Polymer composition, liquid crystal aligning agent, resin film, liquid crystal aligning film, method for manufacturing liquid crystal display element, and liquid crystal display element

Abstract

The present invention provides a polymer composition suitable for a liquid crystal alignment agent which can provide a liquid crystal alignment film having excellent resistance to AC image sticking and high film strength. A polymer composition characterized by containing the following (A) component and (B) component. (A) component: at least one polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (a) and a polyimide which is an imidized product of the polyimide precursor. (B) component: a polyurethane having a repeating unit represented by the following formula (1) and not having the repeating unit represented by the formula (a) and an imidized structure thereof. Formula (a) (definitions of symbols are described in the description.) Formula (1) (definitions of symbols are described in the description).

Description

TECHNICAL FIELD

[0001] The present application relates to a polymer composition, a liquid crystal alignment agent, a resin film, a liquid crystal alignment film, a manufacturing method of a liquid crystal display element, and a liquid crystal display element. BACKGROUND

[0002] In the case of a liquid crystal display element used in a liquid crystal television, a navigator, a smartphone, and the like, generally, a liquid crystal alignment film for controlling the arrangement state of liquid crystals is provided in the element. The liquid crystal alignment film has a function of controlling the orientation of liquid crystal molecules in a certain direction in a liquid crystal display element. For example, the liquid crystal display element has a structure in which liquid crystal molecules forming a liquid crystal layer are sandwiched by liquid crystal alignment films formed on the respective surfaces of a pair of substrates. Therefore, the liquid crystal molecules are oriented in a certain direction by the liquid crystal alignment films, and respond by applying a voltage to an electrode provided between the substrate and the liquid crystal alignment film. As a result, the liquid crystal display element performs display of a desired image using the orientation change due to the response of the liquid crystal molecules. As the liquid crystal alignment film, a polyimide-based liquid crystal alignment film formed by coating a solution of a polyimide precursor such as polyamide acid or a soluble polyimide on a glass substrate or the like and performing baking has been mainly used so far.

[0003] In recent years, with the high performance of liquid crystal display elements, in addition to uses such as large-screen and high-resolution liquid crystal televisions, liquid crystal display elements are also used in car-mounted, for example, car navigation systems, instrument panels; monitors of monitoring cameras, monitors of medical cameras, and the like, and from the viewpoint of the demand for viewing angle characteristics, IPS (In-Plane Switching) mode, FFS (Fringe Field Switching) mode, and the like, which are lateral electric field modes, have been studied (Patent Document 1).

[0004] PRIOR ART DOCUMENTS

[0005] PATENT DOCUMENTS

[0006] Patent Document 1: International Publication No. 2019-082975 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] In a liquid crystal alignment film used in an IPS driving mode, an FFS driving mode liquid crystal display element, an orientation restricting force for suppressing afterimage (hereinafter, also referred to as AC afterimage) due to long-term AC driving is required. In the above-described rapidly high-resolution liquid crystal display element, a high display quality level is valued, and the specifications for display defects such as so-called "afterimage" are becoming increasingly strict.

[0009] Further, as a reliability test of a liquid crystal display element for a vehicle use, a vibration test of a panel is sometimes performed. In the vibration test, generation of a bright spot or the like is required to be avoided.

[0010] Further, in a rubbing alignment treatment applied in a process of producing a liquid crystal alignment film, in a case where an alignment property is embodied by rubbing treatment, there is a problem that dust caused by grinding of the liquid crystal alignment film is easily generated. When the dust is generated, in addition to display failure caused by attachment of the dust to a surface of the liquid crystal alignment film, a circuit of a TFT element is broken, and yield is reduced.

[0011] The present application has been made in view of the above, and has an object to provide a polymer composition suitable for a liquid crystal alignment agent from which a liquid crystal alignment film having excellent resistance to AC image sticking and high film strength can be obtained, the liquid crystal alignment agent, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film.

[0012] Solution to the problem

[0013] The present inventors have made intensive studies in order to achieve the above technical problem, and as a result, have found that it is effective for achieving the above object to form a resin film using a polymer composition containing specific components, thereby completing the present application.

[0014] The present application is based on the above insight, and has the following as its main gist.

[0015] A polymer composition characterized by containing the following (A) component and (B) component.

[0016] (A) component: at least one polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (a) and a polyimide which is an imidized product of the polyimide precursor.

[0017] (B) component: a polyurethane having a repeating unit represented by the following formula (1), and not having a repeating unit represented by the following formula (a) and an imidized structure thereof.

[0018]

[0019] (X represents a tetravalent organic group. Y represents a divalent organic group derived from a diamine. Each of two R's independently represents a hydrogen atom or a monovalent organic group. Each of two Z's independently represents a hydrogen atom or a monovalent organic group.)

[0020]

[0021] (A1 is a divalent organic group derived from a diisocyanate. A2 is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxyl groups from an organic diol. At least one of A1 and A2 has a divalent organic group represented by the following formula (EG).

[0022]

[0023] (n is an integer of 5 or more. R represents a hydrogen atom or a methyl group.)

[0024] Effects of the Invention

[0025] The liquid crystal alignment agent according to the present application makes it possible to obtain a polymer composition suitable for a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film excellent in resistance to AC image sticking and high in film strength, the liquid crystal alignment agent, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film. Further, the liquid crystal display element has a high display quality level with less display defects.

[0026] The mechanism by which the above effects of the present application are obtained is not necessarily clear, but is roughly presumed as follows. That is, it is considered that the film strength is improved due to hydrogen bonding by the polymer composition containing a specific polyurethane, and further, the extensibility of the film is improved by introducing a specific ethylene glycol chain in the specific polyurethane, and thus the above effects are obtained. DETAILED DESCRIPTION

[0027] Hereinafter, each component contained in the liquid crystal alignment agent of the present disclosure and other components arbitrarily blended as needed are described.

[0028] Note that, in the present specification, as halogen atoms, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be exemplified.

[0029] <Polymers (A)>

[0030] The polymer composition of the present application contains a polymer (A) selected from at least one of a polyimide precursor having a repeating unit represented by the above formula (a) (hereinafter, also referred to as a polyimide precursor (A)) and a polyimide which is an imidized product of the polyimide precursor. The polymer (A) can be one or two or more.

[0031] (repeating unit represented by formula (a))

[0032] In the above formula (a), Y represents a divalent organic group derived from a diamine. Note that the divalent organic group derived from a diamine refers to, for example, a divalent organic group obtained by removing two amino groups from a diamine. As the diamine, the following diamines can be exemplified. The diamine can be used alone or two or more can be used in combination.

[0033] diamines represented by the following formula (O); 4,4'-diaminoazobenzene or a diamino- toluene, and the like, which are diamines having a photo-orienting group; diamines having an amide bond or a urea bond, such as diamines represented by the following formulae (h-1) to (h-6); 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, diamines represented by the following formula (d o ) ; diamines having at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocyclic ring, a secondary amino group, and a tertiary amino group (hereinafter, also referred to as a specific nitrogen atom-containing structure); 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 4,4'-diamino-3,3'-dihydroxybiphenyl, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and diamines represented by the following formulae (3b-1) to (3b-4), and the like, which are diamines having a carboxyl group; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine; 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline, which are diamines having a photopolymerizable group at a terminal; cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanylester, 3,5-diaminobenzoic acid cholestenylester, 3,5-diaminobenzoic acid lanostanylester, and 3,6-bis(4-aminobenzoyloxy)cholestan, which are diamines having a steroid skeleton; diamines represented by the following formulae (V-1) to (V-6); diamines having a group "-N(D)-" (D represents a protective group which is substituted with a hydrogen atom by heating, and is preferably a tert-butoxycarbonyl group), such as those represented by the following formulae (5-1) to (5-11); diamines having a siloxane bond, such as diamines represented by the following formula (Ds-1); and diamines having an oxazoline structure, such as diamines represented by the following formulae (Ox-1) to (Ox-2); m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and a diamine in which two amino groups are bonded to a group represented by any of formulae (Y-1) to (Y-167) described in International Publication No. 2018 / 117239.

[0034]

[0035] (Ar represents a divalent benzene ring, a biphenyl structure or a naphthalene ring. Two Ar's are optionally the same or different, and any hydrogen atom of the above benzene ring, biphenyl structure or naphthalene ring is optionally substituted with a monovalent group. p is an integer of 0 or 1. Q2 represents - (CH2) n - (n is an integer of 2 to 18), or a group in which at least a part of - (CH2) n -CH2- is replaced with any of -O-, -C(=O)- or -O-C(=O)-.)

[0036]

[0037] (in the case where m is two or more, the two or more m's are each optionally the same or different. One or more hydrogen atom on the benzene ring is optionally substituted with a monovalent group.)

[0038]

[0039] (in formula (3b-1), A 1 represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, m1 and m2 are each independently an integer of 0 to 4, and m1+m2 is an integer of 1 to 4. In formula (3b-2), m3 and m4 are each independently an integer of 1 to 5. In formula (3b-3), A 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 is an integer of 1 to 5. In formula (3b-4), A 3 and A 4 each independently represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, and m6 is an integer of 1 to 4.)

[0040]

[0041] (in formulae (V-1) to (V-6), X v1 ~X v4 , X p1 ~Xp2 Each can be represented independently as -(CH2) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2O-, -CH2OCO-, -COO- or -OCO-, X v5 This represents -O-, -CH2O-, -CH2OCO-, -COO-, or -OCO-. X a Indicates a single bond, -O-, -NH-, or -O- (CH2). m -O- (m represents an integer from 1 to 6), R v1 ~R v4 R 1a ~R 1b Each of the two k's independently represents an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, or an alkoxyalkyl group with 2 to 20 carbon atoms. The two k's can be the same or different.

[0042]

[0043] (In formulas (5-1) to (5-11), Boc represents tert-butoxycarbonyl.)

[0044]

[0045] In the above formula (d) o In the above-mentioned monovalent groups, the following can be listed: halogen atom, alkyl with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, alkoxy with 1 to 10 carbon atoms, fluoroalkyl with 1 to 10 carbon atoms, fluoroalkenyl with 2 to 10 carbon atoms, fluoroalkoxy with 1 to 10 carbon atoms, carboxyl group, hydroxyl group, alkoxycarbonyl with 1 to 10 carbon atoms, cyano group, nitro group, etc.

[0046] As the above formula (d) o From the viewpoint of improving liquid crystal alignment, the diamine shown in the following formula (d) is preferred. o -1)~(d o The diamines, 3,3'-diaminodiphenyl ethers, 3,4'-diaminodiphenyl ethers, and 4,4'-diaminodiphenyl ethers shown in (-6)

[0047]

[0048] In the diamine represented by the above formula (O), any hydrogen atom of the benzene ring, the biphenyl structure or the naphthalene ring is optionally substituted with a monovalent group. As the above monovalent group, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, and the like can be exemplified.

[0049] As the above diamine represented by the formula (O), from the viewpoint of improving the liquid crystal alignment property, diamines represented by the following formulas (o-1) to (o-16) are preferred.

[0050]

[0051]

[0052] (In the formula (o-14), the two m can be the same or different.)

[0053] As the above diamine having a specific nitrogen atom-containing structure, heterocyclic rings containing a nitrogen atom which can be possessed include, for example, pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthylidine, quinoxaline, phtalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, hexamethyleneimine, and the like. Among them, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole, or acridine is preferred.

[0054] The above diamine having a specific nitrogen atom-containing structure can have a secondary amino group and a tertiary amino group, which are represented by the following formula (n).

[0055]

[0056] In the above formula (n), R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. "*" represents a bonding bond to a hydrocarbon group, and at least one is bonded to an aromatic hydrocarbon group.

[0057] As the monovalent hydrocarbon group of R in the above formula (n), for example, an alkyl group such as methyl group, ethyl group, propyl group, and the like; a cycloalkyl group such as cyclohexyl group, and the like; an aryl group such as phenyl group, methylphenyl group, and the like, and the like can be exemplified. R is preferably a hydrogen atom or a methyl group.

[0058] As specific examples of the diamine having the above-described structure of a specific nitrogen atom, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, diamines represented by the following formulae (Dp-1) to (Dp-8), diamines represented by the following formulae (z-1) to (z-18) can be listed.

[0059]

[0060]

[0061] The above-described Y is preferably a divalent organic group derived from a diamine selected from the group consisting of the diamine represented by the above-described formula (O), a diamine having an amide bond or a urea bond, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, the diamine represented by the above-described formula (d o ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and a diamine having a group "-N(D)-" (D represents a protecting group of a hydrogen atom to be substituted by heating, and is preferably a t-butoxycarbonyl group). By satisfying the constitution by the above-described Y, an effect of reducing afterimage due to long-term alternating drive can be obtained, and is preferable.

[0062] In the above-described formula (a), X represents a tetravalent organic group. X preferably represents a tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof. Note that the tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof means, for example, a tetravalent organic group in which four carboxyl groups are removed from a corresponding tetracarboxylic acid. As the tetravalent organic group, a tetravalent organic group derived from an acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a tetravalent organic group derived from an alicyclic tetracarboxylic dianhydride or a derivative thereof, or a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof can be listed.

[0063] Here, the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. Of these, it is not necessary to be composed only of a chain hydrocarbon structure, and it can have an alicyclic structure or an aromatic ring structure in a part thereof. The alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. Of these, none of the four carboxyl groups is bonded to an aromatic ring. Furthermore, it is not necessary to be composed only of an alicyclic structure, and it can have a chain hydrocarbon structure or an aromatic ring structure in a part thereof. The aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring.

[0064] As the derivative of the above tetracarboxylic dianhydride, a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester, or a tetracarboxylic acid dialkyl ester dihalide can be exemplified.

[0065] The tetracarboxylic dianhydride or the derivative thereof can be used alone or in combination of two or more.

[0066] From the viewpoint of improving the liquid crystal alignment property, as the above acyclic aliphatic or alicyclic tetracarboxylic dianhydride or the derivative thereof, a tetracarboxylic dianhydride or the derivative thereof having at least one partial structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure is preferable.

[0067] The above X is preferably a tetravalent organic group derived from the tetracarboxylic dianhydride or the derivative thereof represented by the following formula (t).

[0068]

[0069] In the formula, X1is a structure selected from the group consisting of the following formulas (X1-1) to (X1-25). * represents a bonding bond.

[0070]

[0071]

[0072] In the formulas (X1-1) to (X1-4), R1to R 21 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. * represents a bonding bond. From the viewpoint of improving the liquid crystal alignment property, R1to R 21 A hydrogen atom, a halogen atom, a methyl group, or an ethyl group is preferable, and a hydrogen atom or a methyl group is more preferable.

[0073] In the formulae (X1-24) to (X1-25), j and k are integers of 0 or 1, and each of A1and A2independently represents a single bond, -0-, -CO-, -COO-, phenylene, sulfonyl, or amido. Each of the plurality of A2is optionally the same or different.

[0074] As specific examples of the formula (X1-1), the following formulae (1-1) to (1-6) can be given. From the viewpoint of improving the liquid crystal alignment property, the formulae (1-1) and (1-2) are particularly preferred.

[0075]

[0076] As preferred specific examples of the formulae (X1-24) and (X1-25), the following formulae (X1-26) to (X1-41) can be given. The meanings are the same as described above.

[0077]

[0078] From the viewpoint of improving the liquid crystal alignment property, the above X1is preferably the formula (X1-1) to (X1-10), (X1-18) to (X1-23), (X1-24) to (X1-25), or (X1-26) to (X1-30), more preferably the formula (X1-1), (X1-5), (X1-7) to (X1-10), (X1-21), (X1-23), (X1-24) to (X1-25), or (X1-26) to (X1-30), further preferably the formula (1-1), (1-2), (X1-5), (X1-7), (X1-9), or (X1-26) to (X1-30).

[0079] As the monovalent organic group in R and Z in the above formula (a), the following can be given: a monovalent hydrocarbon group having 1 to 20 carbon atoms; a methylene group of the hydrocarbon group is replaced with -0-, -S-, -CO-, -COO-, -COS-, -NR 3 - (wherein, R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms), -CO-NR 3 - (wherein, R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms), -Si(R 3 )2- (wherein, R 3a monovalent group A substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxy silyl group, a silanol group, a sulfinyl group, a phosphino group, a carboxyl group, a cyano group, a sulfo group, an acyl group, etc. in place of at least one hydrogen atom bonded to a carbon atom of the monovalent hydrocarbon group or the monovalent group A; a monovalent group having a heterocycle. As the monovalent organic group in R and Z in the above formula (a), an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group are preferred, an alkyl group having 1 to 3 carbon atoms is further preferred, and a methyl group is more further preferred.

[0080] From the viewpoint of obtaining the effects of the present application, R and Z are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0081] In the above formula (a), X, Y, R, and Z can each be one or two or more.

[0082] The content ratio of the polymer (A) is preferably 70 to 99 parts by mass, and more preferably 80 to 98 parts by mass, in 100 parts by mass of the polymer composition.

[0083] (Repeating unit constituting the polymer (A))

[0084] The polymer (A) in the present application is at least one polymer selected from the group consisting of a polyimide precursor having the repeating unit represented by the above formula (a) and a polyimide which is an imidized product of the polyimide precursor. The polymer (A) can also have a terminal group in addition to the repeating unit represented by the above formula (a).

[0085] Here, the terminal group refers to a group bonded to the terminal of the repeating unit constituting the above polymer (A). Examples of the terminal group include an amino group, a carboxyl group, an anhydride group, an isocyanate group, or a derivative thereof. The amino group, the carboxyl group, the anhydride group, and the isocyanate group are obtained by a usual condensation reaction, and the above derivative can be obtained, for example, by capping the terminal group using a capping agent, as described later.

[0086] The total of the repeating unit represented by formula (a) and the imidized structure thereof is preferably 10 mol% or more, and more preferably 20 mol% or more, of the entire repeating unit constituting the polymer (A).

[0087] (Repeating unit represented by formula (U))

[0088] The polymer (A) in the present application can further have a repeating unit represented by the following formula (U).

[0089]

[0090] (U1is a divalent organic group, U 1’ is a divalent organic group derived from a diamine, C1and C 1’ each independently is a hydrogen atom or a monovalent organic group.

[0091] In the above formula (U), U1is a divalent organic group. As examples of U1, divalent organic groups derived from diisocyanates can be listed. The diisocyanate can be used alone or in combination of two or more.

[0092] Here, as the diisocyanate, for example, aromatic diisocyanates, aliphatic diisocyanates can be listed.

[0093] Here, "aromatic diisocyanate" means a diisocyanate having at least one aromatic group. Further, "aliphatic diisocyanate" means a diisocyanate having an aliphatic group and not having an aromatic group.

[0094] As U1, for example, (i) a divalent organic group derived from an aromatic diisocyanate in which R in the diisocyanate structure (O=C=N-R-N=C=O) is an organic group having at least one benzene ring and having 6 to 30 carbon atoms, or (ii) a divalent organic group derived from an aliphatic diisocyanate in which R in the diisocyanate structure (O=C=N-R-N=C=O) is an organic group having an aliphatic group and not having an aromatic group and having 4 to 30 carbon atoms can be listed.

[0095] Note that the aliphatic group includes acyclic aliphatic groups and alicyclic groups.

[0096] As specific examples of U1, mention can be made of divalent organic groups derived from aromatic diisocyanates such as o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate (e.g., toluene-2,4-diisocyanate, toluene-2,6-diisocyanate), 1,4-diisocyanato-2-methoxybenzene, xylene-2,5-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diisocyanatodiphenyl ether, 2,2'-bis(4-diisocyanatophenyl)propane, 4,4'-diisocyanatodiphenylmethane (4,4'-diphenylmethane diisocyanate), 4,4'-diisocyanatodiphenyl ether, 4,4'-diisocyanatodiphenyl sulfone, 3,3'-diisocyanatodiphenyl sulfone, and 2,2'-diisocyanatobenzophenone; and divalent organic groups derived from aliphatic diisocyanates such as isophorone diisocyanate, norbornene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and tetramethylene diisocyanate.

[0097] In the above formula (U), U1, U 1’ is a divalent organic group derived from a diamine. As the diamine, mention can be made of the diamines exemplified in the above repeating unit (a), and the preferred aspects are the same as described above.

[0098] As the monovalent organic groups of C1and C 1’ in the above formula (U), mention can be made of the structures exemplified in R and Z of the above repeating unit (a). From the viewpoint of obtaining the effects of the present application, C1and C 1’ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0099] In the above formula (U), U1, U 1’ , C1, and C 1’ may each be one or two or more.

[0100] In the case of the polymer (A) in the present application, in the case where the repeating unit represented by the above formula (U) is present, from the viewpoint of obtaining the effects of the present application, the content ratio of the repeating unit represented by the above formula (U) is preferably 1 to 30 mol%, and more preferably 2 to 25 mol%, with respect to 100 mol% of the above repeating unit (a), the imidization structure of the repeating unit (a), and the above repeating unit represented by the formula (U) in total.

[0101] < Polyurethane >

[0102] The polymer composition of the present application contains a polyurethane having a repeating unit represented by the above formula (1) and not having a repeating unit represented by the above formula (a) and an imidization structure thereof. At least one of A1and A2in the above formula (1) has a divalent organic group represented by the above formula (EG).

[0103] The polyurethane can be used singly, and two or more kinds thereof can be used in combination.

[0104] (repeating unit represented by formula (1))

[0105] In the above formula (1), A1is a divalent organic group derived from a diisocyanate. Note that the divalent organic group derived from a diisocyanate means, for example, a divalent organic group obtained by removing two isocyanate groups (-N=C=O) from a diisocyanate. The diisocyanate can be used singly, and two or more kinds thereof can be used in combination.

[0106] Here, as the diisocyanate, for example, a diisocyanate (DI EG ) having a divalent organic group represented by the above formula (EG), an aromatic diisocyanate other than the diisocyanate (DI EG ), and an aliphatic diisocyanate can be exemplified.

[0107] Here, the "aromatic diisocyanate" means a diisocyanate having at least one aromatic group. In addition, the "aliphatic diisocyanate" means a diisocyanate having an aliphatic group and not having an aromatic group.

[0108] As the above diisocyanate (DI EG ), for example, a diisocyanate represented by the following formula can be exemplified.

[0109]

[0110] As the aromatic diisocyanate other than the diisocyanate (DI EG ) and the aliphatic diisocyanate, for example, (i) an aromatic diisocyanate in which, in a diisocyanate structure (O=C=N-R-N=C=O), R is an organic group having a carbon number of 6 to 30 and not having a divalent organic group represented by the above formula (EG) and having at least one benzene ring, or (ii) an aliphatic diisocyanate in which, in a diisocyanate structure (O=C=N-R-N=C=O), R is an organic group having a carbon number of 4 to 30 and having an aliphatic group and not having a divalent organic group represented by the above formula (EG) and an aromatic group can be exemplified.

[0111] Note that the aliphatic group includes both a non-cyclic aliphatic group and an alicyclic group.

[0112] In addition to diisocyanate (DI) EG Specific examples of aromatic and aliphatic diisocyanates other than those listed include: o-phenyl diisocyanates, m-phenyl diisocyanates, terephthalic diisocyanates, toluene diisocyanates (e.g., toluene-2,4-diisocyanate, toluene-2,6-diisocyanate), 1,4-diisocyanate-2-methoxybenzene, xylene-2,5-diisocyanates, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenyl diisocyanate, 2... Aromatic diisocyanates such as 2'-bis(4-phenyl diisocyanate), 4,4'-diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), 4,4'-diphenyl sulfone diisocyanate, 3,3'-diphenyl sulfone diisocyanate, and 2,2'-benzophenone diisocyanate; and aliphatic diisocyanates such as isophorone diisocyanate, norbornene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and tetramethylene diisocyanate.

[0113] In formula (1) above, A2 is a divalent organic group formed by removing the hydrogen atoms contained in the two hydroxyl groups from an organic diol. This organic diol can be used alone or in combination with two or more. Examples of such organic diols include: diols containing the divalent organic groups shown in the above formula (EG); and diols not containing the divalent organic groups shown in the above formula (EG), specifically including: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, and other alkylene diols; dimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid), dimethylolbutyric acid (2,2-... Carboxyl-containing diols such as bis(hydroxymethyl)butyric acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid; polypropylene glycol; random copolymers of polypropylene glycol and neopentyl glycol; polyester diols obtained by reacting polyols with polyacids; polycarbonate diols with a carbonate backbone; polycaprolactone diols obtained by ring-opening addition reactions of lactones such as γ-butyrolactone, ε-caprolactone, and δ-valerolactone; bisphenol A; ethylene oxide adducts of bisphenol A; ethylene oxide adducts of hydrogenated bisphenol A; propylene oxide adducts of bisphenol A; hydrogenated bisphenol A; propylene oxide adducts of hydrogenated bisphenol A, etc.

[0114] The diol containing the bivalent organic group represented by the above formula (EG) is not particularly limited as long as it contains the above formula (EG) in the molecule, and is preferably a diol in which hydrogen atoms are bonded to both ends of the above formula (EG). Among the diols in which hydrogen atoms are bonded to both ends of the above formula (EG), the upper limit of n is preferably set so that the upper limit of the weight average molecular weight of the diol becomes 5000 or less, more preferably 4000 or less, and further preferably 3000 or less. From the viewpoint of improving the liquid crystal alignment property, the upper limit of n is preferably 40, more preferably 30, and particularly preferably 20. From the viewpoint of improving the liquid crystal alignment property, the lower limit of n is preferably 5, and more preferably 6.More specific examples of the diol containing the divalent organic group represented by the above formula (EG) include pentaethylene glycol, hexaethylene glycol, PEG-300, PEG-400, PEG-600, PEG-1000, PEG-1500, PEG-2000, PEG-4000N, PEG-4000S, PEG-6000E, PEG-6000P, PEG-10000, PEG-13000, PEG-20000 manufactured by SHIN NIPPON OIL AND FAT CO., LTD., PEG 300, PEG 1000, PEG 2000, PEG 4000, PEG 6000, PEG 8000, PEG 10000, PEG 12000, PEG 20000, PEG 35000 manufactured by Merck, product numbers P2139, P3265, P3515, 81210, 81240, 81260, 81285, 81310, 181986, 181994, 182001, 182028, 189456, 202304, 202312, 202320, 202339, 202398, 202421, 202436, 202444, 202452, 295906, 309028, 372773, 372781, 373001, 412325, 435406, 435422, 435457, 637726 manufactured by SIGMA-ALDRICH, SINOPOL PEG 600, SINOPOL PEG 1500, SINOPOL PEG 4000 manufactured by CHISON, PEG #300, PEG #400, PEG #600, PEG #1000, PEG #1500, PEG #1540, PEG #4000, PEG #6000M manufactured by LION SPECIALTY CHEMICALS, and Polyethylene Glycol 400, Polyethylene Glycol 600 manufactured by Tokyo Chemical Industry Co., Ltd.As preferred specific examples of diols in which hydrogen atoms are bonded to both ends of the bivalent organic group represented by the above formula (EG), there can be mentioned pentaethylene glycol, hexaethylene glycol, PEG-300, PEG-400, PEG-600, PEG-1000 manufactured by Nikko Chemicals Co., Ltd., PEG 300, PEG 1000 manufactured by MERCK, PEG 1000 manufactured by Wako Pure Chemical Industries, Ltd., SINOPOL PEG 600 manufactured by Nippon Fine Chemical Co., Ltd., PEG #300, PEG #400, PEG #600, PEG #1000 manufactured by LION Specialty Chemicals Co., Ltd., polyethylene glycol represented by the product names Polyethylene Glycol 400, Polyethylene Glycol 600 manufactured by Tokyo Chemical Industry Co., Ltd., or penta- propylene glycol, hexa-propylene glycol, polypropylene glycol (more preferably polypropylene glycol having an average molecular weight of 400 to 5,000), a copolymer of ethylene oxide and propylene oxide having an average molecular weight of 500 to 5,000, and the like. The above polyethylene glycol and polypropylene glycol can use a substance obtained by anionic ring-opening polymerization of ethylene oxide and propylene oxide. The polymerization can be performed using a polymerization initiator (for example, water, ethylene glycol, propylene glycol, and the like) and a catalytic amount of a base (for example, potassium hydroxide).

[0115] Note that the average molecular weight of the diols exemplified above in the diols containing the bivalent organic group represented by the above formula (EG) means the weight average molecular weight based on gel permeation chromatography (GPC) and obtained on a polystyrene basis.

[0116] (Repeating unit constituting polyurethane)

[0117] The polyurethane in the present application is a polyurethane having the repeating unit represented by the above formula (1) and not having the repeating unit represented by the above formula (a) and the imide structure thereof. The polyurethane in the present application can also have the repeating unit represented by the above formula (1) and a terminal group. The terminal group is as described above.

[0118] The content ratio of the repeating unit represented by the above formula (1) is preferably 10 mol% or more, more preferably 20 mol% or more, of the entire repeating units constituting the polyurethane.

[0119] Further, the content ratio of the repeating unit represented by the above formula (1) in which A2 is a bivalent organic group derived from a diol in which hydrogen atoms are bonded to both ends of the above formula (EG) is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 50 mol% or more, of the entire repeating units constituting the polyurethane.

[0120] In the above formula (1), A1 and A2 can each be one or two or more.

[0121] The content ratio of the polyurethane in the present application is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, in 100 parts by mass of the polymer composition.

[0122] <Production of Polymer (A)>

[0123] As the polyimide precursor of the above-mentioned polymer (A), for example, polyamic acid, polyamic acid ester, etc. can be exemplified.

[0124] The polyamic acid (polyimide precursor having the repeating unit represented by the formula (a) above in which R is a hydrogen atom) can be produced by the following method. Specifically, it can be synthesized by (polycondensing) reacting a tetracarboxylic acid component containing the above-mentioned tetracarboxylic dianhydride or derivative thereof and a diamine component containing the above-mentioned diamine in the presence of an organic solvent at -20 to 150°C, preferably at 0 to 50°C, for 30 minutes to 24 hours, preferably for 1 to 12 hours of (polycondensation) reaction. In the case where the above-mentioned polyamic acid has the above-mentioned repeating unit (U), it can be synthesized by reacting a diisocyanate compound represented by O=C=N-U1-N=C=O (U1 is the same as U1 in the formula (U)) together with the above-mentioned tetracarboxylic acid component and the above-mentioned diamine component.

[0125] As a specific example of the organic solvent used in the above-mentioned reaction, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone can be exemplified. Further, in the case where the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the solvents represented by the following formulae [D-1] to [D-3] can be used. Two or more of them can be used in mixture.

[0126]

[0127] (In the formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, in the formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, in the formula [D-3], D 3 represents an alkyl group having 1 to 4 carbon atoms.)

[0128] The reaction can be carried out at an arbitrary concentration, preferably at 1 to 50 mass%, more preferably at 5 to 30 mass%. It can be carried out at a high concentration at the initial stage of the reaction, and then the solvent can be added. In the reaction, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. As in the usual polycondensation reaction, the closer the molar ratio to 1.0, the larger the molecular weight of the polyamic acid produced.

[0129] The polyamic acid obtained in the above reaction can be recovered by precipitating the polyamic acid by injecting the reaction solution into a poor solvent while stirring the reaction solution sufficiently. Further, by performing the precipitation several times, washing with the poor solvent, and drying at normal temperature or with heating, a powder of the purified polyamic acid can be obtained. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.

[0130] In the case where the polyimide precursor is a polyamic acid ester, it can be produced by the following known methods: (1) a method of esterifying a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine; (2) a method based on the reaction of a tetracarboxylic acid diester dichloride and a diamine; (3) a method of polycondensing a tetracarboxylic acid diester and a diamine; and the like.

[0131] [End-capping agent]

[0132] An end-capped polymer can also be synthesized using a suitable end-capping agent together with a tetracarboxylic acid component including a tetracarboxylic dianhydride or a derivative thereof, a diamine component, and a diisocyanate compound used as necessary when synthesizing the polymer (A) in the present application.

[0133] As the end-capping agent, for example, an acid monoanhydride such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexane dicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, a compound represented by the following formula (m-1) to (m-6), 3-((3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride, and the like; a diester carbonate compound such as di-t-butyl dicarbonate, diallyl dicarbonate, and the like; a chlorocarbonyl compound such as acryloyl chloride, methacryloyl chloride, nicotinoyl chloride, and the like; a monoamine compound such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and the like; a monoisocyanate compound having an unsaturated bond such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and the like; an isothiocyanate compound such as ethyl isothiocyanate, allyl isothiocyanate, and the like; and the like can be exemplified.

[0134]

[0135] The use ratio of the end-capping agent is preferably 20 mol or less, more preferably 10 mol or less, relative to 100 mol of the total of the diamine component used and the organic diol component used as necessary.

[0136] Further, the polyimide can be obtained by ring-closing (imidization) of the polyimide precursor (A) of the polymer (A). Note that the imidization ratio in the present specification refers to the proportion of imide groups in the total amount of imide groups and carboxyl groups (or derivatives thereof) derived from tetracarboxylic dianhydride or derivatives thereof. The imidization ratio does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the use or purpose.

[0137] As the method of imidizing the polyimide precursor, there are thermal imidization in which a solution of the polyimide precursor is heated while being maintained in this state, and catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.

[0138] The temperature in the case of thermal imidization of the polyimide precursor in a solution is preferably 100 to 400°C, more preferably 120 to 250°C, and it is preferable to perform this while removing water generated by the imidization reaction to the outside of the system.

[0139] The catalytic imidization of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor, and stirring preferably at -20 to 250°C, more preferably at 0 to 180°C. The amount of the basic catalyst is preferably 0.5 to 30 moles, more preferably 2 to 20 moles, relative to the amide acid group, and the amount of the acid anhydride is preferably 1 to 50 moles, more preferably 3 to 30 moles, relative to the amide acid group. As the basic catalyst, there are pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like, among which pyridine is preferable because it has a moderate basicity that allows the reaction to progress. As the acid anhydride, there are acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, among which acetic anhydride is preferable because purification after the reaction becomes easy. The imidization ratio based on the catalytic imidization can be controlled by adjusting the amount of the catalyst and the reaction temperature and reaction time.

[0140] In the case of recovering the generated polyimide precursor or polyimide from the reaction solution of the polyimide precursor or polyimide, it is only necessary to precipitate the reaction solution by pouring it into a solvent. As the solvent for precipitation, there are methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer precipitated by being poured into a solvent can be dried at normal pressure or reduced pressure, at normal temperature or with heating, after being recovered by filtration. Further, when the polymer recovered by precipitation is repeatedly subjected to operations such as redissolution in an organic solvent and recovery by reprecipitation, for example, 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, there are, for example, alcohols, ketones, or hydrocarbons, and when three or more solvents selected from among these are used, the efficiency of purification is further improved, and thus this is preferable.

[0141] As for the molecular weight of the polymer (A) used in the present application, in consideration of the strength of the liquid crystal alignment film thus obtained, the workability and the coatability at the time of film formation, it is preferably set to 5,000 to 1,000,000 in terms of the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, and more preferably 10,000 to 150,000.

[0142] <Manufacture of polyurethane>

[0143] The above polyurethane can be obtained, for example, by reacting the (o) component containing an organic diol having two hydroxyl groups in a molecule with the (i) component containing a compound having two isocyanate groups in a molecule. Here, at least one of the compounds constituting the above (o) component and (i) component has a partial structure represented by the following formula (EG) in a molecule.

[0144]

[0145] (n is an integer of 5 or more. R represents a hydrogen atom or a methyl group.)

[0146] The (o) component and the (i) component can each be one or two or more.

[0147] As the (o) component, for example, the organic diol exemplified in the repeating unit represented by the above formula (1) can be cited, and a diol compound represented by "H-A2-H" (A2 is the same as A2 in formula (1)) can be cited.

[0148] As the (i) component, for example, a diisocyanate compound represented by O=C=N-A1-N=C=O (A1 is the same as A1 in formula (1)) can be cited.

[0149] In the case where the diol compound represented by "H-A2-H" is contained as the (o) component, and the diisocyanate compound represented by O=C=N-A1-N=C=O is contained as the (i) component, at least one of A2 in the diol compound represented by "H-A2-H" and A1 in the diisocyanate compound represented by O=C=N-A1-N=C=O has the partial structure represented by the above formula (EG) in a molecule. Preferred specific examples thereof are as described above.

[0150] (o) component and the (i) component is generally carried out in an organic solvent. As the organic solvent to be used at this time, there is no particular limitation as long as it is a solvent which dissolves the resulting polyurethane. As specific examples, there can be mentioned N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl phosphoric triamide, γ-butyrolactone, isopropyl alcohol, methoxy methyl pentanol, 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 mono isopropyl ether, ethylene glycol mono butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxy butanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1,4-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, 3-methoxy propionic acid methyl ester, 3-ethoxy propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, 3-methoxy propionic acid ethyl ester, 3-ethoxy propionic acid, 3-methoxy propionic acid, 3-methoxy propionic acid propyl ester, 3-methoxy propionic acid butyl ester, diglyme, or 4-hydroxy-4-methyl-2-pentanone, and the like. They can be used alone or in admixture. Also, even a solvent which does not dissolve polyurethane can be used in admixture with the above-mentioned solvents. Furthermore, moisture in the organic solvent becomes a cause of hindering the polymerization reaction, and therefore the organic solvent is preferably an organic solvent which has been dehydrated and dried.

[0151] As for the method of synthesizing the polyurethane obtained by reacting the (o) component containing an organic diol used in the present application with the (i) component containing a diisocyanate compound having two isocyanate groups in the molecule, it is obtained by reacting the (o) component and the (i) component in an organic solvent in such a manner that the ratio of the number of hydroxyl groups to the number of isocyanate groups becomes isocyanate group / hydroxyl group = 0.8 or more and 1.2 or less, preferably 0.9 or more and 1.2 or less, and more preferably 0.9 or more and 1.1 or less.

[0152] Further, in the case where two or more kinds of organic diols are used, the reaction with the diisocyanate compound can be carried out after mixing the two or more kinds of organic diols, or each of the organic diols can be reacted with the diisocyanate compound separately. Further, the obtained terminal isocyanate compound can be further reacted with another organic diol compound after the reaction of the organic diol with the diisocyanate compound, and then reacted with the diisocyanate compound. Further, the same applies to the case where two or more kinds of diisocyanate compounds are used. In this way, the desired polyurethane can be produced.

[0153] The reaction temperature of the component (o) with the component (i) is preferably set to 0 to 160°C, and more preferably to 10 to 150°C. The reaction time can be appropriately selected depending on the reaction scale and the reaction conditions employed. Further, the reaction can be carried out in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a tin, a zinc, a titanium, a cobalt or the like, or a semi-metal compound, as necessary. The concentration of the total amount of the component (o) and the component (i) in the reaction liquid is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. It can be carried out at a high concentration at the initial stage of the reaction, and then an organic solvent can be added.

[0154] As for the molecular weight of the polyurethane used in the present application, in consideration of the strength of the liquid crystal alignment film thus obtained, the workability and the coatability at the time of film formation, it is preferably set to 4000 to 80000, and more preferably to 6000 to 60000, in terms of the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method.

[0155] The polymer composition of the present application can also contain other polymers than the polymer (A) and other polymers than the polyurethane. If specific examples of the other polymers are enumerated, polymers selected from the group consisting of a polyimide precursor other than the polymer (A) or an imidized product thereof, a polyurethane other than the above-mentioned polyurethane, a polysiloxane, a polyester, a polyamide, a polyurea, a polyorganosiloxane, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-maleic anhydride) copolymer, a poly(isobutylene-maleic anhydride) copolymer, a poly(vinyl ether-maleic anhydride) copolymer, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, and the like can be enumerated. As specific examples of the poly(styrene-maleic anhydride) copolymer, SMA 1000, 2000, 3000 (manufactured by Cray Valley), GSM 301 (manufactured by Gifu Shellac), and the like can be enumerated, as specific examples of the poly(isobutylene-maleic anhydride) copolymer, ISOBAM-600 (manufactured by Kuraray) can be enumerated, and as specific examples of the poly(vinyl ether-maleic anhydride) copolymer, GANTREZ AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by ISP Japan) can be enumerated.

[0156] The other polymers can be used singly, and in addition, two or more kinds can be used in combination. The content ratio of the other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and further preferably 20 to 80 parts by mass, relative to 100 parts by mass of the total of the polymers contained in the polymer composition.

[0157] The polymer composition of the present application is preferably a liquid composition in which the above-mentioned polymer (A) and polyurethane are dissolved or dispersed in an organic solvent. Specifically, the organic solvent contained in the above-mentioned polymer composition is not particularly limited as long as it uniformly dissolves the polymer components, and examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyl lactamide, N,N-dimethylpropionamide, tetramethyl urea, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-n-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-t-butyl-2-pyrrolidone, N-n-pentyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone (which are collectively referred to as "good solvents" hereinafter). Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass, of the total amount of the solvent contained in the polymer composition.

[0158] Further, the organic solvent contained in the polymer composition is preferably a mixed solvent in which a solvent (also referred to as a poor solvent) that improves the coatability of the coated polymer composition and the surface smoothness of the coated film is used in addition to the above-mentioned solvent. Specific examples of the poor solvent used in combination are described below, but the present application is not limited thereto. The content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass, of the total amount of the solvent contained in the polymer composition. The type and content of the poor solvent are appropriately selected depending on the coating apparatus, coating conditions, coating environment, and the like of the liquid crystal alignment agent.

[0159] As the poor solvent, for example, the following can be mentioned: diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyric acid, 1-methylamyl acetate, 2-ethylbutyric acid, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, 4-methyl-2-pentyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), and the like.

[0160] Among them, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferable.

[0161] As the combination of the preferred solvent of the good solvent and the poor solvent, there can be mentioned: N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; N-ethyl-2-pyrrolidone and propylene glycol diacetate; N,N-dimethyl lactamide and diisobutyl ketone; N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate; N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate; N-methyl-2-pyrrolidone, ethyl 3-ethoxypropionate and dipropylene glycol monomethyl ether; N-ethyl-2-pyrrolidone, ethyl 3-ethoxypropionate and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone, ethyl 3-ethoxypropionate and diethylene glycol monopropyl ether; N-ethyl-2-pyrrolidone, ethyl 3-ethoxypropionate and diethylene glycol monopropyl ether; N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate; N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether; N,N-dimethyl lactamide and ethylene glycol monobutyl ether; N,N-dimethyl lactamide and propylene glycol diacetate; N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether; N-ethyl-2-pyrrolidone, diethylene glycol monoethyl ether and butyl cellosolve acetate; N-methyl-2-pyrrolidone, diethylene glycol monomethyl ether and butyl cellosolve acetate; N,N-dimethyl lactamide and diethylene glycol diethyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether; N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; N-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate; N-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol dimethyl ether; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl ketone; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl methyl carbinol;N-methyl-2-pyrrolidone, gamma-butyrolactone, and dipropylene glycol dimethyl ether; N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether; N-ethyl-2-pyrrolidone, diethylene glycol diethyl ether, and dipropylene glycol monomethyl ether; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and propylene glycol diacetate; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and diisobutyl ketone; N-ethyl-2-pyrrolidone, gamma-butyrolactone, and diisobutyl ketone; N-ethyl-2-pyrrolidone, N,N-dimethyl lactamide, and diisobutyl ketone; N-methyl-2-pyrrolidone, ethylene glycol monobutyl ether, and ethylene glycol monobutyl ether acetate; gamma-butyrolactone, ethylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; N-ethyl-2-pyrrolidone, ethylene glycol monobutyl ether acetate, and propylene glycol dimethyl ether; N-methyl-2-pyrrolidone, acetic acid 4-methyl-2-pentyl ester, and ethylene glycol monobutyl ether; N-ethyl-2-pyrrolidone, cyclohexyl acetate, and diacetone alcohol; N,N-dimethyl propionamide and 4-hydroxy-4-methyl-2-pentanone; N,N-dimethyl propionamide and propylene glycol diacetate; tetramethyl urea and 4-hydroxy-4-methyl-2-pentanone; tetramethyl urea and propylene glycol diacetate; N,N-dimethyl propionamide and propylene glycol monobutyl ether; tetramethyl urea and propylene glycol monobutyl ether; tetramethyl urea, cyclohexanone, and propylene glycol monomethyl ether; N,N-dimethyl propionamide and propylene glycol monomethyl ether; N,N-dimethyl propionamide and ethylene glycol monobutyl ether acetate; N,N-dimethyl propionamide and ethylene glycol monobutyl ether; tetramethyl urea and propylene glycol monomethyl ether; N,N-dimethyl propionamide, cyclohexanone, and diethylene glycol diethyl ether; N,N-dimethyl formamide and propylene glycol monomethyl ether; N,N-dimethyl formamide and 4-hydroxy-4-methyl-2-pentanone; N,N-dimethyl formamide and propylene glycol monomethyl ether; cyclohexanone and propylene glycol monomethyl ether; cyclopentanone and propylene glycol monomethyl ether; N-methyl-2-pyrrolidone, cyclohexanone, and propylene glycol monomethyl ether, and the like.

[0162] The polymer composition of the present application can also contain, in addition to the polymer component and the organic solvent, a component other than the polymer component and the organic solvent (hereinafter also referred to as an additive component). As the additive component, for example, a cross-linkable compound, a functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, an antioxidant, a sensitizer, a preservative, a compound for adjusting the dielectric constant and resistance of a resin film, and the like can be exemplified.

[0163] As the above cross-linkable compound, for example, at least one cross-linkable compound selected from the group consisting of cross-linkable compound (c-1) having at least one substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, a cyclic carbonate group, a blocked isocyanate group, a hydroxyl group, and an alkoxy group, and cross-linkable compound (c-2) having a polymerizable unsaturated group can be exemplified.

[0164] By containing the above cross-linkable compound, a liquid crystal display element in which generation of so-called flicker or the like due to irradiation of a backlight to the liquid crystal display element immediately after driving of the liquid crystal is reduced can be obtained.

[0165] As a preferable specific example of the above cross-linkable compound (c-1), (c-2), the following compounds can be exemplified.

[0166] As the compound (c-1) having an epoxy group: 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, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, a bisphenol A type epoxy resin such as EPIKOTE 828 (manufactured by MITSUBISHI CHEMICAL CORPORATION), a bisphenol F type epoxy resin such as EPIKOTE 807 (manufactured by MITSUBISHI CHEMICAL CORPORATION), a hydrogenated bisphenol A type epoxy resin such as YX-8000 (manufactured by MITSUBISHI CHEMICAL CORPORATION), an epoxy resin containing a biphenyl skeleton such as YX6954BH30 (manufactured by MITSUBISHI CHEMICAL CORPORATION), a phenol novolak type epoxy resin such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), a (o-, m-, p-)cresol novolak type epoxy resin such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), tetra(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, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like, a compound in which a tertiary nitrogen atom is bonded to an aromatic carbon atom; 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 the like, a compound in which a tertiary nitrogen atom is bonded to an aliphatic carbon atom, a triisocyanuric acid triglycidyl ester such as TEPIC (manufactured by Nissan Chemical Corporation), an isocyanate compound, a compound described in paragraph 0037 of Japanese Patent Application Publication No. 10-338880, a compound described in WO2017 / 170483, and the like.

[0167] As a compound having an isocyanate group: the aforementioned diisocyanate compound, etc.

[0168] As a compound having an oxetanyl group (c-1): 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (ARONE OXETANE OXT-121 (XDO)), di[2-(3-oxetanyl)butyl]ether (ARONE 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), a compound having two or more oxetanyl groups described in paragraphs 0170 to 0175 of WO2011 / 132751, etc.

[0169] As a compound having a cyclic carbonate group (c-1): N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N'-bis[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-benzenediamine, a compound described in WO2011 / 155577, etc.

[0170] As a compound having a blocked isocyanate group: CORONATE AP stable M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS-50 (all manufactured by TOSOH Corporation); TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.); a compound having two or more protected isocyanate groups described in paragraphs 0046 to 0047 of Japanese Patent Application Publication No. 2014-224978, a compound having three or more protected isocyanate groups described in paragraphs 0119 to 0120 of WO2015 / 141598, etc.

[0171] As the compound (c-1) having a hydroxyl group and / or an alkoxy group, N,N,N',N'-tetra(2-hydroxyethyl)adipamide, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, the compound described in paragraph 0058 of International Publication No. 2015 / 072554, Japanese Patent Application Publication No. 2016-118753, the compound described in Japanese Patent Application Publication No. 2016-200798, the compound described in WO 2010 / 074269, and the like are exemplified.

[0172] As the cross-linkable compound (c-2) having a polymerizable unsaturated group, glyceryl mono(meth)acrylate, glyceryl di(meth)acrylate (1,2-, 1,3-type mixture), glyceryl tri(meth)acrylate, glyceryl 1,3-diglyceryl di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, and the like are exemplified.

[0173] As more preferable specific examples of the above-described cross-linkable compounds (c-1), (c-2), compounds represented by any of the following formulas (CL-1) to (CL-12) are exemplified.

[0174]

[0175]

[0176] The above is one example of the cross-linkable compound, and is not limited thereto. Furthermore, the cross-linkable compound used in the liquid crystal alignment agent of the present application can be one, or two or more in combination.

[0177] The content of the cross-linkable compound in the liquid crystal alignment agent of the present application is 0.1 to 150 parts by mass, or 0.1 to 100 parts by mass, or 1 to 50 parts by mass, with respect to 100 parts by mass of the total polymer component.

[0178] As the compound for adjusting the dielectric constant and resistance of the resin film described above, a monoamine having a nitrogen atom-containing aromatic heterocycle such as 3-aminomethylpyridine is exemplified. In the case of using a monoamine having a nitrogen atom-containing aromatic heterocycle, it is preferable that 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, be contained with respect to 100 parts by mass of the polymer component contained in the polymer composition.

[0179] As preferable specific examples of the functional silane compound, silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like can be given. In the case where a functional silane compound is used, the amount thereof used is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, with respect to 100 parts by mass of the polymer component contained in the polymer composition.

[0180] The solid content concentration in the polymer composition (the proportion of the total mass of the components other than the solvent in the polymer composition in the total mass of the polymer composition) is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 1 to 10% by mass. That is, the polymer composition is coated on the surface of a substrate as described later, and a resin film is preferably formed by heating.

[0181] The range of the particularly preferable solid content concentration differs depending on the method used when the polymer composition is coated on a substrate. For example, in the case where a spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. In the case where a printing method is used, the solid content concentration is particularly preferably set to be in the range of 3 to 9% by mass, whereby the solution viscosity is set to be in the range of 12 to 50 mPa-s. In the case where an inkjet method is used, the solid content concentration is particularly preferably set to be in the range of 1 to 5% by mass, whereby the solution viscosity is set to be in the range of 3 to 15 mPa-s. The temperature at the time of preparing the polymer composition is preferably 10 to 50°C, more preferably 20 to 30°C.

[0182] <Usage and Resin Film>

[0183] The polymer composition described above can form a resin film, for example, by coating on a substrate, preferably by heating to volatilize the solvent component. The polymer composition and resin film of the present application can be effectively applied to various technical uses, for example, to liquid crystal alignment agents, electronic circuit materials, semiconductor materials, electrically insulating materials, electric wire coating materials, lighting uses, molding materials, and the like. Specifically, various resin films provided in display elements, semiconductor elements, actuators such as motors, various sensors such as piezoelectric sensors, pyroelectric sensors, and the like can be exemplified by: liquid crystal alignment films (liquid crystal alignment films for phase difference films, liquid crystal alignment films for scanning antennas, liquid crystal alignment films for liquid crystal array antennas, or liquid crystal alignment films for transmissive-scattering type liquid crystal light control elements), protective films (for example, protective films for color filters), spacer films, interlayer insulating films, antireflection films, wiring coating films, charge prevention films, motor insulating films (gate insulating films for flexible displays), and the like. Among them, the polymer composition of the present application can be preferably used as a liquid crystal alignment agent.

[0184] < Liquid crystal alignment agent >

[0185] The liquid crystal alignment agent of the present application is formed from the polymer composition of the present application. That is, the liquid crystal alignment agent of the present application contains the above-described polymer (A) and polyurethane as in the polymer composition. In addition, it is preferable to contain at least any of other polymers, organic solvents, and additive components. Details of specific examples, blending ratios, solid component concentrations, and the like of the above-described polymer (A), polyurethane, other polymers, organic solvents, and additive components can be applied to the description of the polymer composition.

[0186] [ Liquid crystal alignment film and liquid crystal display element ]

[0187] A liquid crystal alignment film can be manufactured in the form of a resin film by using the above-described polymer composition or the above-described liquid crystal alignment agent. In addition, the liquid crystal display element of the present application is provided with a liquid crystal alignment film formed using the above-described polymer composition or the above-described liquid crystal alignment agent. The operation mode of the liquid crystal display element of the present application is not particularly limited, and various operation modes such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, vertical alignment type (including VA-MVA (Multi-domain Vertical Alignment) type, VA-PVA (Patterned Vertical Alignment) type, and the like), in-plane switching type (IPS type), FFS type, optical compensation birefringence type (OCB: Optically Compensated Birefringence type), and the like can be applied.

[0188] The liquid crystal display element of the present application can be manufactured, for example, by a method including the following processes (1) to (4), a method including processes (1) to (2) and (4), a method including processes (1) to (3), (4-2), and (4-4), or a method including processes (1) to (3), (4-3), and (4-4).

[0189] <Process (1): Process of applying liquid crystal alignment agent to substrate>

[0190] Process (1) is a process of applying the liquid crystal alignment agent of the present application to a substrate. Specific examples of process (1) are described below.

[0191] The liquid crystal alignment agent of the present application is applied to one side of a substrate provided with a patterned transparent conductive film, for example, by an appropriate coating method such as a roll coater method, a spin coating method, a printing method, an inkjet method, or the like. Here, as the substrate, there is no particular limitation as long as it is a substrate having high transparency, and plastic substrates such as an acrylic substrate, a polycarbonate substrate, or the like can be used in addition to a glass substrate, a silicon nitride substrate. Further, in the case of a reflective liquid crystal display element, if it is a substrate of only one side, an opaque object such as a silicon wafer can be used, and the electrode in this case can also use a material that reflects light such as aluminum. Further, in the case of manufacturing an IPS-type or FFS-type liquid crystal display element, a substrate provided with an electrode composed of a transparent conductive film or a metal film patterned into a comb-tooth shape and an opposing substrate not provided with an electrode are used.

[0192] As the method of applying the liquid crystal alignment agent to the substrate to form a film, screen printing, offset printing, flexographic printing, an inkjet method, or a spray coating method, or the like can be listed. Among these, a coating and film formation method using an inkjet method can be preferably used.

[0193] <Process (2): Process of baking the applied liquid crystal alignment agent>

[0194] Process (2) is a process of baking the liquid crystal alignment agent applied to the substrate to form a film. Specific examples of process (2) are described below.

[0195] After the liquid crystal alignment agent is applied to the substrate in the process (1), the solvent can be evaporated by a heating unit such as a hot plate, a heat cycle oven, or an IR (infrared) oven, or thermal imidization of the polyamic acid or polyamic acid ester can be performed. The drying and firing processes after the application of the liquid crystal alignment agent of the present application can be performed at any temperature and time, and can be performed multiple times. The temperature for reducing the solvent of the liquid crystal alignment agent can be, for example, 40 to 180°C. From the viewpoint of shortening the process, it can be performed at 40 to 150°C. The firing time is not particularly limited, and can be, for example, 1 to 10 minutes or 1 to 5 minutes. In the case of thermal imidization of the polyamic acid or polyamic acid ester, a process of firing at a temperature in the range of 150 to 300°C or 150 to 250°C can be additionally performed after the above process. The firing time is not particularly limited, and can be, for example, 5 to 40 minutes or 5 to 30 minutes.

[0196] The film thickness of the film after firing is preferably 5 to 300 nm, and more preferably 10 to 200 nm, because if the film thickness is too thin, the reliability of the liquid crystal display element can be reduced.

[0197] Process (3): Process of performing alignment treatment on the film obtained in process (2)

[0198] Process (3) is a process of performing alignment treatment on the film obtained in process (2) as the case requires. That is, in the case of a horizontal alignment type liquid crystal display element such as an IPS mode or an FFS mode, the coating film is subjected to alignment ability imparting treatment. On the other hand, in the case of a vertical alignment type liquid crystal display element such as a VA mode or a PSA mode, the coating film formed can be used as a liquid crystal alignment film as it is, or the coating film can be subjected to alignment ability imparting treatment. As the alignment treatment method of the liquid crystal alignment film, a rubbing treatment method or a photo-alignment treatment method can be mentioned. As the photo-alignment treatment method, a method in which a radiation ray polarized in a certain direction is irradiated to the surface of the above film, and heating treatment is performed at a temperature of 150 to 250°C as the case requires to impart liquid crystal alignment properties (also referred to as liquid crystal alignment ability) can be mentioned. As the radiation ray, ultraviolet rays or visible light having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferred, and ultraviolet rays having a wavelength of 200 to 400 nm are more preferred.

[0199] The irradiation amount of the above radiation ray is preferably 1 to 10,000 mJ / cm 2 . Among them, 100 to 5,000 mJ / cm 2Further, in the case of irradiation of a radioactive ray, in order to improve the liquid crystal alignment property, the substrate having the above-mentioned film can be irradiated while being heated at 50 to 2500C. The above-mentioned liquid crystal alignment film thus produced can stably align the liquid crystal molecules in a certain direction.

[0200] Further, in the above-mentioned method, the liquid crystal alignment film irradiated with the polarized radioactive ray can be subjected to a contact treatment with water or a solvent, or a heat treatment.

[0201] As the solvent used in the above-mentioned contact treatment, there is no particular limitation as long as it is a solvent that dissolves the decomposition product generated from the film by irradiation of a radioactive ray. As specific examples, there can be mentioned water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3-methoxypropyl methylate, 3-ethoxypropyl ethylate, propyl acetate, butyl acetate, cyclohexyl acetate, and the like. Among them, from the viewpoint of versatility and safety of the solvent, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferred, and water, 1-methoxy-2-propanol or ethyl lactate is more preferred. The solvent can be one kind or a combination of two or more kinds.

[0202] The temperature of the heat treatment of the above-mentioned coated film irradiated with a radioactive ray is more preferably 50 to 3000C, and further preferably 120 to 2500C. As the time of the heat treatment, it is preferably set to 1 to 30 minutes, respectively.

[0203] <Step (4): Step of producing liquid crystal cell>

[0204] Two substrates each having a liquid crystal alignment film formed as described above are prepared, and a liquid crystal is disposed between the two substrates disposed in opposition to each other. Specifically, there can be mentioned the following two methods.

[0205] In the first method, first, the two substrates are disposed in opposition to each other with a gap (cell gap) therebetween. Next, the peripheral portions of the two substrates are bonded using a sealant, and a liquid crystal composition is injected into the cell gap divided by the surfaces of the substrates and the sealant, and the injection hole is sealed after coming into contact with the film surface.

[0206] As the above-mentioned liquid crystal composition, there is no particular limitation, and various liquid crystal compositions each containing at least one liquid crystal compound (liquid crystal molecule) and having a positive or negative dielectric anisotropy can be used. Note that, hereinafter, the liquid crystal composition having a positive dielectric anisotropy will also be referred to as a positive liquid crystal, and the liquid crystal composition having a negative dielectric anisotropy will also be referred to as a negative liquid crystal.

[0207] The liquid crystal composition described above can contain a liquid crystal compound having a fluorine atom, a hydroxyl group, an amino group, a group containing a fluorine atom (example: trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocycle, a cycloalkane, a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring, and can also contain a compound having two or more rigid portions (mesogenic skeleton) that exhibit liquid crystallinity within the molecule (for example, a double mesogen compound in which two biphenyl structures or a terphenyl structure are linked by an alkyl group, and the like). The liquid crystal composition can be a liquid crystal composition in a nematic phase, a liquid crystal composition in a smectic phase, or a liquid crystal composition in a cholesteric phase.

[0208] Further, from the viewpoint of improving the liquid crystal alignment properties, the liquid crystal composition described above can further contain an additive. Such an additive can include, for example, a photopolymerizable monomer having a polymerizable group; an optically active compound (for example, S-811 manufactured by MERCK Co., Ltd., and the like); an antioxidant; an ultraviolet absorber; a pigment; an antifoaming agent; a polymerization initiator; or a polymerization inhibitor, and the like.

[0209] As a positive liquid crystal, for example, ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, or MLC-7081 manufactured by MERCK Co., Ltd., and the like can be used.

[0210] As a negative liquid crystal, for example, MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, or MLC-7029 manufactured by MERCK Co., Ltd., and the like can be used.

[0211] Further, in the PSA mode, as a liquid crystal containing a compound having a polymerizable group, MLC-3023 manufactured by MERCK Co., Ltd. can be used.

[0212] Further, the second method is a method called the ODF (One Drop Fill) method. For example, an ultraviolet-curable sealant is applied to a prescribed portion on one of the two substrates on which a liquid crystal alignment film is formed, and further, liquid crystal composition is dropped onto prescribed portions on the surface of the liquid crystal alignment film. Then, the other substrate is attached in opposition to the liquid crystal alignment film, and the liquid crystal composition is spread over the entire surface of the substrate to come into contact with the film surface. Subsequently, ultraviolet light is irradiated over the entire surface of the substrate to cure the sealant. In either case, it is desirable to further slowly cool to room temperature after heating to a temperature at which the liquid crystal composition used becomes an isotropic phase, thereby removing the flow alignment at the time of liquid crystal filling.

[0213] Note that, in the case where the coated films are subjected to brushing treatment, the two substrates are arranged in opposition to each other in such a manner that the brushing directions of the respective coated films become a prescribed angle, for example, become orthogonal or antiparallel.

[0214] As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as spacers, etc. can be used. As the liquid crystal, nematic liquid crystals and smectic liquid crystals can be cited, of which nematic liquid crystals are preferred.

[0215] The liquid crystal alignment agent of the present application is also preferably used for a liquid crystal display element (PSA type liquid crystal display element) manufactured through the following procedures by having a liquid crystal layer between a pair of substrates provided with electrodes: disposing a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates, applying a voltage between the electrodes, and polymerizing the polymerizable compound by at least one of irradiation of active energy rays and heating.

[0216] Further, the liquid crystal alignment agent of the present application is also preferably used for a liquid crystal display element (SC-PVA mode type liquid crystal display element) manufactured through the following procedures by having a liquid crystal layer between a pair of substrates provided with electrodes: disposing a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates, and applying a voltage between the electrodes.

[0217] <Procedure (4-2): In the case of the PSA type liquid crystal display element>

[0218] A liquid crystal composition containing a polymerizable compound is injected or dropped, and the same as the above (4) except for this aspect. As the polymerizable compound, for example, a polymerizable compound having one or more polymerizable unsaturated groups such as an acrylate group, a methacrylate group, etc. in the molecule can be cited.

[0219] <Procedure (4-3): In the case of the SC-PVA mode type liquid crystal display element>

[0220] A method of manufacturing a liquid crystal display element by performing the same as the above (4) and then the following procedure of irradiating ultraviolet rays can also be employed. According to this method, as in the case of manufacturing the above PSA type liquid crystal display element, a liquid crystal display element excellent in response speed under a small amount of light irradiation can be obtained. The compound having a polymerizable group can be a compound having one or more of the above polymerizable unsaturated groups in the molecule, and the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, with respect to 100 parts by mass of the total polymer component. Further, the above polymerizable group can be possessed in a polymer used for the liquid crystal alignment agent, and as such a polymer, for example, a polymer obtained by using a diamine component containing a diamine having the above photopolymerizable group at the terminal for the reaction can be cited.

[0221] <Process (4-4): Process of irradiating ultraviolet rays>

[0222] The liquid crystal cell is irradiated with light under a state where a voltage is applied between the conductive films possessed by the pair of substrates obtained in the above (4-2) or (4-3). The voltage applied here can be, for example, direct current or alternating current of 5 to 50 V. Further, as the light to be irradiated, for example, ultraviolet rays and visible light containing light of a wavelength of 150 to 800 nm, and preferably ultraviolet rays containing light of a wavelength of 300 to 400 nm can be used. As the light source for irradiation, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. As the amount of light to be irradiated, 1000 to 200000 J / m2is preferable, and 10000 to 100000 J / m2is more preferable. 2 2

[0223] Further, a liquid crystal display element can be obtained by, as necessary, bonding a polarizing plate to the outer surface of the liquid crystal cell. As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called "H film" is sandwiched by cellulose acetate protective films, or a polarizing plate composed of the H film itself, which is obtained by stretching and orienting polyvinyl alcohol and absorbing iodine therein, can be used.

[0224] The liquid crystal display element of the present application can be effectively applied to various devices, and for example, can be used for clocks, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs (Personal Digital Assistants), digital cameras, portable telephones, smartphones, various monitors, liquid crystal televisions, information displays, and the like.

[0225] Examples

[0226] Hereinafter, the present application will be specifically described by citing examples, but the present application is not limited to these examples. Note that the abbreviations of the compounds and solvents are as described below.

[0227] (Organic solvents)

[0228] NMP: N-methyl-2-pyrrolidone

[0229] GBL: γ-butyrolactone

[0230] BCS: ethylene glycol monobutyl ether

[0231] (Diamines)

[0232] DA-1 to DA-7: Compounds represented by the following structural formulas (DA-1) to (DA-7), respectively.​​

[0233] (Tetracarboxylic acid derivative)

[0234] CA-1 to CA-3: Compounds represented by the following structural formulas (CA-1) to (CA-3), respectively.

[0235] (Diisocyanate)

[0236] DI-1: 4,4'-diphenylmethane diisocyanate.

[0237] (Diol)

[0238] EG-1: Polyethylene Glycol 400 (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in which R is a hydrogen atom and n is 5 or more in formula (EG)).

[0239] EG-2: Polyethylene Glycol 600 (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in which R is a hydrogen atom and n is 5 or more in formula (EG)).

[0240] EG-3: Ethylene Glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in which R is a hydrogen atom and n is 1 in formula (EG)).

[0241] EG-4: Diethylene Glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in which R is a hydrogen atom and n is 2 in formula (EG)).

[0242] EG-5: Tetraethylene Glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in which R is a hydrogen atom and n is 4 in formula (EG)).

[0243] (Capping agent)

[0244] Boc20: Di-tert-butyl dicarbonate.

[0245] (Additive)

[0246] AD-1 to AD-3: Compounds represented by the following structural formulas (AD-1) to (AD-3), respectively.

[0247]

[0248] <Viscosity>

[0249] In the synthesis examples, the viscosity of the polymer solution was measured using a viscometer, Model E, TVE-22H (manufactured by Tokimec, Inc.), with a sample amount of 1.1 mL, a cone rotor TE-1 (1° 34', R24), and at a temperature of 25°C.

[0250] <Measurement of Imidization Rate of Polyimide>

[0251] The imidization rate of the polyimide in the synthesis examples was measured as follows. To an NMR (nuclear magnetic resonance) sample tube (NMR standard sample tube, φ 5 (manufactured by Sono Science Co., Ltd.)) was added 30 mg of polyimide powder, and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) (0.53 mL) was added, and the mixture was completely dissolved by applying ultrasonic waves. The solution was measured for proton NMR at 500 MHz using an NMR measuring device (JNW-ECA500) (manufactured by JEOL DATUM Co., Ltd.). For the imidization rate, a proton derived from a structure that does not change before and after imidization was determined as a reference proton, and the imidization rate was calculated using the peak integral value of this proton and the peak integral value of the proton derived from the NH group of the amic acid appearing near 9.5 ppm to 10.0 ppm, by the following equation.

[0252] Imidization rate (%) = (1 - α • x / y) x 100

[0253] In the above equation, x is the peak integral value of the proton derived from the NH group of the amic acid, y is the peak integral value of the reference proton, and α is the number ratio of the reference proton to one NH group proton of the amic acid in the case of polyamic acid (imidization rate of 0%).

[0254] [Synthesis of Polymer]

[0255] (Synthesis Example 1)

[0256] Into a 100 mL eggplant-shaped flask equipped with a stirring device and a nitrogen introduction tube were measured DA-1 (8.02 g, 28.0 mmol) and NMP (58.8 g), and the mixture was dissolved while stirring under nitrogen. While stirring the diamine solution under water cooling, CA-1 (5.11 g, 26.0 mmol) and NMP (37.4 g) were added, and the mixture was stirred for 2 hours under a nitrogen atmosphere, whereby a solution of the polymer (polymer-1) was obtained (viscosity: 182 mPa-s).

[0257] (Synthesis Examples 2 to 5)

[0258] Using the diamines and tetracarboxylic acid derivatives shown in Table 1 below, a solution of polymers (polymer-2) to (polymer-5) shown in Table 1 below was obtained in the same order as in Synthesis Example 1, except that. In Table 1, the numerical value written under the name of the compound indicates the mass of each compound used for the synthesis.

[0259] [Table 1]

[0260]

[0261] (Synthesis Example 6)

[0262] Into a 100 mL eggplant-shaped flask equipped with a stirrer and a nitrogen inlet tube, DA-2 (6.84 g, 28.0 mmol) and NMP (61.6 g) were charged, and dissolved with stirring while supplying nitrogen. While stirring the diamine solution under water cooling, CA-2 (4.52 g, 20.2 mmol) and NMP (21.7 g) were added, and stirring was performed at 40°C for 2 hours under a nitrogen atmosphere. Further, DI-1 (1.40 g, 5.60 mmol) and NMP (10.3 g) were added, and stirring was performed at 23°C for 2 hours under a nitrogen atmosphere, to obtain a solution of a polymer (polymer-6) (viscosity: 242 mPa-s).

[0263] (Synthesis Example 7)

[0264] Into a 200 mL eggplant-shaped flask equipped with a stirrer and a nitrogen inlet tube, DA-5 (8.04 g, 40.2 mmol), DA-6 (4.36 g, 10.9 mmol), DA-7 (12.2 g, 21.9 mmol), and NMP (98.4 g) were charged, and dissolved with stirring while supplying nitrogen. While stirring the diamine solution under water cooling, CA-3 (9.40 g, 47.5 mmol) and NMP (37.6 g) were added, and stirring was performed at 50°C for 2 hours under a nitrogen atmosphere. Further, CA-1 (4.65 g, 23.7 mmol) and NMP (18.6 g) were added, and stirring was performed at 23°C for 2 hours under a nitrogen atmosphere, to obtain a solution of a polyamic acid (PAA-I) (viscosity: 1230 mPa-s).

[0265] Into a 200 mL Erlenmeyer flask equipped with a stirrer, the above-obtained solution of a polyamic acid (PAA-I) (100 g) was added, and Boc20 (1.24 g, 5.68 mmol) was added, and stirring was performed at 40°C for 15 hours, to obtain a solution of a capped polyamic acid (PAA-I-1).

[0266] To a 200 mL flask equipped with a stirrer, the above solution of (PAA-I-I) (100 g) was added, followed by NMP (66.7 g), acetic anhydride (14.2 g), and pyridine (4.70 g). After stirring at room temperature for 30 minutes, the mixture was allowed to react at 60°C for 4 hours. The reaction solution was poured into methanol (650 g), and the resulting precipitate was filtered off. The precipitate was washed with methanol, and then dried under reduced pressure at 80°C to obtain a polyimide powder (imide conversion: 90%).

[0267] Further, to a 100 mL flask equipped with a stirrer, the polyimide powder (9.60 g) was added, followed by NMP (70.4 g). The mixture was stirred at 70°C for 24 hours to dissolve, and a solution of polyimide (polymer-7) was obtained (viscosity: 76 mPa-s).

[0268] (Synthetic Example 8)

[0269] To a 100 mL flask equipped with a stirrer and a nitrogen inlet tube, EG-I (4.80 g, 12.0 mmol) and NMP (7.20 g) were added, and the mixture was stirred while being supplied with nitrogen to dissolve. While stirring the solution under water cooling, DI-I (2.97 g, 11.9 mmol) and NMP (4.50 g) were added, and the mixture was stirred under a nitrogen atmosphere for 2 hours. After the reaction, NMP (58.3 g) was added to obtain a solution of polymer (polymer-8) (viscosity: 12 mPa-s).

[0270] (Synthetic Examples 9 to 12)

[0271] Using the diisocyanates and diols shown in Table 2 below, a solution of polymers (polymer-9) to (polymer-12) shown in Table 2 below was obtained in the same order as in Synthetic Example 8. In Table 2, the numerical value written under the compound name indicates the mass of each compound used for the synthesis.

[0272] [Table 2]

[0273]

[0274] [Preparation of liquid crystal alignment agent]

[0275] (Example 1)

[0276] A solution (5.83 g) of the polymer (polymer-1) obtained in Synthesis Example 1 and a solution (0.28 g) of the polymer (polymer-7) obtained in Synthesis Example 7 were measured into a 50 mL flask equipped with a stirrer, NMP (0.59 g), GBL (9.30 g), and BCS (4.00 g) were added, and stirring was performed at room temperature for 2 hours, whereby a liquid crystal aligning agent (1) was obtained.

[0277] (Examples 2 to 12, Comparative Examples 1 to 12)

[0278] The kind and amount of the polymer solution, solvent, and additive used were changed as shown in Table 3 below, and the same operation as in Example 1 was performed, whereby liquid crystal aligning agents (2) to (24) were obtained. Note that, of the additives in Table 3, AD-1 to AD-3 were each added in the form of a solution of 10 mass% of AD-1 to AD-3 in NMP. In the case where the additives (AD-1 to AD-3, EG-1 to EG-2) were added, the additives were added before NMP, GBL, and BCS were added.

[0279] [Table 3]

[0280]

[0281] [Manufacture of liquid crystal display element]

[0282] A liquid crystal cell having a configuration of a liquid crystal display element of a fringe field switching (FFS) mode was manufactured.

[0283] First, a substrate with electrodes was prepared. A glass substrate having a size of 35 mm x 40 mm and a thickness of 0.7 mm was used as the substrate. On the substrate, an ITO electrode having a pattern in a dense state was formed as a first layer to constitute a counter electrode, and a SiN (silicon nitride) film formed by a CVD (chemical vapor deposition) method was formed as a second layer on the counter electrode of the first layer. The SiN film of the second layer was a film having a film thickness of 500 nm that functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an ITO film was arranged as a third layer, and two kinds of pixels, a first pixel and a second pixel, were formed, each of the pixels having a size of 10 mm in length and about 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer were electrically insulated by the SiN film of the second layer.

[0284] The pixel electrode of the third layer had a comb shape in which a plurality of electrode elements having a width of 3 μm curved at an inner angle of 160° were arranged in parallel at an interval of 6 μm, and one pixel had a first region and a second region with a line linking the curved portions of the plurality of electrode elements as a boundary.

[0285] When the first region and the second region of each pixel are compared, the electrode elements constituting the pixel electrodes differ in the direction of formation. That is, in the case where the rubbing direction of the liquid crystal alignment film described later is taken as a reference, the electrode elements formed as pixel electrodes in the first region of the pixel are at an angle of +10° (clockwise), and the electrode elements formed as pixel electrodes in the second region of the pixel are at an angle of -10° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotational movement (in-plane switching) of the liquid crystal in the substrate plane due to the application of voltage between the pixel electrode and the counter electrode are in opposite directions.

[0286] Next, the liquid crystal alignment agent obtained in the above was filtered using a filter having a pore size of 1.0 μm, and then applied to the surface of the substrate (first glass substrate) with electrodes prepared in the above and the surface of a glass substrate (second glass substrate) having a columnar spacer with a height of 4 μm and having an ITO film formed on the back surface, by the spin coating method. Next, after drying on a hot plate at 80°C for 2 minutes, baking was performed in a hot air circulation oven at 230°C for 30 minutes, to obtain a substrate with a liquid crystal alignment film having a film thickness of 60 nm. After rubbing (roll diameter: 120 mm, roll rotation speed: 1000 rpm, moving speed: 20 mm / sec, pressure-in length: 0.4 mm) the surface of the substrate with the liquid crystal alignment film using a rayon cloth (Yoshikawa Chemical Co., Ltd. YA-20R), cleaning was performed by ultrasonic irradiation in pure water for 1 minute, and after removing water droplets by air blowing, drying was performed at 80°C for 15 minutes, to obtain a substrate with a liquid crystal alignment film. Two substrates with the liquid crystal alignment film obtained were used as one set, and a sealant (Mitsui Chemicals, Inc. XN-1500T) was printed on the substrates in a manner so as to leave a liquid crystal injection port, and the other substrate was attached in a manner so that the liquid crystal alignment film faces each other and the rubbing directions are antiparallel. Then, heat treatment was performed at 150°C for 60 minutes to cure the sealant, and an empty cell having a cell gap of 4 μm was produced. Liquid crystal MLC-7026 (MERCK) was injected into the empty cell by the reduced pressure injection method, the injection port was sealed, and a liquid crystal display element of the FFS mode was obtained. Then, the liquid crystal display element obtained was heated at 120°C for 1 hour, and left at 23°C overnight, and used for evaluation.

[0287] [Evaluation of residual image characteristics based on long-term AC drive]

[0288] The FFS drive liquid crystal cell produced in the above was subjected to application of an AC voltage of ±5.8 V at a frequency of 60 Hz for 120 hours in a constant temperature environment at 60°C. Then, the liquid crystal cell was left in a state where the pixel electrode and the counter electrode were in a short-circuit state, and left in this state at room temperature for one day.

[0289] The deviation of the alignment direction of the liquid crystal in the first region of the pixel from the alignment direction of the liquid crystal in the second region of the pixel in the state where no voltage is applied was calculated as an angle Δθ with respect to the liquid crystal cell subjected to the above-mentioned treatment.

[0290] Specifically, the liquid crystal cell was disposed between two polarizing plates disposed in a manner that the polarizing axes were orthogonal, the backlight was lit, the disposition angle of the liquid crystal cell was adjusted so that the transmitted light intensity of the first region of the pixel was minimized, and then the rotation angle (Δθ) required to rotate the liquid crystal cell so that the transmitted light intensity of the second region of the pixel was minimized was found. It can be said that the smaller the value of the rotation angle, the better the residual image characteristics based on long-term AC driving. Specifically, in the case where the rotation angle was 0.15 degrees or less, it was evaluated as "O", if it exceeded 0.15 degrees and was 0.25 degrees or less, it was evaluated as "Δ", and in the case where it exceeded 0.25 degrees, it was evaluated as "X". The results are shown in Table 4.

[0291] [Membrane strength evaluation]

[0292] The liquid crystal alignment agent filtered with a filter having a pore size of 1.0 μm was applied to the ITO surface of a glass substrate having an ITO electrode on the entire surface by spin coating, and dried on a hot plate at 80°C for 2 minutes. Then, baking was performed in a hot air circulation oven at 230°C for 30 minutes to obtain a substrate having a liquid crystal alignment film with a thickness of 60 nm. The liquid crystal alignment film was brushed with a rayon cloth (roll diameter: 120 mm, roll rotation speed: 1000 rpm, moving speed: 20 mm / sec, pressure-in length: 0.6 mm). The haze value of the substrate was measured using a HZ-V3 haze meter manufactured by Suga Test Instruments Co. It can be said that the smaller the haze value, the less the film is ground, that is, the higher the film strength. If the value of the haze was 0.1 or less, it was evaluated as "O", if the value of the haze exceeded 0.1 and was 0.2 or less, it was evaluated as "Δ", and in the case where the value of the haze exceeded 0.2, it was evaluated as "X". The results are shown in Table 4.

[0293] [Table 4]

[0294]

[0295] [Evaluation of flicker generated at the time of driving]

[0296] The FFS mode liquid crystal display element produced in the above was disposed between two polarizing plates disposed in a manner that the polarizing axes were orthogonal, and the backlight was lit in a state where no voltage was applied (light source: LED, luminosity: 20000 cd / m2, voltage: 5 V, frequency: 60 Hz). The transmitted light intensity of the first region of the pixel and the transmitted light intensity of the second region of the pixel were measured with a spectrophotometer (UV-3100 manufactured by Shimadzu Corporation). The results are shown in Table 4. 2), the alignment angle of the liquid crystal cell was adjusted to minimize the luminance of the transmitted light. Next, a V-T curve (voltage-transmittance curve) was measured while applying an alternating voltage of 30 Hz to the liquid crystal cell, and the alternating voltage at which the relative transmittance became 23% was calculated as the driving voltage.

[0297] In the flicker measurement, the backlight that was previously turned on was temporarily turned off, and after the light-blocking was left for 72 hours, the backlight was turned on again. At the same time as the start of the turning on of the backlight, an alternating voltage of 30 Hz at which the relative transmittance became 23% was applied, and the liquid crystal cell was driven for 60 minutes, and the flicker amplitude was tracked. In terms of the flicker amplitude, the transmitted light of the backlight that passed through two polarizing plates and the liquid crystal cell therebetween was read by a data logger switch unit 34970A (manufactured by Agilent technologies) connected via a photodiode and an I-V conversion amplifier. The value calculated based on the data using the following formula was used as the flicker level.

[0298] Flicker level (%) = {flicker amplitude / (2 x z)} x 100

[0299] In the above formula, z is the value of the luminance when driven by the alternating voltage of 30 Hz at which the relative transmittance became 23% that was read by the data logger switch unit 34970A.

[0300] The above evaluation of the flicker was performed under a temperature condition in which the temperature of the liquid crystal cell was 40°C, and the value at 30 minutes from the time point at which the backlight was turned on and the alternating voltage was applied was used as the flicker level (%). The results are shown in Table 5.

[0301] It can be said that the smaller the flicker level, the better the flicker characteristics.

[0302] [Table 5]

[0303]

[0304] By using the liquid crystal alignment agent of the embodiment of the present application, a liquid crystal display element having excellent liquid crystal alignment properties (i.e., excellent AC image sticking characteristics) was obtained.

[0305] Furthermore, the film hardness of the liquid crystal alignment agent described in the embodiment of the present application is good, and thus the film is not easily abraded during brushing treatment.

[0306] Moreover, the liquid crystal alignment agent to which the crosslinkable compound was added as an additive showed good flicker characteristics.

[0307] Note that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2021-004434 filed on January 14, 2021 and the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2021-176483 filed on October 28, 2021 are hereby incorporated by reference as the disclosure of the specification of the present application.

Claims

1. A polymer composition, characterized in that, (A) component and a (B) component, the (A) component: at least one polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (a) and a polyimide which is an imidized product of the polyimide precursor, the (B) component: a polyurethane having a repeating unit represented by the following formula (1) and not having a repeating unit represented by the formula (a) and an imidized structure thereof, In the formula (a), X represents a tetravalent organic group; Y represents a divalent organic group derived from a diamine; each of two R's independently represents a hydrogen atom or a monovalent organic group; each of two Z's independently represents a hydrogen atom or a monovalent organic group, In the formula (1), A1 is a divalent organic group derived from a diisocyanate; A2 is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxyl groups from an organic diol; at least one of A1 and A2 has a divalent organic group represented by the following formula (EG), In the formula (EG), n is an integer of 5 or more, and R represents a hydrogen atom or a methyl group.

2. The polymer composition according to claim 1, wherein In the formula (EG), n is an integer of 5 to 40.

3. The polymer composition according to claim 1 or 2, wherein Y in the formula (a) is a divalent organic group derived from a diamine selected from the group consisting of a diamine represented by the following formula (O), a diamine having an amide bond or a urea bond, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, a diamine represented by the following formula (d o ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and a diamine having a group "-N(D)-" in which D represents a protective group of a hydrogen atom to be detached by heating, In formula (O), Ar represents a divalent benzene ring, a biphenyl structure, or a naphthalene ring; two Ar's are optionally the same or different, any hydrogen atom of the benzene ring, biphenyl structure, or naphthalene ring is optionally substituted with a monovalent group; p is an integer of 0 or 1; Q2 represents - (CH2) n -, or a group in which at least a part of -CH2- of the - (CH2) n - is substituted with any of -O-, -C(=O)-, or -O-C(=O)-, in formula (O) above, n is an integer of 2 to 18, and n -, in formula (O) above, n is an integer of 2 to 18, and In formula (d o ) in the case where m is two or more, each of the two or more m is optionally the same or different; one or more hydrogen atoms on the benzene ring is optionally replaced with a monovalent group.

4. The polymer composition according to claim 1 or 2, wherein A1in the formula (1) is a divalent organic group derived from a diisocyanate DI having a divalent organic group represented by the formula (EG) EG , an aromatic diisocyanate other than the diisocyanate DI EG , or an aliphatic diisocyanate other than the diisocyanate DI EG .

5. The polymer composition according to claim 4, wherein diisocyanates DI having a divalent organic radical of the formula (EG) EG are diisocyanates selected from the group consisting of 6. The polymer composition according to claim 4, wherein The aromatic diisocyanate other than the diisocyanate DI EG The aromatic diisocyanate other than the diisocyanate DI is an aromatic diisocyanate in which, in the diisocyanate structure, O=C=N-R-N=C=O, R is an organic group having a carbon atom number of 6 to 30 which does not have the divalent organic group shown in the formula (EG) and has at least one benzene ring. The aliphatic diisocyanate other than the diisocyanate DI EG The aliphatic diisocyanate other than the diisocyanate DI is an aliphatic diisocyanate in which, in the diisocyanate structure, O=C=N-R-N=C=O, R is an organic group having 4 to 30 carbon atoms having an aliphatic group and not having the divalent organic group and the aromatic group shown by the formula (EG).

7. The polymer composition according to claim 1 or 2, wherein the organic diol in the formula (1) is a diol containing the divalent organic group represented by the formula (EG).

8. The polymer composition according to claim 7, wherein the diol containing the divalent organic group represented by the formula (EG) is a diol in which hydrogen atoms are bonded to both ends of the divalent organic group represented by the formula (EG).

9. The polymer composition according to claim 1 or 2, wherein X in the formula (a) is a tetravalent organic group derived from a non-cyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a tetravalent organic group derived from an alicyclic tetracarboxylic dianhydride or a derivative thereof, or a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof.

10. The polymer composition according to claim 1 or 2, wherein X in the formula (a) is a tetravalent organic group derived from a tetracarboxylic dianhydride represented by the following formula (t) or a derivative thereof, In the formula (t), X1 is a structure selected from the following formulas (X1-1) to (X1-25); * represents a bonding bond, In the formulae (X1-1) to (X1-4), R1to R 21 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms which contains a fluorine atom, or a phenyl group; * represents a bonding bond, In the formulas (X1-24) to (X1-25), j and k are integers of 0 or 1, and each of A1 and A2 independently represents a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amido; a plurality of A2's are each optionally the same or different.

11. The polymer composition according to claim 1 or 2, wherein the polymer (A) further has a repeating unit represented by the following formula (U), In the formula (U), U1 is a divalent organic group, U1' is a divalent organic group derived from a diamine, and each of C1 and C1' is independently a hydrogen atom or a monovalent organic group.

12. The polymer composition according to claim 1 or 2, wherein Polymer (A) is a polymer capped at the terminal.

13. The polymer composition according to claim 1 or 2, wherein The proportion of the repeating unit represented by formula (1) is 10 mol% or more of the entire repeating unit constituting the polyurethane.

14. The polymer composition according to claim 1 or 2, wherein The polymer composition further contains at least one additive component selected from the group consisting of a cross-linking compound, a functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, an antioxidant, a sensitizer, a preservative, and a compound for adjusting the dielectric constant and resistance of a resin film.

15. The polymer composition according to claim 1 or 2, wherein The polymer composition further contains at least one cross-linking compound selected from the group consisting of a cross-linking compound (c-1) having at least one substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group, a cyclic carbonate group, a blocked isocyanate group, a hydroxyl group, and an alkoxy group, and a cross-linking compound (c-2) having a polymerizable unsaturated group.

16. The polymer composition according to claim 15, wherein The cross-linking compound is a compound represented by any one of the following formulae (CL-1) to (CL-12), 17. A liquid crystal alignment agent formed from the polymer composition according to any one of claims 1 to 16.

18. A resin film obtained using the polymer composition according to any one of claims 1 to 16.

19. A liquid crystal alignment film formed using the liquid crystal alignment agent according to claim 17.

20. A liquid crystal display element provided with the liquid crystal alignment film according to claim 19.

21. A method for producing a liquid crystal display element, comprising the following steps 1 to 3, Step 1: a step of applying the liquid crystal alignment agent according to claim 17 to a substrate; Step 2: a step of baking the applied liquid crystal alignment agent to obtain a film; Step 3: a step of performing an alignment treatment on the film obtained in Step 2.

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