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

Abstract

This polymer composition contains a polymer (P) having a photosensitive group (p1) represented by formula (a) in a side chain, wherein the polymer (P) has a structural unit derived from a monomer compound having a polymerizable unsaturated bond. (In formula (a), Ar represents a C6-C30 divalent organic group having an arylene group, and A is bonded to a carbon atom in -CR= by a carbon atom constituting an aromatic hydrocarbon ring.　L represents a single bond or -O-.　M is an integer of 1-12.　R and R' each independently represent a hydrogen atom, a halogen atom, a cyano group, or a C1-C3 alkyl group, some or all of the hydrogen atoms in the alkyl group may be substituted by a fluorine atom, and at least one among R and R' represents a group or atom other than a hydrogen atom.　The symbol * represents a bond.)

Description

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

[0001] The present invention relates to a polymer composition (particularly, a composition for forming a retardation film or a composition for forming an alignment film) containing a polymer and a retardation material. More specifically, the present invention relates to a composition for forming a retardation film or a composition for forming an alignment film that can be suitably used for materials having optical properties suitable for applications such as display devices and recording materials (particularly, optical compensation films such as polarizing plates and retardation plates for liquid crystal displays and organic EL (Electro Luminescence) display devices), and a retardation material obtained from the film-forming composition.

[0002] Due to demands for improved display quality and lighter weight of liquid crystal display devices, there is an increasing demand for polymer films with controlled internal molecular orientation structures as optical compensation films such as polarizing plates and retardation plates. These polymer films are used to change the polarization state of light and are known as films that impart birefringence (also referred to as birefringent films or retardation films). Hereinafter, materials that change the polarization state of light will also be referred to as retardation materials. To meet these demands, birefringent films have been developed that utilize the optical anisotropy of polymerizable liquid crystal compounds. The polymerizable liquid crystal compounds used here are generally liquid crystal compounds having a polymerizable group and a liquid crystal structural portion (a structural portion having a spacer portion and a mesogen portion), and acrylic groups are commonly used as the polymerizable group.

[0003] A polymerizable liquid crystal compound can exhibit optical anisotropy by, for example, contacting it with a substrate that has been subjected to an alignment treatment and irradiating it with radiation such as ultraviolet light. Conventional techniques include a method of supporting a specific polymerizable liquid crystal compound having an acrylic group between supports on which a polymer film having alignment ability (hereinafter also referred to as an alignment film) is formed, and irradiating the compound with radiation while maintaining the compound in a liquid crystal state (Patent Document 1), and a method of adding a photopolymerization initiator to a mixture of two types of polymerizable liquid crystal compounds having an acrylic group or a composition obtained by mixing this mixture with a chiral liquid crystal, and irradiating the mixture with ultraviolet light on an alignment-treated substrate (Patent Document 2).

[0004] In addition, various coating-type birefringent films have been reported, such as birefringent films using polymerizable liquid crystal compounds or their polymers without using an alignment film (Patent Documents 3 and 4), and birefringent films using polymers containing photocrosslinkable moieties (Patent Documents 5 and 6).

[0005] JP-A-62-70407, JP-A-9-208957, Special Publication No. 2002-517605, WO2008 / 031243, JP-A 2008-164925, JP-A 11-189665

[0006] In recent years, the demand for higher quality liquid crystal displays and organic EL displays has increased more than ever before. In particular, from the perspective of obtaining high display quality, there is a need for phase difference materials that can achieve a high degree of orientation, but conventional technology has not always been able to produce materials that meet the high level of requirements.

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

[0008] As a result of diligent research to solve the aforementioned problems, the inventors of the present invention have found that a polymer composition containing a specific polymer is suitable for forming a phase difference film, such as a birefringent film, and for forming an alignment film, and have completed the present invention.

[0009] Accordingly, the present invention encompasses the following embodiments: A polymer composition containing a polymer (P) having a photosensitive group (p1) represented by the following formula (a) in its side chain, wherein the polymer (P) has structural units derived from monomer compounds having polymerizable unsaturated bonds. (In formula (a), Ar represents a divalent organic group having 6 to 30 carbon atoms and an arylene group, and Ar is bonded to the carbon atom in -CR= and to the carbon atoms constituting the aromatic hydrocarbon ring. L represents a single bond or -O-. 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, and at least one of R and R' represents a group or atom other than a hydrogen atom. * represents a bond.)

[0010] The present invention can provide a retardation material that exhibits a high degree of orientation, and an alignment film and a polymer composition that provide the retardation material. The mechanism by which the above-mentioned effects of the present invention are obtained is not necessarily clear, but the following is thought to be one of the reasons. By substituting some of the hydrogen atoms in the cinnamic acid structure with substituents such as methyl groups, (i) the isomerization efficiency is improved, and (ii) the thermal properties of the polymer are slightly lowered, making it easier for the polymer to reorient with less energy overall, which is thought to be why the above-mentioned effects are obtained.

[0011] The following provides a detailed description of polymer compositions containing specific polymers, and alignment films or retardation materials formed using the polymer compositions. However, the following description of the constituent elements is merely an example of one embodiment of the present invention and is not intended to limit the scope of the present invention. In the following description, "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. Furthermore, "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" portion of the polymer, which is the longest chain of atoms. Furthermore, the side chain of a polymer refers to the portion branched from the "trunk" of the polymer.

[0012] Embodiments of the present invention will be described in detail below. [Polymer (P)] (Photosensitive group (p1)) The polymer composition of the present invention contains a polymer (P) having a photosensitive group (p1) represented by the following formula (a) in its side chain. The polymer (P) has structural units derived from monomer compounds having polymerizable unsaturated bonds.

[0013] (In formula (a) above, Ar represents a divalent organic group having 6 to 30 carbon atoms and an arylene group, and Ar is bonded to the carbon atom in -CR= and the carbon atoms constituting the aromatic hydrocarbon ring. L represents a single bond or -O-. 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, and at least one of R and R' represents a group or atom other than a hydrogen atom. * represents a bond.)

[0014] The C1-C3 alkyl group mentioned above may be linear or branched, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl 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. In formula (a) above, Ar and COOH 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 above-mentioned photosensitive group (p1) is preferably a photosensitive group represented by the following formula (a1). In the following formula (a1), the substituted phenylene group and COOH 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. (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-. m is an integer from 1 to 12. 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, and at least one of R and R' represents a group or atom other than a hydrogen atom. 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-. A hydrogen atom on the benzene ring in formula (Ph) may be substituted with a substituent selected from the group consisting of an alkyl group, an alkyloxy group, an alkenyl group, an alkynyl group, and a halogen atom. *1 represents a bond to L in formula (a1). *2 represents a bond to the benzene ring in formula (a1).)

[0016] Examples of the alkyl group as a substituent include alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, and a propyl group. Examples of the alkyloxy group as a substituent include alkyloxy groups having 1 to 3 carbon atoms, such as a methoxy group and an ethoxy group. Examples of the alkenyl group as a substituent include alkenyl groups having 2 to 4 carbon atoms, such as a vinyl group, an allyl group, and a 2-butenyl group. Examples of the alkynyl group as a substituent include alkynyl groups having 2 to 4 carbon atoms, such as a propargyl group.

[0017] The above photosensitive group (p1) is preferably a photosensitive group represented by any of the following formulas (a-1) to (a-4). In the following formulas (a-1) to (a-4), the phenylene group and COOH 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. (In the formula, m is an integer of 1 to 12. * represents a bond.)

[0018] The polymer (P) preferably has a structural unit (X1) having a photosensitive group (p1) in a side chain thereof. The structural unit (X1) having a photosensitive group (p1) in a side chain thereof is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a photosensitive group (p1).

[0019] (Other Functional Groups) The polymer (P) may have other functional groups in addition to the photosensitive group (p1). Examples of the other functional groups include photosensitive groups (p2) other than the photosensitive group (p1), mesogen-forming groups (m), crosslinkable groups, groups having a five- or greater-membered heterocycle, and thermally detachable groups.

[0020] The polymer (P) has, for example, another functional group in its side chain. The polymer (P) may have a structural unit (X2) having another functional group in its side chain. The structural unit (X2) having another functional group in its side chain is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and another functional group.

[0021] ((Other Photosensitive Groups (p2))) Examples of other photosensitive groups (p2) include functional groups capable of undergoing a photocrosslinking reaction (for example, a photodimerization reaction), a photoisomerization reaction, or a photo-Fries rearrangement reaction by light energy, and examples thereof include cinnamic acid groups, azobenzene skeletons, cinnamoyl groups, chalcone groups, coumarin groups, benzophenone groups, phenylbenzoate skeletons, and derivatives thereof, as represented by the following formulas (ca-1) to (ca-2). In the following formulas (ca-1) to (ca-2), the phenylene group and COOH, or the phenylene group and -C(=O)O-*1, may be bonded at either the cis position or the trans position relative to the double bond, but are preferably bonded at the trans position. (*1 represents a bond bonded to an atom other than a hydrogen atom. X １ and X ２ each independently represents 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. * represents a bond.

[0022] If the polymer (P) has other photosensitive groups (p2), the polymer (P) is a structural unit (X) having other photosensitive groups (p2) in its side chains. ｐ２ It is preferable to have a structural unit (X) having other photosensitive groups (p2) in the side chain. ｐ２ ) is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and other photosensitive groups (p2).

[0023] ((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.

[0024] 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) has a structural unit (X) that has a mesogen-forming group (m) in its side chain. ｍ It is preferable to have a structural unit (X) having a mesogen-forming group (m) in the side chain. ｍ ) is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a mesogen-forming group (m).

[0025] The mesogen-forming group (m) may be in an embodiment (A) having a side chain having the above-mentioned photosensitive group (p1) or other photosensitive group (p2), or in an embodiment (B) having a side chain that does not have the above-mentioned photosensitive group (p1) or other photosensitive group (p2), or a combination thereof. Embodiment (A) includes, but is not limited to, an embodiment (A1) in which the mesogen-forming group is provided in the side chain by sharing part or all of the structure of the above-mentioned photosensitive group (p1) or other photosensitive group (p2), and an embodiment (A2) in which the mesogen-forming group is provided in the side chain independently of the structure of the above-mentioned photosensitive group (p1) or other photosensitive group (p2). In embodiment (A2), the mesogen-forming group (m) and the photosensitive group (p1) or other photosensitive group (p2) may be bonded by a single bond, or they may be bonded to each other via a linking group. Examples of the above-mentioned linking groups include alkylene groups, -O-, -S-, -SO-, and -SO-. ２Examples of the alkylene group include -, -CH=CH-, -C≡C-, -N=N-, -COO-, and -OCO-. Examples of the alkylene group include alkylene groups having 1 to 20 carbon atoms, such as 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.

[0026] Examples of the mesogenic group include -Ar １ -Y-Ar ２ -, where Ar １ and Ar ２ are the same or different and represent an arylene group which may have a substituent, a cycloalkylene group which may have a substituent (e.g., a cyclopropylene group, a cyclobutane group, or a cyclohexylene group), or a divalent heterocyclic ring which may have a substituent (e.g., an oxygen-containing heterocyclic ring such as a furan ring or a pyran ring; a nitrogen-containing heterocyclic ring such as a pyrrole ring or an imidazole ring). 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.

[0027] 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.

[0028] The arylene group, cycloalkylene group, and heterocyclic residue 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 an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group. Examples of the alkyloxy group include an alkyloxy group having 1 to 3 carbon atoms such as a methoxy group and an ethoxy group. Examples of the alkenyl group include an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, an allyl group, and a 2-butenyl group. Examples of the alkynyl group include an alkynyl group having 2 to 4 carbon atoms such as a propargyl group. Examples of the haloalkyl group include a haloalkyl group having 1 to 3 carbon atoms such as a trifluoromethyl group. Examples of the cycloalkyl group include a cycloalkyl group having 3 to 6 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. The above-mentioned cycloalkyl group and aryl group may have substituents, such as a methoxy group and a halogen atom.

[0029] A more preferred specific example of the above-mentioned mesogenic group is the following structure. (* represents a bond.)

[0030] 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 where Ar and Ar ３are the same or different and represent an arylene group which may have a substituent. 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 represents an integer of 2 to 3, preferably 2. The arylene group may have a substituent, and examples of the substituent include an alkyl group, a formyl group, an alkyloxy group, an alkenyl group, an alkynyl group, a halogen atom, and a haloalkyl group. Specific examples of the alkyl group, alkyloxy group, alkenyl group, alkynyl group, and haloalkyl group as the substituent 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.

[0031] Other side chains having the above-mentioned photosensitive group (p2) include the following structures. In the formulae (p2-1) to (p2-45), 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. 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.

[0032] Preferred specific examples of the side chain (bm) that does not have the photosensitive group (p1) or other photosensitive groups (p2) but has the mesogen-forming group (m) include the following structures and vinylbenzoic acid residues. (Note, Sp １ is, -(CH ２ )ｓ１ This 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.

[0033] ((Crosslinkable Group)) A crosslinkable group is a functional group selected from the group consisting of an oxetanyl group, an oxyranyl group, a carboxyl group, and a hydroxyl group.

[0034] The polymer (P) has, for example, a crosslinkable group in its side chain. When the polymer (P) has a crosslinkable group, the polymer (P) is a structural unit (X) having a crosslinkable group in its side chain. ＣＬ It is preferable to have a structural unit (X) having a crosslinkable group in the side chain. ＣＬ ) is, for example, a structural unit derived from a monomer compound having polymerizable unsaturated bonds and crosslinkable groups.

[0035] The above structural unit (X ＣＬ Examples of monomer compounds that give ) include (meth)acrylate glycidyl, α-ethylacrylate glycidyl, α-n-propylacrylate glycidyl, α-n-butylacrylate glycidyl, (meth)acrylate 3,4-epoxybutyl, α-ethylacrylate 3,4-epoxybutyl, (meth)acrylate 3,4-epoxycyclohexylmethyl, (meth)acrylate 6,7-epoxyheptyl, α-ethylacrylate 6,7-epoxyheptyl, (meth)acrylate 3-methyl-3-oxetanylmethyl, (meth)acrylate (3-ethyloxetan-3-yl) Examples include methyl, 4-hydroxybutyl glycidyl ether (meth)acrylate, and compounds having an oxetanyl group or an oxyranyl group such as those of the following formulas (G1) to (G3); carboxyl group-containing compounds such as (meth)acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and hydroxyl group-containing compounds such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0036] <Groups having a heterocycle of 5 or more members> Examples of heterocycles in groups having a heterocycle of 5 or more members include cyclic amines such as piperidine, piperazine, 1,2,3-triazole, purine, 1,4-diazabicyclo[2.2.2]octane (triethylenediamine), quinuclidine, morpholin, diazabicycloundecene (DBU), diazabicyclononene (DBN), and N,N-dimethyl-4-aminopyridine (DMAP); and aromatic heterocycles such as pyridine, pyrrole, imidazole, or acridine.

[0037] 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.

[0038] The polymer (P) has, for example, a group having a 5- or larger-membered heterocyclic ring in a side chain. When the polymer (P) has a group having a 5- or larger-membered heterocyclic ring, the polymer (P) has a structural unit (X ｈｔ It is preferable to have a structural unit (X) having a group having a heterocycle of 5 or more members in its side chain. ｈｔ ) is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a group having a heterocyclic ring of five or more members.

[0039] The above structural unit (X ｈｔ Examples of monomeric compounds that give ) include the following compounds (ht-1) to (ht-2).

[0040] ((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.

[0041] 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. ＢＬ It 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.

[0042] The above structural unit (X ＢＬ Examples of the monomer compound that gives the above-mentioned methyl group include the following compounds (BL-1) to (BL-2). (In the formula, "Boc" represents a tert-butoxycarbonyl group.)

[0043] The polymer (P) of the present invention has structural units derived from monomeric compounds having polymerizable unsaturated bonds. Examples of groups or structures having polymerizable unsaturated bonds include (meth)acryloyl groups, maleimide groups, styryl groups, vinyl groups, α-methylene-γ-butyrolactone structures, and the following formulas (PG1) to (PG3). (The dashed lines represent bonds.)

[0044] The polymer (P) of the present invention can be obtained, for example, by polymerizing a monomer compound having at least one polymerizable unsaturated bond and at least one side chain as described above.

[0045] The polymer (P) of the present invention is preferably obtained by polymerizing a monomer compound containing a compound represented by the following formula (MB). Compounds represented by the following formula (MB) are also subject to the present invention.

[0046] (Compound represented by formula (MB)) (In formula (MB), Ar represents a divalent organic group having 6 to 30 carbon atoms and an arylene group, and Ar is bonded to the carbon atom in -CR= and to the carbon atoms constituting the aromatic hydrocarbon ring. L represents a single bond or -O-. 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, and at least one of R and R' represents a group or atom other than a hydrogen atom. Ｂ (This represents a hydrogen atom or a methyl group.)

[0047] The C1-C3 alkyl group mentioned above may be linear or branched, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl 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. In the above formula (MB), Ar and COOH 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.

[0048] This compound can be produced, for example, by the method shown in Scheme 1 below.

[0049] (Scheme 1) In scheme 1, Ar, L, m, R, R' and R Ｂ This is equivalent to the definition in the above formula (MB).

[0050] The compound represented by formula (MB-a2) can be synthesized by the Williamson ether synthesis method in which a compound represented by formula (MB-a1) and a compound represented by formula (MB-r1) are reacted in the presence of a base.

[0051] In the compound represented by formula (MB-r1), LG′ is a substituent capable of being eliminated, and examples thereof include a halogen atom such as F, Cl, Br, or I; a p-toluenesulfonic acid ester group (—OSO ２ C ６ H ４ -p-CH ３ ), methanesulfonic acid ester group (-OSO ２ CH ３ ), trifluoromethanesulfonic acid ester group (-OSO ２ CF ３ Among these, Br, I and trifluoromethanesulfonate groups are preferred from the viewpoint of reactivity.

[0052] The amount of the compound represented by formula (MB-r1) used relative to the compound represented by formula (MB-a1) is not particularly limited, but is preferably 1.0 equivalent to 3.0 equivalents, and more preferably 1.0 equivalent to 1.2 equivalents.

[0053] In this reaction, an appropriate base is used. Typically, the base used may be an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, or cesium carbonate, an organic base such as sodium tert-butoxide or potassium tert-butoxide, or an amine such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, or collidine.

[0054] The amount of the base used is preferably 1.0 to 3.0 equivalents, more preferably 1.0 to 1.5 equivalents, relative to the compound represented by formula (MB-a1).

[0055] Any reaction solvent can be used as long as it is stable, inert, and does not interfere with the reaction under the reaction conditions. Examples of suitable reaction solvents include aprotic polar organic solvents (DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide), DMAc (N,N-dimethylacetamide), NMP (N-methyl-2-pyrrolidone), etc.), ethers (Et ２ O (diethyl ether), i-Pr ２ Examples of solvents that can be used include: hexane (diisopropyl ether), TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), THF (tetrahydrofuran), dioxane, etc.; aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); and nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected taking into consideration the ease of reaction, etc. In this case, the above solvents can be used alone or in combination of two or more. In some cases, a suitable dehydrating agent or drying agent can be used as a non-aqueous solvent.

[0056] The amount of solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, the amount of solvent used may be 0.1 to 100 times by mass, preferably 1 to 10 times by mass, and more preferably 2 to 5 times by mass, relative to the amount of the compound represented by Formula (MB-a1).

[0057] To make the reaction proceed more efficiently, tetra-n-butylammonium iodide, sodium iodide, potassium iodide, etc. may be added.

[0058] The reaction temperature can be selected preferably within the range of from -100°C or higher to the boiling point of the reaction solvent used, more preferably from -50 to 200°C, and particularly preferably from 20 to 150°C. The reaction time is 0.1 to 1000 hours, more preferably from 0.5 to 100 hours. The compound represented by formula (MB-a2) obtained by the method shown in the above reaction scheme is preferably purified by distillation, recrystallization, column chromatography using silica gel or the like, or the like. It is preferable to carry out recrystallization at as low a temperature as possible.

[0059] The compound represented by formula (MB-a3) can be synthesized by subjecting a compound represented by formula (MB-a2) and a compound represented by formula (MB-r2) to a coupling reaction such as a Heck reaction in the presence of a metal complex catalyst, a ligand, and a base.

[0060] In the compounds represented by formula (MB-a1) and formula (MB-a2), LG is a substituent capable of being eliminated, and examples thereof include halogens such as F, Cl, Br, and I; p-toluenesulfonic acid ester group (—OSO ２ C ６ H ４ -p-CH ３ ), methanesulfonic acid ester group (-OSO ２ CH ３ ), trifluoromethanesulfonic acid ester group (-OSO ２ CF ３ Among these, Br, I and trifluoromethanesulfonate groups are preferred from the viewpoint of reactivity.

[0061] The amount of the compound represented by formula (MB-r2) used relative to the compound represented by formula (MB-a2) is not particularly limited, but is preferably 1.0 equivalent to 10.0 equivalents, and more preferably 1.0 equivalent to 4.0 equivalents.

[0062] In this reaction, a metal complex catalyst is formed and used using a suitable metal complex and ligand. Typically, palladium complexes or nickel complexes are used as the metal complexes, and depending on the reaction, it is preferable to have a copper catalyst co-catalyst. Various structures can be used as metal complex catalysts, but it is preferable to use so-called low-valence palladium complexes or nickel complexes, and in particular, zero-valence metal complex catalysts with tertiary phosphines or tertiary phosphites as ligands are preferred. Alternatively, a suitable precursor that is easily converted into a zero-valence metal complex catalyst in the reaction system can also be used. Furthermore, a metal complex that does not contain tertiary phosphines or tertiary phosphites as ligands can be mixed with tertiary phosphines or tertiary phosphites as ligands in the reaction system to generate a low-valence metal complex catalyst with tertiary phosphines or tertiary phosphites as ligands in the reaction system.

[0063] Examples of tertiary phosphines or tertiary phosphites used as ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, trimethylphosphite, triethylphosphite, and triphenylphosphite. Metal complex catalysts containing a mixture of two or more of these ligands are also suitably used.

[0064] As the metal complex catalyst, it is also preferable to use a combination of a palladium complex that does not contain a tertiary phosphine or tertiary phosphite and a metal complex that contains a tertiary phosphine or tertiary phosphite. In this case, the above-mentioned ligands may be further combined. Examples of palladium complexes that do not contain a tertiary phosphine or tertiary phosphite include bis(benzylideneacetone)palladium, tris(benzylideneacetone)dipalladium, bis(acetonitrile)dichloropalladium, bis(benzonitrile)dichloropalladium, palladium acetate, palladium chloride, and palladium-activated carbon. Examples of palladium complexes that contain a tertiary phosphine or tertiary phosphite as a ligand include (ethylene)bis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, and bis(triphenylphosphine)dichloropalladium. The amount of these palladium complexes used may be a so-called catalytic amount, and is preferably 20 mol % or less, and particularly preferably 10 mol % or less, relative to the compound represented by Formula (MB-a2). The copper catalyst used simultaneously as a promoter is preferably a monovalent one, such as copper(I) chloride, copper(I) bromide, copper(I) iodide, copper(I) acetate, etc.

[0065] Examples of the base that can be used include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, collidine, pyrrolidine, piperidine, morpholine, and N-methylmorpholine; and sodium acetate, potassium acetate, and lithium acetate.

[0066] The amount of the base used relative to the compound represented by formula (MB-a2) is not particularly limited, but is preferably 1.0 to 10.0 equivalents, and more preferably 1.0 to 6.0 equivalents.

[0067] Any reaction solvent can be used as long as it is stable, inert, and does not interfere with the reaction under the reaction conditions. Examples of reaction solvents include water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ２ O, i-Pr ２ A range of solvents can be used, including 0, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), and nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected considering the ease of reaction, etc., and can be used individually or in combination of two or more. In some cases, the above solvents can also be used as water-free solvents by using appropriate dehydrating agents or drying agents.

[0068] The amount of solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without a solvent, and if a solvent is used, 0.1 to 100 times the mass of the solvent relative to the compound represented by formula (MB-a2) may be used. Preferably, it is 1 to 10 times the mass, and more preferably 2 to 5 times the mass.

[0069] The reaction temperature can be selected preferably within the range of from -100°C or higher to the boiling point of the reaction solvent used, more preferably from -50 to 200°C, and particularly preferably from 20 to 150°C. The reaction time is 0.1 to 1000 hours, more preferably from 0.5 to 100 hours. The compound represented by formula (MB-a3) obtained by the method shown in Scheme 1 above is preferably purified by distillation, recrystallization, column chromatography using silica gel or the like, or the like. It is preferable to carry out recrystallization at as low a temperature as possible.

[0070] As a method for producing the compound represented by formula (MB-a3), in addition to the scheme shown above, the compound represented by formula (MB-a3) can also be produced by carrying out a coupling reaction such as a Heck reaction using a compound represented by formula (MB-a1) and a compound represented by formula (MB-r2) in the presence of a metal complex catalyst, a ligand, and a base, and then carrying out the reaction with a compound represented by formula (MB-r1) by Williamson ether synthesis.

[0071] The compound represented by formula (MB) can be synthesized by carrying out a condensation reaction between the compound represented by formula (MB-a3) and the compound represented by formula (MB-r3) in the presence of a base.

[0072] The amount of compound represented by formula (MB-r3) used relative to the compound represented by formula (MB-a3) is not particularly limited, but 1.0 to 3.0 equivalents is preferred. More preferably, it is 1.0 to 2.0 equivalents.

[0073] In this reaction, an appropriate base is used. Typically, the base used may be an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, or cesium carbonate, an organic base such as sodium tert-butoxide or potassium tert-butoxide, or an amine such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, or collidine.

[0074] The amount of the base used is preferably 1.0 to 4.0 equivalents, more preferably 1.0 to 2.5 equivalents, relative to the compound represented by formula (MB-a3).

[0075] Any reaction solvent can be used as long as it is stable, inert, and does not interfere with the reaction under the reaction conditions. Examples of suitable reaction solvents include aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ２ O, i-Pr ２ Examples of solvents that can be used include: toluene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, dioxane, etc.; aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); and nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected taking into consideration the ease of reaction, etc., and in this case, the above solvents can be used alone or in combination of two or more. In some cases, a suitable dehydrating agent or drying agent can be used as a non-aqueous solvent.

[0076] The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, the amount of the solvent used may be 0.1 to 100 times by mass, preferably 1 to 10 times by mass, and more preferably 2 to 5 times by mass, relative to the amount of the compound represented by Formula (MB-a3).

[0077] The reaction temperature can be selected preferably within the range of from −100° C. or higher to the boiling point of the reaction solvent used, more preferably −50 to 100° C., particularly preferably 0 to 50° C. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.

[0078] Furthermore, when synthesizing the compound represented by formula (MB) by reacting the compound represented by formula (MB-a3) with the compound represented by formula (MB-r3), the carboxyl group of -CR=CR'-COOH may be protected with a protecting group (e.g., an alkoxyalkyl group), as in the synthesis example in the examples of this specification, and then deprotected.

[0079] The compound represented by formula (MB) obtained by the method shown in the above reaction equation is preferably purified by distillation, recrystallization, or column chromatography using silica gel or similar methods. Recrystallization is preferably performed at the lowest possible temperature.

[0080] 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, and 8-ethyl-8-tricyclodecyl (meth)acrylate; 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.

[0081] In view of photoreactivity, the content of the structural unit (X1) having a photosensitive group (p1) in a side chain in the polymer (P) of the present invention is preferably 5 mol % or more, more preferably 10 mol % or more, relative to 100 mol % of the total structural units contained in the polymer (P), and may be 100 mol % or less, 95 mol % or less, 90 mol % or less, or 80 mol % or less.

[0082] The content of the structural unit (X2) and structural units derived from other monomer compounds in the polymer (P) of the present invention is the remaining portion when the content of the structural unit (X1) is less than 100 mol%. From the viewpoint of photoreactivity, the content of the structural unit (X2) and structural units derived from other monomer compounds in the polymer (P) of the present invention is preferably 5 mol% or more, and more preferably 10 mol% or more, relative to the total 100 mol% of the structural units possessed by the polymer (P). Alternatively, it may be 95 mol% or less, or may be 90 mol% or less.

[0083] (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-type initiators consisting of these peroxides and reducing agents. Among these, azo compounds are preferred, and 2,2'-azobis(isobutyronitrile) or 2,2'-azobis(isobutyric acid)dimethyl is more preferred. As the polymerization initiator, these can be used alone or in combination of two or more. The proportion of the polymerization initiator used is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, per 100 parts by mass of all the monomer compounds used in the reaction.

[0084] 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 thereof 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, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, and propanediol. 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.

[0085] 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).

[0086] 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.

[0087] 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.

[0088] [(B) 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 thereof 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-dimethylpropanamide ...2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone amide, 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 alone or in combination of two or more.

[0089] The polymer composition of the present invention may also contain a solvent (poor solvent) that improves the film thickness uniformity and surface smoothness when the polymer composition is applied.

[0090] 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 having 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.

[0091] The poor solvent may be used alone or in combination of two or more. When a poor solvent is used, its content in the solvent is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, so as not to significantly reduce the solubility of the polymer.

[0092] The content of the organic solvent in the polymer composition is not particularly limited, but is preferably 70 to 99 mass%, more preferably 75 to 99 mass%, and particularly preferably 80 to 99 mass%, relative to 100 mass% of the polymer composition.

[0093] The polymer composition of the present invention may additionally contain components other than the polymer (P) and the solvent (hereinafter also referred to as additive components). Examples of such additive components include compounds that improve film thickness uniformity and surface smoothness, compounds that increase film strength (hereinafter also referred to as crosslinking compounds), adhesion aids that increase adhesion between the film and the substrate, and photosensitizers.

[0094] Compounds that improve the film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples of these include EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), MEGAFAC (registered trademark) F171, F173, F560, F563, R-30, R-40, R-41 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M Limited), Asahiguard (registered trademark) AG710 (manufactured by AGC), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), BYK-302, BYK-331, BYK-348, BYK-360N, BYK-381, BYK-3441 (manufactured by BYK Corporation), and the like. The content of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component (for example, polymer (P)) contained in the polymer composition.

[0095] Examples of the crosslinkable compound include at least one crosslinkable compound selected from the group consisting of a crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an oxetanyl group, an oxazoline structure, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group, and an alkoxy group, 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 2,000 or less. Specific preferred examples of the crosslinkable compounds (c-1) and (c-2) include the following compounds: Examples of 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, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A epoxy resins such as Epikote 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F epoxy resins such as Epikote 807 (manufactured by Mitsubishi Chemical Corporation), and hydrogenated bisphenols such as YX-8000 (manufactured by Mitsubishi Chemical Corporation). phenol A type epoxy resins, 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.), compounds in which a tertiary nitrogen atom is bonded to an aromatic carbon atom such as 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) ) 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 and other compounds in which a tertiary nitrogen atom is bonded to an aliphatic carbon atom; isocyanurate compounds such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.); compounds described in paragraph

[0037] of JP-A-10-338880 and compounds described in WO2017 / 170483; Examples of compounds having an oxetanyl group include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (Aron Oxetane OXT-121 (XDO)), bis[2-(3-oxetanyl)butyl]ether (Aron Oxetane 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 described in paragraphs

[0170] to

[0175] of WO2011 / 132751; Examples of 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 EPOCROS (trade name, manufactured by Nippon Shokubai Co., Ltd.), and compounds described in paragraph

[0115] of Japanese Patent Application Laid-Open 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] Examples of the photosensitizer include benzophenone, benzophenone derivatives such as 2,4-dichlorobenzophenone and N,N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, and 9-hydroxymethylanthracene.

[0103] 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.

[0104] [Preparation of Polymer Composition] The polymer composition of the present invention is preferably prepared as a coating liquid suitable for forming a retardation material. That is, the polymer composition used in the present invention is preferably prepared as a solution in which the polymer (P) is dissolved in the above-mentioned solvent. Here, the content of the polymer (P) in the polymer composition of the present invention is preferably 1 to 30% by mass, more preferably 1 to 20% by mass.

[0105] 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 polymers in the polymer component is preferably 0.5 to 80 mass %, more preferably 1 to 50 mass %. Examples of the other polymers include polymers that are not photosensitive side-chain polymers capable of exhibiting liquid crystallinity, such as poly(meth)acrylate, polyamic acid, and polyimide.

[0106] The polymer composition of the present invention is preferably used as a composition for forming an alignment film or a composition for forming a retardation film.

[0107] [Resin Film, Retardation Material, and Method for Producing Retardation 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 below. The retardation material of the present invention has the resin film of the present invention. The retardation material of the present invention can be produced, for example, by a method including the following steps (1) to (3) (hereinafter referred to as production method (A)). When the polymer composition of the present invention is used as a composition for forming an alignment film, step (4) described below may be added in addition to the above steps (1) to (3) (hereinafter referred to as production method (B)). Step (1): A step of applying the polymer composition of the present invention to 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).

[0108] [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 to a substrate. More specifically, the polymer composition of the present invention is applied to a substrate such as a substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a glass substrate coated with a metal (e.g., aluminum, molybdenum, chromium, etc.), a glass substrate, a quartz substrate, an ITO substrate, etc.) or a film (e.g., a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, or an acrylic film) by a method such as bar coating, spin coating, flow coating, roll coating, slit coating, slit coating followed by spin coating, an inkjet method, or a printing method. After application, the solvent is 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.

[0109] [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.

[0110] [Step (3): Heating Step] In step (3), the coating film irradiated with polarized UV light in step (2) is heated. Heating can impart orientation controllability to the coating film. Heating can be performed using a heating means such as a hot plate, a hot air circulation oven, or an IR (infrared) oven. The heating temperature can be determined taking into account the temperature at which the coating film to be used will exhibit liquid crystallinity. The heating temperature is preferably within the temperature range at which the polymer (P) contained in the polymer composition of the present invention exhibits liquid crystallinity (hereinafter referred to as the liquid crystal onset temperature). The heating temperature range after irradiation with polarized UV light is preferably a temperature ranging from the lower limit of the liquid crystal onset temperature range of the polymer (P) to a temperature 10°C lower than the upper limit of the liquid crystal onset temperature range. The liquid crystal onset temperature refers to a temperature above the liquid crystal transition temperature at which the polymer or coating film surface undergoes a phase transition from a solid phase to a liquid crystal phase, but below the isotropic phase transition temperature (Tiso) at which the liquid crystal phase undergoes a phase transition from an isotropic phase to an isotropic phase. For example, expressing liquid crystallinity at 130° C. or lower means that the liquid crystal transition temperature at which a phase transition from a solid phase to a liquid crystal phase occurs is 130° C. or lower. The thickness of the coating film formed after heating can be appropriately selected taking into consideration the step height and optical properties of the substrate used, and is preferably, for example, 0.5 to 10 μm.

[0111] The retardation material of the present invention may be produced by a method using the above polymer composition as a composition for forming an alignment film, and including the following step (4) in addition to the above steps (1) to (3). In this production method, the thickness of the coating film (alignment film) formed after heating in the above step (3) can be appropriately selected taking into consideration the step height and optical properties of the substrate used, and is, for example, preferably 5 to 300 nm, more preferably 10 to 200 nm.

[0112] [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.

[0113] To apply the polymerizable liquid crystal as described above onto the alignment film formed in step (3), any suitable application method can be used, such as a bar coater method, a roll coater method, a spinner method, a printing method, or an inkjet method. The polymerizable liquid crystal coating formed as described above is then subjected to one or more treatments selected from heating and light irradiation to harden the coating and form a liquid crystal layer. Performing these treatments in a superimposed manner is preferred because good alignment can be obtained. The heating temperature of the coating should be appropriately selected depending on the type of polymerizable liquid crystal used. For example, heating may be performed at a temperature in the range of 40 to 80°C, and the heating time may be, for example, 0.5 to 5 minutes. Unpolarized ultraviolet light having a wavelength in the range of 200 to 500 nm can be preferably used as the irradiation light. The light irradiation dose is 50 to 10,000 mJ / cm. ２ It is preferable to set the exposure dose to 100 to 5,000 mJ / cm. ２ It is preferable to do so.

[0114] The retardation material of the present invention obtained by the above-mentioned production method (A) or (B) is a material having optical properties suitable for applications such as display devices and recording materials, and is particularly suitable as an optical compensation film such as a polarizing plate and a retardation plate for liquid crystal displays and organic EL displays.

[0115] The present invention will be described in more detail below with reference to synthesis examples, preparation examples, working examples and comparative examples, but the present invention is not limited to the following examples.

[0116] The monomers used in the examples are shown below. MA-1 was synthesized according to the synthesis method described in WO 2011 / 084546. MC-1 was synthesized according to the synthesis method described in JP-A-9-118717.

[0117] The abbreviations for the other reagents used in this example are shown below.

[0118] (Organic solvents) DMAc: N,N-dimethylacetamide AcOEt: Ethyl acetate MeCN: Acetonitrile THF: Tetrahydrofuran CPN: Cyclopentanone PGME: Propylene glycol monomethyl ether NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

[0119] (Polymerization initiator) V601: 2,2'-Azobis(isobutyrate)dimethyl

[0120] (Surfactant) AP-001: Marproof AP-001 (manufactured by NOF Corporation)

[0121] < １ H-NMR Measurement> Apparatus: Fourier transform superconducting nuclear magnetic resonance spectrometer (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500 MHz Solvent: deuterated dimethyl sulfoxide (DMSO-d ６ Standard substance: Tetramethylsilane (TMS)

[0122] [1] Synthesis of monomers <<Synthesis of MB-1>>

[0123] A 2 L four-neck flask was charged with 6-(4-bromophenoxy)-1-hexanol (119.0 g, 435 mmol), crotonic acid (150.0 g, 1740 mmol), tripropylamine (374.0 g, 2610 mmol, Pr ３ N), and DMAc (435g) were charged, and after nitrogen purging, palladium(II) acetate (1.95g, 8.7 mmol, Pd(OAc)) was added. ２ ), and tri(o-tolyl)phosphine (5.3g, 17.4 mmol, P(o-Tol) ３ The mixture was prepared and stirred at 130°C. After the reaction was complete, the reaction solution was concentrated, and 650 g of AcOEt (2N) hydrochloric acid aqueous solution (500 g) was added to the concentrate to extract the organic phase. The obtained organic phase was washed twice with 500 g of deionized water and concentrated again. 350 g of MeCN was added to the obtained concentrate and cooled to 0°C, and the precipitate was filtered and dried. 200 g of AcOEt was added to the crude product, recrystallized, filtered, and dried to obtain 27.1 g of MB-1-1 (white solid, yield 22%).

[0124] MB-1-1 (26.9 g, 96.6 mmol) and THF (400 g) were placed in a 1 L four-neck flask, and after replacing the atmosphere with nitrogen, the flask was cooled to 0°C and chloromethyl methyl ether (9.0 g, 111.1 mmol, MOM-Cl) was added dropwise. While maintaining the temperature at 0°C, triethylamine (11.7 g, 115.9 mmol, Et ３ After confirming that the heat generation had subsided, the mixture was stirred at room temperature. Subsequently, triethylamine (15.2 g, 149.7 mmol, Et ３ N) was added and cooled to 0°C. After cooling, methacryloyl chloride (15.2 g, 144.9 mmol) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After completion of the reaction, AcOEt (400 g) and ion-exchanged water (400 g) were added to the reaction solution, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (300 g), and the organic phase was concentrated. The obtained concentrate was subjected to column isolation using silica gel with an AcOEt / Heptane (volume ratio = 1:10) solution, and 20.8 g of MB-1-2 (light yellow liquid, yield 55%) was obtained.

[0125] A 500 mL four-neck flask was charged with MB-1-2 (20.8 g, 53.2 mmol), MeCN (210 g), and ion-exchanged water (21 g) and cooled to 0°C. After cooling, methanesulfonic acid (15.4 g, 159.6 mmol, MsOH) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was poured into ion-exchanged water (630 g), and the precipitate was separated by filtration. The obtained crude product was recrystallized by adding AcOEt (90 g), and the precipitate was separated by filtration and dried to obtain 15.7 g of MB-1 (white solid, 85% yield).

[0126] １ H-NMR (500MHz) in DMSO-d ６ ​: δ (ppm) = 12.06 (s, 1H), 7.49-7.51 (d, 2H), 6.93-6.95 (d, 2H), 6.06 (s, 1H), 6.01 (s, 1H), 5.65 (s, 1H), 4.08-4.1 1 (t, 2H), 3.98-4.00 (t, 2H), 2.46 (s, 3H), 1.87 (s, 3H), 1.71-1.73 (m, 2H), 1.62-1.65 (m, 2H), 1.39-1.45 (m, 4H).

[0127] <<Synthesis of MB-2>>

[0128] In a 1 L four-necked flask, combine 6-(4-bromophenoxy)-1-hexanol (54.6 g, 200 mmol), methacrylic acid (68.9 g, 800 mmol), and tripropylamine (171.9 g, 1200 mmol, Pr ３ N), and DMAc (200g) were charged, and after nitrogen purging, palladium(II) acetate (0.90g, 4.0 mmol, Pd(OAc)) was added. ２ ), and tri(o-tolyl)phosphine (2.4 g, 8.0 mmol, P(o-Tol) ３ The mixture was prepared and stirred at 130°C. After the reaction was complete, the reaction solution was poured into 1000g of deionized water, neutralized with 12N hydrochloric acid solution, filtered off the precipitate, and dried. MeCN (450g) was added to the obtained crude material, washed with slurry, filtered off, and dried to obtain 26.8g of MB-2-1 (white solid, yield 48%).

[0129] MB-2-1 (26.8 g, 96.3 mmol) and THF (400 g) were charged into a 1 L four-necked flask. After purging with nitrogen, the flask was cooled to 0°C and chloromethyl methyl ether (8.9 g, 110.7 mmol, MOM-Cl) was added dropwise. While maintaining 0°C, triethylamine (11.7 g, 115.6 mmol, Et) was added. ３ N) was slowly added dropwise, and after confirming that the exothermic reaction had subsided, the mixture was stirred at room temperature. Subsequently, triethylamine (15.1 g, 149.3 mmol, Et) was added to the reaction mixture. ３N) was added and cooled to 0°C. After cooling, methacryloyl chloride (15.1 g, 144.5 mmol) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After completion of the reaction, AcOEt (400 g) and ion-exchanged water (400 g) were added to the reaction solution, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (300 g), and the organic phase was concentrated. The obtained concentrate was subjected to column isolation using silica gel with an AcOEt / Heptane (volume ratio = 1:10) solution, and 23.5 g of MB-2-2 (light yellow liquid, yield 63%) was obtained.

[0130] A 500 mL four-neck flask was charged with MB-2-2 (23.5 g, 60.2 mmol), MeCN (240 g), and ion-exchanged water (24 g) and cooled to 0°C. After cooling, methanesulfonic acid (17.4 g, 180.6 mmol, MsOH) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was poured into ion-exchanged water (700 g), and the precipitate was separated by filtration. AcOEt (50 g) was added to the obtained crude product, which was recrystallized, filtered, and dried to obtain 17.3 g of MB-2 (white solid, 83% yield).

[0131] １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 12.33 (s, 1H), 7.54 (s, 1H) 7.42-7.43 (d, 2H), 6.96-6.98 (d, 2H), 6.01 (s, 1H), 5.65 (s, 1H), 4.08-4.11 (t, 2H), 3.98-4.01 (t, 2H), 2.03 (s, 3H), 1.87 (s, 3H), 1.70-1.74 (m, 2H), 1.61-1.67 (m, 2H), 1.38-1.48 (m, 4H).

[0132] <<Synthesis of MB-3>>

[0133] In a 1 L four-neck flask, 4-bromo-4'-(6-hydroxyhexyloxy)biphenyl (35.0 g, 100 mmol), crotonic acid (34.5 g, 400 mmol), tripropylamine (86.1 g, 600 mmol, Pr ３ ​N), and DMAc (100 g) were charged, and after purging with nitrogen, palladium (II) acetate (0.45 g, 2.0 mmol, Pd(OAc) ２ ), and tri(o-tolyl)phosphine (1.2 g, 4.0 mmol, P(o-Tol) ３ The mixture was prepared and stirred at 130°C. After the reaction was complete, the reaction solution was concentrated, MeCN (600g) was added to the concentrate, neutralized with 12N hydrochloric acid aqueous solution, and the precipitate was filtered off and dried. THF (160g) was added to the obtained crude product, recrystallized, filtered off and dried to obtain 20.8g of MB-3-1 (pale yellow solid, yield 59%).

[0134] MB-3-1 (20.8 g, 58.6 mmol) and THF (310 g) were charged into a 1 L four-necked flask. After purging with nitrogen, the flask was cooled to 0°C and chloromethyl methyl ether (5.4 g, 67.4 mmol, MOM-Cl) was added dropwise. While maintaining 0°C, triethylamine (7.1 g, 70.3 mmol, Et) was added. ３ After confirming that the heat generation had subsided, the mixture was stirred at room temperature. ３ N) was added and the mixture was cooled to 0°C. After cooling, methacryloyl chloride (9.1 g, 87.9 mmol) was slowly added dropwise, and after confirming that the exothermic reaction had subsided, the mixture was stirred at room temperature. After the reaction was complete, AcOEt (310 g) and deionized water (310 g) were added to the reaction mixture and the organic phase was extracted. The obtained organic phase was washed twice with deionized water (310 g) and concentrated. The obtained concentrate was isolated by silica gel column isolation using an AcOEt / Heptane (volume ratio = 1:10) solution to obtain 14.7 g of MB-3-2 (white solid, yield 54%).

[0135] 14.5 g, 31.0 mmol of MB-3-2, 150 g of MeCN, and 15 g of deionized water were placed in a 500 mL four-necked flask and cooled to 0°C. After cooling, methanesulfonic acid (9.0 g, 93.0 mmol, MsOH) was slowly added dropwise, and after confirming that the exothermic reaction had subsided, the mixture was stirred at room temperature. After the reaction was complete, the reaction solution was poured into 450 g of deionized water, and the precipitate was filtered off. 150 g of AcOEt was added to the resulting crude product, and after recrystallization, the precipitate was filtered and dried to obtain 10.8 g of MB-3 (white solid, yield 82%).

[0136] １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 12.21 (s, 1H), 7.60-7.67 (m, 6H), 7.00-7.02 (d, 2H), 6.16 (s, 1H), 6.02 (s, 1H), 5.66 (s, 1H), 4.09-4.1 2 (t, 2H), 3.99-4.02 (t, 2H), 2.51 (s, 3H), 1.87 (s, 3H), 1.72-1.75 (m, 2H), 1.63-1.66 (m, 2H), 1.40-1.46 (m, 4H).

[0137] <<Synthesis of MB-4>>

[0138] In a 1 L four-neck flask, 4-bromo-4'-(6-hydroxyhexyloxy)biphenyl (30.0 g, 86 mmol), methacrylic acid (29.6 g, 344 mmol), tripropylamine (73.8 g, 515 mmol, Pr ３ N), and DMAc (90g) were charged, and after nitrogen purging, palladium(II) acetate (0.39g, 1.7 mmol, Pd(OAc)) was added. ２ ), and tri(o-tolyl)phosphine (1.1 g, 3.4 mmol, P(o-Tol) ３ The mixture was prepared and stirred at 130°C. After the reaction was complete, the reaction solution was concentrated, MeCN (510 g) was added to the concentrate, neutralized with 12N hydrochloric acid aqueous solution, and the precipitate was filtered off and dried. MeCN (60 g) was added to the obtained crude material, washed with slurry, filtered off and dried to obtain 13.5 g of MB-4-1 (pale yellow solid, yield 52%).

[0139] ​MB-4-1 (13.4 g, 37.8 mmol) and THF (200 g) were placed in a 500 mL four-neck flask, and after replacing the atmosphere with nitrogen, the flask was cooled to 0°C and chloromethyl methyl ether (3.5 g, 43.5 mmol, MOM-Cl) was added dropwise. While maintaining the temperature at 0°C, triethylamine (4.6 g, 45.4 mmol, Et ３ After confirming that the heat generation had subsided, the mixture was stirred at room temperature. ３ N) was added and cooled to 0°C. After cooling, methacryloyl chloride (5.9 g, 56.7 mmol) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After completion of the reaction, AcOEt (200 g) and ion-exchanged water (200 g) were added to the reaction solution, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (200 g), and the organic phase was concentrated. The obtained concentrate was subjected to column isolation using silica gel with an AcOEt / Heptane (volume ratio = 1:10) solution, and 8.7 g of MB-4-2 (white solid, yield 49%) was obtained.

[0140] A 300 mL four-neck flask was charged with MB-4-2 (8.7 g, 18.6 mmol), MeCN (90 g), and ion-exchanged water (9 g) and cooled to 0°C. After cooling, methanesulfonic acid (5.4 g, 55.8 mmol, MsOH) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was poured into ion-exchanged water (270 g), and the precipitate was separated by filtration. AcOEt (130 g) was added to the obtained crude product, which was recrystallized, filtered, and dried to obtain 7.3 g of MB-4 (white solid, yield 92%).

[0141] １ H-NMR (500MHz) in DMSO-d ６ ​: δ (ppm) = 12.49 (s, 1H), 7.68-7.69 (d, 2H) 7.62-7.65 (m, 3H), 7.53-7.54 (d, 2H), 7.00-7.02 (d, 2H), 6.02 (s, 1H), 5.66 (s, 1H) ), 4.09-4.12 (t, 2H), 3.99-4.02 (t, 2H), 2.08 (s, 3H), 1.87 (s, 3H), 1.72-1.75 (m, 2H), 1.63-1.66 (m, 2H), 1.40-1.46 (m, 4H).

[0142] [2] Synthesis of Polymers <Synthesis Example 1> A monomer mixture solution was prepared by dissolving MB-1 (2.60 g, 7.5 mmol), MC-1 (13.02 g, 42.5 mmol), and V601 (0.35 g, 1.5 mmol) in CPN (47.9 g). The monomer mixture solution was added dropwise over 1 hour to CPN (16 g) heated to 70°C under a nitrogen atmosphere. After the addition was complete, the mixture was reacted at 70°C for 10 hours. After the reaction was complete, the reaction solution was added to a mixed solution of methanol (200 g) and pure water (50 g) to reprecipitate the polymer. Subsequently, polymer P-1 was obtained by filtration, methanol washing, and drying.

[0143] <Synthesis Examples 2 and 6> As shown in Table 1 below, polymers P-2 and P-6 were obtained by performing the same procedure as in Synthesis Example 1, except that the type and amount (g) of monomer used were changed.

[0144] <Synthesis Example 3> A monomer mixture solution was prepared by dissolving MB-1 (8.00 g, 24.8 mmol) and V601 (0.17 g, 0.75 mmol) in NMP (32.7 g). The monomer mixture solution was added dropwise over 2 hours to CPN (40.9 g) heated to 60°C under a nitrogen atmosphere. After the addition was complete, the mixture was reacted at 60°C for 20 hours. After the reaction was complete, the polymer was reprecipitated by adding it to a mixed solution of methanol (200 g) and pure water (100 g). Subsequently, polymer P-3 was obtained by filtration, methanol washing, and drying.

[0145] <Synthesis Examples 4, 5, and 7> As shown in Table 1 below, polymers P-4, P-5, and P-7 were obtained by performing the same procedure as in Synthesis Example 3, except that the type and amount (g) of monomer used and the amount (g) of polymerization initiator V601 were changed.

[0146]

[0147] [3] Preparation of polymer film-forming material <Preparation example 1> CPN (16 g) and PGME (80 g) were added to polymer P-1 (4 g) obtained in Synthesis Example 1 and stirred. This was filtered through a 1.0 μm pore size filter to obtain polymer preparation solution T-1. This polymer preparation solution T-1 was used as is as a material for forming a polymer film.

[0148] <Preparation Example 2> To the polymer P-1 (15 g) obtained in Synthesis Example 1, CPN (85 g) and AP-001 (0.15 g) were added and stirred. This was filtered through a 5.0 μm pore size filter to obtain polymer preparation solution T-2. This polymer preparation solution T-2 was used as is as a material for forming a polymer film.

[0149] Preparation Examples 3 and 8 Polymer preparation solutions T-3 and T-8 were obtained by carrying out the same operations as in Preparation Example 1, except that the type of polymer was changed as shown in Table 2 below.

[0150] Preparation Examples 4 and 9 Polymer preparation solutions T-4 and T-9 were obtained by carrying out the same operations as in Preparation Example 2, except that the type of polymer was changed as shown in Table 2 below.

[0151] Preparation Example 5: NMP (72 g) and BCS (20 g) were added to polymer P-3 (6 g) obtained in Synthesis Example 3 and stirred. The mixture was filtered through a filter with a pore size of 1.0 μm to obtain polymer preparation solution T-5. This polymer preparation solution T-5 was used as it was as a material for forming a polymer membrane.

[0152] Preparation Examples 6, 7, and 10 Polymer preparation solutions T-6, T-7, and T-10 were obtained by carrying out the same operations as in Preparation Example 5, except that the type of polymer was changed as shown in Table 2 below.

[0153]

[0154] [4] Preparation of Polymer Film Example 1 Polymer Preparation Solution T-1 was applied to a non-alkali glass substrate using a bar coater to a film thickness of approximately 120 nm. The substrate was dried in a hot air circulating oven at 70°C for 3 minutes, and then 0.6 J / cm of ultraviolet light with a wavelength of 254 nm was applied to the substrate via a cut filter (254 nm bandpass filter) and a polarizer. ２ The substrate was heated in an IR oven at 140° C. for 10 minutes to prepare a polymer film substrate S-1.

[0155] Example 5 Polymer Preparation Solution T-2 was applied to a non-alkali glass substrate using a bar coater to a film thickness of approximately 2.9 μm. The substrate was dried in a hot air circulating oven at 70° C. for 3 minutes, and then 0.5 J / cm of ultraviolet light with a wavelength of 313 nm was applied to the substrate from a high-pressure mercury lamp through a cut filter (313 nm bandpass filter) and a polarizer. ２ The substrate was heated in an IR oven at 140° C. for 10 minutes to prepare a polymer film substrate S-5.

[0156] Example 11 Polymer Preparation Solution T-5 was applied to a non-alkali glass substrate using a bar coater to a film thickness of approximately 120 nm. The substrate was dried in a hot air circulating oven at 70°C for 3 minutes, and then 50 mJ / cm of ultraviolet light with a wavelength of 365 nm was applied to the substrate from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizer. ２ The substrate was heated in an IR oven at 120° C. for 10 minutes to prepare a polymer film substrate S-11.

[0157] <Examples 2-4, Comparative Examples 1-2> As shown in Table 3 below, polymer film substrates S-2 to S-4 and R-1 to R-2 were obtained by performing the same procedure as in Example 1, except that the type of polymer preparation solution, the type of UV cut filter, and the amount of UV exposure were changed.

[0158] <Examples 6-10, Comparative Examples 3-5> As shown in Table 4 below, polymer film substrates S-6 to S-10 and R-3 to R-5 were obtained by performing the same procedure as in Example 5, except that the type of polymer preparation solution, film thickness, type of UV cut filter, and UV exposure amount were changed.

[0159] Examples 12 and 13, Comparative Example 6 Polymer film substrates S-12 to S-13 and R-6 were obtained by performing the same operations as in Example 11, except that the type of polymer preparation solution, the heating temperature in the IR oven, and the UV exposure dose were changed as shown in Table 5 below.

[0160] In the table, BPF and LWPF stand for "Band Pass Filter" and "Long Wavelength Pass Filter," respectively. For example, "254BPF" represents a filter that transmits light of 254 nm, and "300LWPF" represents a filter that cuts off light of 300 nm or shorter.

[0161] The exposure amount at which the retardation value (nm) obtained in the later-described [Evaluation of Alignment] was the largest was taken as the "optimum exposure amount," and is summarized in Tables 3 to 5.

[0162]

[0163]

[0164]

[0165] The orientation (Δn) of each polymer film substrate S-1 to S-13 and R-1 to R-6 was evaluated using the method described below.

[0166] [Orientation Evaluation] The linear phase difference at a wavelength of 550 nm was measured using an Axometrics AxoScan, and the phase difference (nm) obtained was divided by the thickness (nm) of the polymer film to calculate the value. The results are summarized in Tables 6-1 to 6-3.

[0167]

[0168]

[0169]

[0170] From the results of Examples 1-4 and Comparative Examples 1-2 in Table 6-1, Examples 5-10 and Comparative Examples 3-5 in Table 6-2, and Examples 11-13 and Comparative Example 6 in Table 6-3, it was found that the orientation of the polymer is improved by substituting some of the hydrogen atoms in the cinnamic acid structure, which is a photoreactive group (for example, by substituting them with methyl groups). In this material, the double bonds of the cinnamic acid skeleton in a certain direction defined by polarized UV are isomerized, and the polymer is oriented as a result. In the present invention, by substituting some of the hydrogen atoms in the cinnamic acid structure with substituents such as methyl groups, (i) the isomerization efficiency is improved, and (ii) the polymer thermophysical properties are slightly lowered, which is thought to have improved the orientation because the polymer becomes easier to reorient with less energy overall.

Claims

1. A polymer composition containing a polymer (P) having a photosensitive group (p1) represented by the following formula (a) in its side chain, wherein the polymer (P) has a structural unit derived from a monomer compound having a polymerizable unsaturated bond. (In formula (a), Ar represents a divalent organic group having 6 to 30 carbon atoms and an arylene group, and Ar is bonded to the carbon atom in -CR= and to the carbon atoms constituting the aromatic hydrocarbon ring. L represents a single bond or -O-. 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, and at least one of R and R' represents a group or atom other than a hydrogen atom. * represents a bond.) 2. The polymer composition according to claim 1, wherein the polymer (P) has a functional group other than the photosensitive group (p1), and the other functional group is selected from a photosensitive group (p2) other than the photosensitive group (p1), a mesogen-forming group (m), a crosslinkable group, a group having a heterocycle with five or more members, and a thermally cleavable group.

3. The polymer composition according to claim 1, wherein the polymer (P) has a structural unit (X1) having the photosensitive group (p1) in a side chain, and the content of the structural unit (X1) is 5 mol % or more relative to 100 mol % of the total structural units contained in the polymer (P).

4. A composition for forming a phase difference film, which is a polymer composition according to any one of claims 1 to 3.

5. A composition for forming an orientation film, which is a polymer composition according to any one of claims 1 to 3.

6. A method for producing a retardation material, comprising the following steps (1) to (3): (1) a step of applying the polymer composition according to any one of claims 1 to 3 onto a substrate to form a coating film; (2) a step of irradiating the coating film with polarized ultraviolet light; and (3) a step of heating the coating film irradiated with ultraviolet light.

7. A resin film formed from the polymer composition according to any one of claims 1 to 3.

8. A phase difference material comprising the resin film described in claim 7.

9. Compounds represented by the following formula (MB). (In formula (MB), Ar represents a divalent organic group having 6 to 30 carbon atoms and having an arylene group, and Ar is bonded to the carbon atom in -CR= through a carbon atom constituting an aromatic hydrocarbon ring. L represents a single bond or -O-. m is an integer of 1 to 12. R and R' each independently represent a hydrogen atom, a halogen atom, 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, and at least one of R and R' represents a group or atom other than a hydrogen atom. R Ｂ (This represents a hydrogen atom or a methyl group.) 10. A compound represented by any of the following formulas (MB-1) to (MB-4).

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