TW201446839A - Production method for liquid-crystal alignment film, liquid-crystal alignment film, liquid-crystal display element, and liquid-crystal alignment agent - Google Patents

Abstract

A liquid-crystal alignment agent is applied to a substrate and subsequently baked to obtain a liquid-crystal alignment film having an imidization ratio of 50-70%. The liquid-crystal alignment agent includes: a polyimide precursor having repeating units represent by formula [1]; and at least one polymer selected from polyimides which have repeating units represented by formula [1], and which have an imidization ratio of less than 50% (in formula [1]: A1 represents a divalent organic group; A2 represents a divalent organic group; and C1 and C2 each represent hydrogen or a C1-3 alkyl group, and may be the same as or different to each other).

Description

Method for producing liquid crystal alignment film, liquid crystal alignment film, liquid crystal display element, and liquid crystal alignment agent

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

Liquid crystal display elements used in LCD TVs, LCD monitors, etc., are widely used as thinner. Lightweight display unit. Among the liquid crystal display elements, the liquid crystal alignment film serves to align the liquid crystals in a certain direction. The main liquid crystal alignment film currently used in the industry is a liquid crystal alignment agent composed of a solution of polyamic acid, polyamidomate or polyimine from a polyimide precursor. It is formed by coating a substrate and baking it.

In the formation of such a liquid crystal alignment film, since the firing temperature is high, problems such as the inability to use a substrate having low heat resistance are caused, and therefore it is desirable to lower the firing temperature. As a technique for forming a liquid crystal alignment film at a low firing temperature, for example, a liquid crystal alignment film containing a polymer containing a polyurea-based repeating structural unit and a polyfluorene-based repeating structural unit in the same molecule is disclosed (Patent Document) Offer 1 as a reference).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 08-220542

However, the liquid crystal alignment film of Patent Document 1 has a problem that residual DC is high. Moreover, the other electrical characteristics of the liquid crystal alignment film also pursue a high voltage holding ratio.

An object of the present invention is to provide a method for producing a liquid crystal alignment film which can form a liquid crystal alignment film having a low residual DC and a high voltage holding ratio, which can be formed by firing at a low temperature, a liquid crystal alignment film, and a liquid crystal display. The purpose of the component and the liquid crystal alignment agent.

The present invention for solving the above problems is mainly as follows.

A method for producing a liquid crystal alignment film characterized by comprising a polyimine precursor having a repeating unit represented by the following formula [1] and a repeating unit represented by the following formula [1] And a liquid crystal alignment agent of at least one polymer selected from the polyimine having a ruthenium iodization ratio of less than 50% is applied to a substrate and then fired to obtain a liquid crystal having a quinone imidization ratio of 50 to 70%. Orientation film, (In the formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, and C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each may be the same or different).

2. The method for producing a liquid crystal alignment film according to 1, wherein the baking is performed at 210 ° C or lower.

3. The method for producing a liquid crystal alignment film according to the above aspect, wherein the polymer has a side chain represented by the following formula [2]. (In the formula [2], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ₂ Is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ₄ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroidal skeleton having 17 to 51 carbon atoms; And any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom, Y ₅ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on the ring group may be a carbon number of 1 to 3. An alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is an integer of 0 to 4, Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

4. The method for producing a liquid crystal alignment film according to any one of the above aspects, wherein the polymer is obtained by reacting the following components (a), (b) and (c).

(a) component: a compound containing two isocyanate groups in the molecule

(b) Component: a compound containing two grade 1 or 2 amine groups in the molecule

Component (c): a tetracarboxylic acid derivative.

5. The method for producing a liquid crystal alignment film according to the above, wherein the component (b) is a compound having a side chain represented by the above formula [2].

6. The method for producing a liquid crystal alignment film according to the above, wherein the component (b) is a compound represented by the following formula [2a]. (Formula [. 2A] _{is, Y 1, Y 2, Y} 3, Y 4, Y 5, Y 6, n in the formula [2] _{Y 1, Y 2, Y 3} , Y 4, Y 5, Y 6, n is the same, m is an integer of 1 to 4, -(Y ₁ -Y ₂ -Y ₃ -Y ₄ -(Y ₅ ) _n -Y ₆ ) _m represents a substituent Y ₁ -Y ₂ -Y ₃ -Y ₄ - (Y ₅ ) _{n -} Y ₆ has m, and when m is 2 or more, the respective substituents may be the same or different).

The method for producing a liquid crystal alignment film according to any one of the items 4 to 6, wherein the component (c) is a tetracarboxylic dianhydride represented by the following formula [3]. (In the formula [3], Z ₁ is a structure represented by the following formula [3a] to formula [3j])

(In the formula [3a], Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. In the formula [3g], Z ₆ and Z ₇ are a hydrogen atom or a methyl group. , each can be the same or different).

The method for producing a liquid crystal alignment film according to any one of the above aspects, wherein the polymer in the liquid crystal alignment agent is 0.1 to 30% by mass.

9. The method for producing a liquid crystal alignment film according to any one of the preceding claims, wherein the coating is carried out by an inkjet method.

A liquid crystal alignment film produced by the method for producing a liquid crystal alignment film according to any one of 1 to 9.

A liquid crystal alignment film comprising a polyimine having a repeating unit represented by the following formula [1], wherein the ruthenium imidization ratio is 50 to 70%. (In the formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, and C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each may be the same or different).

12. The liquid crystal alignment film according to 10 or 11, which is applicable to a liquid crystal display device having a liquid crystal layer between a pair of substrates including electrodes, and disposed between the pair of substrates A liquid crystal composition of a polymerizable compound polymerized by at least one of an active energy ray and a heat is produced by a step of polymerizing the polymerizable compound while applying a voltage to the electrode.

13. The liquid crystal alignment film according to 10 or 11, which is applicable to a liquid a liquid crystal display device having a liquid crystal layer between a pair of substrates including electrodes, wherein a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates The liquid crystal alignment film is produced by a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

A liquid crystal display device comprising the liquid crystal alignment film according to any one of 10 to 13.

A liquid crystal alignment agent characterized by comprising a polyimine precursor having a repeating unit represented by the following formula [1], (In the formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, and C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each may be the same or different).

According to the present invention, by using a polyimine precursor having a repeating unit represented by the formula [1] or a repeating unit represented by the formula [1], and having a quinone imidization ratio of less than 50% A liquid crystal alignment agent of sulfimine is coated and fired to form a liquid crystal alignment film having a ruthenium iodide ratio of 50 to 70%, thereby obtaining a liquid crystal alignment having a low residual DC and a high voltage retention ratio. membrane. Then, the firing temperature can be, for example, a low temperature of 210 ° C or lower, and a plastic substrate having a low heat resistance can be used as the substrate, and the color filter of the liquid crystal display element accompanying the high-temperature firing can be suppressed. The color characteristics are deteriorated or the energy consumption in the manufacture of the liquid crystal display element can be reduced.

[Best Practice for Carrying Out the Invention]

The invention will be described in detail below.

The method for producing a liquid crystal alignment film of the present invention is obtained by subjecting a polyimine precursor having a repeating unit represented by the above formula [1] and a repeating unit represented by the above formula [1]. A liquid crystal alignment agent of at least one polymer selected from a polyimine having a rate of less than 50% is applied to a substrate and then fired to obtain a liquid crystal alignment film having a ruthenium iodide ratio of 50 to 70%.

The liquid crystal alignment agent used for the production of the liquid crystal alignment film of the present invention contains a polyimine precursor having a repeating unit represented by the above formula [1] or a repeating unit represented by the above formula [1] and is imidized. Polyimine with a rate of less than 50%. It is also possible to contain a polyimine precursor having a repeating unit represented by the above formula [1], and a polyimine having a repeating unit represented by the above formula [1] and having a ruthenium iodide ratio of less than 50%. Both. Further, it may contain a plurality of polyimine precursors having a repeating unit represented by the above formula [1] or a plurality of repeating units represented by the above formula [1] and having a quinone imidization ratio of less than 50. % polyimine. Further, the polyimine precursor refers to polyamic acid or polyphthalate.

A polyimine precursor having a repeating unit represented by the above formula [1] or a polyimine having a repeating unit represented by the above formula [1] and having a ruthenium iodide ratio of less than 50% (hereinafter also referred to as The "polymer having a repeating unit represented by the formula [1]") is preferably a side chain represented by the above formula [2]. When the side chain represented by the above formula [2] is provided, a liquid crystal alignment film which can vertically align the liquid crystal can be produced. For example, when the repeating unit represented by the formula [1] is a side chain represented by the formula [2], A ₁ or A ₂ has a structure represented by the formula [2]. Further, the repeating unit of the polyimine precursor or the polyimine which will be described later may be a side chain represented by the above formula [2].

In the formula [1], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred from the viewpoint of availability of raw materials or ease of synthesis. More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

In the formula [1], Y ₂ is a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferred.

In the formula [1], Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, from the point of synthesis difficulty, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred. More preferably a single _{bond, - (CH 2) c -} (c is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

In the formula [1], Y ₄ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton, and any of the cyclic groups. The hydrogen atom may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Among them, from the point of synthesis difficulty, an organic group having a benzene ring, a cyclohexane ring or a carbon number of 17 to 51 having a steroid skeleton is preferred.

In the formula [1], Y ₅ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and carbon. Alkoxy groups of 1 to 3, fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine-containing alkoxy groups having 1 to 3 carbon atoms or fluorine atoms are substituted. Among them, a benzene ring or a cyclohexane ring is preferred.

In the formula [1], n is an integer of 0 to 4. Among them, the raw material acquisition or the ease of synthesis is preferably 0 to 3. More preferably 0~2.

In the formula [1], Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. . Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

In the formula [1], preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n may be, for example, 13 to 34 in International Publication WO2011/132751 (2011.10.27 publication). The same combinations of (2-1) to (2-629) are shown in Tables 6 to 47 of the items. Further, in the tables of the international publication, Y ₁ to Y ₆ in the present invention are represented by Y1 to Y6, but Y1 to Y6 are those corresponding to Y ₁ to Y ₆ .

The polyimine precursor having the repeating unit represented by the above formula [1] can be, for example, a component (a) having a compound having two isocyanate groups in the molecule and two amines of a first or second order in the molecule. The component (b) of the compound is reacted with the component (c) of the tetracarboxylic acid derivative to produce.

(a) to the component-based _{O = C = NA 1 -N =} C = O (A 1 same as in the formula [1] in the A ₁₎ a compound represented by the. A ₁ may, for example, be a substituent composed of a divalent benzene ring, an alkylene group, an aliphatic ring or a combination thereof in which a hydrogen atom may be substituted with an alkyl group having 1 to 5 carbon atoms. Specific examples of the component (a) include aromatic o-isocyanate, for example, o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and toluene diisocyanate (for example, 2, 4). - phenyl diisocyanate), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylene, 2,2'-bis (4-di Phenyl isocyanate, diphenylmethane 4,4'-diisocyanate, diphenyl ether 4,4'-diisocyanate, diphenyl sulfonium 4,4'-diisocyanate, 3,3'-diphenylphosphonium diisocyanate, 2,2'-diisocyanate benzophenone, etc., aliphatic diisocyanate, for example, isophorone diisocyanate, hexamethylene diisocyanate , tetramethyl-ethyl diisocyanate, and the like. Among them, 2,4-diisocyanatomethylphenylene ester is preferred from the viewpoints of availability, polymerization reactivity, and voltage maintenance ratio.

The component (b) is a compound represented by the following formula [b].

(In the formula [b] _{in, C 1, C 2, A} 2 in the formula [1] of C _1, C _2, A ₂ identical)

A ₂ may, for example, be a divalent organic group derived from the compound of the component (b). Specific examples of the component (b) include a compound represented by the above formula [2a].

The bonding position of the two amine groups (-NH ₂ ) in the above formula [2a] is not limited. Specifically, the position of the 2, 3 on the benzene ring can be exemplified with respect to the bonding group of the side chain (-(Y ₁ -Y ₂ -Y ₃ - Y ₄ -(Y ₅ ) _n -Y ₆ ) _m ) , 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position or 3, 5 position. Among them, from the viewpoint of reactivity in synthesizing a polymer having a repeating unit represented by the formula [1], a position of 2, 4, a position of 2, 5 or a position of 3, 5 is preferred. When the ease of synthesizing the compound represented by the formula [2a] is considered, the position of 2, 4 or 2, 5 is more preferable.

More specifically, the formula [2a] is a structure represented by the following formula [2b-1] to the formula [2b-29].

(In the formula [2b-19]~form [2b-21], R ¹ is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ² is a carbon number An alkyl group of 1 to 18, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formula [2b-22]~form [2b-24], R ³ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - CH ₂ -, R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formula [2b-25] and the formula [2b-26], R ⁷ is an alkyl group having 3 to 12 carbon atoms. Further, the cis-trans isomer of the 1,4-cyclohexyl group is each a trans form The structure is better).

(In the formula [2b-27] and the formula [2b-28], R ⁸ is an alkyl group having a carbon number of 3 to 12. Further, the cis-trans isomer of the 1,4-cyclohexyl group is each a trans form The structure is better).

(In the formula [2b-29], B ⁴ is an alkyl group having 3 to 18 carbon atoms which may be substituted by a fluorine atom, B ³ is a 1,4-cyclohexyl group or a 1,4-phenylene group, and B ² is an oxygen atom. or -COO - * (However, note on "*" is bonded to bond to B ³ are bonded), B ¹ is an oxygen atom or -COO - * (However, note on "*" is bonded to bond with (CH ₂₎ a ² bond). Further, a ¹ is an integer of 2 to 10, and a ³ is an integer of 0 or 1.

When the compound represented by the formula [2a] is used, the liquid crystal can be vertically aligned as described above. The compound represented by the formula [2a] is preferably 5 mol% or more and 80 mol% or less of the entire component (b). More preferably, the compound represented by the formula [2a] is 5 mol% or more and 60 mol% of the total of the component (b) from the viewpoint of liquid crystal alignment. It is particularly preferably 10 mol% or more and 60 mol% or less of the entire component (b).

Component (b) other than the compound represented by the formula [2a], except m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2 , 4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol Further, for example, a diamine compound having a structure represented by the following formula [2b-30] to [2b-41] can be mentioned.

([2b-30] and [2b-31], R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ - or -O-, R ⁶ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group).

(In the formula [2b-32] to the formula [2b-35], A ¹ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

Further, the formula [2b-36] has a photoreactive side chain. Such a photoreactive side chain refers to a portion which is polymerized by irradiation of light, for example, having an acrylic group, a methacrylic group, a lactone group, a maleimine group, a vinyl group, an allyl group or a benzene group. Side chain of vinyl. However, it is not limited to this.

Further, the component (b) other than the compound represented by the formula [2a] may, for example, be 4,4'-diaminobiphenyl or 3,3'-dimethyl-4,4'-diamine group. Benzene, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy- 4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3, 4'-Diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diamino Diphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-di Aminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2' -diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-amine Phenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4' - Thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodi Phenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N -Methyl (3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl (2,2'-diamino) Diphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone , 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1 , 5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diamine Naphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl) Ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1 , 4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3- (4-Aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-amine Benzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methyl)diphenylamine, 4,4'- [1,3-phenylene bis(methyl)diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3,4'-[1,3 -phenylphenylbis(methyl)diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[1,3-phenylene Bis(methyl)diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone], 1,4-phenylphenylbis[(3-aminophenyl)methanone ], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene Bis(4-aminobenzoic acid ester), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoic acid) Ester), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)-p-phenylene Formate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene) Bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene) Bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-amine Phenyl phenyl phthalamide, N, N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl) meta-xylene Indoleamine, N,N'-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-amino group Phenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-double ( 3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2, 2'-bis(3-Amino-4-methyl Phenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy) Butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxyl) Pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminobenzene) Oxy) heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminobenzene Oxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-bis(4-amino Phenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3- Aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-double (3-Aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1 , 4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1 , 9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.

Further, the component (b) may, for example, be an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the side chain of the diamine, and further have a large cyclic substituent composed of the above. Wait. Specifically, for example, a diamine compound represented by the following formulas [DA1] to [DA13].

(In the formula [DA1]~form [DA6], A ¹ is -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ² It is a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(In the formula [DA7], p is an integer from 1 to 10).

Further, as the component (b), a diamine compound represented by the following formula [DA8] to formula [DA13] can also be used.

(In the formula [DA10], m is an integer of 0 to 3, and in the formula [DA13], n is an integer of 1 to 5).

Further, the diamine compound represented by the following formula [DA14] to formula [DA17] can also be used without impairing the effects of the present invention.

(In the formula [DA14], A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O -, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, m ¹ and m ² are each an integer of 0 to 4, and m ¹ + m ² is an integer of 1 to 4, and in the formula [DA15], m ³ and m ⁴ are each An integer of 1 to 5, in the formula [DA16], A ² is a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ is an integer of 1 to 5, and in the formula [DA17], A ³ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N ( CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-,m ⁶ is an integer from 1 to 4).

Further, the diamine compound represented by the following formula [DA18] can also be used without impairing the effects of the present invention.

(In the formula [DA18], A ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ ) - or -N(CH ₃ )CO- selected divalent organic group, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, and A ³ is a single bond , -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or -O(CH ₂ ) _m - (m is an integer from 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4).

Further, as the other diamine compound, a diamine compound represented by the following formula [DA19] and formula [DA20] can also be used.

The component (b) has a solubility in a solvent of a repeating unit represented by the formula [1], a coating property of a liquid crystal alignment agent, an alignment property of a liquid crystal as a liquid crystal alignment film, a voltage retention ratio, and an accumulation. The characteristics such as electric charge can be used in combination of one type or two types or more.

The component (c) is a tetracarboxylic acid derivative, for example, a tetracarboxylic dianhydride represented by the above formula [3]. In the formula [3], Z _{1 is} represented by the formula [3a], the formula [3c], the formula [3d], the formula [3e], and the formula [the ease of synthesis or the ease of polymerization reactivity in the production of a polymer [ The structure represented by 3f] or the formula [3g] is preferred. More preferably, the structure represented by the formula [3a], the formula [3e], the formula [3f] or the formula [3g] is preferably the formula [3a], the formula [3e], the formula [3f] or the formula [3g].

The tetracarboxylic dianhydride represented by the formula [3] is preferably 1 mol% or more of the entire component (c). More preferably, it is 5 mol% or more, and more preferably 10 mol% or more.

Further, when Z ₁ is a tetracarboxylic dianhydride represented by the formula [3] of the formula [3e], the formula [3f] or the formula [3g], the amount of use is 20 mol of the entire component (c). More than % is better, and more preferably 30% or more. Further, all make component (c) is of the formula Z ₁ based [3E], the tetracarboxylic dianhydride of formula [3F] or formula [3G] The configuration of the formula [3] FIG.

The component (c) other than the tetracarboxylic dianhydride represented by the formula [3] may, for example, be a tetracarboxylic acid compound, a tetracarboxylic dianhydride or a tetracarboxylic acid dihalide compound shown below. That is, the component (c) other than the tetracarboxylic dianhydride represented by the formula [3], for example, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalene Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-nonanetetracarboxylic acid, 1,2,5,6-nonanedicarboxylic acid, 3,3', 4, 4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid Acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3, 4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-dual (3,4 -Dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridine four Carboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-nonanedicarboxylic acid Or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

In the component (c), the solubility of the polymer having the repeating unit represented by the formula [1], the solubility of the liquid crystal alignment agent, the alignment property of the liquid crystal as the liquid crystal alignment film, the voltage retention ratio, and the accumulated charge Other characteristics can be used in combination of 1 type or 2 types or more.

By carrying out the polymerization reaction of the component (a), the component (b) and the component (c), a polyimine precursor having a repeating unit represented by the formula [1] can be produced. For example, if tetracarboxylic dianhydride is used as the component (c), a polylysine having a repeating unit represented by the formula [1] can be produced. Next, the obtained carboxyl group of the poly-proline which has the repeating unit represented by the formula [1] is converted into an ester, and a polyphthalate having a repeating unit represented by the formula [1] can be produced. Further, by having such a polyperonucleic acid having a repeating unit represented by the formula [1] or a polyperurethane ring having a repeating unit represented by the formula [1], it is possible to obtain A repeating unit of the polyimine represented by the formula [1].

Here, the component (a) and the component (b) constitute a repeating unit represented by the above formula [1]. Further, the component (b) and the component (c) constitute a repeating unit of a polyimine precursor or a polyimine. The repeating unit of the polyimine precursor or the polyimine composed of the component (b) and the component (c) may, for example, be represented by the following formula [8]. In the above formula [1], A ₁ is a group derived from the component (a) of the raw material, and C ₁ , C ₂ and A ₂ are groups derived from the component (b) of the raw material. Further, in the above formula [8], C ₁ , C ₂ and A ₂ are groups derived from the component (b) of the raw material, and Z ₁ is a group derived from the component (c) of the raw material.

(In the formula [8], A ₂ , C ₁ , C _{2 are the} same as the formula [b], Z _{1 is the} same as Z ₁ of the formula [3], and R ₄₁ and R ₄₂ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Each may be the same or different, and j is a positive integer).

The repeating unit represented by the formula [1] of the polymer having the repeating unit represented by the formula [1] may be only one type of C ₁ , C ₂ , A ₁ and A ₂ and in the same formula [ The repeating unit represented by 1] may be a plurality of C ₁ , C ₂ , A _{1 ,} and A ₂ , and may be a repeating unit represented by a plurality of formulas [1].

Further, the repeating unit represented by the formula [8] of the polymer having the repeating unit represented by the formula [1] may be one type of each of C ₁ , C ₂ , A ₂ , R ₄₁ and R ₄₂ . The repeating unit represented by the same formula [8] may be a repeating unit represented by a plurality of formulas [8] in which C ₁ , C ₂ , A ₂ , R ₄₁ and R ₄₂ are plural.

The reaction of the component (a), the component (b) and the component (c) is usually carried out in an organic solvent. The organic solvent used at this time is not particularly limited as long as it is a polyimide precursor produced by dissolution. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and dimethylene. Bismuth, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, A Ketrinone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve Acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Acetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol Monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl Ether, 3-methyl-3-methoxybutyl acetate, three Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyl ester, butyl ether, Diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate Ester, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate Ester, 3-methoxypropionic acid methyl ester, 3-ethoxypropionic acid methyl ethyl ester, 3-methoxypropionic acid ethyl ester, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, diglyme or 4-hydroxy-4-methyl Ketopentanone and the like. These can be used alone or in combination. Further, even if the solvent which does not dissolve the polyimine precursor is not precipitated in the range in which the produced polyimide precursor is not formed, it can be used in combination with the above solvent. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, the organic solvent is preferably dried by dehydration.

The order in which the component (a), the component (b), and the component (c) are reacted is, for example, a reaction between the component (a) and the component (b), followed by the addition of the component (c). By carrying out the reaction in this manner, the obtained polyimine precursor having the repeating unit represented by the formula [1] becomes a repeating unit represented by the formula [1] and a random unit random bonding represented by the formula [8]. The random copolymer is good.

On the other hand, a step of reacting the component (a) with the component (b) to obtain a urea-based polymer composed of a repeating unit represented by the formula [1], and reacting the component (b) with the component (c) a step of obtaining a polyimine precursor composed of a repeating unit represented by the formula [8], and then bringing the urea-based polymer composed of the repeating unit represented by the formula [1] to the formula [8] a method of reacting a polyimine precursor formed by a repeating unit to obtain a polymer having a repeating unit represented by the formula [1] and a block copolymer of a polyurea and a polyimide precursor. That is, each of them is a polymer structure composed of a urea-based polymer having a higher degree of polymerization and a polyimide precursor than the above-mentioned random copolymer. At this time, there are problems such as a decrease in solubility or a deterioration in coatability when a liquid crystal alignment agent is produced.

The temperature at which the component (a), the component (b), and the component (c) are reacted may be Any temperature from -20 ° C to 150 ° C is selected, preferably in the range of -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration. However, if the concentration is too low, it becomes difficult to obtain a high molecular weight polyimine precursor having a repeating unit represented by the formula [1]. If the concentration is too high, the viscosity of the reaction solution is too high. Excessive and uniform agitation becomes difficult. Therefore, the concentration of the total amount of the component (a), the component (b) and the component (c) is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the reaction liquid. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

The ratio of the component (a), the component (b), and the component (c), for example, the molar ratio, is the total amount of the component (a) and the component (c): (b) component = 0.8:1 to 1.2: 1 is better. The ratio of the component (a) in the total amount of the component (a) to the component (c) is from 20 mol% to 60 mol%, and is preferably a voltage maintenance ratio and residual DC. When the ratio of the component (a) is too small, the voltage maintenance ratio at the time of low-temperature firing is lowered, and if it is too large, the residual DC tends to remain.

Further, the polyamido acid having the repeating unit represented by the above formula [1] or the polyphthalate ring having the repeating unit represented by the above formula [1] is obtained by the polyimine precursor. Amination), a polyimine having a repeating unit represented by the formula [1] can be obtained. However, in the polyimine having the repeating unit represented by the formula [1] contained in the liquid crystal alignment agent used in the method for producing a liquid crystal alignment film of the present invention, a closed loop ratio of a proline group is required (also referred to as a ruthenium group). Amination rate) is less than 50%. In the present specification, the ruthenium imidization ratio means the ratio of the quinone imine group which is derived from the total amount of the quinone imine group and the carboxyl group derived from the tetracarboxylic dianhydride.

For the method of imidating the polyimine precursor ruthenium, for example, the hydrazine imidization of the solution of the polyimide precursor is directly heated or Catalyst oxime imidization is added to the solution of the polyimide precursor.

The temperature at which the polyimine precursor is thermally imidized in a solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, to discharge water generated by the hydrazine imidization reaction to the system. It is better to do it outside.

The ruthenium imide of the polyimide precursor can be stirred at -20 to 250 ° C, preferably 0 to 180 ° C by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor. get on. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the proline group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it maintains moderate alkalinity during the progress of the reaction. The acid anhydride may, for example, be anhydrous acetic acid, anhydrous trimellitic acid or anhydrous pyromellitic acid. Among them, anhydrous acetic acid is used, and purification after completion of the reaction is easy, which is preferable. The imidization rate of the imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be introduced into a solvent and then precipitated. The solvent used for the precipitation may, for example, be methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, pentane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water or the like. After the solvent is added and the precipitated polymer is filtered and recovered, it can be dried under normal pressure or reduced pressure at normal temperature or under heating. Further, the polymer recovered by the precipitation is repeatedly dissolved in an organic solvent, and the operation of reprecipitation recovery is repeated 2 to 10 times to reduce impurities in the polymer. The solvent at this time may, for example, be an alcohol or When a ketone or a hydrocarbon or the like is used, three or more types of solvents selected from these are used, and the efficiency of purification is further improved.

The polyimine precursor having the repeating unit represented by the above formula [1] or the polyimine having the repeating unit represented by the above formula [1] and having a quinone imidization ratio of less than 50%, which is used in the present invention The molecular weight, in consideration of the strength of the liquid crystal alignment film obtained by the film, the workability at the time of film formation, and the film coating property, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000~150,000.

The polyimine precursor having the repeating unit represented by the above formula [1] contained in the liquid crystal alignment agent used in the method for producing a liquid crystal alignment film of the present invention or the repeating unit represented by the above formula [1] The ratio of the polyimine in which the imidization ratio is less than 50% is not particularly limited, and examples thereof include a polyimine precursor having a repeating unit represented by the above formula [1] and having the above formula [1]. The total amount of the polyimine which repeats the unit and the ruthenium imidization ratio is less than 50% is 0.1 to 30% by mass, preferably 3 to 10% by mass.

Further, the liquid crystal alignment agent used for the production of the liquid crystal alignment film may be a polyimine precursor having a repeating unit represented by the above formula [1] or a repeating unit represented by the above formula [1]. The polyimine which has an imidization ratio of less than 50% may be mixed with other polymers other than these. In this case, the content of the other polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass based on the total amount of the polymer component. The polymer other than the polymer may, for example, be a polyimine precursor or a polyimine which does not have the repeating unit represented by the above formula [1]. Further, for example, C An olefin polymer, a methacrylic polymer, polystyrene, polyamine or polyoxyalkylene.

The solvent contained in the liquid crystal alignment agent is a polyimine precursor which can dissolve the repeating unit represented by the above formula [1] or has a repeating unit represented by the above formula [1] and has a quinone imidization ratio of less than 50. The polyaminoimine of the present invention is not particularly limited, and examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methyl. Benzoamine, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl fluorene, γ - Butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, ring An organic solvent such as ketone, ethylene carbonate, propylene carbonate, diglyme or 4-hydroxy-4-methyl-2-pentanone. These can be used alone or in combination.

The solvent contained in the liquid crystal alignment agent is preferably from 70 to 99.9% by mass in terms of the solvent to form a uniform liquid crystal alignment film. The content of the liquid crystal alignment film may be appropriately changed depending on the content.

The liquid crystal alignment agent can use an organic solvent, that is, a poor solvent, which improves the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied, without impairing the effects of the present invention.

Specific examples of the poor solvent for improving the coating property or the surface smoothness include, for example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, and 1-pentane. Alcohol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1, 2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether , dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethyl Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, Ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol Isoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, mercapto alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl ether, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl Ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Ester, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, pyruvic acid Methyl ester, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethyloxypropionate, ethyl 3-methoxypropionate, 3-ethoxyl Propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, An organic solvent having a low surface tension of a solvent such as n-butyl ester lactate or isoamyl lactate.

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

In the liquid crystal alignment agent, a crosslinking compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclic carbonate group may be added without damaging the effects of the present invention, and may have a hydroxyl group, a hydroxyalkyl group and A crosslinkable compound having at least one substituent selected from the group consisting of lower alkoxyalkyl groups or a crosslinkable compound having a polymerizable unsaturated bond. These substituents or polymerizable unsaturated bonds are required to have two or more of the crosslinkable compounds.

a crosslinkable compound having an epoxy group or an isocyanate group, such as bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, four Glycidylamine diphenylene ester, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether Ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetic acid Diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4 -bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl meta-xylenediamine, 2-(4-(2,3- Epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 1, 3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)oxy) Phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetanyl groups represented by the following formula [4].

Specifically, for example, a crosslinkable compound represented by the formula [4a] to the formula [4k] disclosed in pages 58 to 59 of International Publication WO2011/132751 (2011.10.27 publication) is mentioned.

The crosslinkable compound having a cyclic carbonate group is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5].

Specifically, for example, a crosslinkable compound represented by the formula [5-1] to the formula [5-42] disclosed on pages 76 to 82 of International Publication WO2012/01132751 (published on 2012.2.2).

The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group may, for example, be an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or a guanamine resin. , glycoluril-formaldehyde resin, amber-decylamine-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both may be used. The melamine derivative or the benzoguanamine derivative may also be present as a 2-mer or a 3-mer. It is preferred that each of the triazine rings has an average of 3 or more and 6 or less of a methylol group or an alkoxymethyl group.

Examples of such a melamine derivative or a benzoguanamine derivative include, for example, one triazine ring per commercially available product, and an average of 3.7 substituted MX-750 and one triazine ring per methoxymethyl group. The methoxymethyl group has an average of 5.8 substituted MW-30 (manufactured by the above, Sanwa Chemical Co., Ltd.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methylated melamine, Cymel 235, 236, 238, 212, 253, 254, etc. methoxymethylated butoxymethylated melamine, Cymel 506, 508 and other butoxymethylated melamine, Cymel 1141 Carboxy methoxymethylated isobutoxymethylated melamine, Cymel 1123 methoxymethylated ethoxymethylated benzoguanamine, Cymel 1123-10 methoxymethylated butoxy Methylated benzoguanamine, Cymel 1128-butoxymethylated benzoguanamine, Cymel 1125-80 carboxyl-containing methoxymethylated ethoxymethylated benzoguanamine (above, manufactured by Mitsui Cyanamid). Further, examples of the glycoluril include, for example, Cymel 1170-like butoxymethylated glycoluril, Cymel 1172-like methylolated glycoluril, and Powderlink 1174-like methoxymethylolated glycoluril.

A benzene or a phenolic compound having a hydroxyl group or an alkoxy group, for example, 1,3,5-glycol (methoxymethyl)benzene, 1,2,4-para(isopropoxymethyl)benzene, 1 , 4-bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.

More specifically, a crosslinkable compound represented by the formula [6-1] to the formula [6-48] disclosed in pages 62 to 66 of International Publication WO2011/132751 (2011.10.27) is mentioned.

a crosslinkable compound having a polymerizable unsaturated bond, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tris(methyl) a crosslinkable compound having three polymerizable unsaturated groups in the molecule such as acryloyloxyethoxytrimethylolpropane or glycerol polyglycidyl ether poly(meth)acrylate, further, ethylene Alcohol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(methyl) Acrylate, propylene oxide bisphenol type di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(methyl) propyl Ethyl ester, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, diglycidyl phthalate di(methyl) a cross-linking compound having two polymerizable unsaturated groups in the molecule such as acrylate or hydroxypivalic acid neopentyl glycol di(meth)acrylate, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxime Cyclooxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2-(methyl) propylene fluorenyl oxygen A crosslinkable compound having one polymerizable unsaturated group in the molecule such as ethethyl phosphate or N-methylol (meth) acrylamide.

Further, a compound represented by the following formula [7] can also be used.

(In the formula [7], E _{1 is a group} consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring or a phenanthrene ring; The selected group, E ₂ is a group selected by the following formula [7a] or formula [7b], and n is an integer of 1 to 4).

The above compound is an example of a crosslinkable compound, and is not limited thereto. Further, the crosslinkable compound used in the liquid crystal alignment agent may be one type or a combination of two or more types.

The content of the crosslinkable compound in the liquid crystal alignment agent is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. The effect of the crosslinking reaction and the purpose of the performance is preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, per 100 parts by mass of the total polymer component.

When a liquid crystal alignment film is produced by using the liquid crystal alignment agent of the composition of the present invention, a compound which promotes charge transfer in the liquid crystal alignment film and promotes charge extraction of the liquid crystal cell using the liquid crystal alignment film is added. The nitrogen-containing heterocyclic amine compound represented by the formula [M1] to the formula [M156] disclosed on pages 69 to 73 of WO2011/132751 (2011.10.27) is preferred. The amine compound may be directly added to the composition, but it is preferably added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, with a suitable solvent. The solvent is not particularly limited as long as it dissolves the organic solvent of the specific polymerized quinone-based polymer.

The liquid crystal alignment agent may contain a compound which improves the film thickness uniformity or the surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied, without impairing the effects of the present invention. Further, a compound or the like which improves the adhesion between the liquid crystal alignment film and the substrate may be contained.

The compound which improves the uniformity of the film thickness or the surface smoothness of the liquid crystal alignment film may, for example, be a fluorine-based surfactant or an anthrone-based interface. An active agent, a nonionic surfactant, and the like.

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

Specific examples of the compound which enhances the adhesion between the liquid crystal alignment film and the substrate include a functional decane-containing compound or an epoxy group-containing compound shown below.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-( 2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7 - triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9 -triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyl three Methoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltri Ethoxy decane, N-bis(ethylene oxide)-3-aminopropyltrimethoxydecane, N-bis(ethylene oxide)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl Ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4- Hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane or N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

When the compound to be adhered to the substrate is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent. When the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and when it exceeds 30 parts by mass, the storage stability of the liquid crystal alignment agent may be deteriorated.

In the liquid crystal alignment agent, in addition to the above-mentioned poor solvent, a crosslinkable compound, a compound which improves the film thickness uniformity or surface smoothness of the liquid crystal alignment film, and a compound which adheres to the substrate, the effect of the present invention is not impaired. A dielectric or conductive substance for changing the electrical properties such as dielectric constant or conductivity of the liquid crystal alignment film may be added.

In the present invention, after the liquid crystal alignment agent is applied onto a substrate and fired, a liquid crystal having a quinone imidization ratio of 50 to 70% is obtained. Orientation film.

For the substrate, a plastic substrate such as a glass substrate, a tantalum wafer, an acrylic substrate, or a polycarbonate substrate can be used depending on the intended device. Further, from the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for liquid crystal driving is formed. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the substrate on only one side, and a material such as aluminum that reflects light can be used as the electrode. In the present invention, a plastic substrate or the like which is a substrate having low heat resistance can be used because the firing temperature can be lowered.

The method of applying the liquid crystal alignment agent to the substrate is not particularly limited, and industrially, generally, a dipping method, a roll coating method, a slit coating method, a spinner method or a spray method, screen printing, offset printing, flexographic printing or The inkjet method or the like is performed. This can also be used for the purpose.

After the liquid crystal alignment agent is applied onto the substrate, baking is performed. The firing condition is a condition that the sulfhydrylation ratio of the liquid crystal alignment film obtained after firing is 50 to 70%. For example, the firing temperature is 210 ° C or lower, preferably 120 to 200 ° C. Further, the baking time is, for example, 5 minutes to 2 hours, preferably 10 minutes to 30 minutes. Thus, since it can be baked at a low temperature, a plastic substrate with low heat resistance can be used. Moreover, it is possible to suppress the deterioration of the color characteristics of the color filter of the liquid crystal display element accompanying the firing at a high temperature or to reduce the energy consumption in the manufacture of the liquid crystal display element.

Examples of the heating means for baking include a heat cycle type oven or an IR (infrared) type oven. When the thickness of the liquid crystal alignment film obtained by baking is too thick, it becomes unfavorable on the power-consuming surface of the liquid crystal display element, and is too thin. In the case where the reliability of the liquid crystal display element is lowered, it is preferably 5 to 300 nm, more preferably 10 to 100 nm.

When the liquid crystal is aligned horizontally or obliquely, the liquid crystal alignment film obtained by firing is treated by rubbing or polarized ultraviolet irradiation or the like. Further, in the case of vertical alignment use or the like, it can be used as a liquid crystal alignment film even without alignment treatment.

Thus, a polyimine precursor containing a repeating unit represented by the above formula [1] or a polyimine having a repeating unit represented by the above formula [1] and having a ruthenium iodide ratio of less than 50% is used. A liquid crystal alignment agent which is applied to a substrate and fired to obtain a liquid crystal alignment film having a ruthenium iodide ratio of 50 to 60%, which has a low ruthenium iodide ratio and a large amount of carboxyl groups, and has a formula [1] The repeating unit has a low residual DC and a high voltage holding ratio as shown in the examples below. On the other hand, for example, the repeating unit of the polyurea (the general formula (I) of Patent Document 1) and the repeating unit of the polyimine (the general formula (II) of Patent Document 1) are liquid crystals. In the case of an alignment film, the residual DC is very high compared to the present invention. In addition, in the case of applying the liquid crystal alignment agent, the liquid crystal alignment agent is fired at a low temperature, but the liquid crystal alignment agent is in the form of a polyimine at the stage of the formation of the liquid crystal alignment film obtained in Patent Document 1. The imidization ratio is different from the present invention and is very high.

In the liquid crystal display device of the present invention, a liquid crystal alignment element is coated and fired by the above method to obtain a substrate having a liquid crystal alignment film, and a liquid crystal cell is produced by a conventional method to produce a liquid crystal display element. As an example, two substrates having opposite faces, a liquid crystal layer provided between the substrates, and a liquid crystal alignment film provided between the substrate and the liquid crystal layer and having the liquid crystal alignment film of the present invention are provided. A liquid crystal display element of a liquid crystal cell of a liquid crystal alignment film formed by the production method. The liquid crystal display device of the present invention may be, for example, a twisted nematic type (TN: Twisted Nematic) method, a vertical alignment (VA: Vertical Alignment) method, or an IPS (In-Plane Switching) method, or an OCB alignment (OCB alignment). :Optically Compensated Bend) and other species.

As a method of producing the 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, and the liquid crystal alignment film surface is inside and the other substrate is bonded to each other. A method of sealing the liquid crystal after pressure-injection and sealing, or a method of sealing the liquid crystal after the liquid crystal alignment film surface of the separator is dispersed, and then sealing the substrate.

For the liquid crystal, a positive liquid crystal having a positive dielectric anisotropy or a negative liquid crystal having a negative dielectric anisotropy may be used, specifically, for example, MLC-2003, MLC-6608, MLC-6609 manufactured by Merck Co., Ltd., etc. .

Moreover, it is preferable that the liquid crystal alignment film of the present invention has a liquid crystal layer between a pair of substrates having electrodes, and a polymerizable property obtained by polymerization of at least one of an active energy ray and heat is disposed between a pair of substrates. A liquid crystal display device produced by a step of polymerizing a polymerizable compound by applying at least one of irradiation and heating of an active energy ray to a liquid crystal composition of a compound. Here, the active energy ray is preferably ultraviolet light. Ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of heating polymerization, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, it is also possible to carry out ultraviolet rays simultaneously with heating.

The liquid crystal display element is a PSA (Polymer Sustained Alignment) method that controls the pretilt angle of liquid crystal molecules. For example, in the PSA method using an active energy ray, a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed in the liquid crystal material, and after assembling the liquid crystal cell, photopolymerization is performed by applying a specified voltage state to the liquid crystal layer. The compound is irradiated with an active energy ray such as ultraviolet rays to cause polymerization, and the resulting polymer controls the pretilt angle of the liquid crystal molecules. Since the alignment state of the liquid crystal molecules when the polymer is formed is memorized even after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed by the liquid crystal layer or the like. Further, in the PSA method, since the rubbing treatment is not required, it is suitable for the formation of a vertical alignment type liquid crystal layer which is difficult to control the pretilt angle by the rubbing treatment.

In the same manner as described above, the liquid crystal cell of the PSA type is prepared by, for example, preparing a pair of substrates on which a liquid crystal alignment film is formed, and spreading a spacer on the liquid crystal alignment film of one substrate, and bonding the other film so that the liquid crystal alignment film surface is inside. The substrate is a method in which the liquid crystal is pressure-injected and then sealed, or a method in which the liquid crystal is dropped on the liquid crystal alignment film surface of the spacer, and the substrate is bonded and sealed.

Next, in the case of the PSA method, a polymerizable compound polymerized by irradiation with heat or active energy rays is mixed in the liquid crystal. The polymerizable compound may, for example, be a compound having one or more polymerizable unsaturated groups in the molecule such as an acrylate group or a methacrylate group. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the alignment of the liquid crystal cannot be controlled, and is more than 10 parts by mass. Then, the amount of the unreacted polymerizable compound increases, and the afterimage characteristics of the liquid crystal display element are lowered.

After the liquid crystal cell is produced, a voltage of alternating current or direct current is applied to the liquid crystal cell, and the polymerizable compound is polymerized by irradiating heat or an active energy ray. Thereby, the alignment of the liquid crystal molecules can be controlled.

Further, the liquid crystal alignment film of the present invention may be applied to a liquid crystal layer between a pair of substrates including an electrode, and an aggregate polymerized by at least one of an active energy ray and heat may be disposed between the pair of substrates. A liquid crystal display element (SC-PVA) produced by a step of polymerizing a polymerizable group while applying a voltage between electrodes. Here, the active energy ray is preferably ultraviolet light. The ultraviolet wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of heating polymerization, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, ultraviolet rays and heating can be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, for example, a method of adding a compound containing the polymerizable group to the liquid crystal alignment agent may be mentioned. In addition, for example, the polymerizable group-containing compound is used as the component (a), the component (b) or the component (c), and the polysiloxane having the repeating unit represented by the above formula [1] contained in the liquid crystal alignment agent. A method in which an amine precursor or a polyimine having a repeating unit represented by the above formula [1] and having a ruthenium iodide ratio of less than 50% contains a polymerizable group.

Next, a pair of liquid crystal alignment films having such a polymerizable group polymerized by at least one of an active energy ray and heat is prepared. After the substrate, as described above, by dispersing the spacer on the liquid crystal alignment film of one of the substrates, the liquid crystal alignment film surface is formed inside, and the other substrate is bonded to the liquid crystal, and the liquid crystal is injected under pressure to be sealed, or at intervals. A liquid crystal cell can be produced by a method in which a liquid crystal alignment film is dropped on a liquid crystal alignment film, and the substrate is bonded and sealed.

Next, after the liquid crystal cell is produced, the alignment of the liquid crystal molecules can be controlled by applying a voltage of alternating current or direct current to the liquid crystal cell while irradiating the heat or the active energy ray.

As described above, the liquid crystal display device produced by using the liquid crystal alignment film of the present invention has a low residual DC and a high voltage holding ratio, and is excellent in reliability, and can be applied to a large-screen and high-definition liquid crystal television. Further, since the firing temperature is low, a lightweight plastic or the like can be used as the substrate, and the weight of the liquid crystal display element can be reduced.

[Examples]

The following is a description of the examples. Further, the present invention is not limited to these. The abbreviations used below are as follows.

(diisocyanate)

A-1: 2,4-diisocyanate

(tetracarboxylic dianhydride)

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

(diamine compound)

C-1:1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane

C-2: N-(3-pyridylmethyl)-3,5-diaminobenzamide

C-3: 1,3-diamino-4-{4-(4-n-heptylcyclohexyl)phenoxy}benzene

(Organic solvents)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

The measurement method performed in this example is as follows.

(Measurement of molecular weight of polymer)

The molecular weight of polyamic acid and polyimine, and the polyamic acid or polyimine is measured by a GPC (normal temperature colloidal permeation chromatography) apparatus, and the number average molecular weight and the weight average molecular weight are calculated as polyethylene glycol. Polyethylene oxide converted value.

GPC device: GPC-101 manufactured by Showa Denko Co., Ltd. Pipe column: Shodex company pipe column (KD-803, KD-805 series)

Column temperature: 50 ° C

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

Flow rate: 1.0ml/min

Standard sample for the production of calibration lines: TSK standard polyepoxide made by Tosoh Corporation Ethane (molecular weight: about 900,000, 150,000, 100,000, 30,000), and polyethylene glycol (molecular weight of about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories

(Determination of the imidization ratio of polyimine)

The oxime imidization ratio of polyimine was measured as follows.

20 mg of polyimine powder was placed in an NMR sample tube, and 0.53 ml of dimethyl hydrazine (DMSO-d ₆ , 0.05% TMS (tetramethyl decane) mixture) was added thereto to completely dissolve. This solution was measured for proton NMR at 500 MHz using a JEOL NMR measuring machine (JNM-ECA500). The sulfhydrylation rate is determined by using protons from a structure that has no change before and after imidization as a reference proton, and the peak value of the proton is used and the proton peak of the NH group from the vicinity of 9.5 ppm to 10.0 ppm. The cumulative value is obtained by the following equation.

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

In the above formula, x is the proton peak cumulative value of the NH group derived from proline, y is the peak cumulative value of the reference proton, and α is the polyamine (the sulfhydrylation rate is 0%). The ratio of the number of reference protons of one acid NH matrix.

<Synthesis Example 1>

A-1 (1.56 g, 9.00 mmol), C-1 (1.53 g, 8,98 mmol), C-2 (1.30 g, 5.36 mmol), C-3 (1.37 g, 3.59 mmol) in NMP (23 g) Mixing and adding B- after 15 hours of reaction at 40 ° C 1 (1.65 g, 8.46 mmol) and NMP (19 g) were further reacted for 6 hours to obtain a polymer solution A (a solution of a polylysine having a repeating unit represented by the above formula [1]) (polymer concentration 15) quality%). The polymer had a number average molecular weight of 16,020 and a weight average molecular weight of 49,319.

<Synthesis Example 2>

A-1 (0.783 g, 4.50 mmol), C-1 (1.53 g, 8.98 mmol), C-2 (1.30 g, 5.36 mmol), C-3 (1.37 g, 3.59 mmol) in NMP (19 g) After mixing and reacting at 40 ° C for 15 hours, B-1 (2.63 g, 13.4 mmol) and NMP (23 g) were added, and the reaction was further carried out for 6 hours to obtain a polymer solution B (having the above formula [1] A repeating unit of a polylysine solution) (polymer concentration: 15% by mass). The polymer had a number average molecular weight of 11,555 and a weight average molecular weight of 37,656.

<Comparative Synthesis Example 1>

A-1 (3.82 g, 21.9 mmol), C-1 (1.87 g, 10.9 mmol), C-2 (1.59 g, 6.59 mmol), C-3 (1.67 g, 4.38 mmol) in NMP (50 g) After mixing, the reaction was carried out at 40 ° C for 15 hours to obtain a polymer solution C (solution of polyurea) (polymer concentration: 15% by mass). The polymer had a number average molecular weight of 12,731 and a weight average molecular weight of 32,967.

<Comparative Synthesis Example 2>

B-1 (3.35 g, 17.0 mmol), C-1 (1.53 g, 8,98 mmol), C-2 (1.30 g, 5.36 mmol), C-3 (1.37 g, 3.59 mmol) in NMP After mixing in (42 g), the reaction was carried out at 40 ° C for 15 hours to obtain a polymer solution D (a solution of poly-proline) (polymer concentration: 15% by mass). The polymer had a number average molecular weight of 14,833 and a weight average molecular weight of 38,984.

<Comparative Synthesis Example 3>

After adding NMP to the polymer solution A (20 g) described in Synthesis Example 1 and diluting the concentration to 6% by mass, anhydrous acetic acid (3.65 g) and pyridine (1.70 g) as a ruthenium-imiding catalyst were added, and the mixture was carried out at 50 ° C. 3 hours reaction. The reaction solution was poured into methanol (200 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to give a white powder. The polyimine had a hydrazine imidation ratio of 100%, a number average molecular weight of 13,084, and a weight average molecular weight of 40,857.

To 1.99 g of the powder, 11.3 g of NMP was added, and the mixture was stirred at 50 ° C for 30 hr to dissolve, and then a polymer solution E (polycyclic group having the repeating unit represented by the above formula [1] and having an anthraceneization ratio of 100%) was obtained. A solution of the amine) (polymer concentration 15% by mass).

<Example 1> Preparation of liquid crystal alignment agent and production of liquid crystal cell

In the polymer solution A obtained in the synthesis example 1, NMP and BCS were added and stirred, and the preparation was carried out so that the polymer became 6 mass%, the NMP became 64 mass%, and the BCS became 30 mass%. This solution was filtered under pressure with a membrane filter having a pore diameter of 1 μm to obtain a liquid crystal alignment agent.

The obtained liquid crystal alignment agent is applied to the ITO electrode glass substrate After spin coating, it was dried on a hot plate at 80 ° C for 5 minutes, and then fired in an IR oven at 180 ° C for 15 minutes to form a coating film (liquid crystal alignment film) having a thickness of 100 nm to obtain a liquid crystal alignment film. Substrate. Two sheets of the liquid crystal alignment film were prepared, and a spacer of 4 μm was spread on one of the liquid crystal alignment film surfaces, and then a sealant was printed thereon, and the other substrate was bonded to the film surface by the liquid crystal alignment film surface. The sealant is hardened to form an empty unit cell. Liquid crystal MLC-6608 (manufactured by Merck. Japan Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell.

<Example 2 and Comparative Examples 1 to 3>

A liquid crystal alignment agent and a liquid crystal alignment film were obtained in the same manner as in Example 1 except that the polymer solutions A obtained in Synthesis Example 1 and the polymer solutions B to E obtained in Comparative Synthesis Examples 1 and 3 were used. And liquid crystal cell.

<Example 3>

A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal cell were obtained in the same manner as in Example 1 except that the firing temperature was 200 °C.

<Comparative Example 4>

A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal cell were obtained in the same manner as in Example 1 except that the firing temperature was 230 °C.

<Example 4>

In the polymer solution A obtained in Synthesis Example 1, NMP and BCS were added. The mixture was stirred to prepare a polymer of 3.5% by mass, NMP of 66.5 mass%, and BCS of 30 mass%. This solution was subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and stored at -15 ° C for 48 hours, and then the inkjet coating property was evaluated. For the inkjet coater, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used. The film was applied onto an ITO (Indium Tin Oxide) vapor-deposited substrate washed with pure water and IPA, and was carried out at a nozzle pitch of 0.423 mm, a scanning pitch of 0.5 mm, and a coating speed of 40 mm/sec. After leaving it for 60 seconds, it was dried on a hot plate at 80 ° C for 5 minutes, and then fired in an IR oven at 180 ° C for 15 minutes to form a coating film (liquid crystal alignment film) having a thickness of 100 nm to obtain a liquid crystal alignment film. A liquid crystal cell was obtained in the same manner as in Example 1 on the substrate.

<Measurement of voltage maintenance rate>

The liquid crystal cells obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were subjected to a voltage of 1 V for 60 μs at a temperature of 80 ° C, and the voltage after 50 ms was measured, and the voltage was maintained as a voltage maintenance ratio. The results are shown in Table 1.

<Measurement of residual DC>

The liquid crystal cell obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was supplied with an AC voltage of 30 Hz, 6 Vpp, and a DC voltage of 1 V, and was driven at a temperature of 23 ° C for 24 hours. The flicker is then evaluated, with its intensity becoming the minimum and the applied voltage being the residual DC (flicker elimination method). The results are shown in Table 1.

<Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)>

The polymer solution A obtained in Example 1 and Example 2 were obtained. The polymer solution B was filtered under pressure with a membrane filter having a pore diameter of 1 μm, and stored at -15 ° C for 48 hours to prepare a liquid crystal cell and evaluate the liquid crystal alignment (PSA unit cell). The ITO electrode substrate (length 40 mm × width 30 mm, thickness 0.7 mm) and the center 10×40 mm ITO electrode substrate (length 40 mm) of the solution were placed at a center of 10×10 mm in the center of pure water and IPA. The ITO surface of ×30 mm in width and 0.7 mm in thickness was spin-coated, dried on a hot plate at 80 ° C for 5 minutes, and then fired in an IR oven at 180 ° C for 15 minutes to form a film having a film thickness of 100 nm. (Liquid Crystal Alignment Film) A substrate with a liquid crystal alignment film was obtained. After the coating film surface was washed with pure water, the film was heat-treated at 100 ° C for 15 minutes in a heat cycle type dust-free oven to obtain a liquid crystal alignment film substrate.

The liquid crystal alignment film substrate was placed so that the liquid crystal alignment film surface was inside, and a spacer of 6 μm was sandwiched, and a hollow cell was formed by a sealant. The polymerizable compound represented by the following formula [9] is used as a nematic liquid crystal (MLC) in a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.) in a vacuum cell. 100% by mass of -6608), a liquid crystal of 0.3% by mass of a polymerizable compound represented by the following formula [9] was injected, and the injection port was closed to obtain a liquid crystal cell.

A voltage of 5 V was applied to the obtained liquid crystal cell, and a metal halide lamp having an illuminance of 60 mW was used, and a wavelength of 350 nm or less was blocked, and ultraviolet irradiation was performed at 20 J/cm ² in terms of 365 nm to obtain an alignment direction of the liquid crystal. Controlled liquid crystal cell (PSA unit cell). The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 °C.

The response speed of the liquid crystal cell before the ultraviolet irradiation and the liquid crystal after the ultraviolet irradiation was measured. The response speed was determined from a transmittance of 90% to a transmittance of 10% of T90 → T10.

In the PSA unit cell obtained in the example, the response speed of the liquid crystal cell after the ultraviolet irradiation was faster than that of the liquid crystal cell before the ultraviolet irradiation, and it was confirmed that the alignment direction of the liquid crystal was controlled. Further, any liquid crystal cell was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by NIKON Co., Ltd.), and it was confirmed that the liquid crystal was uniformly aligned.

<Measurement of oxime imidization ratio of liquid crystal alignment film>

In Examples 1 to 4 and Comparative Examples 1 to 4, the stage of the substrate to which the liquid crystal alignment film was attached was obtained, and the ruthenium imidization ratio of the liquid crystal alignment film was measured. The method for measuring the ruthenium amination ratio of the liquid crystal alignment film is as follows. The liquid crystal alignment agent was spin-coated on the ITO electrode glass substrate, dried on a hot plate at 80 ° C for 5 minutes, and then fired in an IR oven to form a coating film (liquid crystal alignment film) having a film thickness of 100 nm. A substrate with a liquid crystal alignment film. The liquid crystal alignment film was cut with a utility knife, and the yield of ruthenium iodide was measured by KBr method using FT-IR.

As a result, as shown in Table 1, the liquid crystal alignment agent of Examples 1 to 4 containing the polyimine precursor having the repeating unit represented by the above formula [1] was used, and the oxime imidization ratio was 50. ~70% of the liquid crystal cell of the liquid crystal alignment film has a high voltage maintenance ratio and a small residual DC. On the other hand, in the liquid crystal cell of Comparative Example 1 having a liquid crystal alignment film composed only of polyurea, the voltage holding ratio was high, but the residual DC was high. Further, in the liquid crystal cell of the liquid crystal alignment film having no repeating unit represented by the formula [1] and consisting only of poly-proline, the residual DC was small, but the voltage retention rate was low. Further, in the liquid crystal cell of Comparative Example 3 and Comparative Example 4 having a liquid crystal alignment film having a high ruthenium iodide ratio, the voltage holding ratio was high but the residual DC was large. Moreover, since the electrical characteristics of the residual DC and the voltage maintenance ratio can be measured, the liquid crystal alignment film to be measured has a good liquid crystal alignment property.

Claims (15)

A method for producing a liquid crystal alignment film, which comprises a polyimine precursor having a repeating unit represented by the following formula [1] and a repeating unit represented by the following formula [1], and A liquid crystal alignment agent of at least one polymer selected from a polyimide having an imidization ratio of less than 50% is applied to a substrate and then fired to obtain a liquid crystal alignment film having a quinone imidization ratio of 50 to 70%. , (In the formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, and C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each may be the same or different). The method for producing a liquid crystal alignment film according to claim 1, wherein the baking is performed at 210 ° C or lower. The method for producing a liquid crystal alignment film according to claim 1, wherein the polymer has a side chain represented by the following formula [2]. (In the formula [2], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ₂ Is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ₄ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroidal skeleton having 17 to 51 carbon atoms; And any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom, Y ₅ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on the ring group may be a carbon number of 1 to 3. An alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is an integer of 0 to 4, Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. The method for producing a liquid crystal alignment film according to claim 1, wherein the polymer is obtained by reacting the following component (a), component (b) and component (c), and component (a) contains 2 in the molecule. Component (b) component of isocyanate group: Component (c) component containing two primary or secondary amine groups in the molecule: a tetracarboxylic acid derivative. The method for producing a liquid crystal alignment film according to claim 4, wherein the component (b) is a compound having a side chain represented by the above formula [2]. The method for producing a liquid crystal alignment film according to claim 4, wherein the component (b) is a compound represented by the following formula [2a]. (In the formula [2a], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ₂ Is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ₄ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroidal skeleton having 17 to 51 carbon atoms; Any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Substituted by an oxy group or a fluorine atom, Y ₅ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkane having 1 to 3 carbon atoms a group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is an integer of 0 to 4, Y ₆ It is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms, and m is 1 to 4 An integer of -(Y ₁ -Y ₂ -Y ₃ -Y ₄ -(Y ₅ ) _n -Y ₆ ) _m represents a substituent Y ₁ -Y ₂ -Y ₃ -Y ₄ -(Y ₅ ) _n -Y ₆ There are m, m 2 or more applications, each of the substituents may be the same or different). The method for producing a liquid crystal alignment film according to claim 4, wherein the component (c) is a tetracarboxylic dianhydride represented by the following formula [3]. (In the formula [3], Z ₁ is a structure represented by the following formula [3a] to formula [3j]) (In the formula [3a], Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. In the formula [3g], Z ₆ and Z ₇ are a hydrogen atom or a methyl group. , each can be the same or different). The method for producing a liquid crystal alignment film according to claim 1, wherein the polymer in the liquid crystal alignment agent is 0.1 to 30% by mass. The method for producing a liquid crystal alignment film according to claim 1, wherein the coating is carried out by an inkjet method. A liquid crystal alignment film produced by the method for producing a liquid crystal alignment film according to claim 1. A liquid crystal alignment film characterized by containing a polyimine having a repeating unit represented by the following formula [1], and having a quinone imidization ratio of 50 to 70%, (In the formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, and C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each may be the same or different). The liquid crystal alignment element according to claim 11, wherein the liquid crystal display element is provided with a liquid crystal layer between a pair of substrates including electrodes, and is disposed between the pair of substrates. A liquid crystal composition of a polymerizable compound polymerized by at least one of an energy ray and a heat, and is produced by a step of polymerizing the polymerizable compound while applying a voltage to the electrode. The liquid crystal alignment element according to claim 11, wherein the liquid crystal display element is provided with a liquid crystal layer between a pair of substrates including electrodes, and is disposed between the pair of substrates. A liquid crystal alignment film of a polymerizable group polymerized by at least one of an energy ray and a heat, and is produced by a step of polymerizing the polymerizable group while applying a voltage between the electrodes. A liquid crystal display element comprising the liquid crystal alignment film according to any one of claims 10 to 13. A liquid crystal alignment agent characterized by containing a polyimine precursor having a repeating unit represented by the following formula [1], (In the formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, and C ₁ and C ₂ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each may be the same or different).