WO2019146319A1

WO2019146319A1 - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and method for producing liquid crystal element

Info

Publication number: WO2019146319A1
Application number: PCT/JP2018/046723
Authority: WO
Inventors: 岡田　敬; 嘉崇村上
Original assignee: Jsr株式会社
Priority date: 2018-01-25
Filing date: 2018-12-19
Publication date: 2019-08-01
Also published as: JP6962387B2; TWI786251B; TW201934609A; KR20200073285A; CN111433665A; CN111433665B; JPWO2019146319A1; KR102349617B1

Abstract

The present invention includes polyenamine in a liquid crystal alignment agent as a polymer component. The polyenamine in one embodiment is a reaction product between a diamine compound and an α, β-unsaturated compound which has, in each molecule thereof, two or more of one type of partial structure represented by formula (1) or formula (2). In formula (1) and formula (2), X1 is a carbonyl group or a sulfonyl group, L1 is a leaving group which leaves as a result of a reaction with a diamine compound, L2 is an oxygen atom or a sulfur atom, and R5 is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more.

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, and method of manufacturing liquid crystal element

Cross-reference to related applications

This application is based on Japanese Patent Application No. 2018-10894 filed on Jan. 25, 2018, the contents of which are incorporated herein by reference.

The present disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, and a method of manufacturing the liquid crystal element.

As a liquid crystal element, a liquid crystal element of a horizontal alignment mode using a nematic liquid crystal having positive dielectric anisotropy represented by TN (Twisted Nematic) type, STN (Super Twisted Nematic) type or the like, or negative dielectric anisotropy Various liquid crystal elements such as a VA (Vertical Alignment) liquid crystal element of a (homeotropic) alignment mode using a nematic liquid crystal having properties are known. These liquid crystal elements have a liquid crystal alignment film having a function of aligning liquid crystal molecules in a predetermined direction.

Generally, a liquid crystal aligning film is formed by apply | coating to a board | substrate the liquid crystal aligning agent in which a polymer component is melt | dissolved in an organic solvent, and heating. As polymer components of liquid crystal aligning agents, polyamic acids, soluble polyimides, polyamides, polyesters, polyorganosiloxanes and the like are known, and in particular polyamic acids and soluble polyimides have heat resistance, mechanical strength, and affinity with liquid crystal molecules. It has been used for a long time because it has excellent properties and the like (see Patent Documents 1 to 3).

Japanese Patent Application Laid-Open No. 4-153622 Japanese Patent Application Laid-Open No. 56-91277 Japanese Patent Application Laid-Open No. 11-258605

Polyamic acids and soluble polyimides have relatively low solubility in organic solvents, and high boiling point solvents such as N-methyl-2-pyrrolidone (NMP), which is an aprotic polar solvent, are generally used as the solvent component of liquid crystal aligning agents. It is done. Here, in order to obtain a liquid crystal element having good electrical characteristics and reliability, it is necessary to minimize the residual solvent in the liquid crystal alignment film. However, when heating at a high temperature is required when forming a liquid crystal alignment film, problems such as restriction of the material of the substrate occur, and for example, the application of a film substrate as a substrate of a liquid crystal element is limited. There is. Further, in color liquid crystal display elements, dyes used as colorants for color filters are relatively weak to heat, and the use of dyes may be limited when heating at the time of film formation needs to be performed at high temperature .

As a method for solving such problems, it is conceivable to reduce the amount of use of the high boiling point solvent in preparation of the liquid crystal aligning agent, or to use a low boiling point solvent instead of the high boiling point solvent. However, the solubility of the liquid crystal aligning agent in the polymer component is sufficiently high, and the solvent having a sufficiently low boiling point is limited, and the selection range is narrow. In addition, if the polymer component is not uniformly dissolved in the solvent, coating unevenness (film thickness unevenness) or pinholes may occur in the liquid crystal alignment film formed on the substrate, or linearity can not be ensured at the end of the coating region. There is a concern that the surface may not be flat. In this case, there is a concern that the product yield may decrease or the display performance such as the liquid crystal alignment and the electrical characteristics may be affected.

In addition, although polyamic acid is better in solubility than polyimide, in order to cyclize polyamic acid to polyimide to ensure good electrical characteristics, heating during element production is relatively made. It needs to be done at high temperature.

Therefore, the polymer component of the liquid crystal aligning agent exhibits high solubility even in a low boiling point solvent, so that when it is used as a liquid crystal aligning agent, it exhibits excellent coatability on the substrate, and the liquid crystal alignment and electricity New materials with excellent properties are required. In particular, in recent years, a liquid crystal television with a large screen and high definition is mainly used, and a small display terminal such as a smartphone and a tablet PC is in widespread use, and a demand for high quality liquid crystal panels is further increasing. Therefore, it is important to secure excellent display quality.

The present disclosure has been made in view of the above-described circumstances, and one object thereof is a liquid crystal aligning agent capable of obtaining a liquid crystal element having good coatability on a substrate and excellent liquid crystal alignment and voltage holding ratio. To provide.

According to the present disclosure, the following means are provided.
[1] A liquid crystal aligning agent containing a polyenamine.
[2] A liquid crystal alignment film formed using the liquid crystal alignment agent of the above-mentioned [1].
[3] A liquid crystal element comprising the liquid crystal alignment film of the above [2].
[4] A process of forming a coating on each of the conductive films of a pair of substrates having a conductive film using the liquid crystal aligning agent according to the above [1], a pair of substrates on which the coating is formed, liquid crystal Forming a liquid crystal cell by opposingly arranging the coated films facing each other through a layer, and irradiating the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates; And a method of manufacturing a liquid crystal element.

By using a liquid crystal aligning agent containing polyenamine as a polymer component, it is possible to obtain a liquid crystal element excellent in liquid crystal alignment and voltage holding ratio. Moreover, the said liquid crystal aligning agent is excellent in the coating property with respect to a board | substrate.

Below, each component contained in the liquid crystal aligning agent of this indication, and the other component arbitrarily mix | blended as needed are demonstrated.
In the present specification, "hydrocarbon group" is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The “chain hydrocarbon group” means a straight chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and are composed only of a chain structure. However, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it does not need to be comprised only with the structure of alicyclic hydrocarbon, and the thing which has a chain-like structure in the part is also included. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed of only an aromatic ring structure, and a part thereof may contain a chain structure or an alicyclic hydrocarbon structure.

«Liquid crystal alignment agent»
The liquid crystal aligning agent of this indication contains polyenamine as a polymer component. Polyenamine is a polymer having a carbon-carbon double bond at the position adjacent to the amino group of polyamine, and includes polyenamino ketone, polyenamino ester, polyenamino nitrile and polyenamino sulfonyl. The polyenamine to be used is α, β having one or more of one partial structure represented by the following formula (1) or formula (2) in one molecule, in terms of availability of monomers and ease of synthesis. It is preferably a reaction product of an unsaturated compound and a diamine compound.

(In formula (1) and formula (2), X ¹ is a carbonyl group or a sulfonyl group, L ¹ is a leaving group which leaves by reaction with a diamine compound, and L ² is an oxygen atom or And R ⁵ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, and a plurality of X ¹ , R ⁵ , L ¹ and L ² in one molecule are each independently as defined above “*” Indicates that it is a bond.)

(Α, β-unsaturated compounds)
In the above formulas (1) and (2), X ¹ is preferably a carbonyl group in terms of a high degree of freedom of choice of monomers.
The L ^{1 in the} above formula (1) is not particularly limited as long as it is a group capable of leaving by reaction with the amino group of the diamine compound, and examples thereof include an alkoxy group having 1 to 5 carbon atoms, a pyrrolidinyl group, a halogen atom, a hydroxyl group, Examples thereof include a substituted or unsubstituted phenoxy group, a heterocyclic group, and a monovalent group in which a hydroxyl group or a thiol group is introduced into the ring portion of the heterocyclic ring. When L ¹ is a substituted phenoxy group, examples of the substituent that the phenoxy group has include an alkyl group (for example, a methyl group, an ethyl group and the like) and the like. In the present specification, “heterocyclic group” means that n (n is an integer) hydrogen atoms are removed from the ring of a heterocyclic ring (eg, nitrogen-containing heterocyclic ring, oxygen atom heterocyclic ring, sulfur-containing heterocyclic ring, etc.) Means an n-valent group.

Preferred specific examples of the α, β-unsaturated compound include compounds having two or more of one of the partial structures represented by the following formulas (4-1) to (4-4) in one molecule, At least one selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the following formula (6) (including tautomers). In addition, the structure represented by each of following formula (4-1), formula (4-2), formula (4-4), formula (5) and formula (6) is represented by the said formula (1) The structure corresponds to one having a partial structure, and the structure represented by the following formula (4-3) corresponds to one having a partial structure represented by the above formula (2).

(In the formulas (4-1) to (4-4), (5) and (6), X ¹ represents a carbonyl group or a sulfonyl group, and R ¹ to R ⁵ and R ⁷ to R ¹⁰ represent And R ⁶ independently represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and R ⁶ represents an alkanediyl group having 2 to 5 carbon atoms or —O— or — between carbon-carbon bonds of the alkanediyl group. L ¹ is a leaving group which is eliminated by reaction with a diamine compound, L ² is an oxygen atom or a sulfur atom, and a plurality of X ¹ and R ^{1 in} one molecule. To R ¹⁰ , L ¹ and L ² each independently have the above-mentioned definition, “*” represents a bond.

The formula (4-1), (4-2), specific examples of ^{L 1} in the formula (4-4) and the formula (5), the description of ^{L 1} in the formula (1) is applied Ru.
The monovalent organic group of R ¹ to R ⁵ and R ⁷ to R ¹⁰ is preferably a monovalent alkyl group having 1 to 20 carbon atoms, an alkoxy group or a cycloalkyl group.
When the α, β-unsaturated compound has two or more of one of the partial structures represented by the above formulas (4-1) to (4-4) in one molecule, the moiety in one molecule The number of structures is preferably two to four, more preferably two. Specifically, compounds represented by each of the following formulas (M-1) to (M-4) can be preferably used.

(In Formula (M-1) to Formula (M-4), B ¹ to B ⁴ are a single bond or a divalent organic group. X ¹ , R ¹ to R ⁶ , L ¹ and L ² are It is synonymous with the said Formula (4-1)-Formula (4-4).)

In the above formulas (M-1) to (M-4), examples of the divalent organic group of B ¹ to B ⁴ include a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon of the hydrocarbon group. And-a divalent group having -O-, -S-, -NH- and the like between-carbon bonds, and the like. When B ¹ to B ⁴ are divalent organic groups, B ¹ to B ⁴ may be groups which are bonded to the above-mentioned formulas (4-1) to (4-4) by an aromatic ring group. preferable. The aromatic ring group is preferably a phenylene group or a naphthalene group, and particularly preferably a phenylene group. The aromatic ring group may have a methyl group, an ethyl group, an alkoxy group or the like as a substituent in the ring portion.

Specific examples of the α, β-unsaturated compound include compounds represented by the following formulas (A-1) to (A-14), and the like. In the synthesis of polyenamine, one kind of α, β-unsaturated compound may be used alone, or two or more kinds may be used in combination.

In the present specification, the “α, β-unsaturated compound” is meant to include tautomers of compounds exhibiting tautomerism. For example, the partial structure in which L ¹ in the above formula (4-1) is a hydroxyl group mutually converts with the partial structure represented by the following formula (4-1A), but in the synthesis of polyenamine, the following formula It is allowed that a compound having two or more partial structures represented by (4-1A) in one molecule is present. The same applies to a partial structure in which L ^{1 in the} above formula (4-2) is a hydroxyl group and a compound represented by the above formula (6), and a partial structure represented by the following formula (4-2A) The compounds are mutually converted to each other. The tautomers of the compounds represented by the above formulas (A-5), (A-9) and (A-10) are shown below.

Among the α, β-unsaturated compounds exemplified above, each of the above formulas (A-8), (A-9), (A-11), (A-12) and (A-14) The compound represented corresponds to a compound having two or more partial structures represented by the above formula (4-1) in one molecule, and the compound represented by the above formula (A-10) is a compound represented by the above formula (A) It corresponds to a compound having two or more partial structures represented by 4-2) in one molecule. In addition, the compound represented by the above formula (A-13) corresponds to a compound having two or more partial structures represented by the above formula (4-3) in one molecule, and the above formula (A-6) The compound represented by each of (A-7) and (A-7) corresponds to a compound having two or more partial structures represented by the above formula (4-4) in one molecule. In addition, the compounds represented by the above formulas (A-1) to (A-3) correspond to the compounds represented by the above formula (5), and the above formulas (A-4) and (A-) The compound represented by each of 5) corresponds to the compound represented by the said Formula (6).

(Diamine compound)
The diamine compound used for the synthesis of polyenamine is not particularly limited, and known diamine compounds can be used. Among these, since polyenamine can make the liquid crystal alignment property of the obtained liquid crystal element excellent, a group consisting of compounds represented by the following formulas (d-1) to (d-4) It is preferable to have a partial structure derived from at least one diamine compound selected from the following (hereinafter, also referred to as "specific diamine").

(In formula (d-1), X ¹¹ and X ¹² each independently represent a single bond, —O—, —S—, —OCO— or —COO—, and Y ¹¹ is an oxygen atom or a sulfur atom And R ¹¹ and R ¹² are each independently an alkanediyl group having 1 to 3 carbon atoms, n 1 is 0 or 1, and n 2 and n 3 satisfy n 2 + n 3 = 2 when n 1 = 0. is an integer, for n1 = 1, a n2 = n3 = 1. formula (d-2) ^{in, X 13} is a single bond, -O- or -S-, m1 is an integer of 0 to 3 M2 is an integer of 1 to 12 when m1 = 0, and m2 = 2 if m1 is an integer of 1 to 3. In the formula (d-3), X ¹⁴ and X ¹⁵ are each independently represent a single bond, -O -, - COO- or a ^{-OCO-, R 17} is an alkanediyl group having 1 to 3 carbon atoms ^{There, A 11} is a single bond or an alkanediyl group having a carbon number of 1 ~ 3 .a is 0 or 1, b is an integer of 0 ~ 2, c is an integer of 1 ~ 20, k Is 0 or 1. However, a and b are not simultaneously 0. In formula (d-4), A ¹² is a single bond, an alkanediyl group having 1 to 12 carbon atoms, or 1 to 6 carbon atoms A ¹³ represents -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and A ¹⁴ represents a monovalent organic compound having a steroid skeleton. Group))

(Compound represented by formula (d-1))
In the above formula (d-1), examples of the alkanediyl group having 1 to 3 carbon atoms of R ¹¹ and R ¹² include, for example, methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group And propane-2,3-diyl group. Among these, preferred is a methylene group, an ethylene group or a propane-1,3-diyl group.
X ¹¹ and X ¹² are preferably a single bond, -O- or -S-.
Y ¹¹ is an oxygen atom or a sulfur atom, preferably an oxygen atom.

The two primary amino groups possessed by the compound represented by the formula (d-1) may be bonded to the same benzene ring when n1 = 0, or one bonded to two different benzene rings. It may be In the case of n1 = 1, the two primary amino groups are each bound to different benzene rings.
The bonding position of the primary amino group on the benzene ring is not particularly limited. For example, when there is one primary amino group on the benzene ring, the bonding position may be any of 2-position, 3-position and 4-position with respect to other groups, in 3-position or 4-position. It is preferably present, and more preferred is 4-position. In addition, in the case where there are two primary amino groups on the benzene ring, the bonding position may be, for example, the 2,4-position or the 2,5-position relative to other groups, and in particular, the 2,4-position Is preferred.

The hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent atom in which at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom It may be substituted by a group or a fluorine atom. In this case, examples of the monovalent hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 5 to 10 carbon atoms Examples thereof include phenyl group and tolyl group), aralkyl group having 5 to 10 carbon atoms (such as benzyl group) and the like.

Preferred specific examples of the compound represented by the above formula (d-1) include compounds in which n1 = 0, such as 4,4′-diaminodiphenylamine, 2,4-diaminodiphenylamine and the like; and n1 = 1 Examples of the compound include 1,3-bis (4-aminobenzyl) urea, 1,3-bis (4-aminophenethyl) urea, 1,3-bis (3-aminobenzyl) urea, 1- (4-aminobenzyl) ) -3- (4-aminophenethyl) urea, 1,3-bis (2- (4-aminophenoxy) ethyl) urea, 1,3-bis (3- (4-aminophenoxy) propyl) urea, 1, 3-Bis (4-aminobenzyl) thiourea, 1,3-bis (2-aminobenzyl) urea, 1,3-bis (2-aminophenethyl) urea, 1,3-bis (2- (2 (2 Amino benzoyloxy) ethyl) urea, 1,3-bis (3- (2-amino-benzoyloxy) propyl) urea or the like; may be mentioned, respectively. In addition, as a compound represented by the said Formula (d-1), these compounds can be used individually by 1 type or in combination of 2 or more types.

(Compound represented by formula (d-2))
In the above formula (d-2), X ¹³ is a single bond, -O- or -S-, preferably a single bond or -O-.
When m1 = 0, m2 is an integer of 1 to 12. In this case, from the viewpoint of improving the heat resistance of the obtained polymer, m 2 is preferably 1 to 10, more preferably 1 to 8. Further, in the application of the liquid crystal alignment film, m1 = 0 is preferable from the viewpoint of improving the rubbing resistance while maintaining good liquid crystal alignment, and in the viewpoint of reducing the pretilt angle of liquid crystal molecules, m1 is 1 It is preferable that it is an integer of -3.
Although the bonding position of the primary amino group on the benzene ring is not particularly limited, it is preferable that each primary amino group be in the 3- or 4-position relative to the other group, and more preferably in the 4-position. . The hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom. It may be substituted by a valent group or a fluorine atom.

Preferred specific examples of the compound represented by the above formula (d-2) include, for example, bis (4-aminophenoxy) methane, bis (4-aminophenoxy) ethane, bis (4-aminophenoxy) propane, bis (4) -Aminophenoxy) butane, bis (4-aminophenoxy) pentane, bis (4-aminophenoxy) hexane, bis (4-aminophenoxy) heptane, bis (4-aminophenoxy) octane, bis (4-aminophenoxy) nonane Bis (4-aminophenoxy) decane, bis (4-aminophenyl) methane, bis (4-aminophenyl) ethane, bis (4-aminophenyl) propane, bis (4-aminophenyl) butane, bis (4-aminophenyl) butane Aminophenyl) pentane, bis (4-aminophenyl) hexane, bis (4-aminophen) B) Heptane, bis (4-aminophenyl) octane, bis (4-aminophenyl) nonane, bis (4-aminophenyl) decane, 1,3-bis (4-aminophenylsulfanyl) propane, 1,4-bis (4-aminophenylsulfanyl) butane and the like can be mentioned. In addition, as a compound represented by the said Formula (d-2), the compound of these illustrations can be used individually by 1 type or in mixture of 2 or more types.

(Compound represented by formula (d-3))
In Formula (d-3), ^{^{^{"- X 14 - (R 17 -X}}} 15) k - " as the divalent group represented by the alkanediyl group having 1 to 3 carbon atoms, * - O -, * It is preferable that it is -COO- or * -O-C ₂ H ₄ -O- (wherein the bond with "*" is bonded to a diaminophenyl group).
The group “—C _c H _{2c + 1} ” is preferably linear, and specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group Group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl Groups, n-octadecyl group, n-nonadecyl group and the like.
The two primary amino groups in the diaminophenyl group are preferably in the 2,4- or 3,5-position relative to the group "X ⁴ ", and more preferably in the 2,4-position. The hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent atom in which at least one hydrogen atom on the hydrocarbon group is substituted by a fluorine atom. Or a fluorine atom.

Preferred specific examples of the compound represented by the above formula (d-3) include, for example, compounds represented by each of the following formulas (d-3-1) to (d-3-12) it can.

(Compound represented by formula (d-4))
The alkanediyl group having 1 to 12 carbon atoms in the ^{A 12} in the above formula (d-4), preferably an alkanediyl group having 1 to 4 carbon atoms, a methylene group, an ethylene group, 1,3-propanediyl, 1 More preferred is a 4-butanediyl group. As the fluoroalkanediyl group having 1 to 6 carbon atoms, a perfluoroalkanediyl group having 1 to 4 carbon atoms is preferable, and -CF _2- , perfluoroethylene group, 1,3-perfluoropropanediyl group, 1,4 Perfluorobutanediyl is more preferred.
A ¹³ is preferably -O-.
The steroid skeleton in the A ^14, Shikuropentano - perhydro phenanthridine consisting Ren core structure or a carbon - one or more than one carbon bond refers to a structure in which a double bond. The monovalent organic group having such a steroid skeleton is preferably one having 17 to 40 carbon atoms.

Preferred specific examples of the compound represented by the above formula (d-4) include 1-cholesteryloxymethyl-2,4-diaminobenzene, from the viewpoint of giving a high pretilt angle to a coating film in the use of a liquid crystal alignment film. -(1-Cholesteryloxy-1,1-difluoromethyl) -2,4-diaminobenzene, 1- (1-cholestanyloxy-1,1-difluoromethyl) -3,5-diaminobenzene, 3- (2 , 4-Diaminophenylmethoxy) -4,4-dimethylcholestane, 3- (3,5-diaminophenylmethoxy) -4,4-dimethylcholestane, 3- (1- (3,5-diaminophenyl)- 1,1-Difluoromethoxy) -4,4-dimethylcholestane, 3-((2,4-diaminophenyl) methoxy) cholan-24-acid hexadecyl, 3- ( , 4-Diaminophenylmethoxy) cholan-24-acid stearyl, 3- (1- (2,4-diaminophenyl) -1,1-difluoromethoxy) cholan-24-acid stearyl, 3- (3,5-diamino) Phenylmethoxy) cholan-24-acid stearyl, 1-cholesteryloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, 1-cholestanyloxy-2,4-diaminobenzene and 3,5-diaminobenzoic acid It is preferable to use one or more selected from the group consisting of cholestanyl acid, and among these, 1-cholesteryloxy-2,4-diaminobenzene, 3, from the viewpoint of giving a high pretilt angle at a small usage rate among these. Cholesteryl 5-diaminobenzoate, 1-cholestanyloxy-2,4-diaminoben It is particularly preferred to use at least one selected from the emissions and the group consisting of 3,5-diaminobenzoic acid cholestanyl.

In the synthesis of the polyenamine, the use ratio of the specific diamine can be arbitrarily set according to the diamine compound to be used. When the compound represented by the above formula (d-1) is used, the amount thereof used is preferably 1 mol% or more, and more preferably 3 mol% or more, based on all diamines. Moreover, when using the compound represented by the said Formula (d-2), from the viewpoint of providing a low inclination-orientation angle with respect to a liquid crystal molecule, the amount used is 10 mol% or more with respect to all the diamines. It is preferable to set it as 30 mol% or more, and more preferable to set it as 50 mol% or more.

When using at least one selected from the group consisting of a compound represented by the above formula (d-3) and a compound represented by the above formula (d-4), the use thereof from the viewpoint of imparting good orientation. The proportion (the total amount of two or more compounds used) is preferably 5 mol% or more, more preferably 10 mol% or more, based on all diamines. In addition, as a specific diamine, 1 type of the compounds illustrated above can be used individually or in combination of 2 or more types.

As a diamine compound used for the synthesis of polyenamine, diamine compounds other than the above specific diamines (hereinafter, also referred to as "other diamines") can be used. Specific examples of the other diamine include the compounds shown below. In addition, when synthesizing polyenamine, polyenamine having a structural unit derived from the diamine compound can be obtained by using each diamine compound shown below.

(Diamine compounds having a carboxyl group)
The diamine compound having a carboxyl group (hereinafter, also referred to as “carboxyl group-containing diamine”) can be used for the purpose of improving the electrical characteristics (in particular, the relaxation effect of accumulated charge) of the liquid crystal element obtained. The carboxyl group-containing diamine is preferably used in combination with a diamine compound having a nitrogen-containing aromatic heterocycle, which will be described later, in that the effect of improving the electrical characteristics of the liquid crystal device to be obtained is further enhanced. The carboxyl group-containing diamine used is preferably an aromatic diamine, and specific examples thereof include compounds represented by the following formulas (d-5-1) and (d-5-2), respectively. Be

(In the formula (d-5-1) and the formula (d-5-2), R ²⁰ represents a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Z ¹ represents , A single bond, an oxygen atom, or an alkanediyl group having 1 to 3 carbon atoms, r 2, r 5 and r 6 each independently represents an integer of 1 or 2, and r 1, r 3 and r 4 each independently represent 0 to 2 And r7 and r8 each independently represent an integer of 0 to 2 satisfying r7 + r8 = 2, provided that r3 + r5 + r7 ≦ 5 and r4 + r6 + r8 ≦ 5, wherein a plurality of R ²⁰ are present If you, they R ²⁰ have independently as defined above.)

In Formulas (d-5-1) and (d-5-2), examples of the alkyl group having 1 to 10 carbon atoms for R ²⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. Groups, heptyl groups, octyl groups, nonyl groups, decyl groups and the like, and these may be linear or branched. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a hexyloxy group. Examples of the C 1-3 alkanediyl group as Z ¹ include a methylene group, an ethylene group and a trimethylene group. r1, r3 and r4 are preferably 0 or 1, more preferably 0.

As a specific example of a carboxyl group-containing diamine, examples of the compound represented by the above formula (d-5-1) include 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid and 2,5-diaminobenzoic acid And the like; as a compound represented by the above formula (d-5-2), for example, 4,4′-diaminobiphenyl-3,3′-dicarboxylic acid, 4,4′-diaminobiphenyl-2,2′-dicarboxylic acid Acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-Diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, 4 4'-diaminodiphenyl ethane-3-carboxylic acid, 4,4'-diaminodiphenyl ether 3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl ether-3-carboxylic acid and the like; may be mentioned. In addition, as carboxyl group-containing diamine, 1 type in these can be used individually or 2 types or more can be used.

When a carboxyl group-containing diamine is used, its use ratio is preferably 2 mol% or more, more preferably 3 to 90 mol%, and still more preferably 5 to 70 mol% with respect to the total diamine.

(Diamine compound having nitrogen-containing aromatic heterocycle)
The diamine compound having a nitrogen-containing aromatic heterocyclic ring can be used for the purpose of improving the electrical characteristics (in particular, the effect of reducing burn-in due to a direct current voltage) of the liquid crystal element to be obtained. Examples of the nitrogen-containing aromatic heterocycle possessed by the diamine compound include pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, benzimidazole, purine, quinoline, naphthyridine, carbazole, acridine and the like. Among them, it is preferable to have at least one selected from the group consisting of pyrrole, pyridine, pyrimidine, pyrazine and imidazole.

Specific examples of the diamine compound having a nitrogen-containing aromatic heterocycle include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, and N-methyl-3. , 6-diaminocarbazole, N-ethyl-3, 6-diaminocarbazole, N-phenyl-3, 6-diaminocarbazole, 3, 6-diaminoacridine, the following formula (d-6-1) to formula (d-6) And the compounds represented by each of -8) and the like. In addition, as a diamine compound which has a nitrogen-containing aromatic heterocyclic ring, these 1 type can be used individually or in combination of 2 or more types.

The proportion of the diamine compound having a nitrogen-containing aromatic heterocyclic ring is preferably 2 mol% or more, more preferably 3 to 50 mol%, and still more preferably 5 to 40 mol%, based on all diamines. Is more preferred.

(Diamine compounds having a protective group)
A diamine compound having a protective group (hereinafter, also referred to as "protective group-containing diamine") improves the solubility of polyenamine in a solvent, and when polyenamine is used in combination with another polymer, with other polymers. Can be used to improve the affinity of The protecting group-containing diamine preferably has a partial structure in which a protecting group is bonded to a nitrogen atom, and specifically, a diamine having a group represented by the following formula (7-1) or formula (7-2) Compounds are mentioned.

(In Formula (7-1) and Formula (7-2), A ²¹ is a single bond or a divalent organic group having 1 or more carbon atoms, Y ¹ is a protecting group, and R ²¹ to R ²³ are And each independently represents a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, m is an integer of 0 to 6. "*" represents a bond.

In the above formulas (7-1) and (7-2), the protective group of Y ¹ is preferably a group which is released by heat, and for example, a carbamate type protective group, an amide type protective group, an imide type protective group And sulfonamide protecting groups. As the protective group, a carbamate protective group is particularly preferable. Specific examples thereof include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group and a 1,1-dimethyl- Examples thereof include 2-cyanoethyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, 2- (trimethylsilyl) ethoxycarbonyl group and the like. Among these, tert-butoxycarbonyl group is particularly preferable in that it is highly removable by heat and the amount of remaining of the deprotected portion in the membrane can be further reduced.
The monovalent organic group of R ²¹ and R ²² is preferably a monovalent hydrocarbon group of 1 to 10 carbon atoms, and more preferably an alkyl group or cycloalkyl group of 1 to 10 carbon atoms.
The monovalent organic group of R ²³ is preferably a monovalent alkyl group of 1 to 10 carbon atoms or a protecting group. Examples of the divalent organic group of A ²¹ include a divalent hydrocarbon group, and a group having —O—, —CO—, —COO—, —NH— or the like between carbon-carbon bonds of the hydrocarbon group. It can be mentioned. A ²¹ is preferably bonded to an aromatic ring, and particularly preferably to a benzene ring.

Examples of the protective group-containing diamine include compounds represented by the following formulas (d-7-1) to (d-7-12), and the like. The protective group-containing diamines may be used alone or in combination of two or more.

(Wherein, TMS represents a trimethylsilyl group)

When a protective group-containing diamine is used, its use ratio is preferably 2 mol% or more, more preferably 3 to 80 mol%, and preferably 5 to 70 mol%, based on all diamines. Is more preferred.

(Secondary or tertiary amine structure / nitrogen containing heterocyclic structure containing diamine)
In the synthesis of polyenamine, a diamine compound having at least one selected from the group consisting of a secondary or tertiary amine structure represented by the following formula (9) and a nitrogen-containing heterocyclic structure (hereinafter referred to as “secondary or tertiary Amine structure / nitrogen-containing heterocyclic structure-containing diamine) may also be used. Use of a secondary or tertiary amine structure / nitrogen-containing heterocyclic structure-containing diamine is preferable in that the improvement effect of the reduction in sticking due to a DC voltage can be enhanced.

In formula (9), R ⁵¹ and R ⁵² each independently represent a divalent aromatic ring group, and R ⁵³ represents a hydrogen atom or a monovalent organic group having one or more carbon atoms. Indicates that it is a bond.)

In the formula (9), the divalent aromatic ring group R ⁵¹ and R ^52, an aromatic hydrocarbon group, a nitrogen-containing aromatic heterocyclic group and the like. Preferred is an aromatic hydrocarbon group, and examples thereof include a phenylene group and a naphthylene group. R ⁵¹ and R ⁵² are particularly preferably phenylene groups.
Examples of the monovalent organic group represented by R ⁵³ include alkyl groups such as methyl, ethyl and propyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and methylphenyl, tert-butoxycarbonyl and the like And the like. R ⁵³ is preferably a hydrogen atom or a methyl group.
Examples of the nitrogen-containing heterocycle include nitrogen-containing heteroalicyclic structures such as piperidine, piperazine, pyrrolidine and hexamethyleneimine, and the nitrogen-containing aromatic heterocycles exemplified above. Among these, it is preferable to have at least one selected from the group consisting of pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline and carbazole.

Specific examples of the secondary or tertiary amine structure / nitrogen-containing heterocyclic structure-containing diamine include, for example, bis (4-aminophenyl) amine, 2,4-diaminopyrimidine, 1,4-bis- (4-aminophenyl) -Piperazine, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, a diamine compound having a nitrogen-containing aromatic heterocyclic ring Examples thereof include compounds exemplified in the description, compounds represented by the following formulas (d-9-1) to (d-9-8), and the like. In addition, secondary or tertiary amine structure / nitrogen-containing heterocyclic structure containing diamine may be used individually by 1 type, and may be used combining 2 or more types.

When a secondary or tertiary amine structure / nitrogen-containing heterocyclic structure-containing diamine is used, its use ratio is preferably 2 mol% or more, preferably 3 to 60 mol%, based on all diamines. More preferably, 5 to 50 mol% is more preferable.

(Secondary amino group-containing diamine compounds)
When synthesizing polyenamine, a diamine compound represented by the following formula (8) (hereinafter, also referred to as “secondary amino group-containing diamine compound”) may be used as another diamine. By using a secondary amino group-containing diamine compound, when using polyenamine and another polymer as a polymer component of a liquid crystal aligning agent in combination, it is possible to control phase separation with other polymers. preferable.

In the formula (8), A ³¹ represents a divalent aromatic ring group, R ³¹ represents an alkanediyl group having 1 to 5 carbon atoms, and R ³² represents a monovalent hydrocarbon group having 1 to 4 carbon atoms is there.)

In Formula (8) above, examples of the divalent aromatic ring group of A ³¹ include groups in which two hydrogen atoms have been removed from the ring portion of an aromatic ring such as a benzene ring, a naphthalene ring or an anthracene ring. A ³¹ is preferably a phenylene group.
The alkanediyl group of R ³¹ may be linear or branched, and examples thereof include a methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group.
The monovalent hydrocarbon group represented by R ³² includes alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl; and alkylene groups such as vinyl and propenyl , Etc. R ³² is preferably a methyl group or an ethyl group.

Specific examples of the secondary amino group-containing diamine compound include, for example, compounds represented by the following formulas (d-8-1) to (d-8-4). In addition, a secondary amino group containing diamine compound may be used individually by 1 type, and may be used combining 2 or more types.

When a secondary amino group-containing diamine compound is used, the use ratio thereof is preferably 2 mol% or more, more preferably 3 to 90 mol%, and more preferably 5 to 70 mol% with respect to all diamines. It is further preferable to

As other diamines, in addition to the above, for example, aliphatic diamines such as 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;
1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), the following formula (d-11-1) to the formula (d-11-6)

A cycloaliphatic diamine such as a compound represented by each of
p-phenylenediamine, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 1- ( 4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,4- Diamino-N, N-diallylaniline, 2,5-diamino-N, N-diallylaniline, the following formula (d-10-1) to the formula (d-10-5)

Aromatic diamines such as compounds represented by each of
Diamino organosiloxanes such as 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be mentioned, respectively, and diamines described in JP-A-2010-97188 can be used. In addition, another diamine can be used individually by 1 type or in combination of 2 or more types.

(Other monomers)
In the synthesis of the polyenamine, other monomers other than the α, β-unsaturated compound and the diamine compound may be used. Examples of other monomers include tetracarboxylic acid dianhydride, tetracarboxylic acid diester, tetracarboxylic acid diester dihalide, and a bislactone compound. Among these, tetracarboxylic acid dianhydride can be preferably used.

Examples of tetracarboxylic acid dianhydrides include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride and ethylenediaminetetraacetic acid dianhydride;
1,2,3,4-Cyclobutanetetracarboxylic acid dianhydride, 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-Tricarboxycyclopentylacetic acid dianhydride , 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5- Dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo [ 3.3.0] Octane-2: 4, 6: 8-alicyclic tetracarboxylic acid dianhydride such as dianhydride, cyclopentane tetracarboxylic acid dianhydride, cyclohexane tetracarboxylic acid dianhydride;
Pyromellitic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene glycol bis (anhydrotrimellitate), 1, Besides aromatic tetracarboxylic acid dianhydrides such as 3-propylene glycol bis (anhydrotrimellitate), etc., etc., it is also possible to use the tetracarboxylic acid dianhydride described in JP-A-2010-97188. Can. In addition, tetracarboxylic dianhydride may be used individually by 1 type, and may be used combining 2 or more types.

The tetracarboxylic acid diester can be obtained by ring-opening the above-mentioned tetracarboxylic acid dianhydride using an alcohol such as methanol, ethanol or propanol. The tetracarboxylic acid diester dihalide can be obtained, for example, by reacting the tetracarboxylic acid diester obtained above with a suitable chlorinating agent such as thionyl chloride.

Examples of the bislactone compounds include endocyclic enol esters, exocyclic enol esters, endocyclic acyl imide esters, exocyclic acyl imide esters, oxime esters and the like. Specific examples of the bislactone compound used for the synthesis include, for example, compounds represented by the following formulas (b-1) to (b-11).

In the present specification, “a reaction product of an α, β-unsaturated compound and a diamine compound” means an α, β-unsaturated compound and a diamine as monomers used for synthesis, as long as the effects of the present disclosure are not impaired. It is acceptable to use together with the compound other monomers other than the α, β-unsaturated compound and the diamine compound. The proportion of the other monomer (preferably tetracarboxylic acid dianhydride) to be used is preferably 40 mol% or less, preferably 30 mol% or less, based on the total amount of monomers used in the synthesis of polyenamine. More preferable.

(Synthesis reaction of polyenamine)
Although the synthesis method of polyenamine is not particularly limited, it can be synthesized, for example, by vinyl nucleophilic substitution polymerization. The synthesis reaction is preferably carried out in an organic solvent. Examples of the organic solvent used for the reaction include aprotic polar solvents (N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc.), phenolic solvents (phenol, cresol etc.), Alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like can be mentioned. The proportion of the organic solvent used is preferably such that the total amount of the α, β-unsaturated compound and the diamine compound is 0.1 to 50% by mass with respect to the total amount of the reaction solution. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and the reaction time is preferably 0.1 to 24 hours. The above reaction may be carried out in the presence of a catalyst such as trifluoroacetic acid, if necessary.

When the reaction solution obtained by dissolving polyenamine is obtained by the above reaction, the reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or a precipitate obtained by pouring the reaction solution into a large amount of poor solvent Even if the polyenamine contained in the reaction solution is isolated using a known isolation method such as a method of drying under reduced pressure, a method of evaporating the reaction solution under reduced pressure using an evaporator, etc. Good.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the obtained polyenamine is preferably 1,000 to 300,000, more preferably 2,000 to 100,000. . The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 5 or less, more preferably 3 or less. In addition, the polyenamine used for preparation of a liquid crystal aligning agent may be only 1 type, and may combine 2 or more types.

The content of polyenamine in the liquid crystal aligning agent is the total amount of polymer components contained in the liquid crystal aligning agent from the viewpoint of sufficiently enhancing the coatability to the substrate and improving the liquid crystal alignment and voltage holding ratio of the liquid crystal element. The amount is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. In addition, the content of polyenamine is preferably 90% by mass or less, more preferably 80% by mass or less, and preferably 70% by mass or less based on all polymers contained in the liquid crystal aligning agent. More preferable.

As an example of synthesis of polyenamine, an α, β-unsaturated compound represented by the following formulas (M-1) to (M-4), (5) or (6) and “NH ₂ —Y ² —NH The reaction scheme with the compound represented by ₂ ′ ′ is shown below. In the following scheme, Y ² is a divalent organic group obtained by removing two primary amino groups from a diamine compound.

<Other ingredients>
The liquid crystal aligning agent of this indication may contain other components other than polyenamine as needed. Other components are not particularly limited as long as the effects of the present disclosure are not impaired. Specific examples of the other components include a polymer different from polyenamine (hereinafter, also referred to as “other polymer”), a compound having a crosslinkable group (hereinafter, also referred to as “crosslinkable group-containing compound”), Functional silane compounds, antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants, photosensitizers, solvents and the like can be mentioned. The blend ratio of the other components can be appropriately selected according to each compound, as long as the effects of the present disclosure are not impaired.

(Other polymers)
Other polymers can be used for the purpose of improving the solubility in solvents and electrical properties. Other polymers include, for example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, polystyrene derivative, (styrene-maleimide) type The polymer which has a polymer, a poly (meth) acrylate, etc. as a main frame is mentioned. In addition, (meth) acrylate is meant to include acrylate and methacrylate. In preparation of a liquid crystal aligning agent, another polymer may be used individually by 1 type, and may be used in combination of 2 or more type.

Other polymers have good affinity with polyenamine, and can enhance the liquid crystal alignment and electrical properties of the resulting liquid crystal element, and polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane and (styrene-maleimide) It is preferable that it is at least 1 type chosen from the group which consists of a polymer). Among them, when the liquid crystal aligning ability is imparted to the organic film formed by using a liquid crystal aligning agent by rubbing treatment, the liquid crystal aligning agent of the present disclosure includes polyamic acid, polyamic acid ester and polyimide as other polymers. It is more preferable to contain at least one selected from the group consisting of When a liquid crystal alignment ability is imparted to the organic film by photoalignment treatment or a liquid crystal element is obtained by PSA treatment, the liquid crystal alignment agent of the present disclosure includes polyorganosiloxane and (styrene-maleimide) based on other polymers. It is more preferable to contain at least one selected from the group consisting of polymers. The (styrene-maleimide) polymer is preferably a (styrene-phenylmaleimide) polymer.

When other polymers are contained in the liquid crystal aligning agent, the blending ratio of the other polymers should be 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of polyenamine contained in the liquid crystal aligning agent. Is preferable, and 30 to 500 parts by mass is more preferable.

As preferred embodiments of the polymer component of the liquid crystal aligning agent, the following (I) to (IV) can be mentioned.
(I) The aspect which a polymer component consists of polyenamine and at least 1 type chosen from the group which consists of a polyamic acid, polyamic acid ester, and a polyimide.
(II) An embodiment in which the polymer component comprises polyenamine and polyorganosiloxane.
(III) An embodiment in which the polymer component comprises polyenamine and a (styrene-phenylmaleimide) polymer.
(IV) The aspect which a polymer component consists of polyenamine.
Among these, (I) is particularly preferable in that a liquid crystal element excellent in coating properties, liquid crystal alignment property and electrical property can be obtained.

(Crosslinkable group-containing compound)
The liquid crystal aligning agent of the present disclosure includes at least one crosslinkable group selected from the group consisting of a cyclocarbonate group, an epoxy group, an isocyanate group, a blocked isocyanate group, an oxetanyl group, a trialkoxysilyl group, and a polymerizable unsaturated bond group. You may contain the compound which it has (Hereafter, it is also mentioned a "crosslinkable group containing compound."). The inclusion of the crosslinkable group-containing compound is preferable in that the adhesion of the liquid crystal alignment film to the substrate and the electrical characteristics and reliability of the liquid crystal element can be improved.
When the crosslinkable group-containing compound has a polymerizable unsaturated bond group, examples of the polymerizable unsaturated bond group include a (meth) acryloyl group, an ethylenic carbon-carbon double bond, a vinylphenyl group and a vinyloxy group (CH ₂ CHCH-O-), a vinylidene group, a maleimide group and the like are mentioned, and a cyclocarbonate group, an epoxy group or a (meth) acryloyl group is preferable in that it is highly reactive with light or heat. The molecular weight of the crosslinkable group-containing compound is preferably 3,000 or less, more preferably 2,000 or less in terms of storage stability.

Specific examples of the crosslinkable group-containing compound include, as a cyclocarbonate group-containing compound, for example, a compound represented by the following formula (11-1), a compound represented by the following formula (11-2), etc.
Examples of the compound having an epoxy group include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, triglycidyl isocyanurate, 1,6-hexanediol diglycidyl ether, glycerin di Glycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N -Diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N- Glycidyl - aminomethyl cyclohexane, N, N-diglycidyl - cyclohexylamine and the like;
As a compound having a trialkoxysilyl group, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, a compound represented by the following formula (11-3), a compound represented by the following formula (11-4), etc.
Examples of the compound having a blocked isocyanate group include a compound represented by the following formula (11-5), a compound represented by the following formula (11-6), etc.
Examples of the compound having a (meth) acryloyl group include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and the following formula (11-7) A compound, a compound represented by the following formula (11-8), etc.
Examples of the compound having an oxetanyl group include a compound represented by the following formula (11-9), a compound represented by the following formula (11-10), and the like. In addition, as an example of an epoxy-group containing compound, the epoxy-group-containing polyorganosiloxane of WO2009 / 096598 can be used.

When the crosslinkable group-containing compound is blended in the liquid crystal aligning agent, the blending ratio is preferably 40 parts by mass or less with respect to a total of 100 parts by mass of the polymer contained in the liquid crystal aligning agent. It is more preferable to set it to 30 parts by mass. In addition, a crosslinkable group containing compound can be used individually by 1 type or in combination of 2 or more types.

(solvent)
The liquid crystal aligning agent of the present disclosure is prepared as a composition in the form of a solution in which the polymer component, and the component that is optionally blended, is preferably dissolved in an organic solvent. Examples of the organic solvent include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. The solvent component may be one of these or a mixed solvent of two or more.

The solvent component of the liquid crystal aligning agent of the present disclosure is at least one member selected from the group consisting of compounds represented by the following formulas (E-1) to (E-5), and at 1 atm. A solvent having a boiling point of 180 ° C. or less (hereinafter, also referred to as “specific solvent”) may be used. By using a specific solvent as at least a part of the solvent component, it is possible to obtain a liquid crystal element excellent in liquid crystal alignment and electrical characteristics even when heating at the time of film formation is performed at a low temperature (for example, 200 ° C. or less). Preferred. In addition, polyenamine is excellent in solubility in solvents, and therefore, even when a low boiling point solvent such as a specific solvent is used as a solvent component, coating properties on a substrate (suppression of film thickness unevenness and pinholes, coating area It is preferable in that the liquid crystal element can be obtained which is excellent in the linearity and flatness of the end portions and in which both of the liquid crystal alignment property and the electrical property are excellent.

(In formula (E-1), R ⁴¹ is an alkyl group having 1 to 4 carbon atoms or R ⁴⁰ -CO- (wherein R ⁴⁰ is an alkyl group having 1 to 3 carbon atoms), and R ⁴² is a carbon atom The alkanediyl group of the number 1 to 4 or-(R ⁴⁷ -O) r -R ^48- (wherein R ⁴⁷ and R ⁴⁸ each independently represent an alkanediyl group having 2 or 3 carbon atoms, and r is 1 to R ⁴³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

(In formula (E-2), R ⁴⁴ is an alkanediyl group having 1 to 4 carbon atoms.)

(In formula (E-3), R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 8 carbon atoms.)

(Wherein, in the formula (E-4), R ⁴⁹ is a hydrogen atom or a hydroxyl group, and R ⁵⁰ is a divalent hydrocarbon group having 1 to 9 carbon atoms, or R 3 if the R ⁴⁹ is a hydrogen atom; When R ⁴⁹ is a hydroxyl group, it is a divalent hydrocarbon group having 1 to 9 carbon atoms, or a carbon number of 2 carbon atoms when R ⁴⁹ is a hydroxyl group. A divalent group having an oxygen atom between carbon-carbon bonds of the hydrocarbon groups of to 9)

(In Formula (E-5), R ⁵¹ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, a monovalent group having a hydrogen atom of the hydrocarbon group having 1 to 6 carbon atoms substituted with a hydroxyl group, Or a monovalent group having —CO— between carbon-carbon bonds of a hydrocarbon group having 2 to 6 carbon atoms, and R ⁵² is a monovalent hydrocarbon group having 1 to 6 carbon atoms.

Specific examples of the specific solvent include propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, 3-methoxy-1-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether as a compound represented by the above formula (E-1) Partial ethers of polyhydric alcohols such as ethylene glycol monopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, diethylene glycol dimethyl ether: ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene Glycol monomethyl ether acetate, propylene glycol Polyhydric partial ester of an alcohol, such as glycol monomethyl ether acetate and the like;
As a compound represented by the said Formula (E-2), cyclobutanone, cyclopentanone, cyclohexanone;
Examples of compounds represented by the above formula (E-3) include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone and ethyl n -Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone etc .;
Examples of the compound represented by the above formula (E-4) include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, cyclohexanol, methylcyclohexanol, diacetone alcohol and the like;
As a compound represented by the above formula (E-5), methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, i-butyl acetate, t-butyl acetate, 3-methoxybutyl acetate, methyl acetoacetate, acetoacetate Ethyl, ethyl propionate, n-butyl propionate, isoamyl propionate, methyl lactate, ethyl lactate and the like can be mentioned, respectively. As the specific solvent, one type may be used alone, or two or more types may be used in combination.

The solvent component of the liquid crystal alignment agent may be composed only of the specific solvent, but may be a mixed solvent of another solvent other than the specific solvent and the specific solvent. Other solvents include, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, Besides highly polar solvents such as N, N-dimethylacetamide;
4-hydroxy-4-methyl-2-pentanone, butyl lactate, methyl methoxypropionate, ethyl ethoxy propionate, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isoamyl isobutyrate, diisopentyl Ether, ethylene carbonate, propylene carbonate, cyclohexane, octanol, tetrahydrofuran etc. are mentioned. These can be used individually by 1 type or in mixture of 2 or more types. Among the above-mentioned other solvents, a highly polar solvent can be used for the purpose of further improving the solubility and the leveling property. In addition, hydrocarbon solvents that do not contain an amide structure can be used for the purpose of enabling application to plastic substrates and low temperature firing.

Regarding the solvent component contained in the liquid crystal aligning agent, the content ratio of the specific solvent is preferably 20% by mass or more and 40% by mass or more based on the total amount of the solvent contained in the liquid crystal aligning agent. Is more preferable, 50 mass% or more is further preferable, and 80 mass% or more is particularly preferable. The liquid crystal aligning agent of the present disclosure is preferable in that a liquid crystal element having excellent liquid crystal alignment property and electrical property can be obtained even when the solvent component in the liquid crystal aligning agent is only a specific solvent.

The liquid crystal aligning agent of the present disclosure is preferable in that a liquid crystal element having excellent liquid crystal alignment properties and electrical properties can be obtained even when it does not substantially contain N-methyl-2-pyrrolidone (NMP). In the present specification, “substantially free of NMP” means that the content of NMP is preferably 5% by mass or less, more preferably 3% or less, based on the total amount of the solvent contained in the liquid crystal aligning agent. The content is at most mass%, more preferably at most 0.5 mass%.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. It is in the range of 1 to 10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coatability decreases. There is a tendency.

«Liquid crystal alignment film and liquid crystal element»
The liquid crystal aligning film of this indication is formed of the liquid crystal aligning agent prepared as mentioned above. In addition, the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. For example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS (In-Plane Switching) type, FFS (Fringe) It can be applied to various modes such as Field Switching type, OCB (Optically Compensated Bend) type, and PSA type (Polymer Sustained Alignment). The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. Step 1 differs in the substrate used according to the desired operation mode. Steps 2 and 3 are common to each operation mode.

<Step 1: Formation of Coating Film>
First, a liquid crystal aligning agent is coated on a substrate, and preferably a coated surface is formed to form a coating film on the substrate. As the substrate, for example, glass such as float glass and soda glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and poly (alicyclic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. It can be used. In the case of manufacturing a TN type, STN type or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, in the case of manufacturing an IPS-type or FFS-type liquid crystal element, a substrate provided with electrodes patterned in a comb shape and an opposite substrate provided with no electrodes are used. The application of the liquid crystal alignment agent to the substrate is carried out preferably by offset printing, flexo printing, spin coating, roll coater method or ink jet printing on the electrode formation surface.

After the application of the liquid crystal alignment agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent. The prebake temperature is preferably 30 to 200 ° C., and the prebake time is preferably 0.25 to 10 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amic acid structure in the polymer component. The baking temperature (post-baking temperature) at this time is preferably 80 to 250 ° C., more preferably 80 to 200 ° C. The post bake time is preferably 5 to 200 minutes. In particular, polyenamine has good solubility in a specific solvent, and is excellent in liquid crystal alignment and electrical properties even when the post-baking temperature is, for example, 200 ° C. or less, preferably 180 ° C. or less, more preferably 160 ° C. or less. A liquid crystal element can be obtained. The film thickness of the film thus formed is preferably 0.001 to 1 μm.

<Step 2: Alignment treatment>
In the case of producing a TN type, STN type, IPS type or FFS type liquid crystal element, a treatment (alignment treatment) for imparting liquid crystal alignment ability to the coating film formed in the above step 1 is carried out. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As the orientation treatment, the coating formed on the substrate is rubbed in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon or cotton, or the coating formed on the substrate is irradiated with light. Thus, it is possible to use a photoalignment treatment or the like which imparts a liquid crystal alignment ability to the coating film. On the other hand, when manufacturing a vertical alignment (VA) type liquid crystal device, the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but in order to further enhance the liquid crystal alignment ability The film may be subjected to orientation treatment. A liquid crystal alignment film suitable for a vertical alignment type liquid crystal element can also be suitably used for a PSA type liquid crystal element.

The light irradiation for photo-alignment is a method of irradiating the coating film after the post-baking step, a method of irradiating the coating film after the pre-baking step but before the post-baking step, a pre-baking step and a post-baking step At least one of them can be performed by a method of irradiating the coating film while heating the coating film, or the like. As the radiation to be applied to the coating film, it is possible to use, for example, ultraviolet light and visible light including light of a wavelength of 150 to 800 nm. Preferably, it is ultraviolet light containing light of a wavelength of 200 to 400 nm. If the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or these may be performed in combination. The irradiation direction in the case of non-polarized radiation is oblique.

As a light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be mentioned. The radiation dose is preferably 400 to 50,000 J / m ² , more preferably 1,000 to 20,000 J / m ² . A process of cleaning the substrate surface with, for example, water, an organic solvent (eg, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate etc.) or a mixture thereof after light irradiation for imparting alignment ability, or a substrate May be heated.

<Step 3: Construction of Liquid Crystal Cell>
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is disposed between two substrates disposed opposite to each other to manufacture a liquid crystal cell. In order to manufacture a liquid crystal cell, for example, two substrates are disposed opposite to each other with a gap so that the liquid crystal alignment film faces each other, and peripheral portions of the two substrates are bonded using a sealing agent. A liquid crystal is injected and filled in a cell gap surrounded by a sealing agent to seal the injection hole, a method by an ODF method, and the like. As the sealing agent, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. In the PSA mode, after the liquid crystal cell is constructed, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates.

When producing a PSA type liquid crystal element, a liquid crystal cell is constructed in the same manner as described above except that a photopolymerizable compound is injected or dropped together with the liquid crystal. After that, light is irradiated to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates. The voltage applied here may be, for example, 5 to 50 V direct current or alternating current. Further, as the light to be irradiated, for example, ultraviolet light and visible light containing light of a wavelength of 150 to 800 nm can be used, but ultraviolet light containing light of a wavelength of 300 to 400 nm is preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used, for example. The light irradiation amount is preferably 1,000 to 200,000 J / m ² , and more preferably 1,000 to 100,000 J / m ² .

Subsequently, if necessary, a polarizing plate is attached to the outer surface of the liquid crystal cell to form a liquid crystal element. Examples of the polarizing plate include a polarizing plate in which a polarizing film called “H film” obtained by absorbing iodine while stretching and orienting polyvinyl alcohol is sandwiched by a cellulose acetate protective film or a polarizing plate consisting of the H film itself.

In the manufacturing process of the liquid crystal element, the substrate may be left as it is (drawn) after forming the liquid crystal alignment film on the substrate due to mechanical trouble or tact adjustment. At that time, moisture in the air may be adsorbed or absorbed by the liquid crystal alignment film, and the electric characteristics of the constructed liquid crystal element may be deteriorated, which may cause display unevenness and the like. In this respect, the liquid crystal alignment film obtained by using the above-mentioned liquid crystal alignment agent is a liquid crystal having good electric characteristics (a good resistance to placing) even when the substrate is left with the liquid crystal alignment film formed. It is excellent in the point which can obtain an element.

The liquid crystal element of the present disclosure can be effectively applied to various applications. For example, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors The present invention can be applied to various display devices such as liquid crystal televisions and information displays, light control films, retardation films and the like. In addition, the liquid crystal device of the present disclosure is also suitably used for a liquid crystal device using a dye as a colorant for the color filter layer. Here, as the dye, a known dye that can be used for a liquid crystal element can be used.

Hereinafter, although an example explains concretely, the contents of this indication are not limited to the following examples.
In the following examples, the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer were measured by the following methods.
<Weight average molecular weight, number average molecular weight and molecular weight distribution>
Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. Moreover, the molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn.
GPC column: Tosoh Corp. TSKgel GRC XLII
Mobile phase: lithium bromide and phosphoric acid containing N, N-dimethylformamide solution column temperature: 40 ° C.
Flow rate: 1.0 mL / min Pressure: 68 kgf / cm ²

The abbreviations of the compounds used in the following examples are shown below. In the following, for convenience, the “compound represented by the formula (X)” may be simply referred to as “the compound (X)”.
(Α, β-unsaturated compounds)

(Tetracarboxylic acid dianhydride)

(Diamine compound)

(Crosslinking agent)

<Synthesis of α, β-Unsaturated Compound>
Synthesis Examples 1-1 to 1-8
Compounds (VL-1) to (VL-8) were respectively synthesized according to the methods described in the following documents.
・ Compound (VL-1): Yoshikazu Sato, Yoshihiko Musha, Yasuhiro Amamiya, Masamichi Katayama, Bulletin of Faculty of Engineering, Nihon University, 16, A, 113 (1975)
Compound (VL-2): M. Ueda, K. Kino, T. Hirono, Y. Imai, J. Polym. Sci., Polym. Chem. Ed., 14, 931 (1976)
Compound (VL-3): S. Kimura, Makromol. Chem., 117, 203 (1968)
Compound (VL-4): S. J. Huang, J. Pavlisko, E. Hong, Am. Chem. Soc. Polym. Preprints, 19 [2], 57 (1978)
Compound (VL-5): J. A. Moore, T. D. Mitchell, Am. Chem. Soc. Polym. Preprints, 19 [2], 13 (1978)
・ Compound (VL-6): Shigeo Tanimoto, Masao Kurosaki, Ryohei Oda, Ariake, 26, 361 (1968)
Compound (VL-7): M. Ueda, M. Funayama, Y. Imai, Polym. J., 11, 491 (1979)
Compound (VL-8): Y. Imai, N. Sakai, J. Sasaki, M. Ueda, Makromol. Chem., 180, 1797 (1979)

<Synthesis of Polyenamine>
Synthesis Example 2-1
In a 100 mL two-necked flask, 1.68 g (10 mmol) of the compound (VL-1) and 2.18 (10 mmol) of pyromellitic dianhydride are dissolved in 60 g of N-methyl-2-pyrrolidone (NMP) under nitrogen. 0.60 g (2 mmol) of compound (DA-1) and 4.39 g (18 mmol) of compound (DA-2) as a diamine compound are added, and the reaction is carried out at 60 ° C. for 4 hours to obtain polyenamine polymer (P-1) ) Was obtained.

[Synthesis examples 2-2 to 2-13, 2-20, 2-21]
The same operation as in Synthesis Example 2-1 is carried out except that the type and amount of monomers to be used are changed as shown in Table 1 below, to obtain polyenamines (polymers (P-2) to (P-15), respectively. ) Was obtained. At the time of polymerization, when the solubility of the monomer is insufficient, it is diluted with NMP or m-cresol, and when the polymerization rate is slow, the target polymer is synthesized by heating to 60 ° C. or higher with an oil bath. did.

<Synthesis of polyamic acid>
Synthesis Examples 2-14 to 2-19
The same operation as in Synthesis Example 2-1 is carried out except that the type and amount of monomers to be used are changed as shown in Table 1 below, to obtain polyamic acids (polymers (C-1) to (C-6), respectively. ) Was obtained.

In Synthesis Examples 2-1 to 2-21, the α, β-unsaturated compound and tetracarboxylic acid anhydride are referred to as “monomer group A”, and the diamine compound is referred to as “monomer group B”. When two or more types of monomers are used as the group A, the total of monomers of the monomer group A is 20 mmol, and when two or more types of diamine compounds are used as the monomer group B, diamines are used. It used so that the sum total of a compound might be 20 mmol. Table 1 also shows the molar ratio of the α, β-unsaturated compound and tetracarboxylic acid dianhydride in monomer group A, and the molar ratio of diamine compound in monomer group B.

In Table 1, the solid content concentration of the liquid crystal aligning agent was the same (4.0 mass%) in all the examples. "-" Means that the compound in the corresponding column was not used.

<Synthesis of Polyorganosiloxane>
Synthesis Example 3-1
The polymer (C-7) was synthesized according to the following scheme 1.

In a 1000 ml three-necked flask, 90.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were charged and mixed at room temperature. Next, 100 g of deionized water was added dropwise over 30 minutes from the dropping funnel, and then reaction was performed at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 mass% aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure. An appropriate amount of methyl isobutyl ketone was added to obtain a 50% by mass solution of polyorganosiloxane (E-1) having an epoxy group.
In a 500 ml three-necked flask, 26.69 g (0.3 mol equivalent) of a side chain carboxylic acid (ca-1) shown below, 2.00 g of tetrabutylammonium bromide, 80 g of a solution containing polyorganosiloxane (E-1), and methyl isobutyl 239 g of ketone was added and stirred at 110 ° C. for 4 hours. After cooling to room temperature, the liquid separation washing operation was repeated 10 times with distilled water. Thereafter, the organic layer was recovered, and concentration and NMP dilution were repeated twice using a rotary evaporator to obtain a 15% by mass NMP solution of a polymer (C-7) intermediate. After adding 0.45 g (0.1 mol equivalent) of trimellitic acid anhydride to 50 g of this intermediate solution, the solid content concentration is adjusted to 10% by mass using NMP, and then it is stirred at room temperature for 4 hours By doing this, an NMP solution of polymer (C-7) was obtained.

Synthesis Example 3-2
By performing the same operation as in Synthesis Example 3-1 except that the side chain carboxylic acid (ca-2) shown below is used instead of the side chain carboxylic acid (ca-1) in Synthesis Example 3-1 An NMP solution containing the polymer (C-8) was obtained.

Synthesis Example 3-3
By performing the same operation as in Synthesis Example 3-1 except that the side chain carboxylic acid (ca-3) shown below is used instead of the side chain carboxylic acid (ca-1) in Synthesis Example 3-1 An NMP solution containing the polymer (C-9) was obtained.

<Synthesis of Styrene-Maleimide Copolymer>
Synthesis Example 3-4
1. Synthesis of Compound (MI-1) Compound (MI-1) was synthesized according to the following scheme 2.

In a 100 mL pear-shaped flask containing a stirrer, 11.8 g of (E) -3- (4-((4- (4,4,4-trifluorobutoxy) benzoyl) oxy) phenyl) acrylic acid, 20 g of thionyl chloride, N 0.01 g of N, N-dimethylformamide was added, and the mixture was stirred at 80 ° C. for 1 hour. Thereafter, excess thionyl chloride was removed by a diaphragm pump, and 100 g of tetrahydrofuran was added to make solution A. Freshly, 5.67 g of 4-hydroxyphenyl maleimide, 200 g of tetrahydrofuran and 12.1 g of triethylamine were added to a 500 mL three-necked flask containing a stirrer, and the mixture was ice-bathed. The solution A was dripped there and it stirred at room temperature for 3 hours. The reaction solution was reprecipitated with 800 mL of water, and the obtained white solid was dried under vacuum to obtain 13.3 g of Compound (MI-1).

2. Synthesis of Polymer Under nitrogen, in a 100 mL two-necked flask, 5.00 g (8.6 mmol) of the compound (MI-1) obtained above as a polymerization monomer, 0.64 g (4.3 mmol) of 4-vinylbenzoic acid , 2.82 g (13.0 mmol) of 4- (2,5-dioxo-3-pyrrolin-1-yl) benzoic acid and 3.29 g (17.2 mmol) of 4- (glycidyloxymethyl) styrene, radical polymerization initiation 0.32 g (1.3 mmol) of 2,2'-azobis (2,4-dimethyl valeronitrile) as a curing agent, 0.52 g (2.2 mmol) of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent ) And 25 ml of tetrahydrofuran as a solvent, and polymerized at 70 ° C. for 5 hours. After reprecipitation in n-hexane, the precipitate was filtered and vacuum dried at room temperature for 8 hours to obtain the target polymer (C-10). The weight average molecular weight Mw measured by polystyrene conversion by GPC was 30,000, and the molecular weight distribution Mw / Mn was 2.

<Manufacture and evaluation of rubbing horizontal type liquid crystal display element>
Example 1
1. Preparation of Liquid Crystal Alignment Agent (AL-1) In a solution containing 100 parts by mass of the polymer (P-1) obtained in the above Synthesis Example 2-1, 200 parts by mass of the polymer (C-4), NMP as a solvent, and Butyl cellosolve (BC) was added to form a solution having a solvent composition of NMP / BC = 50/50 (mass ratio) and a solid content concentration of 4.0 mass%. The solution was filtered through a filter with a pore size of 1 μm to prepare a liquid crystal aligning agent (AL-1).

2. Evaluation of coating properties (film thickness unevenness / pinhole, edge shape and film thickness uniformity) The liquid crystal aligning agent (AL-1) prepared above is coated on a glass substrate using a spinner, and a hot plate at 80 ° C. The film was prebaked for 1 minute, and then the inside of the chamber was heated (post-baked) in a 230 ° C. oven purged with nitrogen for 30 minutes to form a coating having an average film thickness of 0.1 μm. This coated film was observed with a microscope with a magnification of 100 times and 10 times to examine the presence of film thickness unevenness and pinholes. The evaluation is “good (A)” when neither film thickness unevenness nor pinhole is observed even when observed with a 100 × microscope, and at least one of film thickness unevenness and pinholes with a 100 × microscope Although observed, when both the film thickness unevenness and the pinhole were not observed with the 10 × microscope, “OK (B)”, and at least one of the film thickness unevenness and the pinhole was clearly observed with the 10 × microscope. When it observed, it was set as "defect (C)." In this example, neither the film thickness unevenness nor the pinhole was observed even with a 100 × microscope, and the coatability was evaluated as “good (A)”.

As a more detailed evaluation of the coatability, the coatability on the edge portion (the outer edge portion of the formed coating) was evaluated. The liquid crystal aligning agent (AL-1) prepared above was applied on a transparent electrode-coated glass substrate made of an ITO film using a printing machine for applying a liquid crystal alignment film, and dried as described above. . Observing the shape and flatness of the edge portion, "Good (A)" when the linearity is high and a flat surface, "Good (B)" when the linearity is high but there are irregularities, and there are irregularities, And when there was liquid return from the edge (the linearity is low), it was regarded as "defect (C)". As a result, in this example, it was judged as "good (A)".
Furthermore, the film thickness is measured at four points in the surface of the coating film using a stylus type film thickness meter, and the variation of the measured value (average film thickness δ (δ of Example 1 = 0.1 μm)) The film thickness uniformity was evaluated by the difference). The evaluation is “good (A)” when the measured values at four points are within ± 25 Å with respect to the average film thickness δ and a uniform film thickness is obtained, ± 25 Å with respect to the average film thickness δ If all the measured values at four points were within the range of ± 50 Å with respect to the average film thickness δ although there were measured values outside the range of “good (B)”, with respect to the average film thickness δ When there was a measured value out of the range of ± 50 Å and the variation of the measured value was large, it was regarded as “defect (C)”. As a result, in this Example, it was evaluation of "good (A)."

3. Preparation of Rubbed Horizontal Liquid Crystal Display Device The liquid crystal aligning agent (AL-1) prepared above was applied on a transparent electrode surface of a glass substrate with a transparent electrode made of ITO film using a spinner, and a hot plate at 80 ° C. Pre-baked for 1 minute. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 μm. The coating film was rubbed at a roll rotational speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair-foot push-in length of 0.1 mm by a rubbing machine having a roll wound with rayon cloth. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. By repeating this series of operations, a pair (two sheets) of substrates having a liquid crystal alignment film was formed.
An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 3.5 μm is applied by screen printing to the outer periphery of the surface of one of the above substrates having a liquid crystal alignment film, and then the liquid crystal alignment film surfaces are superimposed to face each other. It was pressure-bonded together and the adhesive was cured. Next, after filling a nematic liquid crystal (manufactured by Merck, MLC-6221) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and both sides of the substrate are polarized. A horizontal alignment type liquid crystal display element was manufactured by bonding the plates together.

4. Evaluation of Liquid Crystal Alignment With the rubbing horizontal liquid crystal display element manufactured above, the presence or absence of abnormal domain in the change of light and dark when ON / OFF (application / cancellation) of voltage of 5 V is observed with an optical microscope. The liquid crystal orientation was evaluated with “A” in the absence, “B” in the presence of an abnormal domain in part, and “C” in the presence of an abnormal domain as a whole. As a result, in this example, the liquid crystal alignment was "A".

5. Evaluation of voltage holding ratio (VHR) For the rubbing horizontal liquid crystal display device manufactured above, a voltage of 5 V is applied for 60 microseconds and a span of 167 milliseconds for a voltage application time, and then a voltage of 167 milliseconds after application release. The retention rate was measured. The measuring apparatus used VHR-1 manufactured by Toyo Corporation. At this time, "A" when the voltage holding ratio is 95% or more, "B" when 80% or more and less than 95%, "C" when 50% or more and less than 80%, and "C" when less than 50%. "D." As a result, in this example, the voltage holding ratio was evaluated as "A".

6. Evaluation of Lamination Resistance By performing the same operation as the above-mentioned "3. Manufacture of Rubbing Horizontal Liquid Crystal Display Element", two pairs of substrates having a liquid crystal alignment film (four in total) were formed.
In a stainless steel vat (about 20 cm x about 30 cm), put a pair of substrates (2 sheets) out of the substrates created above and a petri dish containing NMP, and put the stainless steel vat containing the substrate and petri dish into aluminum After covering with a foil and leaving at 25 ° C. for 2 hours, the substrate was taken out. By such an operation, a pair of substrates (two sheets) were exposed to the NMP atmosphere. Thereafter, using this pair of substrates, a liquid crystal display element (referred to as "element A") was produced by the same method as in "3. Production of rubbing horizontal type liquid crystal display element" described above.
In addition, the liquid crystal display element (“element” is referred to as “element” in the same manner as the “3. manufacture of a rubbing horizontal type liquid crystal display element” above) without exposing another pair of substrates (two sheets) to the NMP atmosphere. B.) was manufactured.
Subsequently, the pretilt angles of the two liquid crystal display elements are determined according to the method described in Non-patent document (TJ Scheffer et. Al. J. Appl. Phys. Vo. 19. p2013 (1980)), He-Ne. Each was measured by a crystal rotation method using a laser beam, and the tilt difference Δθ [%] was determined by the following formula (2).
Δθ = ((θ1−θ2) / θ1) × 100 (2)
(In the equation (2), θ 1 is the pretilt angle of the element B, and θ 2 is the pretilt angle of the element A.)
Is "A" when Δθ is 5% or less, "B" when 5% or more and less than 10%, and "C" when 10% or more. As a result, in this example, the withdrawal resistance was an evaluation of "A".

[Examples 5 to 7 and 14 to 20 and Comparative Example 1]
Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain liquid crystal aligning agents. Moreover, while evaluating the coating property of a liquid crystal aligning agent similarly to Example 1 using each liquid crystal aligning agent, manufacturing a rubbing horizontal type liquid crystal display element similarly to Example 1 and performing various evaluations The The results are shown in Table 3 below. In Table 3 below, the observation results of film thickness unevenness and pinholes are shown in the column of "coating properties", the observation results of edge portions are shown in the column of "edge shape", and evaluation results based on film thickness variations are shown. It is shown in the column of "film thickness uniformity". In Examples 6 and 7, a crosslinking agent was blended together with the polymer component. In Table 2, "-" means that the polymer in the corresponding column was not used.

<Manufacture and evaluation of optical FFS liquid crystal display device>
Example 2
1. Preparation of Liquid Crystal Alignment Agent (AL-2) The same solvent composition as in Example 1 except that the polymer to be used was changed to 100 parts by mass of the polymer (P-2) and 50 parts by mass of the polymer (C-9) And liquid crystal aligning agent (AL-2) was prepared by solid content concentration.
2. Evaluation of Coating Property The coating property was evaluated in the same manner as in Example 1 except that (AL-2) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in this example, the evaluation results of film thickness unevenness / pinhole, edge shape and film thickness uniformity were all “A”.

3. Production of Optical FFS-Type Liquid Crystal Display Device Above, on the respective surfaces of the glass substrate on which the flat plate electrode, the insulating layer and the comb electrode are laminated in this order on one side and the opposite glass substrate on which the electrode is not provided The prepared liquid crystal aligning agent (AL-2) was applied using a spinner, and was heated (prebaked) for 1 minute on an 80 ° C. hot plate. Then, drying (post-baking) was performed for 30 minutes in the oven of 230 degreeC which substituted the inside of a chamber | room for 30 minutes, and the coating film of average film thickness 0.1 micrometer was formed. The coating film surface is irradiated with ultraviolet light of 1,000 J / m ² including a linearly polarized light emission line of 254 nm from the normal direction of the substrate using an Hg-Xe lamp to perform photoalignment treatment, and liquid crystal alignment on the substrate A film was formed.
Next, a pair of substrates having a liquid crystal alignment film is screen-printed with an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 μm, leaving a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film is formed. The substrates were superposed and pressure-bonded so that the projection directions of the polarization axes on the substrate surface at this time were antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, nematic liquid crystal (manufactured by Merck, MLC-7028) was filled from a liquid crystal injection port between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 120 ° C. and then gradually cooled to room temperature to manufacture a liquid crystal cell. Next, the polarizing plates are attached to both outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and at an angle of 90 ° with the projection direction of the optical axis of the liquid crystal alignment film to the substrate surface. The liquid crystal display element was manufactured by this.

4. Evaluation of Liquid Crystal Alignment Property The liquid crystal alignment property of the optical FFS liquid crystal display element manufactured above was evaluated in the same manner as in Example 1 above. As a result, in this example, the liquid crystal alignment was "A".
5. Evaluation of Voltage Holding Ratio (VHR) The voltage holding ratio was evaluated in the same manner as in Example 1 for the optical FFS liquid crystal display device manufactured above. As a result, in this example, the voltage holding ratio was evaluated as "A".
6. Evaluation of Lamination Resistance By performing the same operation as the above-mentioned "3. Manufacture of an optical FFS-type liquid crystal display device", two pairs of substrates having a liquid crystal alignment film (four in total) were formed. Among these, one pair of substrates is exposed to an NMP atmosphere in the same manner as in Example 1, and thereafter, using this pair of substrates, it is the same as the above-mentioned "3. Production of optical FFS liquid crystal display element". A liquid crystal display device (referred to as “device A”) was manufactured by the method of In addition, the liquid crystal display element (the “element” is selected by the same method as the above “3. manufacture of the optical FFS liquid crystal display element” without exposing the other pair of substrates (two sheets) to the NMP atmosphere. B.) was manufactured. Using the element A and the element B, evaluation of the pull-through resistance was performed in the same manner as in Example 1 above. As a result, in this example, the withdrawal resistance was an evaluation of "A".

Comparative Example 2
Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain a liquid crystal aligning agent (BL-2). Moreover, while evaluating the coating property of a liquid crystal aligning agent similarly to Example 1 using a liquid crystal aligning agent (BL-2), it manufactures an optical FFS type liquid crystal display element similarly to Example 2, and variously I made an evaluation. The results are shown in Table 3 below.

<Manufacture and evaluation of VA type liquid crystal display device>
[Example 3]
1. Preparation of Liquid Crystal Alignment Agent (AL-3) The same solvent composition as in Example 1 except that the polymer used was changed to 100 parts by mass of polymer (P-3) and 300 parts by mass of polymer (C-6). And liquid crystal aligning agent (AL-3) was prepared by solid content concentration.
2. Evaluation of Coating Properties Coating properties were evaluated in the same manner as in Example 1 except that (AL-3) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in this example, the evaluation results of film thickness unevenness / pinhole, edge shape and film thickness uniformity were all “A”.

3. Production of VA-Type Liquid Crystal Display Device The liquid crystal aligning agent (AL-3) prepared above is applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner, and the hot plate is used at 80 ° C. Pre-baking was performed for 1 minute. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 μm. By repeating this operation, a pair of substrates (two sheets) having a liquid crystal alignment film was formed.
An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 3.5 μm is applied by screen printing to the outer periphery of the surface of one of the above substrates having a liquid crystal alignment film, and then the liquid crystal alignment film surfaces are superimposed to face each other. It was pressure-bonded together and the adhesive was cured. Next, after filling a negative type liquid crystal (MLC-6608, manufactured by Merck Ltd.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and both sides of the substrate are sealed. The VA type liquid crystal display element was manufactured by bonding a polarizing plate together.

4. Evaluation of Liquid Crystal Alignment Property The liquid crystal alignment property of the VA type liquid crystal display element manufactured above was evaluated in the same manner as in Example 1 above. As a result, in this example, the liquid crystal alignment was "A".
5. Evaluation of Voltage Holding Ratio (VHR) The voltage holding ratio was evaluated in the same manner as in Example 1 for the VA type liquid crystal display device manufactured above. As a result, in this example, the voltage holding ratio was evaluated as "A".
6. Evaluation of Lamination Resistance By performing the same operation as the above-mentioned "3. Production of VA type liquid crystal display element", two pairs of substrates (four in total) having a liquid crystal alignment film were formed. Among these, one pair of substrates is exposed to an NMP atmosphere in the same manner as in Example 1, and thereafter, using this pair of substrates, it is the same as the above-mentioned "3. A liquid crystal display element (referred to as "element A") was manufactured by a method. Further, a liquid crystal display element (“element B”) is formed by the same method as “3. production of a VA type liquid crystal display element” without exposing the other pair of substrates (two sheets) to the NMP atmosphere. ") Was manufactured. Using the element A and the element B, evaluation of the pull-through resistance was performed in the same manner as in Example 1 above. As a result, in this example, the withdrawal resistance was an evaluation of "A".

Example 4 and Comparative Example 3
Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain liquid crystal aligning agents. Moreover, while evaluating coating property of a liquid crystal aligning agent similarly to Example 1 using each liquid crystal aligning agent, manufacturing a VA type liquid crystal display element similarly to Example 3 and performing various evaluations . The results are shown in Table 3 below.

<Manufacture and evaluation of PSA type liquid crystal display device>
[Example 9]
1. Preparation of Liquid Crystal Alignment Agent (AL-9) Same solvent composition as Example 1 except that the polymer used was changed to 200 parts by mass of Polymer (P-6) and 50 parts by mass of Polymer (C-7) A liquid crystal aligning agent (AL-9) was prepared at a solid content concentration.
2. Evaluation of Coating Property The coating property was evaluated in the same manner as in Example 1 except that (AL-9) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in this example, the evaluation results of film thickness unevenness / pinhole, edge shape and film thickness uniformity were all “A”.

3. Preparation of Liquid Crystal Composition The liquid crystal compound represented by the following formula (L1-1) was represented by 5% by mass with respect to 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck Ltd.), and by the following formula (L2-1) The liquid crystal composition LC1 was obtained by adding 0.3 mass% of the photopolymerizable compounds and mixing them.

4. Production of PSA-type Liquid Crystal Display Device A liquid crystal alignment film printing machine (Nippon Photography printing) on each electrode surface of two glass substrates each having a conductive film consisting of an ITO electrode, the liquid crystal alignment agent (AL-9) prepared above (Presto) for 2 minutes on a hot plate at 80 ° C. to remove the solvent, and then for 10 minutes on a hot plate at 230 ° C. (post bake). A coating having a thickness of 0.06 μm was formed. The coated films were subjected to ultrasonic cleaning in ultrapure water for 1 minute and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a pair (two sheets) of substrates having a liquid crystal alignment film. The pattern of the used electrode is the same pattern as the electrode pattern in the PSA mode.
Subsequently, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 μm is applied to the outer edge of the surface of the one of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces one another. It was pressure-bonded together and the adhesive was cured. Next, the liquid crystal composition LC1 prepared above was filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to manufacture a liquid crystal cell. Thereafter, an AC 10V frequency 60Hz was applied between the conductive film of the liquid crystal cell, in a state where the liquid crystal is driven, using an ultraviolet irradiation apparatus using a metal halide lamp as a light source, the irradiation amount of 100,000J / m ² It irradiated ultraviolet rays at. In addition, this irradiation amount is the value measured using the actinometer measured by wavelength 365 nm reference | standard. Thereafter, polarizing plates are attached to both outer sides of the substrate so that the polarization directions thereof are orthogonal to each other and at an angle of 45 ° with the projection direction of the optical axis of the liquid crystal alignment film to the substrate surface. A liquid crystal display device was manufactured.

5. Evaluation of Liquid Crystal Alignment Property The liquid crystal alignment property of the PSA type liquid crystal display device manufactured above was evaluated in the same manner as Example 1. As a result, in this example, the liquid crystal alignment was "A".
6. Evaluation of Voltage Holding Ratio (VHR) The voltage holding ratio was evaluated in the same manner as in Example 1 for the PSA type liquid crystal display device manufactured above. As a result, in this example, the voltage holding ratio was evaluated as "A".
7. Evaluation of Lamination Resistance By performing the same operation as the above-mentioned "3. Production of PSA type liquid crystal display element", two pairs of substrates having a liquid crystal alignment film (four sheets in total) were formed. Among these, one pair of substrates is exposed to an NMP atmosphere in the same manner as in Example 1, and thereafter, using this pair of substrates, the same as the above-mentioned "4. Production of PSA type liquid crystal display element" A liquid crystal display element (referred to as "element A") was manufactured by a method. Further, a liquid crystal display element (“element B”) is prepared by the same method as the “4. PSA type liquid crystal display element” described above without exposing another pair of substrates (two sheets) to the NMP atmosphere. ") Was manufactured. Using the element A and the element B, evaluation of the pull-through resistance was performed in the same manner as in Example 1 above. As a result, in this example, the withdrawal resistance was an evaluation of "A".

[Examples 10 and 11 and Comparative Example 5]
Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain liquid crystal aligning agents. Further, using the obtained liquid crystal aligning agent, the coating property of the liquid crystal aligning agent is evaluated in the same manner as in Example 1, and in the same manner as in Example 9, a PSA type liquid crystal display element is produced. Various evaluations were performed in the same manner. The evaluation results are shown in Table 3 below. In Examples 10 and 11, a crosslinking agent was blended with the polymer component.

<Manufacture and evaluation of vertical light type liquid crystal display element>
[Example 8]
1. Preparation of Liquid Crystal Alignment Agent (AL-8) The same solvent composition as in Example 1 except that the polymer used was changed to 200 parts by mass of polymer (P-7) and 50 parts by mass of polymer (C-8) And liquid crystal aligning agent (AL-8) was prepared at solid content concentration.
2. Evaluation of Coatability The coatability was evaluated in the same manner as in Example 1 except that (AL-8) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in this example, the evaluation results of film thickness unevenness / pinhole, edge shape and film thickness uniformity were all “A”.

3. Production of Vertical Optical Liquid Crystal Display Device The liquid crystal aligning agent (AL-8) prepared above is applied on a transparent electrode surface of a glass substrate with a transparent electrode made of ITO film using a spinner, and a hot plate at 80 ° C. Pre-baked for 1 minute. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 μm. Then, using a Hg-Xe lamp and a Glan-Taylor prism, this coated film surface is irradiated with polarized ultraviolet light of 1,000 J / m ² containing an emission line of 313 nm from a direction inclined 40 ° from the substrate normal to obtain liquid crystal alignment ability. Granted. The same operation was repeated to form a pair (two sheets) of substrates having a liquid crystal alignment film.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm is applied by screen printing to the outer periphery of the surface having a liquid crystal alignment film of one of the above substrates, and then the liquid crystal alignment film surfaces of a pair of substrates are made to face each other. Pressure bonding was performed so that the projection direction of the optical axis of each substrate to the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C. for one hour. Next, negative liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 130 ° C. and then gradually cooled to room temperature. Next, the polarizing plates are bonded to both outer surfaces of the substrate so that the polarization directions are orthogonal to each other and at an angle of 45 ° with the projection direction of the optical axis of the liquid crystal alignment film to the substrate surface. The liquid crystal display element was manufactured by this.

4. Evaluation of Liquid Crystal Alignment Property The liquid crystal alignment property of the light vertical type liquid crystal display device manufactured above was evaluated in the same manner as in Example 1 above. As a result, in this example, the liquid crystal alignment was "A".
5. Evaluation of Voltage Holding Ratio (VHR) The voltage holding ratio was evaluated in the same manner as in Example 1 for the light vertical type liquid crystal display device manufactured above. As a result, in this example, the voltage holding ratio was evaluated as "A".
6. Evaluation of Lamination Resistance By performing the same operation as the above-mentioned "3. Manufacture of light vertical type liquid crystal display device", two pairs of substrates having a liquid crystal alignment film (four in total) were formed. Among these, one pair of substrates is exposed to an NMP atmosphere in the same manner as in Example 1, and thereafter, using this pair of substrates, it is the same as the above "3. A liquid crystal display device (referred to as “device A”) was manufactured by the method of In addition, the liquid crystal display element (the “element” is formed by the same method as the “3. manufacture of the vertical light type liquid crystal display element” described above without exposing another pair of substrates (two sheets) to the NMP atmosphere. B.) was manufactured. Using the element A and the element B, evaluation of the pull-through resistance was performed in the same manner as in Example 1 above. As a result, in this example, the withdrawal resistance was an evaluation of "A".

[Examples 12, 13 and Comparative Examples 4, 6]
Preparation was carried out at the same solid concentration as in Example 1 except that the composition was changed as shown in Table 2 below, to obtain liquid crystal aligning agents. Moreover, while evaluating the coating property of a liquid crystal aligning agent similarly to Example 1 using each liquid crystal aligning agent, manufacturing an optical perpendicular type liquid crystal display element similarly to Example 8 and performing various evaluations The The results are shown in Table 3 below. In Examples 12 and 13, a crosslinking agent was blended together with the polymer component.

[Examples 21 to 23]
Liquid crystal aligning agents (AL-21) to (AL) were prepared in the same manner as in Example 9 except that the solvent composition in Example 9 was changed as shown in Table 4 below instead of NMP / BC = 50/50 (mass ratio). Each of -23) was prepared. Moreover, while evaluating the coating property of a liquid crystal aligning agent like Example 1 except the point which changed the liquid crystal aligning agent to be used, and the point which changed post-baking temperature from 230 degreeC to 200 degreeC, Example 9 In the same manner as in the above, a PSA type liquid crystal display device was manufactured and various evaluations were performed. The results are shown in Table 5 below.
[Comparative Examples 7 to 9]
In Examples 21 to 23, a liquid crystal aligning agent (BL-) was prepared in the same manner as in Examples 21 to 23 except that 300 parts by mass of polymer (C-5) was used instead of 200 parts by mass of polymer (P-6). 7) to (BL-9) were prepared respectively (see Table 4 below). Moreover, while evaluating the coating property of a liquid crystal aligning agent like Example 1 except the point which changed the liquid crystal aligning agent to be used, and the point which changed post-baking temperature from 230 degreeC to 200 degreeC, Example 9 In the same manner as in the above, a PSA type liquid crystal display device was manufactured and various evaluations were performed. The results are shown in Table 5 below. In Table 5, insufficient solubility of the polymer in the solvent was observed, and the items which could not be evaluated by this were indicated as “−” (the same applies to Comparative Examples 10 and 11).

[Example 24]
A liquid crystal aligning agent (AL-24) was prepared in the same manner as in Example 8 except that the solvent composition was changed as shown in Table 4 below instead of NMP / BC = 50/50 (mass ratio) in Example 8. . Further, the coating property of the liquid crystal aligning agent is evaluated in the same manner as in Example 1 except that the obtained liquid crystal aligning agent is used and the post-baking temperature is changed from 230 ° C. to 200 ° C. A light VA type liquid crystal display device was manufactured and evaluated in the same manner as in 8. The results are shown in Table 5 below.

Comparative Example 10
A liquid crystal aligning agent (BL-10) was prepared in the same manner as in Example 24 except that the polymer composition was changed as shown in Table 4 below. Further, the coating property of the liquid crystal aligning agent is evaluated in the same manner as in Example 1 except that the obtained liquid crystal aligning agent is used and the post-baking temperature is changed from 230 ° C. to 200 ° C. A light VA type liquid crystal display device was manufactured and evaluated in the same manner as in 8. The results are shown in Table 5 below.

[Example 25]
A liquid crystal aligning agent (AL-25) was prepared in the same manner as in Example 2 except that the solvent composition in Example 2 was changed as shown in Table 4 instead of NMP / BC = 50/50 (mass ratio). . Further, the coating property of the liquid crystal aligning agent is evaluated in the same manner as in Example 1 except that the obtained liquid crystal aligning agent is used and the post-baking temperature is changed from 230 ° C. to 200 ° C. A light FFS-type liquid crystal display device was manufactured in the same manner as 2 and various evaluations were performed. The results are shown in Table 5 below.

Comparative Example 11
A liquid crystal aligning agent (BL-11) was prepared in the same manner as in Example 25 except that the polymer composition in Example 25 was changed as shown in Table 4 below. Further, the coating property of the liquid crystal aligning agent is evaluated in the same manner as in Example 1 except that the obtained liquid crystal aligning agent is used and the post-baking temperature is changed from 230 ° C. to 200 ° C. A light FFS-type liquid crystal display device was manufactured in the same manner as 2 and various evaluations were performed. The results are shown in Table 5 below.

In Table 4, the numerical value of the solvent composition represents the mass ratio (mass%) to the total amount of the solvent used for preparation of the liquid crystal aligning agent. The abbreviation of the solvent has the following meaning.
CHN: cyclohexanone DIBK: diisobutyl ketone BC: butyl cellosolve PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate EDM: diethylene glycol methyl ethyl ether

As shown in Table 3, in Examples 1 to 20 using a liquid crystal aligning agent containing polyenamine, the coating properties (including the edge shape and the film thickness uniformity) were all evaluated as "A". Further, in Examples 1 to 20, the liquid crystal alignment and the voltage holding ratio of the obtained liquid crystal display element were also good, and the evaluation of “A” was made in all the examples.
Furthermore, as shown in Table 4, polyenamine is sufficiently high in solubility to a solvent composition not containing an amide polar solvent (NMP), and coating properties (including edge shape and film thickness uniformity), liquid crystal alignment In terms of the sex and voltage holding ratio, the evaluation was "A" or "B", and good results were obtained (Examples 21 to 25). From these results, it can be said that the dye can be suitably used even when a color filter layer of a liquid crystal element is formed using a dye having poor heat resistance as a colorant.
On the other hand, in the comparative example using the liquid crystal aligning agent which does not contain polyenamine as a polymer component, in the comparative examples 1 to 4 and 6 among the examples using the amide type polar solvent (NMP), the evaluation of the edge shape is “ B "and was inferior to the example. Furthermore, in Comparative Example 1, the evaluation of film thickness uniformity was also "B". Further, in Comparative Example 2, the evaluation of the voltage holding ratio was “C”, and in Comparative Example 4, it was “B”. Further, as shown in Table 5, in the comparative example, the solubility was insufficient with respect to the solvent composition not containing the amide polar solvent (NMP), and a good result was not obtained (comparative examples 7 to 11). .
From these results, it was found that the liquid crystal aligning agent containing polyenamine is excellent in coating property, liquid crystal alignment property and voltage holding ratio. In addition, the liquid crystal aligning agent containing polyenamine was also excellent in retention resistance.

Claims

Liquid crystal aligning agent containing polyenamine.
The polyenamine is a reaction product of an α, β-unsaturated compound having two or more of one partial structure represented by the following formula (1) or formula (2) in one molecule, and a diamine compound The liquid crystal aligning agent of Claim 1.

(In formula (1) and formula (2), X 1 is a carbonyl group or a sulfonyl group, L 1 is a leaving group which leaves by reaction with a diamine compound, and L 2 is an oxygen atom or And R 5 is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, and a plurality of X 1 , R 5 , L 1 and L 2 in one molecule are each independently as defined above “*” Indicates that it is a bond.)
The α, β-unsaturated compound is a compound having two or more of one kind of partial structure represented by each of the following formulas (4-1) to (4-4) in one molecule, a compound represented by the following formula (5) The liquid crystal aligning agent of Claim 2 which is at least 1 type chosen from the group which consists of a compound represented by following formula (6) (however, a tautomer is included.), And a compound represented by these.

(In the formulas (4-1) to (4-4), (5) and (6), X 1 represents a carbonyl group or a sulfonyl group, and R 1 to R 5 and R 7 to R 10 represent And R 6 independently represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and R 6 represents an alkanediyl group having 2 to 5 carbon atoms or —O— or — between carbon-carbon bonds of the alkanediyl group. L 1 is a leaving group which is eliminated by reaction with a diamine compound, L 2 is an oxygen atom or a sulfur atom, and a plurality of X 1 and R 1 in one molecule. To R 10 , L 1 and L 2 each independently have the above-mentioned definition, “*” represents a bond.
The said polyenamine has a partial structure derived from at least one diamine compound selected from the group consisting of compounds represented by the following formulas (d-1) to (d-4) respectively: The liquid crystal aligning agent as described in any one.

(In formula (d-1), X 11 and X 12 each independently represent a single bond, —O—, —S—, —OCO— or —COO—, and Y 11 is an oxygen atom or a sulfur atom And R 11 and R 12 are each independently an alkanediyl group having 1 to 3 carbon atoms, n 1 is 0 or 1, and n 2 and n 3 satisfy n 2 + n 3 = 2 when n 1 = 0. is an integer, for n1 = 1, a n2 = n3 = 1. formula (d-2) in, X 13 is a single bond, -O- or -S-, m1 is an integer of 0 to 3 M2 is an integer of 1 to 12 when m1 = 0, and m2 = 2 if m1 is an integer of 1 to 3. In the formula (d-3), X 14 and X 15 are each independently represent a single bond, -O -, - COO- or a -OCO-, R 17 is an alkanediyl group having 1 to 3 carbon atoms There, A 11 is a single bond or an alkanediyl group having a carbon number of 1 ~ 3 .a is 0 or 1, b is an integer of 0 ~ 2, c is an integer of 1 ~ 20, k Is 0 or 1. However, a and b are not simultaneously 0. In formula (d-4), A 12 is a single bond, an alkanediyl group having 1 to 12 carbon atoms, or 1 to 6 carbon atoms A 13 represents -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and A 14 represents a monovalent organic compound having a steroid skeleton. Group))
The polyenamine has a partial structure derived from a diamine compound having at least one selected from the group consisting of a secondary or tertiary amine structure represented by the following formula (9) and a nitrogen-containing heterocyclic structure: The liquid crystal aligning agent as described in any one of -4.

In formula (9), R 51 and R 52 each independently represent a divalent aromatic ring group, and R 53 represents a hydrogen atom or a monovalent organic group having one or more carbon atoms. Indicates that it is a bond.)
The polyenamine according to any one of claims 1 to 5, which has a partial structure derived from a diamine compound having a carboxyl group and a partial structure derived from a diamine compound having a nitrogen-containing aromatic heterocycle. Liquid crystal aligning agent.
The liquid crystal alignment according to any one of claims 1 to 6, wherein the polyenamine has a partial structure derived from a diamine compound having a group represented by the following formula (7-1) or formula (7-2) Agent.

(In Formula (7-1) and Formula (7-2), A 21 is a single bond or a divalent organic group having 1 or more carbon atoms, Y 1 is a protecting group, and R 21 to R 23 are And each independently represents a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, m is an integer of 0 to 6. "*" represents a bond.
The liquid crystal aligning agent according to any one of claims 1 to 7, wherein the polyenamine has a partial structure derived from a diamine compound represented by the following formula (8).

In the formula (8), A 31 represents a divalent aromatic ring group, R 31 represents an alkanediyl group having 1 to 5 carbon atoms, and R 32 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms is there.)
The composition further comprises a compound having at least one crosslinkable group selected from the group consisting of a cyclocarbonate group, an epoxy group, an isocyanate group, a blocked isocyanate group, an oxetanyl group, a trialkoxysilyl group, and a polymerizable unsaturated bond group. Item 9. The liquid crystal aligning agent according to any one of items 1 to 8.
At least one member selected from the group consisting of compounds represented by the following formulas (E-1) to (E-5) and containing an organic solvent having a boiling point of 180 ° C. or less at 1 atmosphere pressure The liquid crystal aligning agent according to any one of claims 1 to 9.

(In formula (E-1), R 41 is an alkyl group having 1 to 4 carbon atoms or R 40 -CO- (wherein R 40 is an alkyl group having 1 to 3 carbon atoms), and R 42 is a carbon atom The alkanediyl group of the number 1 to 4 or-(R 47 -O) r -R 48- (wherein R 47 and R 48 each independently represent an alkanediyl group having 2 or 3 carbon atoms, and r is 1 to R 43 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

(In formula (E-2), R 44 is an alkanediyl group having 1 to 4 carbon atoms.)

(In formula (E-3), R 45 and R 46 are each independently an alkyl group having 1 to 8 carbon atoms.)

(Wherein, in the formula (E-4), R 49 is a hydrogen atom or a hydroxyl group, and R 50 is a divalent hydrocarbon group having 1 to 9 carbon atoms, or R 3 if the R 49 is a hydrogen atom; When R 49 is a hydroxyl group, it is a divalent hydrocarbon group having 1 to 9 carbon atoms, or a carbon number of 2 carbon atoms when R 49 is a hydroxyl group. A divalent group having an oxygen atom between carbon-carbon bonds of the hydrocarbon groups of to 9)

(In Formula (E-5), R 51 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, a monovalent group having a hydrogen atom of the hydrocarbon group having 1 to 6 carbon atoms substituted with a hydroxyl group, Or a monovalent group having —CO— between carbon-carbon bonds of a hydrocarbon group having 2 to 6 carbon atoms, and R 52 is a monovalent hydrocarbon group having 1 to 6 carbon atoms.
The liquid crystal aligning agent according to any one of claims 1 to 10, further comprising a polymer different from the polyenamine.
A liquid crystal alignment film formed using the liquid crystal alignment agent according to any one of claims 1 to 11.
A liquid crystal device comprising the liquid crystal alignment film according to claim 12.
The liquid crystal element according to claim 13, comprising a color filter layer containing a dye.
A process of forming a coating on each of the conductive films of a pair of substrates having a conductive film using the liquid crystal aligning agent according to any one of claims 1 to 11;
Forming a liquid crystal cell by opposingly arranging a pair of substrates on which the coating film is formed such that the coating film faces each other via a liquid crystal layer;
Irradiating the liquid crystal cell with light in a state where a voltage is applied between the conductive films of the pair of substrates;
And a method of manufacturing a liquid crystal element.