TW202330691A - Polymer composition, liquid crystal aligning agent, resin film, liquid crystal alignment film, method for producing liquid crystal display element, and liquid crystal display element - Google Patents

Abstract

The present invention provides a polymer composition that is suitable for a liquid crystal aligning agent which enables the achievement of a liquid crystal alignment film that has excellent resistance to an AC afterimage and a low pretilt angle. This polymer composition is characterized by containing the following (A) component and (B) component. (A) component: at least one polymer (A) which is selected from the group consisting of a polyimide precursor having a repeating unit represented by formula (a) and a polyimide that is an imidized product of the polyimide precursor. (B) component: a polyester (B) which has a repeating unit represented by formula (b1) but does not have the repeating unit represented by formula (a) and an imidized structure thereof. Formula (a) (The definition of each symbol is as described in the description.) Formula (b1) (The definition of each symbol is as described in the description.).

Description

Polymer composition, liquid crystal alignment agent, resin film, liquid crystal alignment film, manufacturing method of liquid crystal display element, and liquid crystal display element

The present invention 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.

Liquid crystal display components used in LCD TVs, navigators, smart phones, etc., usually have a liquid crystal alignment film to control the alignment state of the liquid crystal. The liquid crystal alignment film has the function of controlling the alignment of the liquid crystal molecules in the liquid crystal display element to a certain direction. For example, a liquid crystal display element has a structure in which liquid crystal molecules forming a liquid crystal layer are sandwiched between liquid crystal alignment films formed on the respective surfaces of a pair of substrates. Liquid crystal molecules are aligned in a certain direction due to the liquid crystal alignment film, and respond due to voltage application to electrodes provided between the substrate and the liquid crystal alignment film. As a result, the liquid crystal display element displays a desired image by utilizing the alignment change due to the response of the liquid crystal molecules. So far, the liquid crystal alignment film mainly uses polyamic acid (polyamic acid) and other polyimide precursors and soluble polyimide solutions, which are mainly composed of liquid crystal alignment agents coated on glass substrates, etc. and calcined. Imide-based liquid crystal alignment film. In recent years, with the high performance of liquid crystal display elements, in addition to large-screen and high-definition LCD TVs, it will also be used in automotive applications, such as car navigation systems, instrument panels, surveillance cameras, and medical camera screens. For liquid crystal display elements, in consideration of viewing angle characteristics, transverse electric field methods such as IPS (In Plane Switching) method and FFS (Fringe Field Switching) method have been discussed (Patent Document 1). [Prior Art Literature] [Patent Document]

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

(Problem to be solved by the invention)

The liquid crystal alignment film used in the liquid crystal display elements of the IPS driving method and the FFS driving method needs to have an alignment regulation force for suppressing image sticking (hereinafter also referred to as AC image sticking) caused by long-term AC driving. In liquid crystal display elements that are rapidly becoming higher in definition, high display quality is regarded as important, and the specifications for display defects called "image sticking" are becoming increasingly strict. In addition, with the application of liquid crystal display elements in automotive applications, such as car navigation systems, instrument panels, surveillance cameras, and medical camera screens, a lower pretilt angle is required from the perspective of improving viewing angle characteristics.

In view of the above circumstances, the present invention aims to provide a polymer composition suitable for a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film having excellent resistance to AC sticking and a low pretilt angle, the liquid crystal alignment agent, the liquid crystal alignment film, And a liquid crystal display element with the liquid crystal alignment film. (How to solve the problem)

The inventors of the present invention have studied diligently to achieve the above-mentioned object, and as a result, have found that forming a resin film using a polymer composition containing a specific component is effective for achieving the above-mentioned object, and have completed the present invention.

This invention is based on this knowledge, and makes the following matters into the summary. A polymer composition, characterized by containing the following (A) component and (B) component, (A) component: polymer (A), selected from polyimide precursors having repeating units represented by the following formula (a) and at least one of the group consisting of polyimide which is an imidate of the polyimide precursor, (B) component: polyester (B), having the repetition represented by the following formula (b1) unit and does not have the repeating unit represented by the formula (a) and its imidization structure, [Chem. 1] X represents a tetravalent organic group, Y represents a divalent organic group derived from diamine, two Rs each independently represent a hydrogen atom or a monovalent organic group, and two Zs each independently represent a hydrogen atom or a monovalent organic group, [Chem. 2] X _ar represents a 4-valent organic group derived from an aromatic tetracarboxylic dianhydride or its derivatives, the two Rs independently represent a hydrogen atom or a 1-valent organic group, and E contains two hydroxyl groups removed from an organic diol. A divalent organic group of a hydrogen atom, the organic diol contains a divalent organic group represented by the following formula (EG), [Chemical 3] n is an integer of 5 or more, and R represents a hydrogen atom or a methyl group. (Effect of Invention)

According to the present invention, a polymer composition of a liquid crystal alignment agent suitable for obtaining a liquid crystal alignment film having excellent resistance to AC sticking and a low pretilt angle, the liquid crystal alignment agent, the liquid crystal alignment film, and a liquid crystal alignment film having the liquid crystal alignment film can be obtained. The liquid crystal display element. In addition, this liquid crystal display element has high display quality with few display defects. The mechanism for obtaining the above-mentioned effects of the present invention is not necessarily clear, but it is roughly estimated as follows. That is, by introducing a specific alkylene glycol chain into a specific polyester, the elongation of the film is improved and the flatness of the film surface is improved, so it is considered that the above effects can be obtained.

Each component contained in the polymer composition of the present disclosure and other components arbitrarily blended as necessary will be described below. In the present specification, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Boc represents tertiary butoxycarbonyl.

＜Polymer (A)＞ The polymer composition of the present invention contains a polyimide precursor (hereinafter also referred to as polyimide precursor (A)) selected from a repeating unit represented by the above formula (a) and is the polyimide At least one polymer (A) in the group consisting of polyimide which is an imide of an amine precursor. The polymer (A) may be one type or two or more types.

(repeating unit represented by formula (a)) In the above formula (a), Y represents a divalent organic group derived from diamine. Also, the divalent organic group derived from diamine is, for example, a divalent organic group in which two amine groups were removed from diamine. The following diamines are mentioned as this diamine. These diamines may be used alone or in combination of two or more.

Diamines represented by the following formula (O); diamines with photoalignment groups such as 4,4'-diaminoazobenzene or diaminodiphenylacetylene (diaminotolan); the following formula (h-1)~ Diamines represented by (h-6) have amide bonds or urea bonds; 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 4,4'-diaminodiphenylketone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl ) benzene, 1,4-bis(4-aminobenzyl)benzene, diamine represented by the following formula (d _o ); 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4 -Diaminopyrimidine, 3,6-diaminoxazole, N-methyl-3,6-diaminoxazole, 1,4-bis-(4-aminophenyl)-guanidine, 3 ,6-Diaminoacridine, N-ethyl-3,6-diaminoxazole, N-phenyl-3,6-diaminoxazole, N-[3-(1H-imidazole-1 -yl)propyl]3,5-diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2 -oxazolyl]-aniline, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-2-oxazolyl]-aniline, 1,4-bis(p- Aminobenzyl)guanidine, 4,4'-propane-[1,3-diylbis(piperidine-1,4-diyl)]diphenylamine, 4-(4-aminophenoxycarbonyl) -1-(4-aminophenyl)piperidine, 2,5-bis(4-aminophenyl)pyrrole, 4,4'-(1-methyl-1H-pyrrole-2,5-diyl ) bis[aniline], 1,4-bis-(4-aminophenyl)-guanidine, 2-N-(4-aminophenyl)pyridine-2,5-diamine, 2-N-( 5-aminopyridin-2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-6 -Aminobenzimidazole, 5-(1H-benzimidazol-2-yl)benzene-1,3-diamine, or diamine represented by the following formula (z-1) ~ formula (z-5), etc. Heterocyclic diamine, or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)- Benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'- Diamines with a diphenylamine structure such as dimethyl-1,4-phenylenediamine, which have at least one nitrogen-containing atom selected from the group consisting of nitrogen-containing heterocycles, secondary or tertiary amine groups Diamine of the structure (but not including the amine group derived from -N(D)-(D represents a protecting group that will be removed by heating and replaced by a hydrogen atom. Hereinafter, it is also referred to as a specific structure containing a nitrogen atom.) ;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, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane- 3-Carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diamine Diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-bis Formic acid, 1,2-bis(4-aminophenyl)ethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid, etc. Amine; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl- 1H-indane-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine; methacrylic acid 2 -(2,4-diaminophenoxy)ethyl ester and 2,4-diamino-N,N-diallylaniline and other diamines with photopolymerizable groups at the end; cholestanyloxy -3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-diaminobenzene Cholesteryl formate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate and 3,6-bis(4-aminobenzoyloxy) Diamines having a steroid skeleton such as cholestane; diamines represented by the following formulas (V-1)~(V-2); having a group "-N(D)-" (D means that it will be detached by heating and replaced by The protecting group for hydrogen atom is preferably tert-butoxycarbonyl. ) diamine, preferably the diamine represented by the following formula (d-1)~(d-7); 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, the following formula Diamine represented by (Ds-1) and other diamines with siloxane bonds; m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylene Methyldiamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), International Publication No. 2018 Diamine, etc. in which two amine groups are bonded to the group represented by any one of the formulas (Y-1) to (Y-167) described in No. 117239.

[chemical 4] Ar represents a divalent benzene ring, a biphenyl structure, or a naphthalene ring. The two Ars may be the same or different, and any hydrogen atom of the above-mentioned benzene ring, biphenyl structure, or naphthalene ring may be substituted by a monovalent group. p is an integer of 0 or 1. Q ₂ represents -(CH ₂ ) _n - (n is an integer from 2 to 18.), or at least a part of -CH ₂ - of the -(CH ₂ ) _n - is replaced by -O-, -C(=O)- or a group substituted by any of -OC(=O)-.

[chemical 5]

[chemical 6] In the formula (z-2), the two ms may be the same or different.

[chemical 7] When there are two or more m, each of the two or more m may be the same or different. One or more hydrogen atoms on the benzene ring may be substituted by a monovalent group.

[chemical 8] In formula (V-1), m and n each independently represent an integer of 0 to 3 (only if 1≦m+n≦4), j is an integer of 0 or 1, and X ¹ represents -(CH ₂ ) _a -( a is an integer from 1 to 15.), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ -OCO-, - COO-, or -OCO-. ^R1 represents a fluorine atom, an alkyl group containing a fluorine atom with 1 to 10 carbons, an alkoxy group with a fluorine atom with 1 to 10 carbons, an alkyl group with 3 to 10 carbons, and an alkoxy group with 3 to 10 carbons group, or an alkoxyalkyl group with 3 to 10 carbon atoms. When two of m, n, X ¹ , and R ¹ exist, each independently has the above definition. In formula (V-2), X ² represents -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO-, or -OCO-. [chemical 9] In formulas (d-2), (d-6) and (d-7), R is a hydrogen atom, or -(CH ₂ ) _k -Boc (k is an integer of 0 to 3. Also, when k is 0, (CH ₂ ) _k represents a single bond. [Chem. 10]

In the above formula (d _o ), the monovalent group includes a halogen atom, an alkyl group with 1 to 10 carbons, an alkenyl group with 2 to 10 carbons, an alkoxy group with 1 to 10 carbons, and an alkoxy group with 1 to 10 carbons. Fluoroalkyl, fluoroalkenyl with 2 to 10 carbons, fluoroalkoxy with 1 to 10 carbons, carboxyl, hydroxyl, alkoxycarbonyl with 1 to 10 carbons, cyano, nitro, etc. For the diamine represented by the above formula (d _o ), considering the viewpoint of improving the liquid crystal alignment, the diamine represented by the following formula (d _o -1)~(d _o -6), 3,3'-diaminodiphenyl Ether, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether are preferable. [chemical 11]

In the diamine represented by the above formula (O), arbitrary hydrogen atoms of a benzene ring, a biphenyl structure, or a naphthalene ring may be substituted with a monovalent group. The above monovalent groups, for example: halogen atom, alkyl group with 1~10 carbons, alkenyl group with 2~10 carbons, alkoxyl group with 1~10 carbons, fluoroalkyl group with 1~10 carbons, Fluoroalkenyl with 2 to 10 carbons, fluoroalkoxy with 1 to 10 carbons, alkoxycarbonyl with 1 to 10 carbons, cyano, nitro, etc.

For the diamine represented by the above formula (O), considering the viewpoint of improving the liquid crystal alignment, the following formulas (o-1)~(o-8), p-phenylenediamine, 2,3,5,6-tetramethyl Base-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-p-phenylenediamine, 1,4-diamino-2,5-di Methoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(6-amino-2-naphthyl)ethylamine, 2,2' -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4' -Diaminobiphenyl, 3-trifluoromethyl-4,4'-diaminobiphenyl, 2-trifluoromethyl-4,4'-diaminobiphenyl, 3-fluoro-4,4 '-Diaminobiphenyl, 2-fluoro-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro- 4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4, 4'-Diaminobiphenyl, 3,4'-Diaminobiphenyl, 4,4'-Diaminobiphenyl, 3,3'-Diaminobiphenyl, 2,2'-Diaminobiphenyl Biphenyl, 2,3'-diaminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-diaminonaphthalene, Diamine represented by 2,6-diaminonaphthalene or 2,7-diaminonaphthalene is preferable.

[chemical 12] In formula (o-8), two ms may be the same or different.

The above-mentioned Y is preferably selected from diamines represented by the above formula (O), diamines having amide bonds or urea bonds, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane Phenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis (4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, diamine represented by the above formula (d _o ), 4-(2-(methylamino)ethyl)aniline , 4-(2-aminoethyl) aniline, and a group with "-N(D)-" (D represents a protecting group that will be removed by heating and replaced by a hydrogen atom, preferably tertiary butoxycarbonyl .) The divalent organic groups of diamines in the group consisting of diamines are preferred. It is preferable that the above-mentioned Y can achieve the effect of reducing afterimages caused by long-term AC driving by conforming to this configuration.

In the above formula (a), X represents a tetravalent organic group. X preferably represents a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof. Also, the tetravalent organic group derived from tetracarboxylic dianhydride or its derivatives is, for example, a tetravalent organic group in which four carboxyl groups have been removed from the corresponding tetracarboxylic acid. The 4-valent organic group can be exemplified by a 4-valent organic group derived from acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a 4-valent organic group derived from an alicyclic tetracarboxylic dianhydride or a derivative thereof, or a 4-valent organic group derived from an aromatic Quaternary organic group of tetracarboxylic dianhydride or its derivatives. Here, the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecularly dehydrating four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not need to be composed only of a chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure. The alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecularly dehydrating four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. But these four carboxyl groups are not bonded to the aromatic ring. Moreover, it does not need to consist only of an alicyclic structure, and a part may have a chain hydrocarbon structure and an aromatic ring structure. 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. However, it does not need to be composed only of an aromatic ring structure, and a part thereof may have a chain hydrocarbon structure or an alicyclic structure. As a derivative of the said tetracarboxylic dianhydride, a tetracarboxylic acid dihalide, a tetracarboxylic-acid dialkyl, or a tetracarboxylic-acid dialkyl dihalide is mentioned. This tetracarboxylic dianhydride or its derivative(s) may be used individually by 1 type, and may use it in combination of 2 or more types.

Among the above-mentioned non-cyclophatic aliphatic or alicyclic tetracarboxylic dianhydrides, or their derivatives, it is preferable to have a compound selected from the group consisting of cyclobutane ring structure, cyclopentane ring structure and Tetracarboxylic dianhydrides of at least one substructure in the group formed by the cyclohexane ring structure or derivatives thereof are preferred.

Said X is preferably a tetravalent organic group derived from tetracarboxylic dianhydride represented by the following formula (t) or a derivative thereof.

[chemical 13] In the formula, _X1 is a structure selected from the following formulas (X1-1)~(X1-25). * Indicates an atomic bond. Also, _X1 is a tetracarboxylic dianhydride represented by formula (t) of formulas (X1-1) to (X1-23), which is an example of acyclic aliphatic or alicyclic tetracarboxylic dianhydride. Also, _X1 is tetracarboxylic dianhydride represented by formula (t) of formulas (X1-24) to (X1-25), which is an example of aromatic tetracarboxylic dianhydride.

[chemical 14]

[chemical 15]

[chemical 16]

[chemical 17]

In the formulas (X1-1)~(X1-4), _R1 ~ _R21 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1~6 carbons, an alkenyl group with 2~6 carbons, or an alkenyl group with 2 carbons. ~6 alkynyl groups, monovalent organic groups with 1 to 6 carbon atoms containing fluorine atoms, or phenyl groups. * Indicates an atomic bond. Considering the viewpoint of improving liquid crystal alignment, R ₁ to R ₂₁ are preferably hydrogen atoms, halogen atoms, methyl groups, or ethyl groups, and hydrogen atoms or methyl groups are more preferable. In the formulas (X1-24)~(X1-25), j and k are integers of 0 or 1, and _A1 and _A2 each independently represent a single bond, -O-, -CO-, -COO-, phenylene group, sulfonyl group, or amido group. A plurality of A ₂ may each be the same or different.

Specific examples of the formula (X1-1) include the following formulas (1-1) to (1-6). In view of improving the liquid crystal alignment, formulas (1-1) and (1-2) are particularly preferable. ＊It is synonymous with the above.

[chemical 18]

Desirable specific examples of the above formulas (X1-24) and (X1-25) include the following formulas (X1-26) to (X1-41). ＊It is synonymous with the above. [chemical 19] [chemical 20]

Considering the point of view of improving liquid crystal alignment, the above _X1 is the above formula (X1-1)~(X1-10), (X1-18)~(X1-23), (X1-24)~(X1-25), Or (X1-26)~(X1-30) is more ideal, the above formula (X1-1), (X1-5), (X1-7)~(X1-10), (X1-21), (X1- 23), (X1-24)~(X1-25), or (X1-26)~(X1-30) are better, the above formula (1-1), (1-2), (X1-5), (X1-7), (X1-9), or (X1-26)~(X1-30) are more ideal.

In the above formula (a), the monovalent organic groups of R and Z include monovalent hydrocarbon groups with 1 to 20 carbon atoms, and the methylene groups of the hydrocarbon groups are represented by -O-, -S-, -CO-, -COO- , -COS-, -NR ³ - (only R ³ is a hydrogen atom or a monovalent hydrocarbon group with 1 to 10 carbons.), -CO-NR ³ - (only R ³ is a hydrogen atom or 1 to 10 carbons A monovalent hydrocarbon group.), -Si(R ³ ) ₂ - (except that R ³ is a hydrogen atom or a monovalent hydrocarbon group with a carbon number of 1 to 10.), -SO ₂ - and other substituted monovalent groups A, the monovalent At least one hydrogen atom bonded to a carbon atom of a hydrocarbon group or a monovalent group A is a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, or an alkoxysilyl group , silanol group, sulfinic acid group, phosphino group, carboxyl group, cyano group, sulfo group, acyl group and other substituted monovalent groups, monovalent groups with heterocyclic rings. Among the monovalent organic groups of R and Z in the above formula (a), alkyl with 1 to 10 carbons, alkenyl with 2 to 10 carbons, alkynyl with 2 to 10 carbons, tertiary butoxycarbonyl , or 9-fenylmethoxycarbonyl is more preferable, alkyl having 1 to 3 carbons is more preferable, and methyl is more preferable. Regarding R and Z, in view of obtaining the effects of the present invention, each independently preferably is a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably a hydrogen atom or a methyl group.

In the above formula (a), each of X, Y, R, and Z may be one type, or two or more types. The content ratio of the polymer (A) is preferably 70 to 99 parts by mass, more preferably 80 to 98 parts by mass, based on 100 parts by mass of the polymer composition.

(Repeating unit constituting polymer (A)) The polymer (A) in the present invention is selected from a polyimide precursor having a repeating unit represented by the above formula (a) and a polyimide that is an imide of the polyimide precursor At least one polymer in the group of . The polymer (A) may also have a repeating unit and a terminal group represented by the above formula (a).

Here, the terminal group refers to a group bonded to the terminal of the repeating unit constituting the above-mentioned polymer (A). Examples of terminal groups include amine groups, carboxyl groups, acid anhydride groups, isocyanate groups, and derivatives thereof. Amino groups, carboxyl groups, acid anhydride groups, and isocyanate groups can be obtained by a common condensation reaction, and the above-mentioned derivatives can be obtained, for example, by sealing a terminal group with a blocking agent as described later.

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

(Repeating Unit Represented by Formula (U)) The polymer (A) in the present invention may further have a repeating unit represented by the following formula (U). [chem 21] U ₁ is a divalent organic group, U _1' is a divalent organic group derived from diamine, and C ₁ and C _1' are each independently a hydrogen atom or a monovalent organic group.

In the above formula (U), U ₁ is a divalent organic group. Examples of _U1 include divalent organic groups derived from diisocyanate. These diisocyanates may be used alone or in combination of two or more. Here, diisocyanate includes, for example, aromatic diisocyanate and aliphatic diisocyanate. Here, "aromatic diisocyanate" refers to a diisocyanate having at least one aromatic group. Moreover, "aliphatic diisocyanate" means the diisocyanate which has an aliphatic group and does not have an aromatic group. U ₁ , for example: (i) from diisocyanate structure (O=C=NRN=C=O), R is an aromatic diisocyanate having at least one organic group with 6 to 30 carbon atoms in a benzene ring. or (ii) from a diisocyanate structure (O=C=NRN=C=O), where R is an aliphatic diisocyanate having an organic group of 4 to 30 carbon atoms having an aliphatic group and no aromatic group 2-valent organic group. Also, the aliphatic group includes any of acyclic aliphatic group and alicyclic group. Specific examples of _U1 include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate (for example: 2,4-toluene diisocyanate, 2, 6-diisocyanatotoluene), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 3,3'-dimethyl-4,4 '-Diisocyanate biphenyl, 4,4'-diisocyanate diphenyl ether, 2,2'-bis(4-diisocyanatophenyl) propane, 4,4'-diisocyanate diphenylmethane ( 4,4'-diphenylmethane diisocyanate), 4,4'-diisocyanate, 4,4'-diisocyanate, 3,3'-diisocyanate Divalent organic groups derived from aromatic diisocyanates such as phenylene and 2,2'-diisocyanate diphenyl ketone, isophorone diisocyanate, norcamphene diisocyanate, hexamethylene diisocyanate, tri Divalent organic group of aliphatic diisocyanate such as methylhexamethylene diisocyanate and tetramethylene diisocyanate.

In the above formula (U), U _1' is a divalent organic group derived from diamine. As diamine, the diamine exemplified for the above-mentioned repeating unit (a) can be mentioned, and the ideal aspect is the same as above.

In the above formula (U), the monovalent organic groups of C ₁ and C _1′ include structures exemplified by R and Z of the above repeating unit (a). Regarding C ₁ and C _1' , from the standpoint of obtaining the effect of the present invention, it is preferably independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the above formula (U), each of U ₁ , U _1' , C ₁ , and C _1' may be one type or two or more types.

When the polymer (A) in the present invention has a repeating unit represented by the above formula (U), in consideration of obtaining the effect of the present invention, the content ratio of the repeating unit represented by the formula (U) is relative to the above repeating unit (a ), the imidization structure of the repeating unit (a) and the total 100 mol% of the repeating unit represented by the above formula (U) is preferably 1-30 mol%, more preferably 2-25 mol%.

＜Polyester (B)＞ The polymer composition of the present invention contains a polyester (B) having a repeating unit represented by the above formula (b1) and not having a repeating unit represented by the above formula (a) and its imidized structure. The polyester (B) may be used alone or in combination of two or more.

In the above formula (b1), X _ar represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof. Moreover, an aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecularly dehydrating four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. However, it does not need to be composed only of an aromatic ring structure, and a part thereof may have a chain hydrocarbon structure or an alicyclic structure. X _ar in the above formula (b1) is preferably a tetravalent organic group derived from tetracarboxylic dianhydride represented by the following formula (t) or a derivative thereof. [chem 22] In the formula, _X1 is a structure selected from the following formulas (X1-24) and (X1-25). * Indicates an atomic bond. [chem 23] In the formulas (X1-24)~(X1-25), j and k are integers of 0 or 1, and _A1 and _A2 each independently represent a single bond, -O-, -CO-, -COO-, phenylene group, sulfonyl group, or amido group. A plurality of A ₂ may each be the same or different.

Desirable specific examples of the above formulas (X1-24) and (X1-25) include the following formulas (X1-26) to (X1-41). ＊It is synonymous with the above. [chem 24] [chem 25]

In the above formula (b1), E is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxyl groups from an organic diol containing a divalent organic group represented by the above formula (EG). The organic diol containing the divalent organic group represented by the above formula (EG) is not particularly limited as long as the molecule contains the above formula (EG), preferably a diol with hydrogen atoms bonded to both ends of the above formula (EG) ideal. Among the diols with hydrogen atoms bonded to both ends of the above formula (EG), the upper limit of n should be set as the upper limit of the weight average molecular weight of the diol to be 5,000 or less. The upper limit is more preferably 4,000 or less, and the upper limit of the weight average molecular weight of the diol is more preferably 3,000 or less. In view of improving the liquid crystal alignment, the upper limit of n is preferably 40, more preferably 30, and most preferably 20. The lower limit of n is considered to improve the liquid crystal alignment, 5 is more ideal, and 6 is more ideal. More specifically, diols containing a divalent organic group represented by the above formula (EG) include pentaethylene glycol, hexaethylene glycol, PEG-300, PEG-400, and PEG- 600, PEG-1000, PEG-1500, PEG-2000, PEG-4000N, PEG-4000S, PEG-6000E, PEG-6000P, PEG-10000, PEG-13000, PEG-20000; product name PEG300 manufactured by Merck, PEG1000, PEG2000, PEG4000, PEG6000, PEG8000, PEG10000, PEG12000, PEG20000, PEG35000; SIGMA-ALDRICH product number 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, 43 5422, 435457, 637726; trade name SINOPOL manufactured by China Japan Synthetic Chemical Co., Ltd. PEG600, SINOPOL PEG1500, SINOPOL PEG4000; trade names PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#1540, PEG#4000, PEG#6000M, Tokyo Chemicals, manufactured by LION SPECIALTY CHEMICALS The product names Polyethylene Glycol 400 and Polyethylene Glycol 600 of Kogyosha are commercially available. Ideal specific examples of diols with hydrogen atoms bonded to both ends of the above formula (EG) include pentaethylene glycol, hexaethylene glycol, and trade names PEG-300, PEG-400, and PEG manufactured by Sanyo Chemical Industry Co., Ltd. -600, PEG-1000, product name PEG300 manufactured by Merck, PEG1000, product name PEG300 manufactured by Merck, trade name SINOPOL PEG600 manufactured by Sino-Japanese Synthetic Chemicals, SINOPOL PEG1000, trade name PEG manufactured by LION SPECIALTY CHEMICALS Company # 300, PEG#400, PEG#600, PEG#1000, polyethylene glycol represented by the product name Polyethylene Glycol 400 and Polyethylene Glycol 600 of Tokyo Chemical Industry Co., Ltd., or pentapropylene glycol, hexapropylene glycol, polypropylene glycol (a better average Polypropylene glycol with an average molecular weight of 400-5,000.), a copolymer composed of ethylene oxide and propylene oxide with an average molecular weight of 500-5,000, etc. The aforementioned polyethylene glycol and polypropylene glycol may also be those obtained by anionic ring-opening polymerization of ethylene oxide and propylene oxide. The polymerization reaction can be carried out using water, ethylene glycol, propylene glycol, etc. and a catalyst amount of alkali (eg potassium hydroxide). In addition, the average molecular weight of the diol exemplified by the diol containing the divalent organic group represented by (EG) above is a weight average molecular weight based on polystyrene as measured by gel permeation chromatography (GPC).

The content ratio of the repeating unit represented by the above formula (b1) is preferably 10 mol% or more, more preferably 20 mol% or more, based on the total repeating units constituting the polyester (B). When other repeating units are contained, the upper limit is more preferably not more than 90 mol%, more preferably not more than 80 mol%.

(Repeating Unit Represented by Formula (b2)) The polyester (B) may further have a repeating unit represented by the following formula (b2). The polyester (B) may not have a repeating unit represented by the following formula (b2). [chem 26] A ₁ is a divalent organic group derived from diisocyanate. _A2 is a divalent organic group in which hydrogen atoms contained in two hydroxyl groups are removed from organic diol.

In the above formula (b2), A ₁ is a divalent organic group derived from diisocyanate. Also, the divalent organic group derived from diisocyanate is, for example, a divalent organic group obtained by removing two isocyanate groups (-N=C=O) from diisocyanate. These diisocyanates may be used alone or in combination of two or more. Here, diisocyanate includes, for example, diisocyanate (DI EG ) having a divalent organic group represented by the above formula ( _EG ), aromatic diisocyanate and aliphatic diisocyanate other than diisocyanate (DI _EG ). Here, "aromatic diisocyanate" refers to a diisocyanate having at least one aromatic group. Moreover, "aliphatic diisocyanate" means the diisocyanate which has an aliphatic group and does not have an aromatic group. The aforementioned diisocyanate (DI _EG ) includes, for example, the diisocyanates shown below. [chem 27]

Aromatic diisocyanate and aliphatic diisocyanate other than diisocyanate (DI _EG ), for example: (i) In diisocyanate structure (O=C=NRN=C=O), R is not represented by the above formula (EG) An aromatic diisocyanate having a divalent organic group and an organic group with at least one benzene ring having 6 to 30 carbon atoms, or (ii) in the diisocyanate structure (O=C=NRN=C=O), R is an aliphatic An aliphatic diisocyanate that does not have a divalent organic group represented by the above formula (EG) and an organic group with 4 to 30 carbon atoms in the aromatic group. Also, the aliphatic group includes acyclic aliphatic group and alicyclic group. Specific examples of aromatic diisocyanate and aliphatic diisocyanate other than diisocyanate (DI _EG ) include ortho-phenylene diisocyanate, meta-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate (e.g. : 2,4-diisocyanate toluene, 2,6-diisocyanate toluene), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate toluene class, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 4,4'-diisocyanate diphenyl ether, 2,2'-bis(4-diisocyanatophenyl)propane, 4,4'-diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), 4,4'-diphenylmethane diisocyanate, 3,3'-diisocyanate Aromatic diisocyanates such as diphenylphenone and 2,2'-diisocyanate diphenyl ketone, isophorone diisocyanate, norcamphene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and aliphatic diisocyanate such as tetramethylene diisocyanate.

In the above formula (b2), A ₂ is a divalent organic group in which hydrogen atoms contained in two hydroxyl groups have been removed from the organic diol. These organic diols may be used alone or in combination of two or more. Examples of the organic diol include diols containing a divalent organic group represented by the above formula (EG) and diols that do not contain a divalent organic group represented by the above formula (EG). Specific examples of diols that do not contain a divalent organic group represented by the above formula (EG) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 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-cyclohexanedimethanol and other alkylene glycols; dimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid), dimethylolbutyric acid (2,2-bis(hydroxymethyl) base) butyric acid), 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid , 3,5-dihydroxybenzoic acid and other carboxyl-containing diols; polypropylene glycol; random copolymers of polypropylene glycol and neopentyl glycol; polyester diols obtained by reacting polyols with polyacids; having a carbonate skeleton Polycarbonate diol; polycaprolactone diol obtained by ring-opening addition reaction of γ-butyl lactone, ε-caprolactone, δ-valerolactone and other lactones; bisphenol A; Propylene oxide adduct of bisphenol A; hydrogenated bisphenol A; propylene oxide adduct of hydrogenated bisphenol A, etc. Specific examples of diols containing a divalent organic group represented by the above formula (EG) include the diols exemplified for the repeating unit (b1) above, including ideal aspects.

(repeating unit constituting polyester (B)) The polyester (B) in the present invention is a polyester having a repeating unit represented by the above formula (b1) and not having a repeating unit represented by the above formula (a) and its imidized structure. The polyester (B) in the present invention may also have the above-mentioned repeating unit and terminal group. For terminal groups, as above.

When the polyester (B) contains the repeating unit represented by the above formula (b2), the content ratio of the repeating unit represented by the above formula (b2) is preferably 10 mole % or more of the total repeating units constituting the polyester (B) , more than 20 mol% is more ideal. Moreover, it is more preferably at most 90 mol%, and more preferably at most 80 mol%. Also, when _A2 is a divalent organic group derived from a diol with hydrogen atoms bonded to both ends of the above formula (EG), the content ratio of the repeating unit represented by the formula (b2) is preferably that of the polyester (B). More than 10 mol% of the total repeating unit is more preferable, more preferably 20 mol% or more, and more preferably 50 mol% or more. Moreover, the upper limit is more preferably at most 90 mol%, and more preferably at most 80 mol%.

In the above formula (b2), A ₁ and A ₂ may each be one type, or two or more types. The proportion of polyester (B) in the present invention 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.

<Manufacture of Polymer (A)> It is the polyimide precursor of the above-mentioned polymer (A), for example: polyamic acid, polyamic acid ester, etc. Polyamic acid (a polyimide precursor having a repeating unit represented by the formula (a) in which R in the above formula (a) is a hydrogen atom) can be produced by the following method. Specifically, the tetracarboxylic acid component containing the above-mentioned tetracarboxylic dianhydride or its derivatives and the diamine component containing the above-mentioned diamine can be made, in the presence of an organic solvent, preferably at -20 to 150°C, more preferably at 0~50°C, preferably for 30 minutes to 24 hours, more preferably for 1~12 hours (polycondensation) reaction for synthesis. When the above-mentioned polyamic acid contains the above-mentioned repeating unit (U), the diisocyanate compound represented by O=C=NU ₁ -N=C=O (U ₁ is the same as U ₁ in the formula (U).) It is synthesized by reacting with the above-mentioned tetracarboxylic acid component and the above-mentioned diamine component. Specific examples of the organic solvent used in the above reaction can include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N- Dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone. Also, when the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1] ~ formula [D- 3] The solvent indicated. These can also be used in mixture of 2 or more types.

[chem 28] In formula [D-1], D ¹ represents an alkyl group with 1 to 3 carbons; in formula [D-2], D ² represents an alkyl group with 1 to 3 carbons; in formula [D-3], D ³ Indicates an alkyl group with 1 to 4 carbon atoms. The reaction can be carried out at any concentration, preferably 1-50% by mass, more preferably 5-30% by mass. The initial stage of the reaction is carried out at a high concentration, and a solvent may be added thereafter. During the reaction, the ratio of the total number of moles of the diamine components to the total number of moles of the tetracarboxylic acid components is preferably 0.8 to 1.2. Like the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced will be.

The polyamic acid obtained by the above reaction can be recovered by injecting the reaction solution into a poor solvent while fully stirring to precipitate the polyamic acid. In addition, the precipitation is carried out several times, and after washing with a poor solvent, drying at room temperature or heat drying can obtain a refined polyamic acid powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butylcytosol, acetone, and toluene.

When the polyimide precursor is a polyamide ester (a polyimide precursor having a repeating unit represented by formula (a) in which at least one of R in the above formula (a) is a monovalent organic group), It can be obtained by (1) the method of esterifying polyamic acid obtained from tetracarboxylic dianhydride and diamine, (2) the method of using the reaction of tetracarboxylic diester dichloride and diamine, (3) using Manufactured by a known method such as polycondensation of tetracarboxylic acid diester and diamine.

[blocking agent] When synthesizing the polymer (A) in the present invention, a tetracarboxylic acid component containing tetracarboxylic dianhydride or its derivatives, a diamine component, and a diisocyanate compound can also be synthesized using an appropriate end-capping agent. It is an end-sealed polymer.

Capping agents, such as: acetic anhydride, maleic anhydride, nedylic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3- (3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, Acid monoanhydrides such as 4-ethynyl phthalic anhydride; di-tert-butyl dicarbonate, diallyl dicarbonate and other dicarbonate diester compounds; acryl chloride, methacryl chloride, nicotinyl chloride, etc. Chlorocarbonyl compounds; 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 other monoamine compounds; ethyl isocyanate, benzene isocyanate Monoisocyanate compounds such as esters, naphthyl isocyanate, 2-acryloxyethyl isocyanate, 2-methacryloxyethyl isocyanate and other isocyanates with unsaturated bonds; ethyl isothiocyanate , Allyl isothiocyanate and other isothiocyanate compounds.

The usage ratio of the blocking agent is preferably 20 mol parts or less, more preferably 10 mol parts or less, based on 100 mol parts of the total of the diamine component used and the organic diol component used if necessary. The usage ratio of the end-blocking agent is preferably 0.01 mole parts or more, more preferably 0.1 mole parts or more, relative to 100 mole parts in total of the diamine components used.

In addition, polyimide can be obtained by ring-closing (imidizing) the polyimide precursor (A) of the polymer (A). Moreover, the imidization rate referred to in this specification is the ratio of the imide group to the total amount of the imide group derived from tetracarboxylic dianhydride or its derivative, and a carboxyl group (or its derivative). The imidization rate does not have to be 100%, and can be adjusted arbitrarily according to the application and purpose.

The method of imidizing the polyimide precursor includes thermal imidization by directly heating the solution of the polyimide precursor or adding a catalyst to the solution of the polyimide precursor imidization.

When the polyimide precursor is thermally imidized in the solution, the temperature is preferably 100~400°C, more preferably 120~250°C, and the water generated by the imidization reaction should be discharged to the system It is better to do it outside.

Catalyzed imidization of polyimide precursor can be achieved by adding alkaline catalyst and acid anhydride to the solution of polyimide precursor, preferably at -20~250°C, more preferably at 0 Stirring at ~180°C for implementation. The amount of alkaline catalyst is preferably 0.5~30 mole times of amide acid group, more preferably 2~20 mole times, the amount of acid anhydride is preferably 1~50 mole times of amide acid group, 3~ 30 mol times is more preferable. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is ideal because it has a moderate alkalinity to allow the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferred because it facilitates purification after completion of the reaction. The imidization rate of catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or the reaction solution of polyimide, the reaction solution may be poured into a solvent and precipitated. Solvents used for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butylcytosol, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like. The polymer obtained by putting it into a solvent and precipitating it can be recovered by filtration, and then dried at normal temperature or heated under normal pressure or reduced pressure. In addition, if the operation of redissolving the precipitated polymer in an organic solvent and reprecipitating it is repeated, for example, 2 to 10 times, the impurities in the polymer can be reduced. The solvents at this time are, for example, alcohols, ketones, or hydrocarbons. If three or more solvents selected from these are used, the purification efficiency will be higher, so it is ideal.

The molecular weight of the polymer (A) used in the present invention, when considering the strength of the liquid crystal alignment film obtained therefrom, the workability and coating properties of the film, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is 5,000~1,000,000 is ideal, more preferably 10,000~150,000.

<Manufacture of polyester (B)> The above-mentioned polyester (B) can be obtained, for example, by combining (o) component containing an organic diol having two hydroxyl groups in the molecule with a tetravalent organic diol having X _ar in the molecule. The reaction of component (c) of tetracarboxylic dianhydride or its derivatives is obtained. Here, the above-mentioned component (o) contains an organic diol (o) having a substructure represented by the following formula (EG) in the molecule. [chem 29] n is an integer of 5 or more. R represents a hydrogen atom or a methyl group.

Also, when the above-mentioned polyester (B) contains a repeating unit represented by the above formula (b2), it can be obtained by reacting the component (i) containing a compound having two isocyanate groups in the molecule in addition to the above-mentioned monomer components. get.

(o) component, (c) component, and (i) component used as needed may each be 1 type or 2 or more types.

The organic diol (o), for example: the organic diol exemplified by the repeating unit represented by the above formula (b1), includes diol compounds represented by "H-E-H" (E and E in formula (b1) are synonymous.).

Also, when diol (o') free of the substructure represented by the above formula (EG) is used, the monomer component for obtaining the above polyester (B) contains the above diol (o').

(i) Component, for example: a diisocyanate compound represented by O=C=NA ₁ -N=C=O (A ₁ is the same as A ₁ in formula (b2).).

Reaction of (o) component, (c) component, and (i) component used as needed is usually carried out in an organic solvent. The organic solvent used at this time is not particularly limited as long as it dissolves the produced polyester (B). Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N -Methyl-ε-caprolactam, Dimethyl sulfoxide, Tetramethyl urea, Pyridine, Dimethyl sulfide, Triamine hexamethyl phosphate, γ-Butyrolactone, Isopropanol, Methoxymethane Amyl amyl alcohol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosulfone, ethyl cellosulfate, methyl Rothyl Acetate, Ethyl Cellulose Acetate, Butyl Carbitol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3- Methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetic acid Esters, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, 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 , Methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3 - Methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme or 4-hydroxy-4-methyl-2-pentanone, etc. These may be used alone or in combination. Furthermore, even if it is a solvent in which polyester (B) does not dissolve, it can mix and use with the said solvent. Also, the moisture in the organic solvent will hinder the polymerization reaction, so the organic solvent used should be dehydrated and dried.

In the method for synthesizing polyester (B) obtained by reacting component (o) and component (c) used in the present invention, the blending amounts of component (o) and component (c) are preferably such that the number of hydroxyl groups and The ratio (group (am)/hydroxyl group) of the sum of the amide acid groups or derivatives thereof possessed by tetracarboxylic dianhydride (hereinafter also referred to as group (am)) becomes preferably 0.8 or more and 1.2 or less, more preferably Preferably it is 0.9-1.2, and more preferably 0.9-1.1 is obtained by reacting in an organic solvent.

In addition, when the monomer component of the above-mentioned polyester (B) contains the above-mentioned (i) component, the polyester (B) obtained by reacting the (o) component, (c) component and (i) component In the synthesis method, it is preferable that the blending amount of (o) component, (i) component and (c) component be the ratio of the number of hydroxyl groups, the number of isocyanate groups and the total of groups (am) ((isocyanate group + group ( am))/hydroxyl group) is obtained by reacting in an organic solvent such that it is preferably 0.8 to 1.2, more preferably 0.9 to 1.2, and more preferably 0.9 to 1.1.

Also, when two or more organic diols are used, the reaction of the diisocyanate compound or tetracarboxylic dianhydride or its derivatives may be carried out after mixing two or more organic diols, or the respective organic diols may be mixed. Alcohols are individually reacted with diisocyanate compounds or tetracarboxylic dianhydrides or derivatives thereof. Also, after reacting organic diol with diisocyanate compound, or tetracarboxylic dianhydride or its derivatives, the obtained terminal isocyanate compound or amide acid terminal or its derivatives can be reacted with other organic diol compounds , and react it with a diisocyanate compound or a tetracarboxylic dianhydride or a derivative thereof. Moreover, it is the same when using 2 or more types of diisocyanate compounds, tetracarboxylic dianhydride, or its derivative(s). The desired polyester (B) can be produced in this way.

The reaction temperature of (o) component, (c) component and optionally used (i) component should preferably be 0-160°C, more preferably 10-150°C. The reaction time can be appropriately selected depending on the scale of the reaction and the reaction conditions used. Also, the reaction may be carried out in the presence of catalysts such as tertiary amines, alkali metals, alkaline earth metals, tin, zinc, titanium, cobalt, and other metals or semimetal compounds, if necessary. The concentration of the total amount of the component (o) and the component (i) is preferably 1 to 50% by mass in the reaction solution, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and an organic solvent can also be added later.

The molecular weight of the polyester (B) used in the present invention, when considering the strength of the liquid crystal alignment film obtained therefrom, the workability of the film formation and the coating film property, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is 4,000~80,000 is ideal, more preferably 6,000~60,000. The polyester used in the present invention has a viscosity at 25°C of 10-5,000 mPa·s, more preferably 100-3,000 mPa·s. In addition, the above-mentioned viscosity is an ideal value when the concentration of the solid content in the polyester solution is in the range of 10 to 50% by mass. It is preferable from the viewpoint of obtaining the effects of the present invention that the viscosity is within the above-mentioned range. The above-mentioned viscosity is the value measured at a temperature of 25°C with a conical rotor TE-1 (1°34’, R24) using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL.

The polymer composition of the present invention may contain other polymers other than the polymer (A) and polyester (B). Specific examples of other polymers include polyesters other than polyester (B), polysiloxanes, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, Polystyrene derivatives, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleic anhydride) imide) derivatives, polymers in the group consisting of poly(meth)acrylates, etc. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, and 3000 (manufactured by Cray Valley Co.), GSM301 (manufactured by GIFUSHELLAC Co., Ltd.), and specific examples of poly(isobutylene-maleic anhydride) copolymers include ISOBAM-600 (made by Kuraray) is mentioned, and the specific example of a poly(vinyl ether-maleic anhydride) copolymer includes GANTREZ AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by ISP Japan). The other polymers may be used alone or in combination of two or more. The content ratio of other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and more preferably 20 to 80 parts by mass, based on the total of 100 parts by mass of the polymers contained in the polymer composition.

The polymer composition of the present invention is preferably a liquid composition in which the above-mentioned polymer (A) and polyester (B) 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 the polymer component is uniformly dissolved, and examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N,N-dimethylacrylamide, tetramethylurea, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl Base-2-pyrrolidone, dimethylsulfene, 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-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-3-methoxypropyl -2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (also collectively referred to as as a "good solvent"). Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethyl Acrylamide or γ-butyrolactone is preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, particularly preferably 30 to 80% by mass, of the entire solvent contained in the polymer composition. The total content of the polymer (A) and polyester (B) used in the present invention is preferably 1 to 100 parts by mass, 10 to 100 parts by mass based on 100 parts by mass of the total polymers contained in the liquid crystal alignment agent. More preferably, 20 to 100 parts by mass is especially preferred. Moreover, the total content of the said polymer (A) and polyester (B) may be 90 mass parts or less, 80 mass parts or less with respect to 100 mass parts of polymers contained in the liquid crystal alignment agent in total.

In addition, as the organic solvent contained in the polymer composition, it is preferable to use a solvent (also called a poor solvent) that is used in addition to the above-mentioned solvents to improve the coatability of the polymer composition and the smoothness of the surface of the coating film. A mixed solvent is better. Specific examples of poor solvents used together are as follows but not limited to these solvents. The content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and most preferably 20 to 70% by mass, of the entire solvent contained in the polymer composition. The type and content of the poor solvent can be appropriately selected according to the coating equipment, coating conditions, and coating environment of the polymer composition.

Poor solvents, such as: diisopropyl ether, diisobutyl ether, diisobutylmethanol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Alcohol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 3-Ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene diacetate Alcohol diacetate, propylene carbonate, ethyl carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisopentyl 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, propionate 3-methoxypropionate ester, 3-methoxybutyl propionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), etc.

Among them, diisobutylmethanol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentane Ketone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferred.

Ideal solvent combination of good solvent and poor solvent, such as N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether , N-methyl-2-pyrrolidone and 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 3 -Ethoxyethyl propionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate and dipropylene glycol mono Methyl ether, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate and diethylene glycol Monopropyl ether, N-ethyl-2-pyrrolidone and 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 and diethylene glycol monoethyl ether and butyl cellothreoacetate, N-methyl-2-pyrrolidone and Diethylene glycol monomethyl ether and butyl cellothracetate, N,N-dimethyl lactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-Hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2- Pentanone, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2 -Pentanone and diisobutyl ketone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and 4- Hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and ethylene glycol monobutyl ether, N-methyl Base-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and two Propylene glycol dimethyl ether, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone With propylene glycol diacetate, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol mono Butyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl methanol, N-methyl-2-pyrrolidone and γ-butyrolactone and di Propylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N-ethyl- 2-pyrrolidone and diethylene glycol diethyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and propylene glycol diacetate, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether With diisobutyl ketone, N-ethyl-2-pyrrolidone and γ-butyrolactone and diisobutyl ketone, N-ethyl-2-pyrrolidone and N,N-dimethyl lactamide and diiso Butyl ketone, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate, gamma-butyrolactone and ethylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone and 4-methyl-2-pentyl acetate and ethylene glycol mono Butyl ether, N-ethyl-2-pyrrolidone and cyclohexyl acetate and diacetone alcohol, N,N-dimethylacrylamide and 4-hydroxy-4-methyl-2-pentanone, N,N- Dimethylacrylamide and propylene glycol diacetate, tetramethylurea and 4-hydroxy-4-methyl-2-pentanone, tetramethylurea and propylene glycol diacetate, N,N-dimethyl Acrylamide and propylene glycol monobutyl ether, tetramethylurea and propylene glycol monobutyl ether, tetramethylurea and cyclohexanone and propylene glycol monomethyl ether, N,N-dimethylacrylamide and propylene glycol monomethyl ether, N , N-dimethylacrylamide and ethylene glycol monobutyl ether acetate, N,N-dimethylacrylamide and ethylene glycol monobutyl ether, tetramethylurea and propylene glycol monomethyl ether, N, N-Dimethylacrylamide and cyclohexanone and diethylene glycol diethyl ether, N,N-diethylformamide and propylene glycol monomethyl ether, N,N-diethylformamide and 4-hydroxy -4-methyl-2-pentanone, N,N-diethylformamide and propylene glycol monomethyl ether, cyclohexanone and propylene glycol monomethyl ether, cyclopentanone and propylene glycol monomethyl ether, N-methyl- 2-pyrrolidone, cyclohexanone, propylene glycol monomethyl ether, etc.

The polymer composition of the present invention may additionally contain components other than the polymer component and the organic solvent (hereinafter also referred to as additive components.). This additive component, such as: crosslinking compound, functional silane compound, metal chelate compound, hardening accelerator, surfactant, antioxidant, sensitizer, preservative, used to adjust the dielectric constant of the resin film, Compounds of resistors, etc. The above-mentioned cross-linking compounds are selected from, for example, cross-linking compounds having at least one substituent selected from epoxy groups, isocyanate groups, epoxypropylene groups, cyclocarbonate groups, blocked isocyanate groups, hydroxyl groups, and alkoxy groups. At least one crosslinkable compound in the group consisting of the compound (c-1) and the crosslinkable compound (c-2) having a polymerizable unsaturated group. By containing the above-mentioned cross-linking compound, there is also an effect of obtaining a liquid crystal display element in which occurrence of so-called flicker (flicker) or the like caused by backlight irradiation on the liquid crystal display element at the beginning of driving of the liquid crystal is reduced.

Desirable specific examples of the above-mentioned crosslinkable compounds (c-1) and (c-2) include the following compounds. Compounds (c-1) having an epoxy group include: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Propylene Glycol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerin Diglycidyl Ether, Dibromoneopentyl Glycol Diglycidyl Ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, bisphenol A epoxy resin such as EPIKOTE828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F such as EPIKOTE807 (manufactured by Mitsubishi Chemical Corporation) Type epoxy resin, hydrogenated bisphenol A type epoxy resin such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), epoxy resin containing a biphenyl skeleton such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), EPPN-201 (manufactured by Nippon Kayaku Co., Ltd. ) and other phenol novolac epoxy resins, EOCN-102S (Nippon Kayaku Co. ,N,N',N'-tetraepoxypropyl-1,4-phenylenediamine, N,N,N',N'-tetraepoxypropyl-2,2'-dimethyl-4.4' -Diaminobiphenyl, 2,2-bis[4-(N,N-diepoxypropyl-4-aminophenoxy)phenyl]propane, N,N,N',N'-tetra Epoxypropyl-4,4'-diaminodiphenylmethane and other compounds bonded by tertiary nitrogen atoms and aromatic carbon atoms; N,N,N',N'-tetraepoxypropyl-1, 2-Diaminocyclohexane, N,N,N',N'-tetraepoxypropyl-1,3-diaminocyclohexane, N,N,N',N'-tetraepoxypropyl -1,4-Diaminocyclohexane, Bis(N,N-Diepoxypropyl-4-aminocyclohexyl)methane, Bis(N,N-Diepoxypropyl-2-methyl -4-aminocyclohexyl)methane, bis(N,N-diepoxypropyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diepoxypropylamine (methyl)cyclohexane, 1,4-bis(N,N-diecidylaminomethyl)cyclohexane, 1,3-bis(N,N-diecidylaminomethyl)benzene, 1,4-bis(N,N-diepoxypropylaminomethyl)benzene, 1,3,5-paraffin(N,N-diepoxypropylaminomethyl)cyclohexane, 1,3,5- Compounds with tertiary nitrogen atoms bonded to aliphatic carbon atoms such as (N,N-diglycidylaminomethyl)benzene, isocyanurates such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Co., Ltd.) Ester compounds, compounds described in paragraph [0037] of JP-A-10-338880, compounds described in WO2017/170483, etc.; Compounds having an isocyanate group include the above-mentioned diisocyanate compounds, etc.; Compounds (c-1) having a propylene oxide group include 1,4-bis{[(3-ethyl-3-epoxypropylene)methoxy]methyl}benzene (ARON OXETANE OXT-121 (XDO )), bis[2-(3-epoxypropylene)butyl] ether (ARON OXETANE OXT-221(DOX)), 1,4-bis[(3-ethyloxetane-3-yl )methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyl oxetan-3-yl)methoxy]benzene (CTOX), compounds having two or more propylene oxide groups described in paragraphs [0170]~[0175] of WO2011/132751, etc.; Compounds (c-1) having a cyclocarbonate group include N,N,N',N'-tetra[(2-oxo-1,3-dioxolane-4-yl)methyl]- 4,4'-Diaminodiphenylmethane, N,N'-bis[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-benzenedi Amines, compounds described in WO2011/155577, etc.; Compounds having blocked isocyanate groups include CORONATEAP STABLE M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATEMS-50 (manufactured by Tosoh Corporation), TAKENATE B-830, B-815N, B-820NSU, B-842N , B-846N, B-870N, B-874N, B-882N (the above are manufactured by Mitsui Chemicals Co., Ltd.), paragraphs [0046]~[0047] of Japanese Patent Laid-Open No. 2014-224978 have two or more protections Compounds with isocyanate groups, compounds with three or more protected isocyanate groups described in paragraphs [0119] to [0120] of WO2015/141598, etc.; Compounds (c-1) having hydroxyl and/or alkoxy groups include N,N,N',N'-tetra(2-hydroxyethyl)adipamide, 2,2-bis(4-hydroxy- 3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, 2,2-bis(4-hydroxy-3,5- Dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, compound described in paragraph [0058] of International Publication No. 2015/072554, Japanese Patent Laid-Open No. 2016-118753, Japanese Patent Application Compounds described in Publication No. 2016-200798, compounds described in WO2010/074269, etc.; Examples of the crosslinkable compound (c-2) having a polymerizable unsaturated group include glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-, 1,3-body mixture), glycerin Glycerin (meth)acrylate, glycerol 1,3-diglycerinic acid 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.

Among the above-mentioned crosslinkable compounds (c-1) and (c-2), N,N,N',N'-tetraglycidyl m-xylylenediamine, 1,3-bis(N,N -Diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N, 1,3,5-ginseng (2-hydroxyethyl) isocyanurate, isocyanuric acid Triglycidyl, 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 is preferred.

The above is an example of the cross-linkable compound and is not limited thereto. Moreover, the crosslinkable compound used for the polymer composition of this invention may be 1 type or it may combine 2 or more types. In the polymer composition of the present invention, the content of the crosslinkable compound is 0.1 to 150 parts by mass, or 0.1 to 100 parts by mass, or 1 to 50 parts by mass relative to 100 parts by mass of all polymer components.

The above-mentioned compound for adjusting the dielectric constant and resistance of the resin film includes monoamines such as 3-picolylamine having an aromatic heterocyclic ring containing a nitrogen atom. When using a monoamine having a nitrogen-containing aromatic heterocycle, it is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the polymer composition.

Ideal specific examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-amine Aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl base)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyl trimethoxysilane Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methyl Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methyl Acryloxypropyl triethoxysilane, 3-acryloxypropyltrimethoxysilane, ginseng (3-trimethoxysilylpropyl) isocyanurate, 3-mercaptopropyl methyl Dimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. When using a functional silane compound, the usage-amount is preferably 0.1-30 mass parts with respect to 100 mass parts of polymer components contained in a polymer composition, More preferably, it is 0.1-20 mass parts.

The solid content concentration in the polymer composition (the ratio of the total mass of components other than the solvent of the polymer composition to the total mass of the polymer composition) can be appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1 ~10% by mass. That is, the polymer composition is coated on the surface of the substrate as described later, preferably heated, to form a resin film.

The particularly desirable range of solid content concentration varies depending on the method used when coating the polymer composition on the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. When using the printing method, the solid content concentration is in the range of 3 to 9% by mass, and the viscosity of the solution is preferably in the range of 12 to 50 mPa·s. When using the inkjet method, the solid content concentration is in the range of 1 to 5% by mass, and the viscosity of the solution is preferably in the range of 3 to 15 mPa·s. The temperature for preparing the polymer composition is preferably 10-50°C, more preferably 20-30°C.

＜Application and resin film＞ The polymer composition described above can form a resin film by, for example, coating on a substrate, preferably by heat treatment to volatilize the solvent component. The polymer composition and resin film of the present invention can be effectively applied to various technical applications, such as liquid crystal alignment agents, electronic circuit materials, semiconductor materials, electrical insulation materials, wire coating materials, lighting applications, molding materials and other applications. Specifically, it can be applied to various resin films provided in various sensors such as display elements, semiconductor elements, motors and other actuators, piezoelectric sensors, pyroelectric sensors, etc., and liquid crystal alignment films (phase Liquid crystal alignment film for poor film, scanning antenna, liquid crystal alignment film for liquid crystal array antenna or liquid crystal alignment film for transmission scattering type liquid crystal dimming element), protective film (for example: protective film for color filter), Spacer film, interlayer insulating film, antireflection film, wiring coating film, antistatic film, motor insulating film (gate insulating film for flexible displays), etc. Among them, the polymer composition of the present invention can be ideally used as a liquid crystal alignment agent.

＜Liquid crystal alignment agent＞ The liquid crystal alignment agent of the present invention is composed of the polymer composition of the present invention. That is, the liquid crystal alignment agent of this invention contains the said polymer (A) and polyester (B) like a polymer composition. Moreover, it is preferable to contain at least any one of other polymers, organic solvents, and additive components. The description of the above-mentioned polymer composition is applicable to the details of the above-mentioned polymer (A), polyester (B), other polymers, organic solvents, and specific examples of additive components, blending ratios, solid content concentrations, and the like.

[Liquid crystal alignment film and liquid crystal display element] By using the above-mentioned polymer composition or the above-mentioned liquid crystal alignment agent, a liquid crystal alignment film as a resin film can be produced. Moreover, the liquid crystal display element of this invention is equipped with the liquid crystal alignment film formed using the said polymer composition or the said liquid crystal alignment agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited, for example, TN type, STN (Super Twisted Nematic) type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type ( IPS type), FFS type, optical compensation bending type (OCB type) and other various operation modes.

The liquid crystal display element of the present invention can, for example, include the following steps (1) to (4), the method including steps (1) to (2) and (4), including the steps (1) to (3), ( 4-2) and (4-4), or a method including steps (1) to (3), (4-3) and (4-4).

<Step (1): The step of coating the liquid crystal alignment agent on the substrate> Step (1) is a step of coating the liquid crystal alignment agent of the present invention on the substrate. The specific example of step (1) is as follows. On one side of the substrate provided with the patterned transparent conductive film, the liquid crystal alignment agent of the present invention is coated using an appropriate coating method such as roll coating method, spin coating method, printing method, inkjet method and the like. Here, the substrate is not particularly limited as long as it is highly transparent, and a glass substrate, a silicon nitride substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used together. In addition, if the reflective liquid crystal display element is only on one side of the substrate, it can also use opaque objects such as silicon wafers. In this case, the electrodes can also use materials that reflect light such as aluminum. Also, when manufacturing IPS or FFS liquid crystal display elements, a substrate provided with electrodes made of a comb-shaped transparent conductive film or metal film and a counter substrate without electrodes are used.

For the method of coating the liquid crystal alignment agent on the substrate and forming a film, screen printing, offset printing, flexo printing, inkjet method, or spraying method, etc. can be mentioned. Among them, the coating and film-forming methods by the inkjet method can be preferably used.

<Step (2): The step of calcining the coated liquid crystal alignment agent> Step (2) is a step of calcining the liquid crystal alignment agent coated on the substrate to form a film. The specific example of step (2) is as follows. After the liquid crystal alignment agent is coated on the substrate in step (1), the solvent can be evaporated, or the polyamide acid or polyamide Thermal imidization of esters. For the drying and calcining steps after coating the liquid crystal alignment agent of the present invention, any temperature and time can be selected, and multiple times can also be performed. To reduce the temperature of the solvent of the liquid crystal alignment agent, for example, it can be carried out at 40~180°C. Considering the point of view of reducing treatment, it can be carried out at 40~150°C. The calcination time is not particularly limited, and examples thereof include 1 to 10 minutes or 1 to 5 minutes. When thermal imidization of polyamic acid or polyamic acid ester is performed, after the above steps, a step of calcining at a temperature range of 150~300°C or 150~250°C can be added. The calcination time is not particularly limited, and may be 5 to 40 minutes, or 5 to 30 minutes. If the calcined film is too thin, the reliability of the liquid crystal display element will be reduced, so 5~300nm is more ideal, and 10~200nm is more ideal.

<Step (3): The step of aligning the film obtained in step (2)> Step (3) is a step of performing alignment treatment on the film obtained in step (2) as the case may be. That is, in a liquid crystal display element of a horizontal alignment type such as an IPS method or an FFS method, an alignment ability-imparting treatment is performed on the coating film. On the other hand, in a vertical alignment type liquid crystal display device such as VA mode or PSA mode, the formed coating film can be used as a liquid crystal alignment film as it is, but the coating film can also be subjected to an alignment ability imparting treatment. The alignment treatment method of the liquid crystal alignment film includes a rubbing treatment method and a photo-alignment treatment method. For the photo-alignment treatment method, the method of irradiating the surface of the above-mentioned membranous material with radiation deflected in a certain direction, and depending on the situation, heat treatment to impart liquid crystal alignment (also called liquid crystal alignment ability) can be mentioned. As the radiation, ultraviolet rays or visible rays having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm, more preferably 200 to 400 nm are preferred.

The exposure dose of the above-mentioned radiation is preferably 1~10,000mJ/cm ² . Among them, 100~5,000mJ/cm ² is preferable. In addition, when irradiating radiation, in order to improve the liquid crystal alignment, it may be irradiated while heating the above-mentioned substrate having the membranous substance at 50 to 250°C. The liquid crystal alignment film fabricated in such a manner can stably align liquid crystal molecules in a certain direction. In addition, the liquid crystal alignment film irradiated with polarized radiation as described above may be contact-treated with water or a solvent, or the liquid crystal alignment film irradiated with radiation may be heat-treated.

The solvent used in the above-mentioned contact treatment is not particularly limited as long as it dissolves the decomposed product generated from the film-like material due to radiation exposure. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butylcylonol, Ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, etc. Among them, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate are more ideal in consideration of generality and safety of solvents, water, 1-methoxy-2-propanol Alcohol or ethyl lactate are more desirable. A solvent may be used alone or in combination of two or more.

The temperature for heat treatment of the coating film irradiated with radiation is more preferably 50 to 300°C, more preferably 120 to 250°C. The heat treatment time is preferably 1 to 30 minutes.

＜Step (4): Steps for making liquid crystal cells＞ Two substrates on which a liquid crystal alignment film was formed as described above were prepared, and liquid crystals were arranged between the two substrates facing each other. Specifically, the following two methods can be mentioned. In the first method, two substrates are arranged facing each other through a cell gap in such a manner that the liquid crystal alignment films face each other. Then, bond the peripheral parts of the two substrates with a sealant, inject and fill the liquid crystal composition into the cell gap separated by the substrate surface and the sealant, and seal the injection hole after contacting the film surface. . The above-mentioned liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used. Hereinafter, a liquid crystal composition having a positive dielectric anisotropy is also referred to as a positive type liquid crystal, and a liquid crystal composition having a negative dielectric anisotropy is also referred to as a negative type liquid crystal. The above liquid crystal composition may also contain a fluorine atom, a hydroxyl group, an amino group, a group containing a fluorine atom (for example: trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, Liquid crystal compounds of heterocycles, cycloalkanes, cycloalkenes, steroid skeletons, benzene rings, or naphthalene rings may also contain compounds with two or more rigid sites (mesogen skeletons) exhibiting liquid crystallinity in the molecule (for example: rigid Two biphenyl structures, or a double mesogen compound formed by linking two terphenyl structures with an alkyl group, etc.). The liquid crystal composition may also 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. In addition, in the above-mentioned liquid crystal composition, additives may be further added from the viewpoint of improving the alignment of liquid crystals. Examples of such additives include photopolymerizable monomers such as compounds having a polymerizable group (methacryl group, etc.); optically active compounds (for example: S-811 manufactured by Merck & Co., etc.); antioxidants; ultraviolet absorbers agent; pigment; defoamer; polymerization initiator or polymerization inhibitor, etc. Examples of positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by Merck & Co., Ltd. Examples of negative liquid crystals include 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. wait. Moreover, in PSA mode, MLC-3023 by Merck is mentioned as a liquid crystal containing the compound which has a polymeric group.

Also, the second method is a method called ODF (One Drop Fill) method. On one of the two substrates on which the liquid crystal alignment film has been formed, apply, for example, a UV-curable sealant, and then drop the liquid crystal composition on several predetermined positions on the surface of the liquid crystal alignment film. Afterwards, another substrate is bonded in such a way that the liquid crystal alignment film faces each other, and the liquid crystal composition is pressed against the entire surface of the substrate to make it contact the film surface. Then, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant. When using either method, it is advisable to further heat until the liquid crystal composition used becomes the temperature of the isotropic phase, and then slowly cool down to room temperature to remove the flow alignment during liquid crystal filling. Also, when performing rubbing treatment on the coating film, two substrates are arranged facing each other such that the rubbing directions of the respective coating films are at a predetermined angle, for example, perpendicular to or antiparallel to each other. For the sealant, for example, an epoxy resin containing alumina balls as a curing agent and a spacer can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.

The liquid crystal alignment agent of the present invention is also suitable for use in a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal composition is a liquid crystal display element (PSA type liquid crystal display element) produced by applying a voltage between electrodes and polymerizing a polymerizable compound by at least one of active energy ray irradiation and heating. In addition, the liquid crystal alignment agent of the present invention is also suitable for use in a liquid crystal layer between a pair of substrates with electrodes, and a liquid crystal layer that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. A liquid crystal display element (SC-PVA mode type liquid crystal display element) manufactured by applying a voltage between electrodes using a polymeric-based liquid crystal alignment film.

<Step (4-2): In the case of a PSA type liquid crystal display element> The procedure is carried out in the same manner as in (4) above except for injecting or dropping the liquid crystal composition containing the polymerizable compound. Examples of the polymerizable compound include polymerizable compounds having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule.

<Step (4-3): In the case of SC-PVA mode type liquid crystal display element It is also possible to employ a method of producing a liquid crystal display element through the step of irradiating ultraviolet rays described later in the same manner as in (4) above. According to this method, a liquid crystal display element with excellent response speed can be obtained with a small amount of light irradiation as in the case of manufacturing the above-mentioned PSA type liquid crystal display element. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups in the molecule, and its content is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of all polymer components, more preferably 1 ~20 parts by mass. In addition, the above-mentioned polymerizable group may be contained in a polymer used in a liquid crystal alignment agent. Examples of such a polymer include a polymer obtained by using a diamine component containing a diamine having the above-mentioned photopolymerizable group at the end for reaction. thing.

<Step (4-4): In the step of irradiating ultraviolet rays, light is irradiated to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates obtained in the above (4-2) or (4-3). Here, the applied voltage may be, for example, 5-50V direct current or alternating current. Also, as the light to be irradiated, for example, ultraviolet rays and visible rays including light with a wavelength of 150 to 800 nm can be used, but ultraviolet light including light with a wavelength of 300 to 400 nm is preferable. As a light source for irradiating light, 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. The amount of light irradiation is preferably 1,000-200,000 J/m ² , more preferably 1,000-100,000 J/m ² .

In addition, if necessary, a polarizing plate can be attached to the outer surface of the liquid crystal cell to obtain a liquid crystal display element. The polarizing plate attached to the outer surface of the liquid crystal cell includes a polarizing film called "H film" that absorbs iodine while stretching polyvinyl alcohol and sandwiching it with a cellulose acetate protective film; or Polarizing plate composed of H film itself.

The liquid crystal display device of the present invention can be effectively applied to various devices, such as clocks, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, etc. , Various displays, LCD TVs, information displays and other display devices. [Example]

Examples are given below to describe the present invention in more detail, but the present invention is not limited to these examples. In addition, the abbreviations of compounds and solvents are as follows. (Organic solvent) NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: Ethylene glycol monobutyl ether (diamine) DA-1~DA-3: Each is the following formula (DA-1) Compounds (tetracarboxylic dianhydrides) represented by ~(DA-3) CA-1~CA-2: Each is a compound (diisocyanate) represented by the following formulas (CA-1)~(CA-2) DI-1: 4,4'-Diphenylmethane diisocyanate (diol) EG-1: Polyethylene Glycol 600 (manufactured by Tokyo Chemical Industry Co., Ltd.) (Additive) AD-1: Compound represented by the following formula (AD-1) [Chemical 30] [chem 31] [chem 32]

＜Viscosity＞ In the synthesis example, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL, a conical rotor TE-1 (1°34', R24), and a temperature of 25°C. condition determination.

[Synthesis of Polymer] (Synthesis Example 1) DA-1 (4.81g, 16.8mmol), DA-3 (1.25g, 4.20mmol), DA-3 (1.25g, 4.20mmol), NMP (27.3 g) and GBL (27.3 g) were stirred and dissolved while feeding nitrogen gas. While stirring the diamine solution under water cooling, add CA-1 (3.83g, 19.5mmol), NMP (17.2g) and GBL (17.2g), and stir for 2 hours under a nitrogen atmosphere to obtain a polyamic acid solution (PAA-1) (viscosity: 108mPa・s). (Synthesis Example 2) Measure DA-1 (3.15g, 11.0mmol), DA-2 (2.69g, 11.0mmol), NMP (26.3g) and GBL (26.3 g) was dissolved by stirring while feeding nitrogen gas. While stirring this diamine solution under water cooling, CA-1 (4.01g, 20.5mmol), NMP (18.1g) and GBL (18.1g) were added, and stirred for 2 hours under a nitrogen atmosphere to obtain a polyamic acid solution ( PAA-2) (viscosity: 119mPa・s). (Synthesis Example 3) Measure EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) in a 100 mL eggplant-shaped flask with a stirring device and a nitrogen gas introduction tube, and stir while feeding nitrogen gas Let it dissolve. While stirring this diamine solution under water cooling, CA-2 (4.09 g, 18.8 mmol), NMP (3.07 g) and GBL (3.07 g) were added, and stirred at 70° C. for 20 hours under a nitrogen atmosphere. Afterwards, DI-1 (1.38g, 5.50mmol), NMP (1.03g) and GBL (1.03g) were added, and stirred at 23°C for 6 hours under a nitrogen atmosphere to obtain a polymer solution (viscosity: 423mPa·s). In a 30mL Erlenmeyer flask equipped with a stirrer, divide the polymer solution (5.0g) obtained above, add NMP (7.5g) and GBL (7.5g), and stir at room temperature for 2 hours to obtain a diluted polymer Solution (Polymer-1). (Synthesis Example 4) Measure EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) in a 100 mL eggplant-shaped flask with a stirring device and a nitrogen gas introduction tube, and stir while feeding nitrogen gas Let it dissolve. While stirring this diamine solution under water cooling, CA-2 (2.73 g, 12.5 mmol), NMP (2.04 g) and GBL (2.04 g) were added, and stirred at 70° C. for 20 hours under a nitrogen atmosphere. Then, add DI-1 (2.94g, 11.8mmol), NMP (1.03g) and GBL (1.03g), and stir at 23°C for 6 hours under nitrogen atmosphere to obtain a polymer solution (viscosity: 520mPa·s) . In a 30mL Erlenmeyer flask equipped with a stirrer, divide the polymer solution (5.0g) obtained above, add NMP (7.5g) and GBL (7.5g), and stir at room temperature for 2 hours to obtain a diluted polymer Solution (Polymer-2). (Synthesis Example 5) Measure EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) in a 100 mL eggplant-shaped flask with a stirring device and a nitrogen gas introduction tube, and stir while feeding nitrogen gas Let it dissolve. While stirring this diamine solution under water cooling, CA-2 (1.64 g, 7.50 mmol), NMP (1.23 g) and GBL (1.23 g) were added, and stirred at 70° C. for 20 hours under a nitrogen atmosphere. Then, add DI-1 (4.19g, 16.8mmol), NMP (3.14g) and GBL (3.14g), and stir at 23°C for 6 hours under nitrogen atmosphere to obtain a polymer solution (viscosity: 367mPa·s) . In a 30mL Erlenmeyer flask equipped with a stirrer, divide the polymer solution (5.0g) obtained above, add NMP (7.5g) and GBL (7.5g), and stir at room temperature for 2 hours to obtain a diluted polymer Solution (Polymer-3). (Synthesis Example 6) Measure EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) in a 100 mL eggplant-shaped flask with a stirring device and a nitrogen gas introduction tube, and stir while feeding nitrogen gas Let it dissolve. While stirring this diamine solution under water cooling, CA-2 (0.82 g, 3.75 mmol), NMP (0.61 g) and GBL (0.61 g) were added, and stirred at 70° C. for 20 hours under a nitrogen atmosphere. Then, add DI-1 (5.13g, 20.5mmol), NMP (3.85g) and GBL (3.85g), and stir at 23°C for 6 hours under nitrogen atmosphere to obtain a polymer solution (viscosity: 1120mPa·s) . In a 30mL Erlenmeyer flask equipped with a stirrer, divide the polymer solution (5.0g) obtained above, add NMP (7.5g) and GBL (7.5g), and stir at room temperature for 2 hours to obtain a diluted polymer solution (polymer-4). (Synthesis Example 7) Measure EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) in a 100 mL eggplant-shaped flask with a stirring device and a nitrogen gas inlet tube, and stir while feeding nitrogen gas Let it dissolve. While stirring the diamine solution under water cooling, add CA-2 (5.34g, 24.5mmol), NMP (4.00g) and GBL (4.00g), and stir at 70°C for 20 hours under a nitrogen atmosphere to obtain a polymer solution (viscosity: 375mPa·s). In a 30mL Erlenmeyer flask equipped with a stirrer, divide the polymer solution (5.0g) obtained above, add NMP (7.5g) and GBL (7.5g), and stir at room temperature for 2 hours to obtain a diluted polymer solution (polymer-5). The specifications of the polymer solutions obtained in the above synthesis examples are shown in Table 1. In Table 1, the values in parentheses of the solvent composition represent the amount (parts by mass) of each solvent relative to the total of 100 parts by mass of the solvents in each solution. [Table 1]

[Preparation of liquid crystal alignment agent] (Example 1) In a 50mL Erlenmeyer flask equipped with a stirring bar, measure the polyamic acid solution (PAA-1) (6.00g) obtained in Synthesis Example 1 and the diluted solution of the polymer obtained in Synthesis Example 3 (polymer-1) (0.48 g), adding NMP solution (additive solution) (0.30g) containing NMP (1.31g), GBL (3.91g), BCS (4.00g), and 10% by mass of AD-1, stirred at room temperature for 2 hours, To obtain the liquid crystal alignment agent (1).

(Examples 2-10, Comparative Examples 1-2) The type and amount of the polymer solution and solvent used are changed to the following list 2, except that it is implemented in the same way as Example 1 to obtain liquid crystal alignment agent (2)- (12). [Table 2]

[Fabrication of FFS-driven liquid crystal cell] A liquid crystal cell with a configuration of a fringe field switching (Fringe Field Switching: FFS) mode liquid crystal display element was fabricated. First prepare the substrate with electrodes. The substrate is a glass substrate with a size of 30mm×35mm and a thickness of 0.7mm. Form an ITO electrode with a full-surface pattern on the substrate as the counter electrode of the first layer, and form a film by CVD (chemical vapor deposition) method as the second layer on the counter electrode of the first layer SiN (silicon nitride) film. The thickness of the SiN film of the second layer is 300nm, which acts as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning the ITO film as the third layer is arranged, and two pixels of the first pixel and the second pixel are formed, each pixel The size is 10mm in length and 5mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the function of the SiN film of the second layer. The pixel electrode on the third layer, the central part is bent at an inner angle of 160°, and the electrode elements with a width of 3 μm are spaced in parallel at intervals of 6 μm. It has a comb-tooth shape arranged in many places, and one pixel is used to connect multiple electrode elements. The line of the Ministry is the boundary, with the first and second districts. Comparing the first area and the second area of each pixel, the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the direction of the bent portion connecting the plurality of electrode elements is used as a reference, the first region of the pixel is formed such that the electrode elements of the pixel electrode form an angle of 80° clockwise, and the second region of the pixel The two regions are formed so that the electrode elements of the pixel electrodes form an angle of 80° counterclockwise. That is, in the first area and the second area of each pixel, the direction of the rotation of the liquid crystal in the substrate surface (in-plane switching) caused by the voltage application between the pixel electrode and the counter electrode, The system is formed in such a way that they become opposite directions of each other. Then, the liquid crystal alignment agent obtained above was filtered through a filter with a pore size of 1.0 μm, and then coated on the surface of the prepared substrate with electrodes (the first glass substrate) and the surface of the ITO film formed on the back by the spin coating method. The surface of the glass substrate (second glass substrate) of the columnar spacer with a height of 4 μm. Then, it was dried on a hot plate at 80° C. for 5 minutes, and then calcined in a hot air circulation oven at 230° C. for 20 minutes to obtain a polyimide film with a thickness of 100 nm. This polyimide film was rubbed with a yarn cloth (YA-20R manufactured by Yoshikawa Chemical Co., Ltd.) (roll diameter: 120 mm, roll rotation speed: 500 rpm, moving speed: 30 mm/sec, pushing length: 0.3 mm, rubbing direction: opposite After connecting the pixel electrodes of the third layer with the direction of the bending part of the above-mentioned multiple electrode elements being 180°), irradiate with ultrasonic wave in pure water for 1 minute and wash, and blow air to remove water droplets. Then, it was dried at 80° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film. The obtained 2 substrates with liquid crystal alignment film were used as a group, and a sealant (XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) was printed on the substrate in the form of retaining the liquid crystal injection port, and the other substrate was connected with the liquid crystal alignment film surface. Facing, the rubbing direction becomes antiparallel to fit. Afterwards, heat treatment was carried out at 150°C for 60 minutes to harden the sealant, and to produce empty cells with a unit cell gap of 4 μm. Negative-type liquid crystal MLC-7026-100 (manufactured by Merck & Co.) was injected into this ghost cell by the depressurized injection method, and the injection port was sealed to obtain a liquid crystal cell of the FFS method. Afterwards, the obtained liquid crystal cells were heated at 120° C. for 1 hour, and left overnight at 23° C. for evaluation. [Evaluation of Alignment Stability Influenced by Long-term AC Driving] This evaluation is to evaluate the residual image (also called AC residual image) caused by the decrease of the alignment performance of the liquid crystal alignment film under long-term AC driving. Using the liquid crystal cells produced above, an AC voltage of ±12V was applied at a frequency of 60Hz for 120 hours on a high-brightness backlight (luminosity: 20000cd/m ² ) with a surface temperature of 50°C. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for one day in this state. After placement, place the liquid crystal cell between two polarizers whose polarization axes are perpendicular to each other, turn on the backlight in the state where no voltage is applied, and adjust the arrangement angle of the liquid crystal cell so that the first area of the first pixel The transmitted light intensity becomes the minimum, and then, the rotation angle until the liquid crystal cell is rotated until the transmitted light intensity of the second region of the first pixel becomes minimum is calculated as the angle Δθ. Similarly, the second pixel compares the second area with the first area, and calculates the same angle Δθ. And calculate the average value of the angle Δθ between the first pixel and the second pixel as the rotation angle Δθ of the liquid crystal cell. Regarding the stability of liquid crystal alignment, the smaller the value of the rotation angle Δθ, the better it is. In terms of evaluation criteria, when the value of the rotation angle Δθ of the liquid crystal cell obtained above is 0.10 degrees or less, it is rated as "0", when it exceeds 0.10 degrees and is 0.20 degrees or less, it is rated as "△", and when it exceeds 0.20 degrees, it is rated as "×". . The results are shown in Table 3. [Fabrication of liquid crystal cell for evaluation of pretilt angle] First, a substrate with electrodes was prepared. The substrate is a glass substrate with a size of 30mm×40mm and a thickness of 1.1mm. ITO electrodes with a film thickness of 35nm were formed on the substrate, and the electrodes were in the shape of stripes with intervals of 40mm in length and 10mm in width. Then, the liquid crystal alignment agent obtained above was filtered through filters with a pore size of 1.0 μm, and then coated on the prepared substrate with electrodes by spin coating. Then, it was dried on a hot plate at 80°C for 2 minutes, and then calcined in an infrared heating furnace at 230°C for 20 minutes to form a coating film with a thickness of 100 nm, and obtain a substrate with a liquid crystal alignment film. This liquid crystal alignment film was subjected to rubbing treatment (roller diameter: 120mm, roll speed: 1000rpm, moving speed: 20mm/sec, pushing length: 0.4mm) with a rayon cloth (manufactured by Yoshikawa Chemical Co., Ltd., YA-20R). Ultrasonic waves were irradiated in water for 1 minute to clean, and the water droplets were removed by blowing air, and then dried at 80°C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Prepare 2 substrates with liquid crystal alignment film, spread spherical spacers with a particle size of 4 μm on the surface of one of the liquid crystal alignment films, keep the liquid crystal injection port and print a sealant around it (XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) , another substrate was bonded so that the rubbing direction was reversed and the film surfaces faced each other. Thereafter, heat treatment was performed at 150° C. for 60 minutes to harden the sealant and produce void cells. Negative-type liquid crystal MLC-7026 (manufactured by Merck & Co.) was injected into the ghost cell by a reduced-pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. Afterwards, the obtained liquid crystal cell was heated at 120° C. for 1 hour, and left overnight at 23° C. for each evaluation. [Measurement of Pretilt Angle] Using AxoScan Mueller matrix polarimeter (Mueller matrix polarimeter) manufactured by OPTOMETRICS, the pretilt angle in the above-mentioned liquid crystal cell was measured. The lower the value of the pretilt angle, the better. The results are shown in Table 3.

[table 3]

By using the liquid crystal alignment agent of the embodiment of the present invention, a pretilt angle of less than 1.5 degrees can be obtained. Also, generally, it is difficult to obtain good liquid crystal alignment when negative liquid crystal is used as the liquid crystal material, but by using the liquid crystal alignment agent of the embodiment of the present invention, even when negative liquid crystal is used as the liquid crystal material, good liquid crystal alignment can still be obtained (that is, those with excellent AC afterimage characteristics) liquid crystal display elements.

In addition, the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2021-176518 filed on October 28, 2021 are hereby cited and quoted as the disclosure content of the specification of the present invention.

Claims (22)

A polymer composition, characterized by containing the following (A) component and (B) component, (A) component: polymer (A), selected from polyimide precursors having repeating units represented by the following formula (a) and at least one of the group consisting of polyimide which is an imidate of the polyimide precursor, (B) component: polyester (B), having the repetition represented by the following formula (b1) unit and does not have the repeating unit represented by the formula (a) and its imidized structure, X represents a tetravalent organic group, Y represents a divalent organic group derived from diamine, two Rs each independently represent a hydrogen atom or a monovalent organic group, and two Zs each independently represent a hydrogen atom or a monovalent organic group, X _ar represents a 4-valent organic group derived from an aromatic tetracarboxylic dianhydride or its derivatives, the two Rs independently represent a hydrogen atom or a 1-valent organic group, and E contains two hydroxyl groups removed from an organic diol. A divalent organic group with a hydrogen atom, the organic diol contains a divalent organic group represented by the following formula (EG), n is an integer of 5 or more, and R represents a hydrogen atom or a methyl group. The polymer composition according to claim 1, wherein, in the formula (EG), n is an integer of 5-40. The polymer composition according to Claim 1 or 2, wherein the organic diol in the formula (b1) is a diol in which hydrogen atoms are bonded to both ends of the divalent organic group represented by the above formula (EG). The polymer composition according to any one of claim items 1 to 3, wherein X _ar in the formula (b1) is derived from a tetravalent organic group of tetracarboxylic dianhydride represented by the following formula (t) or derivatives thereof , In the formula, _X is a structure selected from the following formulas (X1-24) and (X1-25), * represents an atomic bond, In the formulas (X1-24)~(X1-25), j and k are integers of 0 or 1, and _A1 and _A2 each independently represent a single bond, -O-, -CO-, -COO-, phenylene A group, a sulfonyl group, or an amido group, and a plurality of A ₂ may be the same or different. The polymer composition as claimed in item 4, wherein the formulas (X1-24) and (X1-25) are any one of the following formulas (X1-26)~(X1-41), . The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the polyester (B) further has a repeating unit represented by the following formula (b2), A ₁ is a divalent organic group derived from diisocyanate, and A ₂ is a divalent organic group in which hydrogen atoms contained in two hydroxyl groups are removed from organic diol. The polymer composition according to any one of claims 1 to 6, wherein Y in the formula (a) is selected from diamines represented by formula (O), diamines having amide bonds or urea bonds, 3,3'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane Ketone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, the following formula ( Diamine represented by d _o ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and diamine having the group "-N(D)-" The divalent organic group of the diamine in the group, D represents the protective group that will be removed by heating and replaced by a hydrogen atom, Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring. The two Ars can be the same or different. Any hydrogen atom in the above-mentioned benzene ring, biphenyl structure, or naphthalene ring can also be substituted by a monovalent group, and p is 0 or an integer of 1, Q ₂ represents -(CH ₂ ) _n -, or at least a part of -CH ₂ - of the -(CH ₂ ) _n - is replaced by -O-, -C(=O)- or -OC(= O)-the base substituted by any one of them, n is an integer of 2~18, When there are two or more m, each of the two or more m may be the same or different, and one or more hydrogen atoms on the benzene ring may be substituted by a monovalent group. As the polymer composition of claim item 6 or 7, wherein, _A in the formula (b2) is derived from diisocyanate (DI EG ), diisocyanate (DI _EG ) having a divalent organic group represented by the formula (EG ₎ ) divalent organic group of aromatic diisocyanate other than diisocyanate (DI _EG ) or aliphatic diisocyanate other than diisocyanate (DI EG ). The polymer composition according to any one of claims 6 to 8, wherein the organic diol in the formula (b2) is a diol containing a divalent organic group represented by the above formula (EG). Such as the polymer composition of claim item 9, wherein the diol containing the divalent organic group represented by the formula (EG) is one in which hydrogen atoms are bonded to both ends of the divalent organic group represented by the above formula (EG) diol. The polymer composition according to any one of claims 1 to 10, wherein X in (a) is derived from a 4-valent organic group derived from acyclic aliphatic tetracarboxylic dianhydride or derivatives thereof, derived from aliphatic A tetravalent organic group derived from a cyclic tetracarboxylic dianhydride or a derivative thereof, or a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof. The polymer composition according to any one of Claims 1 to 11, wherein X in (a) is a tetravalent organic group derived from tetracarboxylic dianhydride represented by formula (t) or a derivative thereof, In the formula, _X is selected from the structures in the following formulas (X1-1) ~ (X1-25), * represents an atomic bond, In the formulas (X1-1)~(X1-4), _R1 ~ _R21 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1~6 carbons, an alkenyl group with 2~6 carbons, or an alkenyl group with 2 carbons. ~6 alkynyl groups, monovalent organic groups with 1 to 6 carbon atoms containing fluorine atoms, or phenyl groups, * represents atomic bonds, and in formulas (X1-24)~(X1-25), j and k are 0 or An integer of 1, A ₁ and A ₂ each independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amido, and a plurality of A ₂ may be the same or different. As the polymer composition according to any one of claims 1 to 12, the polymer (A) further has a repeating unit represented by the following formula (U), U ₁ is a divalent organic group, U _1′ is a divalent organic group derived from diamine, and C ₁ and C _1′ are each independently a hydrogen atom or a monovalent organic group. The polymer composition according to any one of claims 1 to 13, wherein the polymer (A) is a polymer whose ends are sealed. The polymer composition according to any one of claims 5 to 14, wherein the content ratio of the repeating unit represented by (b1) is 10 mol% or more of the total repeating units constituting the polyester (B). The polymer composition according to any one of claims 1 to 15, further containing a compound selected from crosslinking compounds, functional silane compounds, metal chelate compounds, hardening accelerators, surfactants, antioxidants, and sensitizers , preservatives, and at least one additive component in the group consisting of compounds for adjusting the dielectric constant and/or resistance of the resin film. The liquid crystal alignment agent according to Claim 1, wherein the polyester (B) does not have a repeating unit represented by the following formula (b2), A ₁ is a divalent organic group derived from diisocyanate, and A ₂ is a divalent organic group in which hydrogen atoms contained in two hydroxyl groups are removed from organic diol. A liquid crystal alignment agent is composed of the polymer composition according to any one of claims 1 to 17. A resin film obtained by using the polymer composition according to any one of claims 1 to 17. A liquid crystal alignment film formed by using the liquid crystal alignment agent according to claim 18. A liquid crystal display element comprising the liquid crystal alignment film according to claim 20. A method for manufacturing a liquid crystal display element, comprising the following steps (1) to (3), Step (1): Coating the liquid crystal alignment agent according to claim 18 on the substrate, Step (2): calcining the coated liquid crystal alignment agent to obtain a film, Step (3): performing alignment treatment on the film obtained in step (2).