparon® LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, UVX-36, LHP-810 (manufactured by Kusumoto Chemical Co., Ltd.), etc. 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 polymer components (e.g., polymer (P)) contained in the polymer composition.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] [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.

[0084] 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.

[0085] 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.

[0086] [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)

[0087] [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.

[0088] [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.

[0089] [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.

[0090] 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.

[0091] [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.

[0092] 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.

[0093] 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.

[0094] The present invention will be described more specifically below with reference to synthesis examples, preparation examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0095] The monomers used in the examples are shown below. M1 was synthesized according to the synthesis method described in International Publication No. 2011 / 084546. M2 was synthesized according to the synthesis method described in Japanese Patent Publication No. 9-118717. M3 was synthesized according to the synthesis method described in International Publication No. 2023 / 171757.

[0096]

[0097] The abbreviations for the reagents used in this example are shown below.

[0098] (Organic solvent) CPN: Cyclopentanone

[0099] (Polymerization initiator) V-601: 2,2'-Azobis(2-methylpropionic acid)dimethyl

[0100] (Surfactant) 361N: BYK-361N (Manufactured by BYK Corporation)

[0101] (Base catalyst) TPA: Trin-normal propylamine DEAEM: Compound represented by the following formula U-CAT 18X: Methyltriethylammonium 2-ethylhexanoate (manufactured by Sunapro, a thermobase generator) U-CAT 1102: 2-ethylhexanoate of 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) (manufactured by Sunapro, a thermobase generator)

[0102] (Crosslinking agent) HDBMA: 1,6-hexylenebis[α-(bromomethyl)acrylate] (manufactured by Chemicrea)

[0103] (Thermal radical generator) BPO: Benzoyl peroxide

[0104] (Molecular Weight Measurement of Polymers) The conditions for measuring the molecular weight of polymers are as follows: Apparatus: Shimadzu Nexera GPC System (Shimadzu SCL-40) Column: Shodex column (LF-804, KF-801) Column temperature: 40°C Eluent: Tetrahydrofuran (HPLC grade) Flow rate: 1.0 ml / min Standard sample for calibration curve preparation: Polystyrene (PStQuick E / PStQuick F) (Tosoh Corporation)

[0105] [1] Synthesis of Polymers <Synthesis Example 1> A monomer mixture solution was prepared by dissolving M1 (2.99 g, 9.0 mmol) and M2 (15.6 g, 51.0 mmol) in CPN (38.5 g). Under a nitrogen atmosphere, at 70°C, an initiator solution prepared with CPN (16.5 g) and V-601 (0.69 g, 3.0 mmol) was added dropwise to the monomer mixture solution over 1 hour. After addition, the mixture was reacted at 70°C for 6 hours. After the reaction was complete, the reaction solution was poured into a methanol / pure water mixed solvent to precipitate the polymer, which was then filtered, washed with methanol, and dried to obtain polymer powder P1. The number average molecular weight of P1 was 34,000, and the weight average molecular weight was 97,800.

[0106] <Synthesis Example 2> A monomer mixture solution was prepared by dissolving M1 (2.99 g, 9.0 mmol), M2 (9.19 g, 30.0 mmol), M3 (3.96 g, 9.0 mmol), and M4 (1.20 g, 12.0 mmol) in CPN (35.4 g). Under a nitrogen atmosphere, at 70°C, an initiator solution prepared with CPN (16.5 g) and V-601 (0.41 g, 1.8 mmol) was added dropwise to the monomer mixture solution over 1 hour. After addition, the reaction was carried out at 70°C for 6 hours. After the reaction was complete, the reaction solution was poured into a methanol / pure water mixed solvent to precipitate the polymer, which was then filtered, washed with methanol, and dried to obtain polymer powder P2. The number average molecular weight of P2 was 30,000, and the weight average molecular weight was 110,000.

[0107] [2] Preparation of phase difference film forming material <Preparation example 1> Polymer solution T1 was obtained by adding CPN (8.57 g) and 361N (5% by mass CPN solution, 0.028 g) to polymer powder P1 (1.40 g) and stirring. This polymer solution T1 was used as is as the material for forming the phase difference film.

[0108] <Preparation Example 2> Polymer solution T2 was obtained by adding CPN (8.29 g), HDBMA (5% by mass CPN solution, 0.28 g), and 361N (5% by mass CPN solution, 0.028 g) to polymer powder P1 (1.40 g) and stirring. This polymer solution T2 was used as is as a material for forming a phase difference film.

[0109] <Preparation Example 3> Polymer solution T3 was obtained by adding CPN (8.29 g), TPA (5% by mass CPN solution, 0.28 g), and 361N (5% by mass CPN solution, 0.028 g) to polymer powder P1 (1.40 g) and stirring. This polymer solution T3 was used as is as a material for forming a phase difference film.

[0110] <Preparation Example 4> Polymer solution T4 was obtained by adding CPN (7.87 g), DEAEM (5% by mass CPN solution, 0.70 g), and 361N (5% by mass CPN solution, 0.028 g) to polymer powder P1 (1.40 g) and stirring. This polymer solution T4 was used as is as a material for forming a phase difference film.

[0111] <Preparation Example 5> Polymer solution T5 was obtained by adding CPN (8.01 g), HDBMA (5% by mass CPN solution, 0.28 g), TPA (5% by mass CPN solution, 0.28 g), and 361N (5% by mass CPN solution, 0.028 g) to polymer powder P1 (1.40 g) and stirring. This polymer solution T5 was used as is as a material for forming a phase difference film.

[0112] <Preparation Example 6> Polymer solution T6 was obtained by adding CPN (8.01 g), HDBMA (5% by mass CPN solution, 0.28 g), DEAEM (5% by mass CPN solution, 0.28 g), and 361N (5% by mass CPN solution, 0.028 g) to polymer powder P1 (1.40 g) and stirring. This polymer solution T6 was used as is as a material for forming a phase difference film.

[0113] <Preparation Example 7> Polymer solution T7 was obtained by adding CPN (7.59 g), HDBMA (5% by mass CPN solution, 0.28 g), DEAEM (5% by mass CPN solution, 0.70 g), and 361N (5% by mass CPN solution, 0.028 g) to polymer powder P1 (1.40 g) and stirring. This polymer solution T7 was used as is as a material for forming a phase difference film.

[0114] <Preparation Example 8> Polymer solution T8 was obtained by adding CPN (8.01 g), HDBMA (5% by mass CPN solution, 0.28 g), U-CAT 18X ​​(5% by mass CPN solution, 0.28 g), and 361N (5% by mass CPN solution, 0.028 g) to polymer powder P1 (1.40 g) and stirring. This polymer solution T8 was used as is as a material for forming a phase difference film.

[0115] <Preparation Example 9> Polymer solution T9 was obtained by adding CPN (8.01 g), HDBMA (5% by mass CPN solution, 0.28 g), U-CAT 1102 (5% by mass CPN solution, 0.28 g), and 361N (5% by mass CPN solution, 0.28 g) to polymer powder P1 (1.40 g) and stirring. This polymer solution T9 was used as is as a material for forming a phase difference film.

[0116] <Preparation Example 10> Polymer solution T10 was obtained by adding CPN (8.29 g), 361N (5% by mass CPN solution, 0.028 g), and BPO (5% by mass CPN solution, 0.28 g) to polymer powder P2 (1.40 g) and stirring. This polymer solution T10 was used as is as a material for forming a phase difference film.

[0117] <Preparation Example 11> Polymer solution T11 was obtained by adding CPN (7.73 g), HDBMA (5% by mass CPN solution, 0.28 g), DEAEM (5% by mass CPN solution, 0.28 g), BPO (5% by mass CPN solution, 0.28 g), and 361N (5% by mass CPN solution, 0.028 g) to polymer powder P2 (1.40 g) and stirring. This polymer solution T11 was used as is as a material for forming a phase difference film.

[0118] Table 1 shows the composition of the polymer solutions obtained in Preparation Examples 1 to 11. In Table 1, the numbers in parentheses for the crosslinking agent, base catalyst, radical generator, and surfactant represent the amount (mass %) of each component relative to the polymer solids contained in the solution.

[0119]

[0120] [3] Production of polymer film <Comparative Example 1> After filtering polymer solution T1 through a filter with a pore size of 5.0 μm, it was bar-coated onto a COP (cycloolefin polymer) film (Zeon Corporation, ZF16-100) and dried in a hot air circulating oven at 70°C for 3 minutes to form a phase difference film with a thickness of 3.3 to 3.5 μm. Next, polarized 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, it was heated in a 140°C hot air circulating oven for 4.5 minutes to fabricate substrate R1 with a phase difference film.

[0121] <Comparative Examples 2-4, Examples 1-5> Except for changing the polymer solution used from T1 to T2-T9, the same procedure as in Comparative Example 1 was followed to produce substrates R2-R4 and S1-S5 with phase difference films.

[0122] <Comparative Example 5> Polymer solution T10 was filtered through a 5.0 μm pore size filter, then bar-coated onto a COP film (Zeon Corporation, ZF16-100), and dried in a 70°C hot air circulating oven for 3 minutes to form a phase difference film with a thickness of 3.2 μm. Next, polarized ultraviolet light with wavelengths below 325 nm cut off was applied through a polarizing plate at a wire grid at a rate of 50 mJ / cm². ２ The coated surface was then irradiated. Subsequently, it was heated in a 120°C hot air circulating oven for 4.5 minutes to fabricate substrate R5 with a phase difference film.

[0123] <Example 6> A substrate S6 with a phase difference film was fabricated in the same manner as in Comparative Example 5, except that the polymer solution used was changed from T10 to T11.

[0124] The phase difference values ​​and mechanical properties of the phase difference films obtained in Examples 1 to 6 and Comparative Examples 1 to 5, specifically the substrates S-1 to S-6 and R-1 to R-5, were evaluated using the following method.

[0125] [Phase Difference Value Evaluation] The linear phase difference Re at a wavelength of 550 nm was evaluated using an AxoScan from Axometrics. The results are shown in Table 2.

[0126] [Mechanical Properties Evaluation] The phase difference film of a COP film with a phase difference film (4 x 4 cm) was bonded to a glass substrate with an adhesive layer (3.5 x 3.5 cm) using a roller. For the adhesive layer, an optical double-sided adhesive sheet M3D49 manufactured by Mikan Imaging Co., Ltd. was used. Next, the excess COP film with the phase difference film was cut off using a cutter, and the COP film was peeled off to obtain a glass substrate with a phase difference film. The obtained glass substrate with a phase difference film was visually inspected, and the number of cracks was checked. The fewer the number of cracks, the better the mechanical properties can be evaluated. The results are shown in Table 2.

[0127]

[0128] As shown in Table 2, when a polymer solution containing HDBMA and a base catalyst was used, the number of cracks was reduced compared to when a polymer solution lacking at least one of HDBMA and the base catalyst was used, indicating an improvement in mechanical properties.

Claims

1. A polymer composition containing the following polymer (P) and the following compound (A), as well as a base, a thermobase generator, or a photobase generator. Polymer (P): A reorienting polymer having a photosensitive group (p) in its side chain, and further having a nucleophilic group X in its side chain. Polymer compound (A): A compound represented by the following formula (a-1). (In formula (a-1), Z represents a divalent group, and Qa is -Cl, -Br, -I, -OCOR, or -OSO) ２ R represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a p-methylphenyl group. The two Qa may be the same or different.

2. The polymer composition according to claim 1, wherein the nucleophilic group X is a carboxyl group.

3. The polymer composition according to claim 1, wherein Qa in formula (a-1) is -Cl, -Br, or -OCOR.

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

5. A composition for forming a phase difference film, which is a polymer composition according to any one of claims 1 to 4.

6. A composition for forming an orientation film, which is a polymer composition according to any one of claims 1 to 4.

7. A method for producing a phase difference material, comprising the following steps (1) to (3): (1) Applying the polymer composition according to any one of claims 1 to 4 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.

8. A resin film formed from the polymer composition according to any one of claims 1 to 4.

9. A phase difference material comprising the resin film described in claim 8.

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