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

Abstract

Provided is a polymer composition which 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 (X1) that is derived from a monomer compound having a polymerizable unsaturated bond with the photosensitive group (p1). (In formula (a), Ar represents a divalent organic group having an arylene group and 6 to 30 carbon atoms, and Ar is bonded to a carbon atom in -CR= by a carbon atom that constitutes an aromatic hydrocarbon ring.　L represents a single bond or -O-.　RM represents a monovalent organic group having 1 to 4 carbon atoms.　m is an integer of 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, some or all of the hydrogen atoms in the alkyl group may be each substituted by a fluorine atom, and at least one of R and R' represents a halogen atom or a group other than a hydrogen atom.　The symbol * represents an atomic 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] The above-mentioned conventional technology uses a photo-alignment technique in which a resin film having a photosensitive group such as a cinnamic acid skeleton is irradiated with polarized ultraviolet light to control molecular alignment.

[0007] The inventors have found that conventional resin films having a cinnamic acid skeleton do not always provide sufficient properties when used to form retardation materials. For example, a sufficient amount of exposure is required to irradiate the resin film with polarized ultraviolet light to produce a high retardation, or a stable retardation is not obtained even with the same amount of exposure.

[0008] An object of the present invention is to provide a polymer composition, a composition for forming a retardation film, and a composition for forming an alignment film, which are capable of forming a resin film having high photosensitivity, as well as a retardation material using the composition.

[0009] The present inventors have conducted extensive research to solve the above problems, and as a result have found that a polymer composition containing a specific polymer has high photosensitivity and is suitable for a retardation film-forming composition that can reduce the amount of exposure required to exhibit retardation, and for an alignment film-forming composition that forms an alignment film, and have completed the present invention.

[0010] Therefore, the present invention encompasses the following aspects: A polymer composition containing a polymer (P) having a photosensitive group (p1) represented by the following formula (a) in a side chain, wherein the polymer (P) has the photosensitive group (p1) and a structural unit (X1) 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 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-. R Ｍ represents a monovalent organic group having 1 to 4 carbon atoms. m is an integer of 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, in which 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 other than a hydrogen atom or a halogen atom. * represents a bond.

[0011] According to the present invention, it is possible to provide a polymer composition, a composition for forming a retardation film, and a composition for forming an alignment film, which are capable of forming a resin film having high photosensitivity, as well as a retardation material using the composition.

[0012] 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.

[0013] Hereinafter, embodiments of the present invention will be described in detail. [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) on its side chain. The polymer (P) has the photosensitive group (p1) and a structural unit (X1) derived from a monomer compound (mp1) having a polymerizable unsaturated bond. (In the above formula (a), 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-. R Ｍ represents a monovalent organic group having 1 to 4 carbon atoms. m is an integer from 1 to 12. R and R' each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms, in which 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 other than a hydrogen atom or a halogen atom. * represents a bond.

[0014] The above R Ｍ Preferred specific examples of the monovalent organic group in formula (a) include an alkyl group or an alkoxyalkyl group. The alkyl group may be either linear or branched, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkoxyalkyl group include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group. The alkyl group having 1 to 3 carbon atoms in R and R' may be either linear or branched, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. m is an integer of 1 to 12, preferably an integer of 2 to 10, and more preferably an integer of 2 to 6. In formula (a) above, Ar and COOR Ｍ may be bonded at the cis position or the trans position relative to the double bond, but is preferably bonded at the trans position.

[0015] The photosensitive group (p1) is preferably a photosensitive group represented by the following formula (a1): In the following formula (a1), an optionally substituted phenylene group and COOR Ｍ may be bonded at the cis position or the trans position relative to the double bond, but is preferably 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—. R Ｍ represents a monovalent organic group having 1 to 4 carbon atoms. m is an integer of 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, in which 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 other than a hydrogen atom or a halogen atom. A hydrogen atom on the benzene ring in formula (a1) 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. * 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 photosensitive group (p1) is preferably a photosensitive group represented by any one of the following formulae (a-1) to (a-2): In the following formulae (a-1) to (a-2), an optionally substituted phenylene group and —COOCH ３may be bonded at the cis position or the trans position relative to the double bond, but is preferably bonded at the trans position. (In the formula, m is an integer of 1 to 12. * represents a bond.)

[0018] Examples of the monomer compound having a photosensitive group (p1) and a polymerizable unsaturated bond include compounds represented by the following formula (MB). (In formula (MB), Ar, L, R Ｍ , m, R, and R′ are Ar, L, R in formula (a), respectively. Ｍ , m, R, and R′. Ｂ represents a hydrogen atom or a methyl group.

[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 when exposed to 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 optionally substituted phenylene group and COOH, or the optionally substituted 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] When the polymer (P) has another photosensitive group (p2), the polymer (P) contains a structural unit (X) having the other photosensitive group (p2) in a side chain. ｐ２ It is preferable that the structural unit (X) has another photosensitive group (p2) in the side chain. ｐ２ ) is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and another photosensitive group (p2).

[0023] ((Mesogen-forming group (m))) The mesogen-forming group (m) is not particularly limited as long as it can impart liquid crystallinity, and includes not only mesogenic groups but also hydrogen-bonding mesogenic groups that exhibit liquid crystallinity through intermolecular hydrogen bonding.

[0024] The polymer (P) has, for example, a mesogen-forming group (m) in a side chain. When the polymer (P) has a mesogen-forming group (m), the polymer (P) contains a structural unit (X ｍ It is preferable that the structural unit (X) has 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 embodiment (A) having a side chain containing the photosensitive group (p1) or another photosensitive group (p2), or in embodiment (B) having a side chain not containing the photosensitive group (p1) or another photosensitive group (p2), or a combination thereof. The embodiment (A) may include, but is not limited to, embodiment (A1) having a mesogen-forming group in the side chain sharing part or all of the structure of the photosensitive group (p1) or another photosensitive group (p2), or embodiment (A2) having a mesogen-forming group in the side chain independently of the structure of the photosensitive group (p1) or another photosensitive group (p2). In embodiment (A2), the mesogen-forming group (m) and the photosensitive group (p1) or another photosensitive group (p2) may be bonded to each other by a single bond or via a linking group. Examples of the linking group include an alkylene group, —O—, —S—, —SO—, and —SO ２ Examples 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 ２are 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 bonds of the arylene group and heterocyclic residue are not particularly limited as long as they impart liquid crystallinity, but the phenylene group is preferably bonded at the p-position, and the naphthylene group is preferably bonded 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 cycloalkyl group and aryl group may have a substituent, and examples of the substituent include a methoxy group and a halogen atom.

[0029] More preferred examples of the mesogenic group include the following structures. (* represents a bond.)

[0030] Examples of the hydrogen-bonding mesogenic group include the following structure in addition to a hydroxybenzoic acid residue: -Ar-X-Ar ３ -COOH -Ar-X-Ar ３ -(Z) ｊ —COOH where Ar and Ar ３ are 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 the alkyl group, alkyloxy group, alkenyl group, alkynyl group, and haloalkyl group mentioned in the explanation of "-" include:

[0031] Examples of the side chain having the other 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 -, Sp ２ is -(CH ２ ) ｓ２-. s1 and s2 each independently represent an integer of 1 to 12. * represents a bond.

[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 In the above formulas (bm-1) to (bm-4), s1 each independently represents an integer of 1 to 12. * represents a bond.

[0033] ((Crosslinkable Group)) The crosslinkable group may be one functional group selected from the group consisting of an oxetanyl group, an oxiranyl group, a carboxy group, and a hydroxy group.

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

[0035] The structural unit (X ＣＬExamples of the monomer compounds which give the copolymer (meth)acrylate include glycidyl (meth)acrylate, glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxybutyl α-ethylacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 6,7-epoxyheptyl α-ethylacrylate, 3-methyl-3-oxetanylmethyl (meth)acrylate, and 3-ethyloxetan-3-yl (meth)acrylate. ) methyl, (meth)acrylate 4-hydroxybutyl glycidyl ether, compounds having an oxetanyl group or an oxiranyl group, such as those represented by the following formulae (G1) to (G3); carboxy 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 hydroxy group-containing compounds, such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0036] <Group Having a Five- or More-Membered Heterocycle> Examples of the heterocycle in the group having a five- or more-membered heterocycle include cyclic amines such as piperidine, piperazine, 1,2,3-triazole, purine, 1,4-diazabicyclo[2.2.2]octane (triethylenediamine), quinuclidine, morpholine, diazabicycloundecene (DBU), diazabicyclononene (DBN), and N,N-dimethyl-4-aminopyridine (DMAP); and aromatic heterocycles such as pyridine, pyrrole, imidazole, and acridine.

[0037] The group having a 5 or more membered heterocyclic ring is, for example, a residue obtained by removing a hydrogen atom from a 5 or more membered heterocyclic ring.

[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 ｈｔIt is preferable that the structural unit (X) has a group having a 5- or more-membered heterocyclic ring in a side chain. ｈｔ ) is, for example, a structural unit derived from a monomer compound having a polymerizable unsaturated bond and a group having a five- or greater-membered heterocyclic ring.

[0039] The structural unit (X ｈｔ Examples of the monomer compound that gives the above-mentioned compound (ht-1) include the following compounds (ht-1) to (ht-2).

[0040] ((Thermal-Leaving Group)) Examples of the thermal-leaving group include carbamate-based protecting groups such as a tert-butoxycarbonyl group (Boc group), a 9-fluorenylmethyloxycarbonyl group (Fmoc group), a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, an allyloxycarbonyl group, or a 2-(trimethylsilyl)ethoxycarbonyl group.

[0041] When the polymer (P) has a thermally detachable group, the polymer (P) contains a structural unit (X ＢＬ It is preferable that the structural unit (X) has a thermally detachable 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 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 may have a structural unit other than the structural unit (X1) (hereinafter also referred to as an "other structural unit"), and the other structural unit is preferably a structural unit derived from a monomer compound having a polymerizable unsaturated bond.

[0044] Examples of the group or structure having a polymerizable unsaturated bond include a (meth)acryloyl group, a maleimide group, a styryl group, a vinyl group, and an α-methylene-γ-butyrolactone structure.

[0045] The polymer (P) of the present invention can be obtained, for example, by polymerizing a monomer compound having at least one of the above-described polymerizable unsaturated bonds and at least one of the above-described side chains. When the polymer (P) of the present invention has the above-described structural unit (X2), it can be obtained by polymerizing a monomer compound having at least one of the above-described polymerizable unsaturated bonds and at least one of the above-described side chains having another photosensitive group (p2).

[0046] The polymer (P) of the present invention is preferably obtained by polymerizing a monomer compound containing a compound represented by the following formula (MB): The compound represented by the following formula (MB) is also within the scope of the present invention.

[0047] (Compound represented by formula (MB)) (In formula (MB), Ar, L, R Ｍ , m, R, and R′ are Ar, L, R in formula (a), respectively. Ｍ , m, R, and R′. Ｂ represents a hydrogen atom or a methyl group.

[0048] The compound represented by the above formula (MB) can be produced, for example, by the method shown in Scheme 1 below.

[0049] (Scheme 1) In Scheme 1, Ar, L, R Ｍ , m, R, R′ and R Ｂ has the same definition as in formula (MB) above.

[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 CH３ ), a 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 ２Examples 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 ), a 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 using an appropriate metal complex and ligand and used. Typically, a palladium complex or nickel complex is used as the metal complex, and depending on the reaction, it is preferable to use a copper catalyst as a co-catalyst. While various structures can be used as the metal complex catalyst, it is preferable to use a so-called low-valent palladium complex or nickel complex, and in particular, a zero-valent metal complex catalyst having a tertiary phosphine or tertiary phosphite as a ligand. Alternatively, a suitable precursor that can be easily converted to a zero-valent metal complex catalyst in the reaction system can be used. Furthermore, a metal complex that does not contain a tertiary phosphine or tertiary phosphite as a ligand can be mixed with a tertiary phosphine or tertiary phosphite as a ligand in the reaction system to produce a low-valent metal complex catalyst having a tertiary phosphine or tertiary phosphite as a ligand in the reaction system.

[0063] Examples of the tertiary phosphine or tertiary phosphite ligand 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, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc. 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 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 can be used alone or in combination of two or more. In some cases, the above solvents can be used as water-free solvents by using an appropriate dehydrating agent or drying agent.

[0068] 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-a2).

[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 condensation reaction of a compound represented by formula (MB-a3) and a compound represented by formula (MB-r3) in the presence of a base.

[0072] The amount of the compound represented by formula (MB-r3) used relative to the compound represented by formula (MB-a3) is not particularly limited, but is preferably 1.0 equivalent to 3.0 equivalents, and more preferably 1.0 equivalent 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] The compound represented by formula (MB) obtained by the method shown in the above reaction scheme is preferably purified by distillation, recrystallization, column chromatography on silica gel, etc. It is preferable to carry out recrystallization at as low a temperature as possible.

[0079] The polymer (P) of the present invention may also contain structural units derived from other monomer compounds than the above-mentioned monomer compounds. Specific examples of the other monomer compounds include the following (meth)acrylic acid ester compounds, maleimide compounds, maleic anhydride, styrene compounds, vinyl compounds, and (meth)acrylamide compounds.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.

[0080] 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.

[0081] 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.

[0082] (Synthesis of Polymer (P)) The polymer (P) can be obtained by a polymerization reaction using a monomer compound having a polymerizable unsaturated bond, and is preferably obtained by a radical polymerization reaction. Examples of the polymerization initiator used in this polymerization reaction include initiators typically 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(dimethylisobutyrate); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, and 1,1'-bis(t-butylperoxy)cyclohexane; hydrogen peroxide; and redox initiators composed of these peroxides and a reducing agent. Among these, azo compounds are preferred, and 2,2'-azobis(isobutyronitrile) or 2,2'-azobis(dimethylisobutyrate) are 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.

[0083] The polymerization reaction of the polymer (P) is preferably carried out in an organic solvent, such as 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 of the organic solvent 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 monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-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, 3-butoxy-N,N-dimethylpropanamide, etc. These organic solvents can be used alone or in combination of two or more. In addition, in a radical polymerization reaction, oxygen in the organic solvent can inhibit the polymerization reaction, so it is preferable to use an organic solvent that has been degassed to the greatest extent possible.

[0084] In the polymerization reaction of the polymer (P), the reaction temperature is preferably 30 to 120°C, more preferably 60 to 110°C. The reaction time is preferably 1 to 36 hours, more preferably 2 to 24 hours. The amount of organic solvent (a) used is preferably such that the total amount of monomers (b) used in the reaction is 0.1 to 50 mass% with respect to the total amount of the reaction solution (a + b).

[0085] In consideration of the strength of the coating film to be obtained, the workability during coating film formation, and the uniformity of the coating film, the polymer (P) of the present invention preferably has a weight average molecular weight, measured by GPC (Gel Permeation Chromatography), of 2,000 to 2,000,000, more preferably 2,000 to 1,000,000, and even more preferably 5,000 to 200,000.

[0086] The content of the polymer (P) in the polymer composition is not particularly limited, but is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, in the polymer composition.

[0087] [(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.

[0088] 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.

[0089] Specific examples of the solvent (poor solvent) that improves the film thickness uniformity 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, and 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-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, acetic acid 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, 3-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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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; Examples of compounds having a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, and Millionate MS-50 (all manufactured by Tosoh Corporation), and Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals, Inc.). Specific examples of commercially available compounds such as the above, compounds represented by the following formulae (bL-1) to (bL-3), compounds having two or more protected isocyanate groups described in paragraphs

[0046] to

[0047] of JP 2014-224978 A, compounds having three or more protected isocyanate groups described in paragraphs

[0119] to

[0120] of WO 2015 / 141598 A, and the like;

[0095] Examples of compounds having a hydroxy group and / or an alkoxy group include N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide, compounds represented by the following formulae (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 JP2016-118753A, compounds described in JP2016-200798A, and compounds described in WO2010 / 074269A;

[0096] Examples of crosslinkable compounds having a polymerizable unsaturated group 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, and hexaethylene glycol mono(meth)acrylate.

[0097] The above compounds are examples of crosslinkable compounds, and are not limited thereto. For example, components other than those described above are disclosed on pages 53

[0105] to 55

[0116] of WO2015 / 060357. Two or more types of crosslinkable compounds may be combined.

[0098] When a crosslinkable compound is used, 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, relative to 100 parts by mass of the polymer component (e.g., polymer (P)) contained in the polymer composition.

[0099] Specific examples of compounds that improve adhesion between a film and a 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, and 3-ureidopropyltriethoxysilane. 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-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, 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 that can be used include silane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0100] 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.

[0101] 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.

[0102] The content of the photosensitizer is not particularly limited, but is preferably 0.2 parts by mass to 10 parts by mass, and more preferably 0.5 parts by mass to 7 parts by mass, relative to 100 parts by mass of the polymer component (e.g., polymer (P)) contained in the polymer composition.

[0103] [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.

[0104] 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.

[0105] 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.

[0106] [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).

[0107] [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.

[0108] [Step (2): Light Irradiation Step] In step (2), polarized ultraviolet light is irradiated onto the coating film obtained in step (I). When irradiating the surface of the coating film with polarized ultraviolet light, the polarized ultraviolet light is irradiated onto the substrate from a specific direction via a polarizing plate. The ultraviolet light can have a wavelength in the range of 100 to 400 nm. For example, ultraviolet light having a wavelength in the range of 290 to 400 nm can be selected and used so as to selectively induce a photocrosslinking reaction. Preferably, an optimal wavelength is selected using a filter or the like depending on the type of coating film used. For example, light with a wavelength of 313 nm can be reduced using a bandpass filter (BPF) with a center wavelength of 365 nm or a long wavepass filter (LWPF) that transmits wavelengths longer than 313 nm. Examples of light sources that can be used for the irradiation light include 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), and microwave-excited electrodeless lamps.

[0109] [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.

[0110] 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.

[0111] [Step (4): Forming a Liquid Crystal Layer] Step (4) is a step of applying and curing a polymerizable liquid crystal onto the alignment film obtained in step (3) to form a liquid crystal layer. This results in the formation of a coating film (liquid crystal layer) containing the polymerizable liquid crystal. The polymerizable liquid crystal used here is a polymerizable liquid crystal compound or liquid crystal composition that polymerizes upon at least one of heating and light irradiation. Such polymerizable liquid crystals can be conventionally known, including nematic liquid crystal compounds. Cholesteric liquid crystals, discotic liquid crystals, and twisted nematic alignment liquid crystals containing chiral agents may also be used. The polymerizable liquid crystal compound preferably has a polymerizable functional group capable of three-dimensional crosslinking within the molecule. Examples of the polymerizable functional group include those that polymerize upon the action of ionizing radiation such as ultraviolet light or electron beams, or heat. Representative examples of these polymerizable functional groups include radically polymerizable functional groups and cationically polymerizable functional groups. Representative examples of radically polymerizable functional groups include functional groups having at least one addition-polymerizable ethylenically unsaturated double bond. Specific examples include vinyl groups with or without substituents, and acrylate groups (a general term including acryloyl groups, methacryloyl groups, acryloyloxy groups, and methacryloyloxy groups). Specific examples of cationically polymerizable functional groups include epoxy groups. Other polymerizable functional groups include 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 a polymerizable functional group at their terminals are particularly preferred. The polymerizable liquid crystal may be a mixture of multiple liquid crystal compounds, or may be a composition containing other liquid crystal compounds (excluding polymerizable liquid crystal compounds) other than those listed above, other polymerizable compounds (excluding polymerizable liquid crystal compounds), known polymerization initiators, surfactants, photosensitizers, chain transfer agents, antioxidants, UV absorbers, radical scavengers, light stabilizers, optically active compounds, silane coupling agents, solvents, etc. Commercially available polymerizable liquid crystals include, for example, RMS03-013C and RMS16-089 manufactured by Merck.

[0112] 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 more preferable to set the following.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] The abbreviations of the other reagents used in this example are as follows: (Organic solvents) DMF: N,N-dimethylformamide AcOEt: ethyl acetate THF: tetrahydrofuran NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve CPN: cyclopentanone PGME: propylene glycol monomethyl ether

[0117] (Polymerization initiator) V601: 2,2'-azobis(isobutyrate) dimethyl (Surfactant) AP-001: Marproof AP-001 (manufactured by NOF Corp.)

[0118] < 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)

[0119] [1] Synthesis of Monomer <<Synthesis of MB-1>>

[0120] Methyl (2E)-3-(4-hydroxyphenyl)-2-methyl-2-propenoate (synthesized with reference to the method described in Journal of the American Chemical Society, 2001, vol. 123, No. 29, pp. 6989-7000, 40.4 g, 210.0 mmol), 6-chloro-1-hexanol (34.4 g, 252.0 mmol), potassium carbonate (43.5 g, 315.0 mmol), potassium iodide (3.5 g, 21.0 mmol), and DMF (340 g) were charged into a 1 L four-neck flask and stirred at 100°C. After completion of the reaction, the reaction solution was concentrated, and AcOEt (350 g) and ion-exchanged water (250 g) were added to the resulting concentrate, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (200 g) and then concentrated to obtain 61.4 g of MB-1-1 (brown liquid, yield 100%).

[0121] A 2 L four-neck flask was charged with MB-1-1 (61.4 g, 210.0 mmol), pyridine (21.6 g, 273.0 mmol), dimethylaminopyridine (DMAP, 2.6 g, 21.0 mmol), and THF (600 g) and cooled to 0°C. After cooling, methacryloyl chloride (26.3 g, 252.0 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, the reaction solution was concentrated, and AcOEt (600 g) and ion-exchanged water (450 g) were added to the obtained concentrate, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (450 g) and then concentrated. The resulting concentrate was subjected to column isolation on silica gel using an AcOEt / Heptane (volume ratio=1:20) solution to obtain 20.4 g of MB-1 (yellow liquid, yield 27%).

[0122] １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 7.56 (s, 1H), 7.43-7.45 (d, 2H), 6.97-6.98 (d, 2H), 6.01 (s, 1H), 5.65 (s, 1H), 4.08-4.11 (t, 2H), 3.9 8-4.01 (t, 2H), 3.73 (s, 3H) 2.06 (s, 3H), 1.87 (s, 3H), 1.71-1.74 (m, 2H), 1.62-1.65 (m, 2H), 1.39-1.44 (m, 4H).

[0123] <<Synthesis of MB-2>>

[0124] ​Methyl (2E)-3-(4-hydroxyphenyl)-2-butenoate (synthesized with reference to the method described in Letters in Organic Chemistry, 2006, vol. 3, No. 1, pp. 16-20, 40.4 g, 210.0 mmol), 6-chloro-1-hexanol (34.4 g, 252.0 mmol), potassium carbonate (43.5 g, 315.0 mmol), potassium iodide (3.5 g, 21.0 mmol), and DMF (310 g) were charged into a 1 L four-neck flask and stirred at 100°C. After completion of the reaction, the reaction solution was concentrated, and AcOEt (350 g) and ion-exchanged water (250 g) were added to the obtained concentrate, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (200 g) and then concentrated to obtain 61.4 g of MB-2-1 (brown liquid, yield 100%).

[0125] A 2 L four-neck flask was charged with MB-2-1 (61.4 g, 210.0 mmol), pyridine (21.6 g, 273.0 mmol), dimethylaminopyridine (DMAP, 2.6 g, 21.0 mmol), and THF (600 g) and cooled to 0°C. After cooling, methacryloyl chloride (26.3 g, 252.0 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, the reaction solution was concentrated, and AcOEt (600 g) and ion-exchanged water (450 g) were added to the obtained concentrate, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (450 g) and then concentrated. The resulting concentrate was subjected to column isolation on silica gel using an AcOEt / Heptane (volume ratio=1:20) solution to obtain 28.8 g of MB-2 (yellow liquid, yield 38%).

[0126] １ H-NMR (500MHz) in DMSO-d ６ ​: δ (ppm) = 7.53-7.56 (d, 2H), 6.93-6.96 (d, 2H), 6.13 (s, 1H), 6.01 (s, 1H), 5.65 (s, 1H), 4.08-4.11 (t, 2H), 3.98 -4.02 (t, 2H), 3.66 (s, 3H), 2.50 (s, 3H), 1.87 (s, 3H), 1.69-1.75 (m, 2H), 1.62-1.66 (m, 2H), 1.39-1.46 (m, 4H).

[0127] [2] Polymer Synthesis <Synthesis Example 1> MB-1 (7.21 g, 20 mmol) and V601 (0.14 g, 0.6 mmol) were dissolved in NMP (49.6 g) to prepare a mixed monomer solution. Under a nitrogen atmosphere, the mixed monomer solution was added dropwise to NMP (16.5 g) heated to 60°C over 1 hour. After completion of the dropwise addition, the mixture was allowed to react at 60°C for 20 hours. After completion of the reaction, the reaction solution was added to a mixed solution of methanol (200 g) and pure water (50 g) to reprecipitate the polymer. Subsequently, the mixture was filtered, washed with methanol, and dried to obtain polymer P-1.

[0128] Synthesis Example 4 Polymer P-4 was obtained by carrying out the same procedure as in Synthesis Example 1, except that the types and amounts (g) of the monomers used were changed as shown in Table 1 below.

[0129] Synthesis Example 2 MB-1 (2.70 g, 7.5 mmol), MC-1 (13.02 g, 42.5 mmol), and V601 (0.35 g, 1.5 mmol) were dissolved in CPN (48.2 g) to prepare a mixed monomer solution. Under a nitrogen atmosphere, the mixed monomer solution was added dropwise to CPN (16.1 g) heated to 70°C over 1 hour. After completion of the dropwise addition, the mixture was allowed to react at 70°C for 10 hours. After completion of the reaction, the reaction solution was added to a mixed solution of methanol (200 g) and pure water (50 g) to reprecipitate the polymer. Subsequently, the mixture was filtered, washed with methanol, and dried to obtain polymer P-2.

[0130] Synthesis Examples 3 and 5 Polymers P-3 and P-5 were obtained by carrying out the same operations as in Synthesis Example 4, except that the types and amounts (g) of the monomers used were changed as shown in Table 1 below.

[0131]

[0132] [3] Preparation of polymer membrane-forming material <Preparation Example 1> NMP (74 g) and BCS (20 g) were added to polymer P-1 (6.0 g) obtained in Synthesis Example 1 and stirred. This was filtered through a filter with a pore size of 1.0 μm to obtain polymer preparation solution T-1. This polymer preparation solution T-1 was used as it is as a material for forming a polymer membrane.

[0133] Preparation Example 4 As shown in Table 2 below, the same procedure as in Preparation Example 1 was carried out except that the polymer was changed, to obtain a polymer preparation solution T-4.

[0134] Preparation Example 2 CPN (16 g) and PGME (80 g) were added to polymer P-2 (4.0 g) obtained in Synthesis Example 2 and stirred. The mixture was filtered through a filter with a pore size of 1.0 μm to obtain polymer preparation solution T-2. This polymer preparation solution T-2 was used as it was as a material for forming a polymer membrane.

[0135] Preparation Examples 3 and 5 As shown in Table 2 below, polymer preparation solutions T-3 and T-5 were obtained by carrying out the same operations as in Preparation Example 2, except that the polymer was changed.

[0136]

[0137] [4] Production 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. Subsequently, ultraviolet light with a wavelength of 365 nm was applied to the substrate at 25 mJ / cm from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter; 365BPF) and a polarizer. ２ ~150 mJ / cm ２ in the range of 25 mJ / cm ２ The irradiation was carried out under the condition of interval 6. The substrate was heated in an IR oven at 140° C. for 10 minutes to prepare a polymer film substrate S-1.

[0138] Comparative Example 1 A polymer membrane substrate R-1 was obtained by carrying out the same operations as in Example 1, except that the type of polymer preparation solution was changed as shown in Table 3-1 below.

[0139] Example 2 Polymer Preparation Solution T-2 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. Subsequently, ultraviolet light with a wavelength of 254 nm was irradiated onto the substrate from a high-pressure mercury lamp at 200 mJ / cm through a cut filter (254 nm bandpass filter; 254BPF) and a polarizer. ２ ~800 mJ / cm ２ in the range of 200 mJ / cm ２ The irradiation was carried out under four interval conditions, and the substrate was heated in an IR oven at 140° C. for 10 minutes to prepare a polymer film substrate S-2.

[0140] Comparative Example 2 A polymer membrane substrate R-2 was obtained by carrying out the same operations as in Example 2, except that the type of polymer preparation solution was changed as shown in Table 3-2 below.

[0141] Example 3 Polymer Preparation Solution T-2 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. Subsequently, ultraviolet light with a wavelength of 313 nm was irradiated onto the substrate at 2000 mJ / cm from a high-pressure mercury lamp through a cut filter (313 nm bandpass filter; 313BPF) and a polarizer. ２ ~10000mJ / cm ２ in the range of 2000 mJ / cm ２ The irradiation was carried out under the condition of interval 5. The substrate was heated in an IR oven at 140° C. for 10 minutes to prepare a polymer film substrate S-3.

[0142] Example 4, Comparative Example 3 Polymer membrane substrates S-4 and R-3 were obtained by the same procedure as in Example 3, except that the type of polymer preparation solution was changed as shown in Table 3-3 below.

[0143] The exposure dose of each of the polymer film substrates S-1 to S-4 and R-1 to R-3 was evaluated by the following method.

[0144] [Evaluation of optimal exposure dose] The linear retardation at a wavelength of 550 nm was measured using an Axometrics AxoScan, and the exposure dose at which the retardation value (nm) obtained under the conditions of varying the exposure dose was the largest was designated the "optimum exposure dose." In addition, the retardation value when the exposure dose was designated the "optimum exposure dose" was defined as an orientation degree of 100%, and the orientation degree when irradiated at a predetermined exposure dose was calculated using the following formula: A (%) = [B / C] x 100 A: Orientation degree (%) when irradiated at a predetermined exposure dose B: Retardation value when irradiated at a predetermined exposure dose C: Retardation value at the optimal exposure dose The results are summarized in Tables 3-1 to 3-3.

[0145]

[0146]

[0147]

[0148] The results of Example 1 and Comparative Example 1 in Table 3-1, Example 2 and Comparative Example 2 in Table 3-2, and Examples 3 to 4 and Comparative Example 3 in Table 3-3 demonstrate that the amount of UV exposure required for polymer orientation can be reduced by substituting (for example, with methyl groups) some of the hydrogen atoms (hydrogen atoms bonded to the carbon-carbon double bond) in the cinnamic acid structure, which is a photoreactive group. This material utilizes the absorption of UV light by the cinnamic acid skeleton and the isomerization of the double bond to orient the polymer. In the present invention, substituting some of the hydrogen atoms (hydrogen atoms bonded to the carbon-carbon double bond) in the cinnamic acid structure with substituents such as methyl groups shifts the absorption wavelength to shorter wavelengths, improving isomerization efficiency, which is thought to be why the amount of UV exposure required for polymer orientation was reduced.

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 the photosensitive group (p1) and a structural unit (X1) 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 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-. R Ｍ represents a monovalent organic group having 1 to 4 carbon atoms. m is an integer of 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, in which 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 other than a hydrogen atom or a halogen 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) contains the structural unit (X1) in an amount of 5 mol % or more relative to 100 mol % of the total structural units contained in the polymer (P).

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

5. A composition for forming an alignment film, which is the 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 retardation material comprising the resin film according to claim 7.

9. A compound 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 represents a monovalent organic group having 1 to 4 carbon atoms. 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, in which 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 other than a hydrogen atom or a halogen atom. R Ｂ represents a hydrogen atom or a methyl group.

10. A compound represented by any one of the following formulas (MB-1) to (MB-2):

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