TWI596201B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment agent used for producing a liquid crystal alignment film, a liquid crystal alignment film using the same, and a liquid crystal display element.

Liquid crystal display elements are now widely used as display devices. The liquid crystal alignment film of the constituent members of the liquid crystal display element is a film for uniformly aligning liquid crystals, but not only the alignment uniformity of the liquid crystal but also various characteristics are required.

For example, in the production step of the liquid crystal alignment film, the rubbing of the surface of the polymer film is generally performed by using a cloth to perform an alignment treatment. However, when the friction resistance of the liquid crystal alignment film is insufficient, the film is cut to cause scratches or dust, or the film is peeled off, and the display quality of the liquid crystal display element is lowered. Further, a liquid crystal display element is driven by applying a voltage to the liquid crystal. Therefore, when the voltage holding ratio (VHR) of the liquid crystal alignment film is low, a sufficient voltage is not applied to the liquid crystal, and the display contrast is lowered. Further, when the voltage of the liquid crystal is driven, the liquid crystal alignment film generates electric charge accumulation, or when the accumulated electric charge is removed, it takes a time to cause image sticking or burn-in of the display.

There are various proposals that meet some of the above requirements. example As proposed in Patent Document 1, a method of obtaining a liquid crystal alignment film having excellent friction resistance and having a residual image or residual image can be obtained. Further, Patent Document 2 proposes a method of obtaining a liquid crystal alignment film having a liquid crystal alignment property, an alignment restraining force, a friction resistance, a high voltage holding ratio, and a low charge accumulation.

[prior technical literature] [Patent Document]

[Patent Document 1] International Publication No. WO02/33481

[Patent Document 2] International Publication No. WO2004/053583

In recent years, high-definition images such as photographs are displayed by a multi-function mobile phone (smartphone) or a tablet terminal, or an animation or the like is displayed. For a liquid crystal display device mounted thereon, it is necessary to communicate with a television or a computer. High quality display performance of equal or higher.

However, the display screen for the use of a mobile phone or a tablet terminal is not used for other purposes, in the case of frequent on-off display (or frequent on-off of the backlight), and at the moment after the display, the point that the user is watching. Too often characteristic. Therefore, the charge accumulation and the like are required to be more severe than ever.

An object of the present invention is to solve the above problems of the prior art and to provide a frictional resistance, a high voltage holding ratio, and a charge. A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element which accumulate a very small liquid crystal alignment film.

In order to achieve the above object, the inventors of the present invention have carefully studied the results and have achieved the present invention which is hereinafter required.

A liquid crystal alignment agent comprising the following component (A) and the following component (B).

(A) component: at least one selected from the polyimine precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, and the polyimine obtained by subjecting the polyimine precursor to ruthenium imidization a polymer,

The tetracarboxylic acid component comprises 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride and 3,4-dicarboxy-1,2,3,4-tetrahydrogen. At least one selected from the group consisting of 1-naphthalene succinate diester and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinate diester dichloride, and the aforementioned diamine component is included A polymer of a diamine having a side chain represented by the following formula (1).

(In the formula (1), P ¹ represents a single bond or a divalent organic group, and Q ¹ , Q ² and Q ³ each independently represent a divalent benzene ring or a cyclohexane ring, and p, q and r each independently represent 0 or An integer of 1 , P ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton)

(B) component: at least one selected from the polyimine precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, and the polyimine obtained by subjecting the polyimine precursor to ruthenium imidization a polymer,

The tetracarboxylic acid component comprises 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride and 3,4-dicarboxy-1,2,3,4-tetrahydrogen. At least one selected from the group consisting of 1-naphthyrusuccinate diester and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinate diester dichloride, and the aforementioned diamine component is only A polymer comprising a diamine having a -CR ²¹ ₂ - group in the main chain (wherein two R ²¹ each independently represent a hydrogen atom or an organic group, and two R ²¹ together form a cyclic structure).

2. The liquid crystal alignment agent of the above-mentioned item (1), wherein the diamine component is composed of only a diamine represented by the following formula (2).

(In the formula (2), two X each independently represent an oxygen atom or a single bond, n represents an integer of 1 to 10, and two R ²² each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 2; A fluoroalkyl group or a fluorine atom of 5 or 2 R ²² together form an alkylene group having 2 to 7 carbon atoms, which may also form a cyclic structure).

3. The liquid crystal alignment agent according to item 1 or 2 above, wherein In the component (A), the diamine having a side chain represented by the formula (1) is a diamine represented by the following formula (3).

(In the formula (3), P ¹ represents a single bond or a divalent organic group, and Q ¹ , Q ² , and Q ³ each independently represent a divalent benzene ring or a cyclohexane ring, and p, q, and r each independently represent 0 or An integer of 1 and P ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton).

A liquid crystal alignment film which is obtained by applying the liquid crystal alignment agent according to any one of the above items 1 to 3 to a substrate and firing it.

A liquid crystal display element characterized by having the liquid crystal alignment film of the above item 4.

Since the liquid crystal alignment agent of the present invention contains specific (A) component and (B) component, it can form frictional resistance which maintains the characteristics necessary for the past, has high voltage holding ratio, and satisfies the strict requirements of modern times, and the charge accumulation is very high. Small liquid crystal alignment film.

[Formation of the Invention]

The invention is described in detail below.

The liquid crystal alignment agent of the present invention contains the component (A) and the component (B). The liquid crystal alignment agent refers to a solution for producing a liquid crystal alignment film, and the liquid crystal alignment film refers to a film for alignment of liquid crystal in a predetermined direction. The components contained in the liquid crystal alignment agent of the present invention are described in detail below.

<(A) component>

The component (A) contained in the liquid crystal alignment agent of the present invention is obtained by polymerizing a tetracarboxylic acid component and a diamine component, and preliminarily polymerizing the polyimide precursor. A polymer obtained by amination of at least one selected polyimine. The polyimine precursor is, for example, polylysine (also called polyamic acid) or polyphthalate.

In the component (A), the tetracarboxylic acid component contains 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (hereinafter also referred to as "TDA"), 3, 4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid diester (hereinafter also referred to as "TDA diester"), and 3,4-dicarboxy-1,2,3,4 At least one selected from tetrahydro-1-naphthalene succinate diester dichloride (hereinafter also referred to as "TDA diester dichloride"). Therefore, as described later, the polymer of the component (A) has a tetravalent structure represented by the following formula (4) derived from TDA, TDA diester or TDA diester dichloride.

The content of the total amount of TDA, TDA diester and TDA diester dichloride in the component (A) is, for example, 20 to 100 mol%, preferably 40 to 100 mol%. %.

Further, in the component (A), the diamine component which is subjected to a polymerization reaction with the tetracarboxylic acid component contains a diamine having a side chain represented by the above formula (1). The main chain of the diamine means a structure in which two amine groups of the diamine are bonded, and the side chain of the diamine means a structure branched by a structure in which two amine groups of the diamine are bonded. Therefore, the polymer of the component (A) contains a diamine of a side chain represented by the formula (1) which the diamine component of the raw material has, and the polymer of the component (A), for example, has a benzene ring in the main chain, as described later in detail, and There is a structure in which -P ¹ -(Q ¹ ) _p -(Q ² ) _q -(Q ³ ) _r -P ² bonded to the benzene ring is a side chain.

In the side chain represented by the formula (1), a TN (Twisted Nematic) mode requiring a lower pretilt angle of 3 to 5°, or an OCB (Optically Compensated Bend) mode requiring a higher pretilt angle of 8 to 20°, It is preferred that (-P ¹ -(Q ¹ ) _p -(Q ² ) _q -(Q ³ ) _r -P ² ) exhibits a lower side chain with a slope.

The tilt exhibits a smaller structure. For example, in the formula (1), P ¹ is -O-, -NHCO- or -CONH-, p is 0 to 1, q is 0 to 1, and r is preferably 0. When p and/or q is 1, P ² is preferably a linear alkyl group having 1 to 12 carbon atoms, and when p=q=r=0, P ² is a linear alkyl group having 10 to 22 carbon atoms or The divalent organic group selected from the organic group having 12 to 25 carbon atoms of the steroid skeleton is preferred. The specific structure in which the side chain which exhibits lower energy is inclined is shown in Table 1, but is not limited thereto. Further, in the present specification, the organic group means, for example, -O-, -NHCO-, -CONH-, -COO- or a hydrocarbon group which may have N or O.

From the viewpoint of electrical properties, a diamine having a long-chain alkyl side chain of [1-1] in Table 1 is preferable, and from the viewpoints of liquid crystal alignment property and stability of pretilt angle, it is preferred that [1- 9] shows the diamine of the side chain.

Further, in the VA (Vertical Alignment) mode or the like, vertical alignment can be obtained by using a side chain which exhibits a large potential by tilting. A preferred structure of the formula (1) in the VA mode, for example, P ¹ is -O-, -COO-, or -CH ₂ O-, p is 0 to 1, q is 0 to 1, r is preferably 0 to 1, and P ^{2 is} preferably 2 to 22. When p = q = r = 0, P ^{2 is} preferably a linear alkyl group having 18 to 22 carbon atoms or a divalent organic group having an organic group having 12 to 25 carbon atoms of a steroid skeleton. The specific structure of the side chain which exhibits a larger tilt is shown in Table 2-1 and Table 2-2.

These side chains are inclined to exhibit high energy and are preferably used in the VA mode. In particular, a diamine having a side chain of [1-15], [1-31] or the like has a high tilt display energy and a vertical alignment with a relatively small amount of side chains, and thus is preferable, particularly having [1-18] Or the diamine of the side chain of [1-34] has an extremely high tilt display property and can be vertically aligned with a very small amount of side chains, so that it is preferable in terms of printability of the liquid crystal alignment agent.

Further, the diamine having a side chain represented by the formula (1), P ^{1 is} preferably -NHCO-, and the P ² is an alkyl group having 1 to 16 carbon atoms, preferably 3 to 10 carbon atoms. Further, Q ¹ , Q ² , Q ³ and p, q, and r may be selected as appropriate. Further, when the diamine has a benzene ring in the main chain and has a structure in which -P ¹ -(Q ¹ ) _P -(Q ² ) _q -(Q ³ ) _r -P ^{2 is} bonded to the benzene ring as a side chain The position of each substituent on the benzene ring is not particularly limited, and it is preferred that the positional relationship of the two amine groups is meta or para.

Examples of the diamine having the side chain represented by the above formula (1) include the following [DA-1] to [DA-26].

(In the formula [DA-1] to the formula [DA-5], R ₆ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(In the formula [DA-6] to the formula [DA-9], the S ₅ systems may each be the same or different, and represent -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O -, -CO-, or -NH-, R ₆ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(In the formula [DA-10] and the formula [DA-11], S ₆ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, or -CH ₂ OCO-, R ₇ -based carbon Alkyl groups of 1 to 22, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups).

(In the formula [DA-12] to the formula [DA-14], S ₇ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, or -CH ₂ -, R ₈ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formula [DA-15] and the formula [DA-16], S ₈ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O-, or -NH-, R ₉ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, Ethyloxy, or hydroxy).

(In the formula [DA-17] to the formula [DA-20], R ₁₀ is an alkyl group having 3 to 12 carbon atoms, and a cis-trans isomerism system of 1,4-cyclohexylene group is each Trans isomer).

The content of the diamine having the side chain represented by the above formula (1) is preferably from 5 to 50 mol% based on the total amount of the diamine component, and is particularly preferably from the viewpoint of uniformity of pretilt angle or printability. 30 moles %.

In the component (A), the diamine having a side chain represented by the formula (1) is a diamine represented by the above formula (3), that is, the main chain has a benzene ring, and has a -P ¹ - bonded to the benzene ring. Q ¹ ) _p -(Q ² ) _q -(Q ³ ) _r -P ² is a diamine having a side chain structure, and is preferable from the viewpoint of availability and the like.

In the diamine represented by the formula (3), the position of each substituent on the benzene ring is not particularly limited, and it is preferred that the positional relationship of the two amine groups is meta or para.

The tetracarboxylic acid component of the raw material of the component (A) may contain a tetracarboxylic acid derivative other than the above-mentioned TDA, TDA diester or TDA diester dichloride. As the other tetracarboxylic acid derivative in the component (A), for example, the following tetracarboxylic dianhydride is available.

a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4 - cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2, 4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, bicyclo [3.3.0 Octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid Anhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, tricyclo[4.2.1.0 ^2,5 ]decane- 3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride, hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ] Alkane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride and the like.

The aromatic tetracarboxylic dianhydride is, for example, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid Acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,2,5,6 - naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like.

The tetracarboxylic dianhydride may be used in combination with the liquid crystal alignment property, the voltage holding ratio, and the accumulated charge of the liquid crystal alignment film to be formed, and may be used in one type or in combination of two or more types.

The tetracarboxylic acid component of the raw material of the component (A) may contain other tetracarboxylic acid derivatives, for example, a dicarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl diester dichloride. Further, when the tetracarboxylic acid component contains such a dialkyl tetracarboxylate or a dialkyl dicarboxylate dichloride, the polymer becomes a polyimide precursor, that is, a polyphthalate. The dicarboxylic acid dialkyl ester which can be used is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters. Its specific example The following.

Specific examples of the aliphatic tetracarboxylic acid diester include, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane. Dialkyl tetracarboxylate, dialkyl 1, 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylate, 1,2,3,4-tetramethyl-1,2,3 , 4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2 , 4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro- Dialkyl 1-naphthalene succinate, dialkyl 1,2,3,4-butanetetracarboxylate, dicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3',4,4'-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetic acid dialkyl ester, cis-3,7-dibutylcyclooctane- 1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0 ^2,5 ]decane-3,4,7,8-tetracarboxylic acid-3,4 : 7,8-Dialkyl ester, hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ]hexadecane-4,5,11,12-tetracarboxylic acid- 4,5:11,12-dialkyl ester and the like.

The aromatic tetracarboxylic acid dialkyl esters are, for example, dialkyl pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2',3,3'-biphenyl. Dialkyl tetracarboxylic acid, dialkyl 2,3,3',4'-biphenyltetracarboxylate, dialkyl 3,3',4,4'-benzophenone tetracarboxylate, 2 , 3,3',4'-dibenzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-dicarboxyphenyl)decane Ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl ester, and the like.

Further, the tetracarboxylic acid component of the raw material of the component (A) may contain a tetracarboxylic acid dialkyl diester dichloride of another tetracarboxylic acid derivative, for example There is a dichloride of the above tetracarboxylic acid diester.

The content of the total amount of the tetracarboxylic acid component other than the tetracarboxylic acid component (T), the TDA diester, and the other tetracarboxylic acid derivative other than the TDA diester dichloride is preferably 0 to 80 m. %, more preferably 0 to 40% by mole.

Further, the diamine component of the raw material of the component (A) may contain a diamine other than the diamine having the side chain represented by the above formula (1). The other diamine in the component (A) may, for example, be an alicyclic diamine, an aromatic diamine, a heterocyclic diamine, an aliphatic diamine or a urea-bonded diamine.

Examples of the alicyclic diamine are, for example, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'- Diamino-3,3'-dimethyldicyclohexylamine, isophorone diamine, and the like.

Examples of the aromatic diamines include, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-di Aminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-di Aminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2 , 2'-Dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminopurine, 4,4'-diaminopurine, 4,4'-di Aminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'- Diaminodiphenyl hydrazine, 4,4'-diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic acid, 4 , 4'-bis(4-aminophenoxy)bibenzyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-(4-amino) Phenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]anthracene , bis[4-(4-aminophenoxy)phenyl]anthracene, 1,1-bis(4-aminophenyl)cyclohexane, α,α'-bis(4-aminophenyl) -1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-dual (4 -aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diamine Naphthalene, 1,5-diaminoguanidine, 1,3-diaminoguanidine, 1,6-diaminoguanidine, 1,8-diaminopurine, 2,7-diaminoguanidine, 1 , 3-bis(4-aminophenyl)tetramethyldioxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4-aminophenyl) Ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1 , 7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl)decane, 1,10 - bis(4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5- Bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8 - bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, di 4-aminophenyl)propane-1,3-dicarboxylate, di(4-aminophenyl)butane-1,4-dicarboxylate, bis(4-aminophenyl)pentane Alkane-1,5-diester, bis(4-aminobenzene Hexane-1,6-diester, bis(4-aminophenyl)heptane-1,7-diester, bis(4-aminophenyl)octane-1,8-di Acid ester, bis(4-aminophenyl)decane-1,9-diester, bis(4-aminophenyl)decane-1,10-diester, 1,3-double [4 -(4-Aminophenoxy)phenoxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4 -aminophenoxy)phenoxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-amine Phenoxy)phenoxy]heptane, 1,8-bis[4-(4-aminophenoxy)phenoxy]octane, 1,9-bis[4-(4-aminobenzene) Oxy)phenoxy]decane, 1,10-bis[4-(4-aminophenoxy)phenoxy]nonane, and the like.

Examples of the aromatic-aliphatic diamine include a diamine represented by the following formula [DAM].

(In the formula [DAM], Ar represents a benzene ring or a naphthalene ring, R ₁ is an alkylene group having 1 to 5 carbon atoms, and R ₂ is a hydrogen atom or a methyl group.

Specific examples of the aromatic-aliphatic diamine include, for example, 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methyl Benzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine 3-(3-amine Propyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4 -aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylaminobutyl)aniline, 3- (5-Aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl)aniline, 2-(6-Aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-(6-aminonaphthalene) Ethylamine and the like.

Examples of the heterocyclic diamine include, for example, 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-di Aminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-amino Phenyl)-1,3,4-oxadiazole and the like.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1, 3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane 1,7-Diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 1 , 12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, and the like.

Examples of the urea bond-containing diamine include N,N'-bis(4-aminophenethyl)urea and the like.

Further, the diamine component in the component (A) may contain the following diamine.

In the formula [DA-31], m is an integer of 0 to 3, and in the formula [DA-34], n is an integer of 1 to 5. By introducing [DA-27] or [DA-28], the voltage holding ratio (also referred to as VHR) of the liquid crystal display element using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention can be further improved. And [DA-29]~[DA-34] is due to the accumulated charge drop of this liquid crystal display element. It is low and has an effect, so it is preferable.

In addition, the diamine component in the component (A) is, for example, a diamine sulfoxane represented by the following formula [DA-35].

(in the formula [DA-35], m is an integer from 1 to 10).

The diamine component in the component (A) is used in combination with one or two or more types of the properties of the liquid crystal alignment, the voltage retention property, and the charge accumulation when the liquid crystal alignment film is used. The ratio at which the mixture is present at this time is not particularly limited.

Further, the molecular weight of the polymer (polyimine imine precursor or polyimine) of the component (A) is considered in consideration of the strength of the obtained liquid crystal alignment film and the workability at the time of formation of the liquid crystal alignment film, and the uniformity of the liquid crystal alignment film. The weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

Further, the polymer of the component (A) is preferably a polyimine. When the component (A) is used as a liquid crystal alignment film, it tends to exist on the surface of the liquid crystal alignment film (that is, on the side opposite to the substrate), and the polymer present on the surface of the liquid crystal alignment film is in contact with the liquid crystal, and directly contributes to the value of VHR. because Therefore, it is preferred that most of the quinone imine groups which do not cause a reversible reaction are preferred. Further, the polyimide imidization ratio of the polyimine is preferably from 60 to 90%.

<(B) component>

The component (B) contained in the liquid crystal alignment agent of the present invention is a polyimine precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, and the ruthenium imidization of the polyimide precursor. A polymer of at least one selected from the obtained polyimine. Examples of the polyimine precursor include polylysine (also referred to as polyamide acid) or polyphthalate.

In the component (B), the tetracarboxylic acid component comprises 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3 At least one of 4-tetrahydro-1-naphthalene succinate diester and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinate diester dichloride. Therefore, as will be described later in detail, the polymer of the component (B) is also a polymer having a tetravalent structure represented by the above formula (4) derived from TDA, TDA diester or TDA diester dichloride.

In the component (B), the content of the total amount of TDA, TDA diester and TDA diester dichloride in the total amount of the tetracarboxylic acid component is 20 to 100 mol%, preferably 40 to 100 mol%.

In the component (B), the diamine component which is polymerized with the tetracarboxylic acid component has only a -CR ²¹ ₂ - group in the main chain (wherein two R ²¹ independently represent a hydrogen atom or an organic group, and two R groups) ²¹ may together form a cyclic structure) diamine (hereinafter, also referred to as "backbone having -CR ²¹ ₂ - groups diamine") is constituted. When the diamine having a -CR ²¹ ₂ - group in the main chain is used, it may be one type or two or more types. The diamine component of the polymer-based raw material of the component (B) is only a diamine having a -CR ²¹ ₂ - group in the main chain, and as described later in detail, the polymer of the component (B) has -CR ²¹ ₂ in the main chain. Structure. Further, the main chain of the diamine means a structure in which two amine groups of a diamine are bonded. Further, the organic group of R ²¹ of the -CR ²¹ ₂ group may, for example, be an alkyl group having 1 to 5 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, or a fluorine atom. Further, two R ²¹ together form, for example, an alkylene group having 2 to 7 carbon atoms, and a cyclic structure can be formed.

Such a diamine having a -CR ²¹ ₂ - group in the main chain, for example, an alicyclic diamine, an aromatic diamine, an aromatic-aliphatic diamine, an aliphatic diamine, a diamine containing a urea bond Wait.

Examples of the alicyclic diamine are, for example, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'- Diamino-3,3'-dimethyldicyclohexylamine, isophorone diamine, and the like.

Examples of the aromatic diamine include, for example, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl (Bibenzyl). 4,4'-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3 , 3'-dimethyldiphenylmethane, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-(4-aminophenoxy)benzene Hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1-bis(4-aminophenyl)cyclohexane, α,α'- Bis(4-aminophenyl)-1,4-diisopropylbenzene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl) Hexafluoropropane, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1 , 8-bis(4-aminophenyl) octane Alkane, 1,9-bis(4-aminophenyl)decane, 1,10-bis(4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)anthracene Alkane, 1,10-bis(4-aminophenoxy)decane, bis(4-aminophenyl)propane-1,3-dicarboxylate, bis(4-aminophenyl)butane- 1,4-diester, bis(4-aminophenyl)pentane-1,5-diester, bis(4-aminophenyl)hexane-1,6-diester, di( 4-aminophenyl)heptane-1,7-diester, bis(4-aminophenyl)octane-1,8-diester, bis(4-aminophenyl)decane- 1,9-diester, bis(4-aminophenyl)decane-1,10-diester, 1,3-bis[4-(4-aminophenoxy)phenoxy]propane , 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4-aminophenoxy)phenoxy]pentane, 1 ,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-aminophenoxy)phenoxy]heptane, 1,8 - bis[4-(4-aminophenoxy)phenoxy]octane, 1,9-bis[4-(4-aminobenzene) Yl) phenoxy] nonane, 1,10-bis [4- (4-aminophenoxy) phenoxy] decane.

Examples of the aromatic-aliphatic diamine include a diamine represented by the following formula [DAM].

(In the formula [DAM], Ar represents a benzene ring or a naphthalene ring, R ₁ is an alkylene group having 1 to 5 carbon atoms, and R ₂ is a hydrogen atom or a methyl group.

Specific examples of the aromatic-aliphatic diamine include, for example, 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methyl Benzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine , 3-(3-Aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl) Aniline, 3-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylamino group Butyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methyl Aminopentyl)aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3 -(6-Aminonaphthyl)ethylamine or the like.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1, 3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane 1,7-Diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1 , 12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, and the like.

Examples of the urea bond-containing diamine include N,N'-bis(4-aminophenethyl)urea and the like.

In addition, the diamine having a -CR ²¹ ₂ - group in the main component of the component (B) is preferably a diamine represented by the above formula (2) from the viewpoint of availability and the like. In the description of the diamine, for example, the component (B), for example, a diamine exemplified by an aromatic diamine or the like may be mentioned.

In this way, it is presumed that a diamine having a -CR ²¹ ₂ - group in the main chain and a tetracarboxylic acid component containing TDA, TDA diester or TDA diester dichloride (hereinafter also referred to as "TDA or the like" are polymerized. The polyimine precursor or polyimine is contained in the liquid crystal alignment agent together with the component (A), and a liquid crystal alignment film having a very high electric resistance can be obtained. When the voltage is applied, the liquid crystal alignment film having a very high resistance is less likely to flow than the liquid crystal alignment agent having a low resistance. Therefore, the voltage of the liquid crystal alignment film itself is hard to accumulate, and it is presumed that the charge accumulation is extremely small in the present invention. Liquid crystal alignment film. Further, since the accumulated electric charge itself is extremely small, there is no problem that it takes time to remove the accumulated electric charge, and residual image or residual image is generated.

The tetracarboxylic acid component of the raw material of the component (B) may contain a tetracarboxylic acid derivative other than the above-mentioned TDA, TDA diester or TDA diester dichloride. The other tetracarboxylic acid derivative in the component (B) is, for example, another tetracarboxylic acid derivative in the above component (A).

The content of the total amount of the tetracarboxylic acid component other than the tetracarboxylic acid component (T), the TDA diester, and the other tetracarboxylic acid derivative other than the TDA diester dichloride is preferably 0 to 80 m. %, more preferably 0 to 60% by mole.

The tetracarboxylic acid component in the component (B) may be the same as or different from the tetracarboxylic acid component in the component (A).

Further, the molecular weight of the polymer (polyimine imine precursor or polyimine) of the component (A) is considered in consideration of the strength of the obtained liquid crystal alignment film, the workability at the time of formation of the liquid crystal alignment film, and the uniformity of the liquid crystal alignment film. The weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

Further, the polymer of the component (B) is preferably a polyimide precursor. When the component (B) is used as a liquid crystal alignment film, it tends to exist on the substrate side on which the liquid crystal alignment agent is applied (that is, on the side opposite to the surface of the liquid crystal alignment film), and the polymer of the component (B) which is in contact with the substrate has a majority polarity. The base has good adhesion to the substrate and is excellent in printability.

The ratio of the component (A) to the component (B) contained in the liquid crystal alignment agent of the present invention is not particularly limited, and is represented by, for example, a mass ratio: (A) component: (B) component = 5 to 50: 95 to 50, Jia is expressed by mass ratio, (A) component: (B) component = 5~30: 95~70.

In this way, the liquid crystal alignment agent of the present invention contains a specific polymer (A) obtained by reacting a tetracarboxylic acid component containing TDA or the like with a diamine component containing a diamine having a side chain represented by the above formula (1). The component is a specific component (B) containing a tetracarboxylic acid component such as TDA and a diamine component composed only of a diamine having a -CR ²¹ ₂ - group in the main chain, and therefore, as described later, As shown in the examples, it is possible to form a liquid crystal alignment film having a very low charge retention rate while maintaining the friction resistance which maintains the characteristics required in the related art, and having a high voltage holding ratio. Therefore, it can be applied to a mobile phone that has a frequent on-off display (or a frequent on-off of the backlight), a point that the user is gazing at the moment after the display, and the like, and has a mobile phone that is less common in other uses. Or tablet terminal use.

The effect of the present invention is a specific polymer (A) obtained by reacting a diamine component containing a tetracarboxylic acid component such as TDA and a diamine containing a side chain represented by the above formula (1). a component, a liquid crystal alignment agent containing a specific component (B) of a polymer obtained by reacting a tetracarboxylic acid component such as TDA and a diamine component having only a diamine having a —CR ²¹ ₂ - group in a main chain, The effect that can be played at the beginning. For example, when a polymer which does not use TDA or the like as a raw material is used, the RDC is large, that is, the charge accumulation is large, and the abrasion resistance is also poor, and the effect of the liquid crystal alignment agent of the present invention cannot be exhibited. Further, when the polymer (B) is a polymer which does not use TDA or the like as a raw material, the RDC is large. Further, even when TDA or the like is used as a raw material, when the diamine component of the raw material does not have a diamine of -CR ²¹ ₂ - in the main chain, the RDC is large.

Further, when a polymer of the above component (A) or a polymer of the component (B) is obtained by polymerization of a tetracarboxylic acid component and a diamine component of the respective raw materials, a known synthetic method can be used. A method of reacting a tetracarboxylic acid component and a diamine component in an organic solvent is generally employed. The reaction of the tetracarboxylic acid component and the diamine component is relatively easy to carry out in an organic solvent, and is preferable in that no by-product is produced.

The organic solvent used for the reaction between the tetracarboxylic acid component and the diamine component is not particularly limited as long as it is a polylysine which is formed by dissolution. Its specific example is as follows.

For example, there are N,N-dimethylformamide, N,N-dimethylacetamidine Amine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, γ-butyl Lactone, isopropanol, methoxymethylpentanol, dipentene, ethyl pentanone, methyl fluorenone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, methyl 赛苏苏(Cellosolve), ethyl celecoxib, methyl sarbuta acetate, ethyl sarbuta acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetic acid Ester, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethyl 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 b Acid ester, butyl butyrate, dibutyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, Cyclohexanone, ethyl acrylate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, pyruvic acid Ethyl ester, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid , 3-methoxypropionic acid propyl ester, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, and the like. These can be used alone or in combination. Even if it does not dissolve polylysine The solvent can be used in combination with the above solvent insofar as it does not precipitate the produced polyamic acid.

Further, since the water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polylysine, it is preferred that the organic solvent be dried as described above.

When the tetracarboxylic acid component and the diamine component are reacted in an organic solvent, the diamine component is dispersed or dissolved in a solution of an organic solvent and stirred, and the tetracarboxylic dianhydride is directly added or dispersed or dissolved in an organic solvent. In contrast, a method in which a diamine component is added to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method in which a tetracarboxylic acid component and a diamine component are alternately added, and the like can be used. Further, when the tetracarboxylic acid component or the diamine component is composed of a plurality of compounds, the reaction may be carried out in a premixed state, or may be sequentially reacted, and a low molecular weight body of each reaction may be subjected to a mixed reaction. After that, it is a high molecular weight body.

The polymerization temperature at this time may be selected from any temperature of from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes too high, making uniform stirring difficult. Therefore, the total concentration of the tetracarboxylic acid component and the diamine component in the reaction solution is preferably from 1 to 50% by mass, preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter an organic solvent can be added.

In the polymerization reaction of polyamine, the total molar ratio of the molar number of the tetracarboxylic acid component to the diamine component is preferably 0.8 to 1.2. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the resulting poly The greater the molecular weight of the proline.

The polyimine is obtained by subjecting the polyimine precursor such as polylysine or polyperurethane to dehydration ring closure. In the polyimine, the dehydration ring closure ratio of the proline group (the imidization ratio) is not necessarily 100%, and can be arbitrarily adjusted in the range of 0% to 100% in accordance with the purpose or purpose.

A method for subjecting a polyimine precursor to ruthenium imidization, for example, a hydrazine imidization in which a solution of a poly phthalic acid or a poly phthalate is directly heated, a catalyst added to a poly phthalic acid or a poly The catalyst oxime in the solution of the glutamate is imidized.

The temperature at which the polyaminic acid or the polyamidomate is thermally imidated in a solution is 100 to 400 ° C, preferably 120 to 250 ° C, and the water formed by the hydrazine imidization reaction It is preferred to carry out the reaction while excluding the outside of the system.

The ruthenium imidization of polylysine or polyamidolate is carried out by adding a basic catalyst and an acid anhydride to a solution of polyaminic acid or polyglycolate at -20 to 250 ° C, preferably It is carried out by stirring at 0 to 180 °C. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. The basic catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity required for the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, purification after completion of the reaction is easy, which is preferable. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

A method of synthesizing a polyphthalate, for example, a chlorine of the above tetracarboxylic acid diester and Thionyl Chloride, sulfuryl chloride, ethylene dichloride, phosphorus oxychloride or the like a reaction of a tetracarboxylic acid diester dichloride obtained by a chemical reaction with a diamine component, or a reaction of a tetracarboxylic acid diester and a diamine component in the presence of a suitable condensing agent or a base, or may be preliminarily polymerized The proline acid is polymerized and obtained by esterification of a carboxylic acid in proline by a polymer reaction.

Specifically, the tetracarboxylic acid diester dichloride and the diamine can be reacted in the presence of a base and an organic solvent at -20 to 150 ° C, preferably 0 to 50 ° C, by reacting for 30 minutes to 24 hours. In hours, preferably 1 to 4 hours to synthesize.

As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, but in order to carry out the reaction stably, pyridine is preferred. The amount of the base to be added is preferably from 2 to 4 times the molar amount of the tetracarboxylic diester dichloride, from the viewpoint of easily removing the amount and easily obtaining a high molecular weight body.

When the polycondensation reaction is carried out in the presence of a condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbon can be used. Diterpenoid hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-three Methylformin, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazole- 1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzo Diphenylzolylphosphonate, 4-(4,6-dimethoxy-1,3,5-tri -2-yl) 4-methoxymorpholine quinone chloride n-hydrate and the like.

Further, in the method using the above condensing agent, when a Lewis acid is added as an additive, the reaction can be efficiently carried out. The Lewis acid is preferably lithium chloride such as lithium chloride or lithium bromide. The amount of the Lewis acid added is preferably 0.1 to 1.0 times the molar amount based on the tetracarboxylic acid diester.

The solvent used in the above reaction may be a solvent used for polymerizing polylysine as described above, but in terms of solubility of the monomer and the polymer, N-methyl-2-pyrrolidone and γ are preferred. - Butyrolactone may be used alone or in combination of two or more. Further, the concentration at the time of synthesis is less likely to occur from the precipitation of the polymer, and is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint of easily obtaining a high molecular weight body. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent for the synthesis of the polyphthalate is preferably dehydrated as much as possible, and it is preferred to prevent the external air from entering in a nitrogen atmosphere.

The polyimine precursor such as polylysine or polylysine is recovered from a reaction solution of a polyamidene precursor such as polyglycolic acid or polyamidomate or a polyimide reaction. In the case of quinone imine, the reaction solution is poured into a weak solvent to precipitate. Examples of the weak solvent for precipitation include methanol, acetone, hexane, butyl sirolimus, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The precipitated polymer is filtered and recovered in a weak solvent, and then dried at normal temperature or under heat at normal pressure or reduced pressure. Further, the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times to reduce impurities in the polymer. In the weak solvent at this time, for example, an alcohol, a ketone, a hydrocarbon or the like is used, and when three or more types of weak solvents selected from the above are used, the purification efficiency can be further improved, which is preferable.

The polyimine precursor obtained by polymerizing the tetracarboxylic acid component and the diamine component is, for example, a polymer containing a repeating unit represented by the following formula [a]. Further, the polyimine precursor having such a repeating unit is subjected to dehydration and ring closure.

(In the formula [a], R ₁₁ is a tetravalent organic group derived from a tetracarboxylic acid component of a raw material (for example, the following formula (c)), and R ₁₂ is derived from a diamine component of a raw material (for example, the following formula (b)) The divalent organic group, A ₁₁ and A ₁₂ hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, each of which may be the same or different, and j represents a positive integer).

In the above formula [a], each of R ₁₁ and R ₁₂ is 1 type, and may be a polymer having the same repeating unit, and R ₁₁ or R ₁₂ is plural, and may be a polymerization of repeating units having different structures. Things.

In the above formula [a], R ₁₁ is a group derived from a tetracarboxylic acid component of a raw material, and therefore, a polyimine precursor of the component (A) and the component (B), wherein R ₁₁ has the above formula (4) The structure. Further, R ₁₂ is a group derived from a diamine component of a raw material, and therefore, a polyimine precursor of the component (A) wherein R ₁₂ has -P ¹ -(Q ¹ ) _p -(Q ² ) _q - (Q ³ ) a side chain of _r -P ² , and a polyimine precursor of the component (B), wherein R ₁₂ has -CR ²¹ ₂ - in the main chain.

(In the formula [b] and the formula [c], R ₁₁ and R ₁₂ are the same as those defined by the formula [a]).

The liquid crystal alignment agent of the present invention contains an organic solvent in addition to the above components (A) and (B). The liquid crystal alignment agent of the present invention is in the form of a solution in which the component (A) and the component (B) are dissolved in an organic solvent.

When the liquid crystal alignment agent of the present invention has a solution form in which the component (A) and the component (B) are dissolved in an organic solvent, the production thereof is not limited. For example, a method of mixing a powder of the component (A) and the component (B), a method of dissolving in an organic solvent, a method of mixing a solution of the powder of the component (A) with a solution of the component (B), mixing a solution of the component (A), and (B) A method of mixing a powder of a component, a method of mixing a solution of the component (A) and a solution of the component (B). When the good solvent in which the component (A) is dissolved is different from the good solvent in which the component (B) is dissolved, a mixed solution of the component (A) and the component (B) can be obtained, and thus the mixture is mixed. A method of combining the solution of the component (A) with the solution of the component (B) is more preferable.

In the case where the solution of the component (A) or the solution of the component (B) is obtained by synthesizing the component (A) or the component (B) in an organic solvent, the obtained reaction solution itself or the reaction solution may be a suitable solvent. Dilution. Further, when the component (A) or the component (B) is obtained as a powder, it may be a solution in which the solution is dissolved in an organic solvent.

The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is uniformly dissolved in the component (A) or the component (B). Specifically, for example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl -2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, γ-butyrolactone, 1,3-dimethyl Imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, and the like. These may be used alone or in combination of two or more. In addition, when it is not possible to dissolve the component (A) or the component (B) uniformly, the solvent may be mixed with the organic solvent as long as the component (A) or the component (B) does not precipitate.

In addition to the above, the liquid crystal alignment agent of the present invention may contain, as a polymer component, a polymer other than the components (A) and (B), insofar as the effect of the present invention is not impaired. Examples of the other polymer include polyacrylic acid, polyamidomate, polyimine or polyamine which are not used as a raw material of any of TDA, TDA diester and TDA diester dichloride.

The polymer component contained in the liquid crystal alignment agent of the present invention The content (concentration) can be appropriately changed depending on the thickness of the liquid crystal alignment film (polyimine film) to be formed, but the content of the polymer component is relatively higher than that of the organic solvent from the viewpoint of forming a uniform and defect-free coating film. The content is preferably 0.5% by mass or more, and is preferably 15% by mass or less, and more preferably 1% to 10% by mass, from the viewpoint of storage stability of the solution. Further, at this time, a thick solution of a polymer component is prepared in advance, and when a thick solution is used as a liquid crystal alignment agent, it can be further diluted. The concentration of the concentrated solution of the polymer component is preferably from 10 to 30% by mass, more preferably from 10 to 15% by mass. Further, when the powder of the polymer component is dissolved in an organic solvent to prepare a solution, heating can be performed. The heating temperature is preferably from 20 ° C to 150 ° C, particularly preferably from 20 ° C to 80 ° C. In addition, when the polymer other than the component (A) and the component (B) is contained, the content of the polymer other than the component (A) and the component (B) in the polymer component is 0.5% by mass to 15% by mass. % is preferably from 1% by mass to 10% by mass.

Further, the liquid crystal alignment agent of the present invention may contain components other than the polymer component. For example, a solvent or a compound which improves the film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied, a compound which improves the adhesion between the liquid crystal alignment film and the substrate, and the like.

Specific examples of the solvent (weak solvent) for increasing the uniformity of the film thickness or the surface smoothness are as follows.

For example, isopropanol, methoxymethylpentanol, methyl stilbene, ethyl celecoxib, butyl sedum, methyl sarbuta acetate, ethyl serosu acetate, Butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, C Glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol Methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, dibutyl ether, diisobutyl ketone , methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-heptane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid n-Butyl ester, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate , 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1- Ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, C Glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxyl) A solvent having a low surface tension such as propyloxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate.

These weak solvents can be used in one type or in a mixture of plural types. When the weak solvent is used, it is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass based on the total of the organic solvent contained in the liquid crystal alignment agent.

Examples of the compound which improves film thickness uniformity or surface smoothness include a fluorine-based surfactant, a polyoxyn-based surfactant, and a nonionic surfactant.

More specifically, for example, Eftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710 , Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include, for example, a compound containing a functional decane or a compound containing an epoxy group.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxy decane, N-ethoxycarbonyl-3-aminopropyl three Ethoxy decane, N-triethoxymethane alkyl propyl triethylamine, N-trimethoxymethyl propyl propyl triethylamine, 10-trimethoxymethyl decyl-1 , 4,7-triaza (aza) decane, 10-triethoxycarbamido-1,4,7-triazadecane, 9-trimethoxyformamido-3,6-di Azaindenyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N- Phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyl Triethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol condensate Glycerol ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2 , 4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane , N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

Further, in addition to improving the adhesion between the substrate and the film, in order to prevent deterioration of electrical characteristics due to the backlight, an phenoplast-based additive such as the following may be introduced into the liquid crystal alignment agent. The specific phenolic plastic additive is as follows, but is not limited to this structure.

When the compound to be adhered to the substrate is used, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. When the amount used is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the liquid crystal alignment property may be deteriorated.

In addition to the above, the liquid crystal alignment agent of the present invention may be added with a dielectric or a conductive material for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film, as long as the effect of the present invention is not impaired, and A crosslinkable compound for increasing the hardness or tightness of the film as a liquid crystal alignment film may be added.

<Liquid alignment film, liquid crystal display element>

The liquid crystal alignment agent of the present invention is applied to a substrate, and after being fired, it is subjected to alignment treatment by rubbing treatment or light irradiation, and when it is used for vertical alignment or the like, it can be used as a liquid crystal alignment film even if it is not subjected to alignment treatment. The substrate to be used at this time is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. From the viewpoint of simplification of the process, it is preferred to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a liquid crystal is formed. Further, in the case of a reflective liquid crystal display device, an opaque substrate such as a germanium wafer may be used as the substrate on one side, and a material such as aluminum or the like may be used as the electrode.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, and industrially, generally, screen printing, lithography, letterpress printing, and inkjet printing are used. Etc. Other coating methods include, for example, a dipping method, a roll coating method, a die coating method, a spin coating method, and the like, and these methods can be used for the purpose. In the present invention, when the liquid crystal alignment agent is applied to the substrate, it is presumed that the layer of the component (A) and the layer of the component (B) are separated.

The baking of the liquid crystal alignment agent onto the substrate is carried out by heating means such as a hot plate at 50 ° C to 300 ° C, preferably 80 ° C to 250 ° C, to evaporate the solvent to form a coating film. After the firing, the thickness of the formed coating film is too large, which is disadvantageous in terms of power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5~ 300 nm, more preferably 10 to 100 nm. When the liquid crystal is aligned horizontally or obliquely, the coating film after firing is treated by rubbing or polarized ultraviolet irradiation or the like. It is presumed that the liquid crystal alignment film thus obtained is separated into two layers of a layer derived from the component (A) and a layer derived from the component (B).

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention, and a liquid crystal cell is produced by a known method to obtain a liquid crystal display element. In one embodiment, a liquid crystal display device comprising a liquid crystal cell, wherein the liquid crystal cell has two substrates disposed opposite to each other, a liquid crystal layer disposed between the substrates, and disposed between the substrate and the liquid crystal layer, wherein the liquid crystal of the present invention The above liquid crystal alignment film formed by the alignment agent. Such a liquid crystal display element of the present invention has, for example, a twisted nematic (TN: Twisted Nematic) method, a vertical alignment (VA: Vertical Alignment) method, or an IPS (In-Plane Switching) method, and an OCB alignment (OCB: Optically). Various liquid crystal display elements such as Compensated Bend).

In the method for producing a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a spacer is spread on a liquid crystal alignment film of one of the substrates, so that the liquid crystal alignment film surface becomes inside, and then another substrate is bonded, and the liquid crystal is injected under reduced pressure. A method of encapsulating, a method of depositing a liquid crystal alignment film surface with a spacer, a method of laminating a liquid crystal, bonding a substrate, and packaging. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

The liquid crystal has, for example, a positive liquid crystal having a positive dielectric anisotropy or a negative liquid crystal having a negative dielectric anisotropy. Specifically, for example, MLC-2003, MLC-6608, MLC-6609 manufactured by Merck Co., Ltd., or the like can be used.

The liquid crystal display element produced by using the liquid crystal alignment agent of the present invention is also applicable to, for example, a mobile phone, in which the friction resistance of the conventionally required characteristics is maintained, the voltage holding ratio is high, and the charge accumulation which satisfies the modern strict requirements is extremely small. (smartphone) or tablet terminal (terminal).

[Examples]

The invention is illustrated in more detail in the following examples, but the invention is not limited to the examples. The abbreviations used in the following examples and the methods for measuring the respective characteristics are as follows.

(tetracarboxylic dianhydride)

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

PPHT: N,N'-bis(1,2-cyclohexanedicarboxylic anhydride-4-ylcarbonyl)-1,4-phenylenediamine

(diamine)

DBA: 3,5-diaminobenzoic acid

p-PDA: p-phenylenediamine

DDM: 4,4'-diaminodiphenylmethane

BAPU: 1,3-bis(4-aminophenethyl) urine

APC16: 1,3-diamino-4-hexadecyloxybenzene

APC18: 1,3-diamino-4-octadecyloxybenzene

DADPA: 4,4'-diaminodiphenylamine

DA-5MG: 1,5-bis(4-aminophenoxy)pentane

(Organic solvents)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cyrus

GBL: γ-butyrolactone

(additive)

LS-2450: 3-Aminopropyldiethoxymethylnonane

LS-3150: 3-Aminopropyltriethoxydecane

TM-BIP: 2,2'-bis[4-hydroxy-3,5-bis(hydroxymethyl)phenyl]propane

In addition, LS-2450 and LS-3150 are respectively Shin-Etsu Chemical Industry Co., Ltd. The trade name of the division.

[Measurement of molecular weight of polymer]

The molecular weight of the polyimine and the poly-proline in the synthesis example is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight is calculated by the value of polyethylene glycol or polyethylene oxide (hereinafter, Also referred to as Mn) and weight average molecular weight (hereinafter also referred to as Mw).

GPC device: (share) made by Shodex (GPC-101)

Pipe column: (share) made by Shodex company (inline of KD803, KD805)

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (additive: lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol/L, phosphoric acid. anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) 10ml/L)

Flow rate: 1.0 mL/min

Standard samples for the production of calibration lines: TSK standard polyethylene oxide (weight average molecular weight of about 900,000, 150,000, 100,000, 30,000) manufactured by TOSOH Co., Ltd. and polyethylene glycol (Polymer top molecular weight (Mp) of about 12,000, manufactured by Polymer Laboratories). 4,000, 1,000). In order to avoid overlapping of the peaks, two samples of nine types of samples of 900,000, 100,000, 12,000, and 1,000, and two types of samples of 150,000, 30,000, and 4,000 were mixed and measured.

[Determination of sulfhydrylation rate]

The oxime imidization ratio of polyimine was determined as follows. 20 mg of polyimine powder was placed in an NMR (Nuclear Magnetic Resonance) sample tube, and 0.53 ml of dihydroquinone (DMSO-d6, 0.05% TMS mixture) was added thereto to completely dissolve it. This solution was measured for proton NMR at 500 MHz by a NMR measuring instrument (JNM-ECA500) manufactured by JEOL DATUM. The ruthenium imidization rate is determined by protons derived from a structure which has no change before and after imidization, and the peak value of the proton is used and the NH group derived from polyamine which is present in the vicinity of 9.5 ppm to 10.0 ppm. The cumulative value of the proton peak is obtained by the following formula.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is the cumulative value of the proton peak derived from the NH group of polylysine, y is the peak cumulative value of the reference proton, and α is the poly-proline (the imidization ratio is 0%), relative to the poly One of the NH protons of proline, the ratio of the number of reference protons.

[Production of liquid crystal cell]

The liquid crystal alignment agent was spin-coated on a substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C for 60 seconds, and then fired in an IR (infrared) oven at 220 ° C for 20 minutes in a nitrogen atmosphere to form a substrate. A film having a film thickness of 100 nm. This coating film surface was rubbed by a friction device having a roll diameter of 120 mm, and was rubbed with a cotton cloth (YA-25C manufactured by Yoshikawa) at a roll rotation speed of 1000 rpm, a roll travel speed of 50 mm/sec, and a pushing amount of 0.4 mm to obtain a liquid crystal alignment film. Substrate.

Prepare two sheets of the above substrate with a liquid crystal alignment film, of which 1 On the liquid crystal alignment film surface of the film, after spreading a spacer of 4 μm, a sealant (Sumitomo Chemical Co., Ltd. NX-1500T) was printed thereon using a Seal dispenser, so that the liquid crystal alignment film faces, the rubbing direction In the orthogonal state, after bonding the other substrate, the sealant was cured (temporarily cured: 80 ° C for 10 minutes, and the present curing: 150 ° C for 1 hour and 45 minutes) to prepare an empty liquid crystal cell. The liquid crystal cell was injected into the liquid crystal cell MLC-2003 (manufactured by Merck Japan Co., Ltd.) by a vacuum injection method, and the liquid crystal cell which was twisted nematic was obtained by closing the injection port. These operations were carried out using the respective liquid crystal alignment agents obtained in Examples 1 to 8 and Comparative Examples 1 to 5.

[Evaluation of friction resistance]

At the stage of obtaining a substrate with a liquid crystal alignment film, the surface of the liquid crystal alignment film was observed by a confocal laser microscope and visually observed, and evaluated based on the following criteria. The results are shown in Table 3.

○: No shaving or frictional damage was observed by a visual or laser microscope.

△: No shaving or rubbing was observed by visual observation, but shaving or rubbing was observed by a laser microscope.

×: Film peeling or rubbing injury was observed by a laser microscope or visual observation.

[VHR (voltage retention rate) measurement]

In the twisted nematic liquid crystal cell produced by the method described in the above [Production of Liquid Crystal Cell], a voltage of 4 V is applied for 60 μs at a temperature of 60 ° C, and a voltage after 166.7 ms is measured, and the voltage can be maintained as a voltage holding ratio. To calculate and evaluate on the basis of the following criteria. Also, the measurement of the voltage holding ratio The VHR-1 voltage retention rate measuring device manufactured by Dongyang Technology Co., Ltd. was used. The results are shown in Table 3.

◎: more than 85%

○: 80%~85%

△: less than 80%

[Measurement of volume resistivity]

Each of the compositions [AL-1] to [AL-10] was filtered through a 0.2 μm filter, and then applied to a glass substrate with an ITO transparent electrode by a spin coater, and dried on a hot plate at 80 ° C for 1 minute. Thereafter, the film was fired at 220 ° C for 20 minutes to form a film having a film thickness of 220 nm. The surface of the coating film was vapor-deposited by vacuum evaporation at a vacuum of 1.0×10 ⁻³ Pa at a vapor deposition rate of 1 nm/s to form 1.0 mm. The upper electrode was used as a sample for volume resistivity measurement.

A voltage of 10 V was applied between the ITO electrode and the aluminum electrode of the sample, and the current value after 180 seconds from the start of application of the voltage was measured. From this value, the measured value of the electrode area and the film thickness was used to calculate the volume resistivity.

Further, the resistance value was measured under the sample substrate, and the backlight of the LED was placed, and the measurement was performed under lighting. The apparatus for measurement was measured under a nitrogen atmosphere using a 6517A ELECTROMETER manufactured by KEITHLEY and a shield box SM-1 equipped with a positioner manufactured by MEASURE Jig Co., Ltd. The results are shown in Table 4.

[RDC (Residual DC Voltage) Measurement]

In the twisted nematic liquid crystal cell produced by the method described in the above [Production of Liquid Crystal Cell], a DC voltage is applied from 0 V at a temperature of 23 ° C, and is applied to 1.0 V at intervals of 0.1 V, and flicker of each voltage is used ( The flicker) amplitude level photoelectric conversion device measures and produces a calibration curve in the flicker amplitude level and the applied voltage. After the liquid crystal cell was placed on the ground for 5 minutes, the AC voltage V50 (voltage at half the luminance) and the DC voltage of 5.0 V were applied for 1 hour, and then the flash voltage amplitude at which only the DC voltage became 0 V was measured, and the previously prepared calibration curve was measured. Control, estimate RDC. The prediction method of this RDC is called the scintillation reference method. Further, when the RDC is small, it means that the charge accumulation is small. The results are shown in Table 3.

◎: not up to 0.05

○: 0.05 or more, less than 0.08

△: 0.08 or more, less than 0.20

×: 0.20 or more

[Synthesis example]

The numerical value in the parentheses described later after the tetracarboxylic acid component or the diamine component or the like indicates the molar fraction of the raw material monomers at the time of polymer synthesis.

(Synthesis Example 1) Modulation of Polymerization and Composition [AL-1: TDA (50) CBDA (50) / DDM (100)] of Polylysine [PAA-1: TDA (50) CBDA (50) / DDM (100)]

In a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, 2.78 g (14.01 mmol) of DDM was weighed, and 17.40 g of GBL was added to dissolve. The solution was cooled to about 10 ° C under a nitrogen atmosphere, and 2.10 g (6.99 mmol) of TDA was added a little at a time, and after returning to room temperature, the reaction was carried out for 2 hours. Then, 1.26 g (6.42 mmol) of CBDA and 17.40 g of NMP were added, and after returning to room temperature, the reaction was carried out for 4 hours to obtain a solution of 15% by mass of polylysine [PAA-1]. The obtained polyaminic acid [PAA-1] had a number average molecular weight of 15,200 and a weight average molecular weight of 47,500.

In a 50 ml Erlenmeyer flask equipped with a stirrer, 15.02 g of a 15 mass% polylysine [PAA-1] solution was weighed, and 16.8 g of GBL and 5.64 g of BCS were added, and the mixture was stirred at room temperature for 2 hours. A composition [AL-1] having a solid content concentration of 6.0% by mass, a GBL of 59% by mass, an NMP of 20% by mass, and a BCS of 15% by mass was obtained.

(Synthesis Example 2) Modulation of composition [AL-2: TDA (50) CBDA (50) / DDM (100) + LS-3150 (1)]

In a 50 ml Erlenmeyer flask equipped with a stirrer, 14.12 g of a 15 mass% polylysine [PAA-1] solution obtained in Synthesis Example 1 was weighed, and GBL 15.56 g, BCS 5.56 g, and LS-3150 were added as NMP. 0.42 g of the solution diluted to 2% by mass and stirred at room temperature for 2 hours to obtain a composition having a solid content concentration of 6.0% by mass, a GBL of 59% by mass, an NMP of 20% by mass, and a BCS of 15% by mass [AL-2] ].

(Synthesis Example 3) Composition [AL-3: TDA (50) CBDA (50) / DDM (100) + LS-3150 (1) + Modulation of TM-BIP(1)]

In a 50 ml Erlenmeyer flask equipped with a stirrer, 14.12 g of a solution of 15% by mass of polylysine [PAA-1] obtained in Synthesis Example 1 was weighed, and 15.35 g of GBL, 5.35 g of BCS, and NMP of LS-3150 were added. 0.42 g of a solution diluted to 5% by mass, 0.42 g of a solution of TM-BIP diluted to 5 mass% with NMP, and stirred at room temperature for 2 hours to obtain a solid content concentration of 6.0% by mass, a GBL of 59% by mass, and NMP of A composition [AL-3] of 20% by mass and a BCS of 15% by mass.

(Synthesis Example 4) Polymerization and Composition of Polylysine [PAA-2: TDA (50) CBDA (50) / BAPU (20) DDM (80)] [AL-4: TDA (50) CBDA (50) / BAPU (20) Modulation of DDM(80)+LS-3150(1)+TM-BIP(1)]

In a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, 0.71 g (2.38 mmol) of BAPU and 1.90 g (9.58 mmol) of DDM were weighed, and 20.18 g of GBL was added to dissolve, and the mixture was cooled to about 10 ° C under a nitrogen atmosphere. TDA 1.80 g (6.30 mmol) was added a little at a time, and after returning to room temperature, the reaction was carried out for 2 hours. Then, 1.08 g (5.44 mmol) of CBDA and 20.18 g of NMP were added, and after returning to room temperature, the reaction was carried out for 4 hours to obtain a solution of 12% by mass of polylysine [PAA-2]. The obtained polyaminic acid [PAA-2] had a number average molecular weight of 12,700 and a weight average molecular weight of 38,200.

In a 50 ml Erlenmeyer flask equipped with a stirrer, 15.01 g of a solution of 12% by mass of polyglycine (PAA-2) obtained was weighed, and GBL was added. 9.78 g, BCS 4.50 g, LS-3150 was diluted with NMP to a solution of 5% by mass of 0.36 g, TM-BIP was diluted with NMP to a solution of 5% by mass of 0.36 g, and stirred at room temperature for 2 hours to obtain a solid concentration. The composition [AL-4] was 6.0% by mass, GBL was 59% by mass, NMP was 20% by mass, and BCS was 15% by mass.

(Synthesis Example 5) Polymerization and Composition of Polylysine [PAA-3: TDA (30) CBDA (70) / DDM (100)] [AL-5: TDA (30) CBDA (70) / DDM (100) + LS-3150 (1) Modulation of +TM-BIP(1)]

In a 50 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, 2.97 g (14.98 mmol) of DDM was weighed, and 18.09 g of GBL was added thereto to dissolve, and the mixture was cooled to about 10 ° C under a nitrogen atmosphere, and TDA 1.35 g (4.50 mmol) was used. After a little addition, after returning to room temperature, the reaction was carried out for 2 hours. Then, CBDA 2.05 g (10.50 mmol) and NMP 18.09 g were added, and after returning to room temperature, the reaction was carried out for 4 hours to obtain a solution of 15% by mass of polyglycine [PAA-3]. The obtained polyaminic acid [PAA-3] had a number average molecular weight of 11,000 and a weight average molecular weight of 41,000.

In a 50 ml Erlenmeyer flask equipped with a stirrer, 15.00 g of a solution of 15% by mass of polyglycine (PAA-3) obtained was weighed, and 15.17 g of GBL, 5.63 g of BCS were added, and LS-3150 was diluted to 5 by NMP. 0.45 g of a mass % solution, 0.45 g of TM-BIP diluted with NMP to a 5% by mass solution, and stirred at room temperature for 2 hours to obtain a solid content concentration of 6.0% by mass, a GBL of 59% by mass, and an NMP of 20% by mass. , BCS is 15 quality % composition [AL-5].

(Synthesis Example 6) Polymerization and composition of polylysine [PAA-4: TDA (70) CBDA (30) / DDM (100)] [AL-6: TDA (70) CBDA (30) / DDM (100) + LS-3150 (1) Modulation of +TM-BIP(1)]

In a 50 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, 2.97 g (14.98 mmol) of DDM was weighed, and 19.86 g of GBL was added thereto to dissolve, and the mixture was cooled to about 10 ° C under a nitrogen atmosphere to give TDA 3.15 g (10.48 mmol) per After a little addition, after returning to room temperature, the reaction was carried out for 2 hours. Then, 0.88 g (4.50 mmol) of CBDA and 19.86 g of NMP were added, and after returning to room temperature, the reaction was carried out for 4 hours to obtain a solution of 15% by mass of polyamic acid [PAA-4]. The obtained polyaminic acid [PAA-4] had a number average molecular weight of 14,500 and a weight average molecular weight of 45,100.

In a 50 ml Erlenmeyer flask equipped with a stirrer, 15.00 g of a solution of 15% by mass of polyglycine (PAA-4) obtained was weighed, and 15.75 g of GBL, 5.63 g of BCS, and LS-3150 were diluted to 5 by NMP. 0.45 g of a mass % solution, 0.45 g of TM-BIP diluted with NMP to a 5% by mass solution, and stirred at room temperature for 2 hours to obtain a solid content concentration of 6.0% by mass, a GBL of 59% by mass, and an NMP of 20% by mass. BCS was 15% by mass of the composition [AL-6].

(Synthesis Example 7) Polymerization of polyaminic acid [PAA-5: TDA (100) / p-PDA (90) APC18 (10)]

In a 50 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, TDA 9.00 g (0.030 mol), p-PDA 2.92 g (0.027 mol), and APC18 1.13 g (0.0030 mol) were used, among NMP 73.40 g, The reaction was carried out at 50 ° C for 24 hours to obtain a solution of polylysine [PAA-5]. The obtained polyaminic acid [PAA-5] had a number average molecular weight of 15,800 and a weight average molecular weight of 49,200.

(Synthesis Example 8) Modulation of Polyimine [SPI-1: TDA (100) / p-PDA (90) APC18 (10)]

In a 100 ml Erlenmeyer flask equipped with a stirrer, 20.00 g of a solution of polylysine [PAA-5] obtained in Synthesis Example 7, 30.67 g of NMP, 7.16 g of acetic anhydride, and 3.32 g of pyridine were added at room temperature. After stirring for 30 minutes, it was stirred at 40 ° C for 3 hours. After the completion of the reaction, 214 g of methanol was slowly injected to precipitate a polymer (polyimine), and after stirring for 30 minutes, the solid was recovered by filtration. The obtained solid was sufficiently washed with methanol, and then vacuum dried at 100 ° C to obtain a polyimine powder. The obtained polyamidimide [SPI-1] had an oxime imidization ratio of 85%.

To 2.60 g of the obtained polyimine powder, 29.00 g of GBL was added, and the mixture was stirred at 50 ° C for 24 hours to be dissolved. After confirming complete dissolution, 6.15 g of GBL 4.00 g and LS-2450 of 2% by mass GBL solution were added at 50 ° C. The mixture was stirred for 24 minutes to obtain a polyimine solution [SPI-1a] having a solid content concentration of 6.0% by mass and a GBL of 94% by mass.

(Synthesis Example 9) Polymerization of polyaminic acid [PAA-6: TDA/BAPU (30) p-PDA (60) APC18]

In a 50 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, TDA 9.31 g (0.031 mol), BAPU 2.77 g (0.0093 mol), p-PDA 2.01 g (0.019 mol), and APC18 1.17 g (0.0031 mol) were used. A solution of polylysine [PAA-6] was obtained by reacting at 50 ° C for 24 hours in NMP 86.38 g. The obtained polyaminic acid [PAA-6] had a number average molecular weight of 10,500 and a weight average molecular weight of 35,900.

(Synthesis Example 10) Modulation of Polyimine [SPI-2: TDA/BAPU (30) p-PDA (60) APC18]

In a 100 ml Erlenmeyer flask equipped with a stirrer, 30.00 g of a solution of the polyamic acid [PAA-6] obtained in Synthesis Example 9, 50.50 g of NMP, 10.01 g of acetic anhydride, and 4.65 g of pyridine were added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was stirred at 40 ° C for 3 hours. After the completion of the reaction, 580 g of methanol was slowly injected to precipitate a polymer, and after stirring for 30 minutes, the solid was recovered by filtration. The obtained solid was sufficiently washed with methanol, and then vacuum dried at 100 ° C to obtain a polyimine powder. The obtained polyamidimide [SPI-2] had a ruthenium iodide ratio of 82%.

To 2.66 g of the obtained polyimine powder, 30.59 g of GBL was added, and the mixture was stirred at 50 ° C for 24 hours to be dissolved. After confirming complete dissolution, 6.35 g of GBL 6.55 g and LS-2450 of 2 mass % GBL solution were added, at 50 ° C. The mixture was stirred for 24 minutes to obtain a polyimine solution [SPI-2a] having a solid content concentration of 6.0% by mass and a GBL of 94% by mass.

(Synthesis Example 11) Polymerization of polyaminic acid [PAA-7: TDA (100) / p-PDA (90) APC16 (10)]

In a 50 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, TDA 7.51 g (0.025 mol), p-PDA 2.43 g (0.023 mol), and APC16 0.87 g (0.0025 mol) were used, among NMP 61.26 g, The reaction was carried out at 50 ° C for 24 hours to obtain a solution of polylysine [PAA-7]. The obtained polyaminic acid [PAA-7] had a number average molecular weight of 13,600 and a weight average molecular weight of 50,200.

(Synthesis Example 12) Modulation of Polyimine [SPI-3: TDA (100) / p-PDA (90) APC16 (10)]

In a 100 ml Erlenmeyer flask equipped with a stirrer, 20.00 g of a solution of polylysine [PAA-7] obtained in Synthesis Example 11, 30.67 g of NMP, 7.18 g of acetic anhydride, and 3.33 g of pyridine were added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was stirred at 40 ° C for 3 hours. After the completion of the reaction, 214 g of methanol was slowly injected to precipitate a polymer, and after stirring for 30 minutes, the solid was recovered by filtration. The obtained solid was sufficiently washed with methanol, and then vacuum dried at 100 ° C to obtain a polyimine powder. The obtained polyamidiamine [SPI-3] had a ruthenium iodide ratio of 88%.

To 2.60 g of the obtained polyimine powder, 29.90 g of GBL was added, and the mixture was stirred at 50 ° C for 24 hours to be dissolved. After confirming complete dissolution, 6.15 g of GBL 4.00 g and LS-2450 of 2% by mass GBL solution were added at 50 ° C. Stir for 24 minutes to obtain a solids concentration of 6.0. %, GBL is a 94% by mass solution of polyimine [SPI-3a].

(Comparative Synthesis Example 1) Polymerization of polyaminic acid [PAA-8: PPHT (90) CBDA (10) / p-PDA (90) APC18 (10)]

In a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, PPHT 2.44 g, CBDA 0.12 g, p-PDA 0.58 g, and APC18 0.26 g were reacted in NMP 19.11 g for 4 hours to obtain polylysine [PAA]. -8] solution. The obtained polyglycolic acid [PAA-8] had a number average molecular weight of 13,000 and a weight average molecular weight of 45,000.

(Comparative Synthesis Example 2) Modulation of Polyimine [SPI-4: PPHT (90) CBDA (10) / p-PDA (90) APC18 (10)]

In a 100 ml Erlenmeyer flask equipped with a stirrer, 22.49 g of a solution of the polylysine [PAA-8] obtained in Comparative Synthesis Example 1, 33.72 g of NMP, 5.96 g of acetic anhydride, and 2.77 g of pyridine were added, and stirred at room temperature. After the minute, the reaction was carried out by stirring at 70 ° C for 3 hours. After the completion of the reaction, 250 g of methanol was slowly injected to precipitate a polymer, and after stirring for 30 minutes, the solid was recovered by filtration. The obtained solid was sufficiently washed with methanol, and then vacuum dried at 100 ° C to obtain a polyimine powder. The obtained polyamidiamine [SPI-4] had a ruthenium iodide ratio of 88%.

To 2.60 g of the obtained polyimine powder, 33 L of GBL was added, and the mixture was stirred at 50 ° C for 24 hours to dissolve, and it was confirmed to be completely dissolved. Thereafter, a polyimine solution [SPI-4a] having a solid content concentration of 6.0% by mass and a GBL of 94% by mass was obtained.

(Comparative Synthesis Example 3) Polymerization and Composition of Polylysine [PAA-9: TDA (50) CBDA (50) / DDM (20) p-PDA (80)] [AL-7: TDA (50) CBDA (50) / DDM ( 20) Modulation of p-PDA(80)+LS-3150(1)]

A 100 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer was weighed, 1.58 g (8.00 mmol) of DDM, 3.46 g (32.00 mmol) of p-PDA, and dissolved in 41.32 g of GBL, and cooled to about 10 in a nitrogen atmosphere. At ° C, TDA 6.00 g (20.00 mmol) was added a little at a time, and after returning to room temperature, the reaction was carried out for 2 hours. Then, 3.52 g (18.00 mmol) of CBDA and 41.32 g of NMP were added, and after returning to room temperature, the reaction was carried out for 4 hours to obtain a solution of 15% by mass of polyglycine (PAA-9). The obtained polyaminic acid [PAA-9] had a number average molecular weight of 7,100 and a weight average molecular weight of 15,000.

To a solution of the obtained 15% by mass of poly-proline (PAA-9), GBL 97.2 g, BCS 48.6 g, and LS-3150 0.15 g were added, and the mixture was stirred at room temperature for 2 hours to obtain a solid content concentration of 6.0% by mass. A composition [AL-7] having a GBL of 59% by mass, an NMP of 20% by mass, and a BCS of 15% by mass.

(Comparative Synthesis Example 4) Polylysine [PAA-10: TDA (70) CBDA (30) / DDM (20) p- Modulation of the polymerization and composition of PDA (80)] [AL-8: TDA (70) CBDA (30) / DDM (20) p-PDA (80) + LS-3150 (1)]

A 100 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer was weighed, 1.58 g (8.00 mmol) of DDM, 3.46 g (32.00 mmol) of p-PDA, and dissolved in 43.46 g of GBL, and cooled to about 10 in a nitrogen atmosphere. At ° C, 8.40 g (28.00 mmol) of TDA was added a little at a time, and after returning to room temperature, the reaction was carried out for 2 hours. Then, 1.88 g (9.60 mmol) of CBDA and 43.46 g of NMP were added, and after returning to room temperature, the reaction was carried out for 4 hours to obtain a solution of 15% by mass of polylysine [PAA-10]. The solution of the obtained poly-proline (PAA-10) had a number average molecular weight of 7,100 and a weight average molecular weight of 15,000.

To the solution of the obtained poly-proline (PAA-10), GBL 97.2 g, BCS 48.6 g, and LS-3150 0.15 g were added, and the mixture was stirred at room temperature for 2 hours to obtain a solid content concentration of 6.0% by mass and a GBL of 59 mass. %, NMP was 20% by mass, and BCS was 15% by mass of the composition [AL-8].

(Comparative Synthesis Example 5) Polymerization and Composition of Polylysine [PAA-11: TDA (50) CBDA (50) / DBA (30) DDM (70)] [AL-9: TDA (50) CBDA (50) / DBA (30) Modulation of DDM(70)+LS-3150(1)+TM-BIP(1)]

In a 100-ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, DDM 2.08 g (10.50 mmol) and DBA 0.68 g (4.50 mmol) were weighed, and GBL 18.06 g was added to dissolve, and the mixture was cooled to about 10 ° C under a nitrogen atmosphere. 2.25 g (7.5 mmol) of TDA was added a little at a time, and after returning to room temperature, the reaction was carried out for 2 hours. Then, add CBDA 1.35g (6.90mmol) and NMP 18.06 g, after returning to room temperature, the reaction was carried out for 4 hours to obtain a solution of 15% by mass of polylysine [PAA-11]. The obtained polyaminic acid [PAA-11] had a number average molecular weight of 9,400 and a weight average molecular weight of 25,900.

In a 50 ml Erlenmeyer flask equipped with a stirrer, 15.05 g of a solution of the obtained polyaminic acid [PAA-11] was weighed, and a solution of GBL 16.02 g, BCS 5.64 g, and LS-3150 diluted with NMP to 5 mass% was added. 0.45 g, TM-BIP was diluted with NMP to 0.45 g of a 5% by mass solution, and stirred at room temperature for 2 hours to obtain a solid content concentration of 6.0% by mass, a GBL of 59% by mass, an NMP of 20% by mass, and a BCS of 15 % by mass of the composition [AL-9].

(Comparative Synthesis Example 6) Polymerization and Composition of Polylysine [PAA-12: TDA (20) CBDA (80) / DADPA (80) DDM (20)] [AL-10: TDA (20) CBDA (80) / DADPA (80) Modulation of DDM(20)]

In a 100-ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, 2.39 g (12.00 mmol) of DADPA and 0.59 g (3.00 mmol) of DDM were weighed, and 55.37 g of NMP was added thereto to dissolve, and the mixture was cooled to about 10 ° C under a nitrogen atmosphere. TDA 0.90 g (3.0 mmol) and CBDA 2.26 g (11.55 mmol) were added a little at a time, and after returning to room temperature, the reaction was carried out for 4 hours to obtain a solution of polylysine [PAA-12].

In a 200 ml Erlenmeyer flask equipped with a stirrer, 61.01 g of a solution of the obtained polyaminic acid [PAA-12] was weighed, 24.60 g of BCS and 36.91 g of NMP were added, and the mixture was stirred at room temperature for 2 hours to obtain a solid fraction. The composition [AL-10] having a concentration of 5.0% by mass, NMP of 75% by mass, and BCS of 20% by mass.

(Comparative Synthesis Example 7) Polymerization of Polylysine [PAA-13:TDA(100)/DA-5MG(100)] and Modulation of Polyimine [SPI-5:TDA(100)/DA-5MG(100)]

In a 100-ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, 3.72 g of DA-5MG and 3.70 g of TDA were reacted in NMP 66.88 g for 4 hours to obtain a solution of polyglycine [PAA-13].

In a 200 ml Erlenmeyer flask equipped with a stirrer, 74.31 g of a solution of the obtained polylysine [PAA-13], 72.31 g of NMP, 15.48 g of acetic anhydride, and 7.19 g of pyridine were added, and the mixture was stirred at room temperature for 30 minutes, and then 40 Stir at °C for 3 hours. After the completion of the reaction, 500 g of methanol was slowly injected to precipitate a polymer, and after stirring for 30 minutes, the solid was recovered by filtration. The obtained solid was sufficiently washed with methanol, and then vacuum dried at 100 ° C to obtain a polyimine [SPI-5] powder.

5.00 g of the obtained polyimine powder was added with 80.00 g of GBL and 15.00 g of BCS, and the mixture was stirred at 50 ° C for 6 hours to obtain a polymer having a solid content concentration of 5.0% by mass, NMP of 80% by mass, and BCS of 15% by mass. Sodium imine solution [SPI-5a].

(Example 1) [AL-1]: [SPI-1a] = 80: 20

The mass ratio of [AL-1] to [SPI-1a] was 80:20, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Example 2) [AL-2]: [SPI-1a] = 80: 20

[AL-2] and [SPI-1a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Example 3) [AL-3]: [SPI-1a] = 80: 20

[AL-3] and [SPI-1a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Example 4) [AL-3]: [SPI-2a] = 80: 20

[AL-3] and [SPI-2a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Example 5) [AL-5]: [SPI-1a] = 80: 20

[AL-5] and [SPI-1a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Example 6) [AL-6]: [SPI-1a] = 80: 20

[AL-6] and [SPI-1a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Example 7) [AL-3]: [SPI-3a] = 80: 20

[AL-3] and [SPI-3a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Example 8) [AL-4]: [SPI-1a] = 80: 20

[AL-4] and [SPI-1a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Comparative Example 1) [AL-9]: [SPI-1a] = 80: 20

[AL-9] and [SPI-1a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Comparative Example 2) [AL-3]: [SPI-4a] = 80: 20

[AL-3] and [SPI-4a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Comparative Example 3) [AL-7]: [SPI-1a] = 80: 20

[AL-7] and [SPI-1a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Comparative Example 4) [AL-8]: [SPI-1a] = 80: 20

[AL-8] and [SPI-1a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

(Comparative Example 5) [AL-10]: [SPI-5a] = 80: 20

[AL-10] and [SPI-5a] were mixed at a mass ratio of 80:20, and stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent.

As shown in Table 3, a polymer obtained by reacting a tetracarboxylic acid component containing TDA with a diamine component containing a diamine having a side chain represented by the above formula (1), and a tetracarboxylic acid component containing TDA and only Examples 1 to 8 of the liquid crystal alignment agent of the polymer obtained by reacting a diamine component having a -CR ²¹ ₂ -diamine in the main chain were excellent in VHR and friction resistance, and the RDC was also very low.

Further, in Comparative Example 2 using a polymer which does not use TDA as a raw material, Comparative Examples 1 and 3 in which a diamine component containing a raw material of the component (B) was used as a polymer having no -CR ²¹ ₂ -diamine as a main chain was used. And 4, Comparative Example 5 in which the component (A) is a diamine having a side chain represented by the formula (1), and the RDC was significantly larger than those of Examples 1 to 8. Further, as is clear from Table 4, the composition [AL-7] to [AL-10] of the polymer having a diamine having no -CR ²¹ ₂ - in the main chain has a low volume resistivity, and thus the composition [AL] -7]~[AL-10] Comparative examples 1 and 3 to 5 used as the component (B) have large RDCs.

Claims (3)

A liquid crystal alignment agent comprising the following component (A) and the component (B): (A) component: a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, and a polymer obtained by subjecting the polyimine precursor to at least one selected from the group consisting of polyamidiamine obtained by ruthenium imidization, wherein the tetracarboxylic acid component comprises 3,4-dicarboxy-1,2,3,4- Tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid diester and 3,4-dicarboxy-1,2,3, At least one selected from the group consisting of 4-tetrahydro-1-naphthalene succinate diester dichloride, and the aforementioned diamine component is a polymer comprising a diamine having a side chain represented by the following formula (1). (In the formula (1), P ¹ represents a single bond or a divalent organic group or an oxygen atom, and Q ¹ , Q ² and Q ³ each independently represent a divalent benzene ring or a cyclohexane ring, and p, q and r are each independently An integer of 0 or 1, wherein P ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton) (B) component: a tetracarboxylic acid component and two a polymer obtained by polymerization of an amine component and at least one polymer selected from the polyimine obtained by ruthenium imidization of the polyimine precursor, wherein the tetracarboxylic acid component comprises 3 , 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid diester And at least one selected from the group consisting of 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinate diester dichloride, and the aforementioned diamine component has only -CR ²¹ ₂ in the main chain. a polymer composed of a diamine in which two R ²¹ each independently represent a hydrogen atom, an organic group or a halogen atom, and two R ²¹ together form a cyclic structure, but in the component (B), the aforementioned two The amine component is composed only of a diamine represented by the following formula (2). (In the formula (2), two X each independently represent an oxygen atom, n represents an integer of from 1 to 10, and two R ²² each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a fluorine having 1 to 5 carbon atoms. The alkyl group or the fluorine atom, or two R ²² together form a C 2 to 7 alkyl group, and may form a cyclic structure. Among the components (A), the diamine having the side chain represented by the formula (1) is a diamine represented by the following formula (3), (In the formula (3), P ¹ represents a divalent organic group or an oxygen atom, and Q ¹ , Q ² and Q ³ each independently represent a divalent benzene ring or a cyclohexane ring, and p, q and r each independently represent 0 or An integer of 1 and P ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton). A liquid crystal alignment film characterized in that a liquid crystal alignment agent according to claim 1 of the patent application is applied to a substrate and fired. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 2 of the patent application.