TW201934609A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and method for producing liquid crystal element - Google Patents

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 [alpha], [beta]-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 for manufacturing liquid crystal element

[Cross Reference to Related Applications]
This application is based on Japanese Patent Application No. 2018-10894 filed on January 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 for manufacturing a liquid crystal element.

As the liquid crystal element, a horizontal alignment mode using a nematic liquid crystal having positive dielectric anisotropy, such as a Twisted Nematic (TN) type and a Super Twisted Nematic (STN) type, is known. Various liquid crystal elements, such as a vertical alignment (Vertical Alignment, VA) type liquid crystal element using a homeotropic alignment mode of nematic liquid crystal with negative dielectric anisotropy. These liquid crystal elements include a liquid crystal alignment film having a function of aligning liquid crystal molecules in a certain direction.

Generally, a liquid crystal alignment film is formed by applying a liquid crystal alignment agent obtained by dissolving a polymer component in an organic solvent on a substrate and heating the substrate. As the polymer component of the liquid crystal alignment agent, polyamic acid, soluble polyimide, polyimide, polyester, polyorganosiloxane, and the like are known. In particular, polyamic acid and soluble polyimide are heat-resistant Since it has excellent properties, mechanical strength, and affinity with liquid crystal molecules, it has been preferably used since ancient times (see Patent Documents 1 to 3).
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 4-153622
[Patent Document 2] Japanese Patent Laid-Open No. 56-91277
[Patent Document 3] Japanese Patent Laid-Open No. 11-258605

[Problems to be Solved by the Invention]
Polyamic acid and soluble polyimide have relatively low solubility in organic solvents. As the solvent component of liquid crystal alignment agents, N-methyl-2-pyrrolidone (N-methyl) is generally used as an aprotic polar solvent. -2-pyrrolidone (NMP) and other high boiling point solvents. 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, if heating at a high temperature is required when forming a liquid crystal alignment film, disadvantages such as restrictions on the material of the substrate may occur. For example, as a substrate of a liquid crystal element, the application of a film substrate may be limited. In addition, in a color liquid crystal display element, a dye used as a coloring agent for a color filter is relatively heat-resistant, and when heating during film formation at a high temperature is required, the use of the dye may be restricted.

As a method for eliminating such a problem, it is conceivable to reduce the use amount of a high boiling point solvent when preparing a liquid crystal alignment agent, or to use a low boiling point solvent instead of a high boiling point solvent. However, there are practical cases in which a solvent having a sufficiently high solubility in a polymer component of a liquid crystal alignment agent and a sufficiently low boiling point is limited, and a selection range is narrow. In addition, if the polymer component is not uniformly dissolved in the solvent, there is a concern that a coating unevenness (film thickness unevenness) or pinholes may occur in the liquid crystal alignment film formed on the substrate, and the end of the coating area The part cannot ensure linearity or cannot be a flat surface. In this case, there is a possibility that the yield of the product is lowered and the display performance such as liquid crystal alignment or electrical characteristics is affected.

In addition, polyamic acid is better than polyimide in terms of solubility, but in order to cyclize polyamic acid to polyimide and ensure good electrical characteristics, it needs to be performed at a relatively high temperature Heating during component manufacturing.

Therefore, as a polymer component of the liquid crystal alignment agent, it is required to exhibit high solubility even with a low-boiling-point solvent, and when the liquid crystal alignment agent is prepared, it has to exhibit good coatability to the substrate, and liquid crystal alignment and electrical characteristics. Excellent new material. Especially in recent years, large-screen and high-definition LCD TVs have become the mainstay. In addition, the popularity of small display terminals such as smart phones or tablet personal computers (tablet PCs) has progressed. Requirements are being further increased. Therefore, it is important to ensure excellent display quality.

This disclosure is made in view of the said situation, and one of the objective is to provide the liquid crystal aligning agent which is excellent in the coating | coated property to a board | substrate, and can obtain the liquid crystal element excellent in liquid crystal alignment property and a voltage retention.

[Means for solving problems]
According to the present disclosure, the following methods are provided.
[1] A liquid crystal alignment agent containing polyenamine.
[2] A liquid crystal alignment film formed using the liquid crystal alignment agent of [1].
[3] A liquid crystal element including the liquid crystal alignment film of [2].
[4] A method for manufacturing a liquid crystal element, comprising: using the liquid crystal alignment agent of [1] to form a coating film on each of the conductive films of a pair of substrates having a conductive film; and forming the coating film. A step of constructing a liquid crystal cell in which a pair of substrates of the coating film are arranged to face each other through the liquid crystal layer so that the coating film faces each other; and The liquid crystal cell performs a step of light irradiation.

[Effect of the invention]
By using a liquid crystal alignment agent containing polyenamine as a polymer component, a liquid crystal element having excellent liquid crystal alignment and voltage retention can be obtained. In addition, the liquid crystal alignment agent is excellent in coatability to a substrate.

Hereinafter, each component contained in the liquid crystal aligning agent of this disclosure, and other components arbitrarily mix | blended as needed are demonstrated.
In addition, the "hydrocarbon group" in this specification means the meaning which consists of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that have only a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to 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 of the structure of an alicyclic hydrocarbon, and it is also included in the part which has a chain structure. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof.

＜ Liquid crystal alignment agent ＞＞
The liquid crystal alignment agent of the present disclosure contains polyenamine as a polymer component. Polyenamine is a polymer having a carbon-carbon double bond in the ortho position of the amine group of a polyamine, and contains polyenamino ketone, polyenamino ester, polyenamino nitrile, and polyenaminosulfonium base. In terms of easy availability of monomers or ease of synthesis, the polyenamine used preferably has two or more partial structures represented by the following formula (1) or formula (2) in one molecule. A reaction product of α, β-unsaturated compound and diamine compound.
[Chemical 1]



(In formulas (1) and (2), X ¹ is a carbonyl group or a sulfofluorenyl group, L ¹ is a leaving group which is released by reaction with a diamine compound, L ² is an oxygen atom or a sulfur atom, and R ⁵ is A hydrogen atom or a monovalent organic group having a carbon number of 1 or more. A plurality of X ¹ , R ⁵ , L ^1, and L ^{2 in} one molecule each independently have the definition. “*” Represents a bonding bond)

(Α, β-unsaturated compounds)
In the formulas (1) and (2), X ^{1 is} preferably a carbonyl group in terms of a high degree of freedom in selection of a monomer.
L ^{1 in} the formula (1) is not particularly limited as long as it is a group that is released by reaction with an amine group of a diamine compound, and examples thereof include alkoxy groups having 1 to 5 carbon atoms, and pyrrole. A pyridyl group, a halogen atom, a hydroxyl group, a substituted or unsubstituted phenoxy group, a heterocyclic group, a monovalent group in which a hydroxyl group or a thiol group is introduced into a ring portion of a heterocyclic ring, and the like. When L ¹ is a substituted phenoxy group, examples of the substituent included in the phenoxy group include an alkyl group (for example, methyl, ethyl, etc.). The term “heterocyclic group” used in this specification refers to removing n (n is an integer) hydrogen atoms from a ring of a heterocyclic ring (for example, a nitrogen-containing heterocyclic ring, an oxygen atom heterocyclic ring, a sulfur-containing heterocyclic ring, and the like). Into an n-valent group.

Preferred specific examples of the α, β-unsaturated compound include those selected from those having a partial structure represented by the following formulae (4-1) to (4-4) in one molecule. At least one of the group consisting of a compound represented by the following formula (5), and a compound represented by the following formula (6) (including a tautomer). In addition, the structures represented by the following formulae (4-1), (4-2), (4-4), (5), and (6) correspond to those having the formula (1). In the case of a partial structure, the structure represented by the following formula (4-3) corresponds to a structure having the partial structure represented by the formula (2).
[Chemical 2]



(In the formulae (4-1) to (4-4), (5), and (6), X ¹ is a carbonyl group or a sulfonyl group, and R ¹ to R ⁵ and R ⁷ to R ¹⁰ are each independently A hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and R ⁶ is an alkanediyl group having 2 to 5 carbon atoms or a group having -O- or -S- between carbon-carbon bonds of the alkanediyl group. L ¹ is a leaving group which is detached by a reaction with a diamine compound, and L ² is an oxygen atom or a sulfur atom. A plurality of X ¹ , R ¹ to R ¹⁰ , L ¹ and L ^{2 in} one molecule each have an independent group. The definition. "*" Means a bond key)

With respect to the formula (4-1), (4-2), L specific example of formula (4-4) and Formula (5) ¹ of L ¹ described may be applied (1) of the formula .
The monovalent organic group of R ¹ to R ⁵ and R ⁷ to R ¹⁰ is preferably a monovalent alkyl group, alkoxy group or cycloalkyl group having 1 to 20 carbon atoms.
When an α, β-unsaturated compound has one or more of the partial structures represented by the formulae (4-1) to (4-4) in one molecule, the mechanism in the molecule in one molecule The number is preferably 2 to 4, and more preferably 2. Specifically, compounds represented by the following formulae (M-1) to (M-4) can be preferably used.
[Chemical 3]



(In formulas (M-1) to (M-4), B ¹ to B ⁴ are single bonds or divalent organic groups. X ¹ , R ¹ to R ⁶ , L ¹ and L ² and the formula (4 -1) to formula (4-4) have the same meaning)

Examples of the divalent organic group of B ¹ to B ⁴ in the formulae (M-1) to (M-4) include a divalent hydrocarbon group having 1 to 20 carbon atoms, and a carbon-carbon of the hydrocarbon group. There are divalent groups such as -O-, -S-, -NH-, etc. between the bonds. When B ¹ to B ⁴ are divalent organic groups, B ¹ to B ^{4 are} preferably a group bonded to the formulae (4-1) to (4-4) by using an aromatic ring group. The aromatic ring group is preferably a phenylene group or a naphthyl 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 formulae (A-1) to (A-14). When synthesizing polyenamine, the α, β-unsaturated compound may be used alone or in combination of two or more.
[Chemical 4]



[Chemical 5]

In the present specification, in the "α, β-unsaturated compound", a compound that exhibits tautomerism has a meaning including a tautomer. For example, the partial structure in which L ¹ of the formula (4-1) is a hydroxyl group is mutually converted with the partial structure represented by the following formula (4-1A). When synthesizing polyenamine, it is allowed in one molecule. A compound having two or more partial structures represented by the following formula (4-1A) exists. The same applies to the partial structure in which L ¹ of the formula (4-2) is a hydroxy group and the compound represented by the formula (6), and the partial structure represented by the following formula (4-2A) and the following formula ( The compounds represented by 6A) are mutually converted. The tautomers of the compounds represented by the formulas (A-5), (A-9), and (A-10) are shown below.
[Chemical 6]



[Chemical 7]

Furthermore, in the exemplified α, β-unsaturated compounds, the formula (A-8), formula (A-9), formula (A-11), formula (A-12), and formula (A- 14) The compound represented by each is equivalent to a compound having two or more partial structures represented by the formula (4-1) in one molecule, and the compound represented by the formula (A-10) corresponds to one molecule. A compound having two or more partial structures represented by the formula (4-2). The compound represented by the formula (A-13) corresponds to a compound having two or more partial structures represented by the formula (4-3) in one molecule. The formula (A-6) and formula The compounds represented by (A-7) each correspond to a compound having two or more partial structures represented by the formula (4-4) in one molecule. The compounds represented by the formulae (A-1) to (A-3) correspond to the compounds represented by the formula (5), and the formulae (A-4) and (A-5) The compounds represented by the respective compounds correspond to the compounds represented by the formula (6).

(Diamine compound)
The diamine compound used in the synthesis of the polyenamine is not particularly limited, and a known diamine compound can be used. Among these, in order to improve the liquid crystal alignment of the obtained liquid crystal element, it is preferable that the polyenamine has a source selected from the group consisting of the following formulae (d-1) to (d-4). A partial structure of at least one diamine compound (hereinafter, also referred to as a "specific diamine") in the group consisting of the represented compounds.
[Chemical 8]



(In formula (d-1), X ¹¹ and X ¹² are each independently a single bond, -O-, -S-, -OCO-, or -COO-, 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. N1 is 0 or 1, and when n1 = 0, n2 and n3 are integers satisfying n2 + n3 = 2, and when n1 = 1, n2 and n3 are n2 = n3 = 1. In formula (d-2), X ¹³ is a single bond, -O- or -S-, and m1 is an integer from 0 to 3. When m1 = 0, m2 is An integer of 1 to 12, and when m1 is an integer of 1 to 3, m2 is m2 = 2. In formula (d-3), X ¹⁴ and X ¹⁵ are each independently a single bond, -O-, -COO -Or -OCO-, R ¹⁷ is an alkanediyl group having 1 to 3 carbon atoms, and A ¹¹ is a single bond or alkanediyl group having 1 to 3 carbon atoms. A is 0 or 1, b is an integer of 0 to 2, and c Is an integer of 1 to 20, and k is 0 or 1. Among them, a and b do not become 0 at the same time. In formula (d-4), A ¹² represents a single bond, an alkanediyl group having 1 to 12 carbon atoms, or a carbon number. 1 to 6 fluoroalkanediyl, A ¹³ represents -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and A ¹⁴ represents a monovalent organic group having a steroid skeleton)

(Compound represented by formula (d-1))
Examples of the alkanediyl group having 1 to 3 carbon atoms in R ¹¹ and R ¹² in the formula (d-1) include methylene, ethylene, propane-1,2-diyl, and propane- 1,3-diyl, propane-2,3-diyl, etc. Among these, a methylene group, an ethylene group, or a propane-1,3-diyl group is preferable.
X ¹¹ and X ^{12 are} preferably a single bond, -O- or -S-.
Y ¹¹ is an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

When n1 = 0, the two primary amine groups of the compound represented by formula (d-1) may be bonded to the same benzene ring, or may be bonded to two different benzene rings one by one. . In the case of n1 = 1, the two primary amine groups are respectively bonded to different benzene rings.
The bonding position of the primary amine group on the benzene ring is not particularly limited. For example, when there is only one primary amine group on the benzene ring, its bonding position may be any of the 2-position, 3-position, and 4-position relative to other groups, and the 3-position is preferred. Or 4-position, more preferably 4-position. In addition, when there are two primary amine groups on the benzene ring, the positions of the bonds with respect to other groups include, for example, the 2,4-position and the 2,5-position. Among them, 2,4- is preferred. Bit.

The hydrogen atom on the benzene ring bonded to the primary amine group may also be a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group in which at least one hydrogen atom on the hydrocarbon group is replaced by a fluorine atom, or a fluorine atom. To replace. Examples of the monovalent hydrocarbon group in this case 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 ( Phenyl, tolyl, etc.), aralkyls (such as benzyl) having 5 to 10 carbon atoms, and the like.

Regarding preferable specific examples of the compound represented by the formula (d-1), examples of the compound having n1 = 0 include 4,4'-diaminodiphenylamine and 2,4-diamine. Diphenylamine and the like; examples of the compound of n1 = 1 include 1,3-bis (4-aminobenzyl) urea, 1,3-bis (4-aminophenethyl) urea, and 1,3 -Bis (3-aminobenzyl) urea, 1- (4-aminobenzyl) -3- (4-aminophenethyl) urea, 1,3-bis (2- (4-aminophenylbenzene) (Oxy) 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-aminobenzyloxy) ethyl) Urea, 1,3-bis (3- (2-aminobenzyloxy) propyl) urea and the like. Furthermore, as the compound represented by the formula (d-1), these compounds may be used singly or in combination of two or more kinds.

(Compound represented by formula (d-2))
In the 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 1-12. In this case, from the viewpoint of improving the heat resistance of the obtained polymer, m2 is preferably 1 to 10, and more preferably 1 to 8. In addition, in the application of the liquid crystal alignment film, from the viewpoint of maintaining good liquid crystal alignment and improving friction resistance, m1 = 0 is preferred, and from the viewpoint of reducing the pretilt angle of the liquid crystal molecules, Preferably, m1 is an integer of 1 to 3.
The bonding position of the primary amine group on the benzene ring is not particularly limited, and each primary amine group is preferably at the 3-position or the 4-position with respect to other groups, and more preferably at the 4-position. Furthermore, the hydrogen atom on the benzene ring bonded to the primary amine group may also be a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group in which at least one hydrogen atom on the hydrocarbon group is replaced by a fluorine atom, Or fluorine atom substitution.

Preferred specific examples of the compound represented by the formula (d-2) include, for example, bis (4-aminophenoxy) methane, bis (4-aminophenoxy) ethane, and 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 Alkane, bis (4-aminophenyl) methane, bis (4-aminophenyl) ethane, bis (4-aminophenyl) propane, bis (4-aminophenyl) butane, bis ( 4-aminophenyl) pentane, bis (4-aminophenyl) hexane, bis (4-aminophenyl) heptane, bis (4-aminophenyl) octane, bis (4- Aminophenyl) nonane, bis (4-aminophenyl) decane, 1,3-bis (4-aminophenylmercapto) propane, 1,4-bis (4-aminophenylmercapto) Butane and so on. In addition, as the compound represented by the formula (d-2), one of these exemplified compounds may be used alone or two or more thereof may be used in combination.

(Compound represented by formula (d-3))
In the formula (d-3), the divalent group represented by "-X ^14- (R ¹⁷ -X ¹⁵ ) _k- " is preferably an alkanediyl group having 1 to 3 carbon atoms, * -O-, * -COO- or * -OC ₂ H ₄ -O- (where a bond with "*" is bonded to a diaminophenyl group).
The group "-C _c H _{2c + 1} " is preferably linear, and specific examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl N-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, N-octadecyl, n-nonadecyl and the like.
The two primary amine groups in the diaminophenyl group are preferably the 2,4-position or the 3,5-position, and more preferably the 2,4-position with respect to the group "X ⁴ ". Furthermore, the hydrogen atom on the benzene ring bonded to the primary amine group may also be a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group in which at least one hydrogen atom on the hydrocarbon group is replaced by a fluorine atom, Or fluorine atom substitution.

Preferred specific examples of the compound represented by the formula (d-3) include, for example, compounds represented by the following formulae (d-3-1) to (d-3-12).
[Chemical 9]



[Chemical 10]

(Compound represented by formula (d-4))
The alkanediyl group having 1 to 12 carbon atoms in A ¹² in the formula (d-4) is preferably an alkanediyl group having 1 to 4 carbon atoms, and more preferably methylene, ethylidene, or 1, 3-propanediyl, 1,4-butanediyl. The fluoroalkanediyl group having 1 to 6 carbon atoms is preferably a perfluoroalkanediyl group having 1 to 4 carbon atoms, more preferably -CF _2- , perfluoroethylene, and 1,3-perfluoropropanediyl. And 1,4-perfluorobutanediyl.
A ^{13 is} preferably -O-.
The steroid skeleton in A ¹⁴ refers to a structure containing a cyclopentano-perhydrophenanthrene core or a structure in which one or two or more carbon-carbon bonds are double bonds. The monovalent organic group having the steroid skeleton is preferably a group having 17 to 40 carbon atoms.

As a preferable specific example of the compound represented by the formula (d-4), in terms of imparting a high pretilt angle to the coating film in the application of the liquid crystal alignment film, it is preferred to use a material selected from the group consisting of a 1-cholesteryl group. Oxymethyl-2,4-diaminobenzene, 1- (1-cholesteryloxy-1,1-difluoromethyl) -2,4-diaminobenzene, 1- (1-cholesterol Alkoxy-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) choline-24-acid cetyl ester, 3- (2,4-Diaminophenylmethoxy) choline-24-stearate, 3- (1- (2,4-diaminophenyl) -1,1-difluoromethoxy ) Cholan-24-stearate, 3- (3,5-diaminophenylmethoxy) cholan-24-stearate, 1-cholesteryloxy-2,4-diamine Group consisting of phenylbenzene, cholesterol 3,5-diaminobenzoate, 1-cholestoxy-2,4-diaminobenzene, and cholesteryl 3,5-diaminobenzoate More than one of the group, and furthermore, among these, less From the aspect of giving a high pretilt angle by proportion, it is particularly preferable to use a member selected from the group consisting of 1-cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoate, and 1-cholestane. One or more of the group consisting of oxy-2,4-diaminobenzene and cholesteryl 3,5-diaminobenzoate.

When synthesizing a polyenamine, the use ratio of a specific diamine can be arbitrarily set according to the diamine compound used. When using the compound represented by said formula (d-1), it is preferable that it is 1 mol% or more with respect to all diamines, and it is more preferable that it is 3 mol% or more. In addition, when the compound represented by the formula (d-2) is used, from the viewpoint of providing a low-tilt alignment angle to the liquid crystal molecules, the amount used is preferably 10 moles relative to all the diamines. Ear mole% or more, more preferably 30 mole% or more, and still more preferably 50 mole% or more.

When using at least one selected from the group consisting of the compound represented by the formula (d-3) and the compound represented by the formula (d-4), a viewpoint of imparting good alignment is used. Specifically, the use ratio (the total amount when two or more compounds are used) is preferably 5 mol% or more, and more preferably 10 mol% or more, with respect to all the diamines. As the specific diamine, one of the exemplified compounds may be used alone or in combination of two or more.

As the diamine compound used in the synthesis of the polyenamine, a diamine compound other than the specific diamine (hereinafter, also referred to as “other diamine”) may be used. Specific examples of other diamines include the compounds shown below. When synthesizing a polyenamine, by using each of the diamine compounds shown below, a polyenamine having a structural unit derived from the diamine compound can be obtained.

(Diamine compound having a carboxyl group)
A diamine compound having a carboxyl group (hereinafter, also referred to as a "carboxyl-containing diamine") can be used for the purpose of improving the electrical characteristics (especially the effect of reducing the accumulated charge) of the obtained liquid crystal element. In terms of further improving the effect of improving the electrical characteristics of the obtained liquid crystal element, it is preferred that the carboxyl group-containing diamine be used in combination with a diamine compound having a nitrogen-containing aromatic heterocyclic ring described later. The carboxyl group-containing diamine used is preferably an aromatic diamine, and specific examples thereof include compounds represented by the following formulae (d-5-1) and (d-5-2), respectively.
[Chemical 11]



(In formulas (d-5-1) and (d-5-2), R ²⁰ is 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 is a single bond. , An oxygen atom or an alkanediyl group having 1 to 3 carbon atoms. R2, r5, and r6 are each independently an integer of 1 or 2, r1, r3, and r4 are each independently an integer of 0 to 2, and r7 and r8 are each independently An integer of 0 to 2 that satisfies r7 + r8 = 2, where r3 + r5 + r7 ≦ 5, r4 + r6 + r8 ≦ 5. In the formula, when there are multiple R ²⁰ , these R ^{20 are} independent With the definition)

Regarding formula (d-5-1) and formula (d-5-2), examples of the alkyl group having 1 to 10 carbon atoms in R ²⁰ include methyl, ethyl, propyl, butyl, and pentyl. Groups, hexyl, heptyl, octyl, nonyl, decyl, etc. These groups 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 alkanediyl group having 1 to 3 carbon atoms in Z ¹ include methylene, ethylene, and trimethylene. r1, r3, and r4 are preferably 0 or 1, and more preferably 0.

As specific examples of the carboxyl group-containing diamine, examples of the compound represented by the formula (d-5-1) include 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, and 2 , 5-diaminobenzoic acid, etc .; Examples of the compound represented by the formula (d-5-2) include 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4 , 4'-diaminobiphenyl-2,2'-dicarboxylic 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'-diaminodiphenylethyl Alkane-3-carboxylic acid, 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylether-3-carboxylic acid, and the like. In addition, as the carboxyl group-containing diamine, one kind of these may be used alone or two or more kinds may be used.

In the case of using a carboxyl group-containing diamine, its use ratio is preferably 2 mol% or more, more preferably 3 mol% to 90 mol%, and still more preferably 5 mol relative to the total diamine. % To 70 mole%.

(Diamine compound having a nitrogen-containing aromatic heterocyclic ring)
The diamine compound having a nitrogen-containing aromatic heterocyclic ring can be used for the purpose of improving the electrical characteristics of the obtained liquid crystal element (especially the effect of reducing burn marks due to a DC voltage). Examples of the nitrogen-containing aromatic heterocyclic ring possessed by the diamine compound include pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, benzimidazole, purine, quinoline, and naphthyridine (Naphthyridine), carbazole, acridine, etc. 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 heterocyclic ring include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6 -Diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole Azole, 3,6-diaminoacridine, compounds represented by the following formulae (d-6-1) to (d-6-8), and the like. In addition, as the diamine compound having a nitrogen-containing aromatic heterocyclic ring, one kind of these may be used alone or two or more kinds may be used in combination.
[Chemical 12]

The use ratio of the diamine compound having a nitrogen-containing aromatic heterocycle is preferably 2 mol% or more, more preferably 3 mol% to 50 mol%, and more preferably It is 5 mol% to 40 mol%.

(Diamine compound with protective group)
A diamine compound having a protecting group (hereinafter, also referred to as a "protecting group-containing diamine") can improve the solubility of polyenamine in a solvent, and improve the combination of polyenamine with other polymers. Other polymers are used for the purpose of affinity. The protecting group-containing diamine preferably has a partial structure in which a protecting group is bonded to a nitrogen atom, and specifically, a group having a group represented by the following formula (7-1) or (7-2) Diamine compound.
[Chemical 13]



(In formulas (7-1) and (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 each independently a hydrogen atom or A monovalent organic group having a carbon number of 1 or more. M is an integer from 0 to 6. "*" represents a bonding bond)

In the formula (7-1) and the formula (7-2), the protecting group of Y ¹ is preferably a group that is detached by heat, and examples thereof include a urethane-based protecting group and an amidine-based system. Protecting group, hydrazone-based protecting group, sulfamidamide-based protecting group, and the like. As the protecting group, a urethane-based protecting group is preferred, and specific examples thereof include a third butoxycarbonyl group, a benzyloxycarbonyl group, and 1,1-dimethyl-2-haloethyl group. Oxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) ethoxy Carbonyl, etc. Among these, a third butoxycarbonyl group is particularly preferred in terms of a high releasability by heat and a point that the remaining amount of the deprotected portion in the film can be further reduced.
The monovalent organic group of R ²¹ and R ²² is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably an alkyl group or cycloalkyl group having 1 to 10 carbon atoms.
The monovalent organic group of R ²³ is preferably a monovalent alkyl group or protecting group having 1 to 10 carbon atoms. Examples of the divalent organic group of A ²¹ include a divalent hydrocarbon group and a group having -O-, -CO-, -COO-, -NH- between carbon-carbon bonds of the hydrocarbon group. A ^{21 is} preferably bonded to an aromatic ring, and more preferably bonded to a benzene ring.

Examples of the protective group-containing diamine include compounds represented by the following formulae (d-7-1) to (d-7-12). Moreover, the diamine containing a protective group may be used individually by 1 type, and may use 2 or more types together.
[Chemical 14]



[Chemical 15]



(Where TMS stands for trimethylsilyl)

In the case where a diamine containing a protective group is used, its use ratio is preferably 2 mol% or more, more preferably 3 mol% to 80 mol%, and more preferably relative to all diamines. It is set to 5 mol% to 70 mol%.

(Diamine containing secondary or tertiary amine structure / nitrogen-containing heterocyclic structure)
When synthesizing a 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 may be used. (Hereinafter also referred to as "diamine containing secondary or tertiary amine structure / nitrogen-containing heterocyclic structure"). By using a diamine containing a secondary amine or a tertiary amine structure / nitrogen-containing heterocyclic structure, the effect of improving the reduction of burn marks due to a DC voltage is improved, which is preferable in this respect.
[Chemical 16]



(In formula (9), R ⁵¹ and R ⁵² are each independently a divalent aromatic ring group, and R ⁵³ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more. "*" Represents a bonding bond)

Examples of the divalent aromatic ring group of R ⁵¹ and R ⁵² in the formula (9) include an aromatic hydrocarbon group and a nitrogen-containing aromatic heterocyclic group. Aromatic hydrocarbon groups are preferred, and examples thereof include phenylene and naphthyl. R ⁵¹ and R ^{52 are} particularly preferably phenylene.
Examples of the monovalent organic group of R ⁵³ include alkyl groups such as methyl, ethyl, and propyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and methylphenyl; and third butoxycarbonyl groups. Protective groups, etc. R ^{53 is} preferably a hydrogen atom or a methyl group.
Examples of the nitrogen-containing heterocyclic ring include nitrogen-containing heteroalicyclic structures such as piperidine, piperazine, pyrrolidine, hexamethyleneimine, and the above-exemplified nitrogen-containing aromatic heterocyclic rings. 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 diamine containing a secondary amine or tertiary amine structure / nitrogen-containing heterocyclic structure 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, Compounds exemplified in the description of N'-dimethylbenzidine, a diamine compound having a nitrogen-containing aromatic heterocyclic ring, and the following formulae (d-9-1) to (d-9-8) Compounds. Moreover, the diamine containing a secondary amine or a tertiary amine structure / nitrogen-containing heterocyclic structure may be used individually by 1 type, and may use 2 or more types together.
[Chemical 17]

When a diamine containing a secondary amine or a tertiary amine structure / nitrogen-containing heterocyclic structure is used, its use ratio is preferably 2 mol% or more, and more preferably 3, relative to the total diamine. Molar% to 60 Molar%, and more preferably 5 Molar% to 50 Molar%.

(Diamine compounds containing secondary amine groups)
When synthesizing a polyenamine, as another diamine, you may use the diamine compound represented by following formula (8) (henceforth a "diamine compound containing a secondary amine group"). By using a diamine compound containing a secondary amine group and using a polyenamine and another polymer as the polymer component of the liquid crystal alignment agent, phase separation with other polymers can be controlled. In this respect, Better.
[Chemical 18]



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

Examples of the divalent aromatic ring group of A ³¹ in the formula (8) include a group obtained by removing two hydrogen atoms from a ring portion of an aromatic ring such as a benzene ring, a naphthalene ring, and an anthracene ring. A ^{31 is} preferably phenylene.
The alkanediyl group of R ³¹ may be linear or branched, and examples thereof include methylene, ethylene, propanediyl, butanediyl, and pentanediyl.
Examples of the monovalent hydrocarbon group of R ³² include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and third butyl; and alkylene groups such as vinyl and propenyl. . R ^{32 is} preferably methyl or ethyl.

Specific examples of the secondary amine group-containing diamine compound include compounds represented by the following formulae (d-8-1) to (d-8-4). Moreover, the diamine compound containing a secondary amine group may be used individually by 1 type, and may be used in combination of 2 or more type.
[Chemical 19]

In the case of using a diamine compound containing a secondary amine group, its use ratio is preferably 2 mol% or more, and more preferably 3 mol% to 90 mol% relative to the total diamine. Further, it is preferably set to 5 mol% to 70 mol%.

Examples of other diamines include, in addition to the above, aliphatic diamines such as 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine;
1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and the following formulae (d-11-1) to (d-11-6)
[Chemical 20]



Alicyclic diamines such as the compounds represented respectively;
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-phenylene diimide (Propyl) 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 formula (d-10-5)
[Chemical 21]



Aromatic diamines such as the compounds represented respectively;
Diamine-based organosiloxanes such as 1,3-bis (3-aminopropyl) -tetramethyldisilazane and the like may be used, and diamines described in Japanese Patent Laid-Open No. 2010-97188 may be used. Furthermore, other diamines may be used alone or in combination of two or more.

(Other singular bodies)
When synthesizing a polyenamine, other singular bodies other than α, β-unsaturated compounds and diamine compounds may be used. Examples of the other monomers include tetracarboxylic dianhydride, tetracarboxylic diester, tetracarboxylic diester dihalide, and dilactone compounds. Among these, tetracarboxylic dianhydride can be preferably used.

Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride and ethylenediamine tetraacetic dianhydride;
1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxyl Cyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-di Ketone, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-di Ketone, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc. Alicyclic tetracarboxylic dianhydride;
Pyromellitic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene glycol bis (trimellitic acid Aromatic tetracarboxylic dianhydrides such as acid anhydride) and 1,3-propanediol bis (trimellitic anhydride). In addition, tetracarboxylic dianhydrides described in Japanese Patent Laid-Open No. 2010-97188 can be used. In addition, tetracarboxylic dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.

The tetracarboxylic acid diester can be obtained by ring-opening the tetracarboxylic dianhydride using alcohols such as methanol, ethanol, and propanol. A tetracarboxylic acid diester dihalide can be obtained, for example, by reacting the obtained tetracarboxylic acid diester with an appropriate chlorinating agent such as thionyl chloride.

Examples of the dilactone compounds include cycloendenol esters, exocyclic enol esters, cycloendenylfluorenimide esters, cycloexenylfluorenimide esters, and oxime esters. Specific examples of the dilactone compound used in the synthesis include compounds represented by the following formulae (b-1) to (b-11).
[Chemical 22]

Furthermore, the "reaction product of an α, β-unsaturated compound and a diamine compound" in the present specification allows the α, β-unsaturated compound and the diamine compound, and Monomers other than β-unsaturated compounds and diamine compounds are used as monomers used in the synthesis. The use ratio of other monomers (preferably tetracarboxylic dianhydride) is preferably 40 mol% or less, more preferably 30, relative to the total amount of monomers used in the synthesis of the polyenamine. Moore% or less.

(Synthesis reaction of polyenamine)
The synthesis method of polyenamine is not specifically limited, For example, it can synthesize | combine by nucleophilic substitution polymerization of a vinyl group. The synthesis reaction is preferably performed in an organic solvent. Examples of the organic solvent used in the reaction include aprotic polar solvents (N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamidine). Amines, etc.), phenol-based solvents (phenol, cresol, etc.), alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. The use ratio of the organic solvent is preferably such that the total amount of the α, β-unsaturated compound and the diamine compound is 0.1 to 50% by mass based on 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 hour to 24 hours. The reaction may be carried out in the presence of a catalyst such as trifluoroacetic acid, if necessary.

In the case where a reaction solution obtained by dissolving polyenamine is obtained through the reaction, the reaction solution may be directly used for the preparation of a liquid crystal alignment agent, or the reaction solution may be used in the reaction solution using a well-known separation method as follows. The contained polyenamine is separated and used for the preparation of a liquid crystal alignment agent. The separation method is a method of drying a precipitate obtained by injecting a reaction solution into a large amount of a poor solvent under reduced pressure, and using an evaporator to react the reaction. A method for removing the solution by distillation under reduced pressure.

The polyeneamine obtained has a polystyrene-equivalent weight average molecular weight (Mw) measured by Gel Permeation Chromatography (GPC) of preferably 1,000 to 300,000, and 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, and more preferably 3 or less. Moreover, the polyenamine used in the preparation of the liquid crystal alignment agent may be only one kind, or two or more kinds may be combined.

From the viewpoint of sufficiently coating the substrate and improving the liquid crystal alignment and voltage retention of the liquid crystal element, the amount of the polymer component contained in the liquid crystal alignment agent relative to the total amount of the polymer components contained in the liquid crystal alignment agent. The content rate of the polyenamine is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. In addition, the content ratio of the polyenamine is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less with respect to all the polymers contained in the liquid crystal alignment agent. .

As an example of a synthesis example of polyenamine, α, β-unsaturated compounds represented by the following formulae (M-1) to (M-4), (5), or (6) are shown below, and Reaction scheme of the compound represented by "NH ₂ -Y ² -NH ₂ ". In the following scheme, Y ² is a divalent organic group obtained by removing two primary amine groups from a diamine compound.
[Chemical 23]



[Chemical 24]



[Chemical 25]



[Chemical 26]



[Chemical 27]



[Chemical 28]

＜ Other ingredients ＞
The liquid crystal alignment agent of this disclosure may contain components other than a polyenamine as needed. The 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 polymers different from polyenamine (hereinafter, also referred to as “other polymers”), compounds having a crosslinkable group (hereinafter, also referred to as “crosslinkable group-containing group”). Compounds "), functional silane compounds, antioxidants, metal chelate compounds, hardening accelerators, surfactants, fillers, dispersants, photosensitizers, solvents, and the like. The blending ratio of other components may be appropriately selected depending on each compound within a range that does not impair the effects of the present disclosure.

(Other polymers)
Other polymers can be used for the purpose of improving the solubility in solvents, electrical properties, and the like. Examples of other polymers include polyamic acid, polyamidate, polyamidoimide, polyorganosiloxane, polyester, polyamidoamine, polybenzoxazole precursor, and polybenzoxamine. An azole, a cellulose derivative, a polyacetal, a polystyrene derivative, a (styrene-maleimide) -based polymer, or a polymer having a main skeleton such as a poly (meth) acrylate. In addition, (meth) acrylate means including an acrylate and a methacrylate. In the preparation of the liquid crystal alignment agent, other polymers may be used alone, or two or more of them may be used in combination.

The other polymer is preferably one selected from the group consisting of polyamic acid, polyamic acid, and poly (methacrylic acid), in terms of good affinity with polyeneamine and improvement in liquid crystal alignment and electrical characteristics of the obtained liquid crystal element. At least one of the group consisting of fluorene imine, polyorganosiloxane, and (styrene-maleimide) -based polymer. Among these, in the case where the liquid crystal alignment ability is provided to an organic film formed using a liquid crystal alignment agent by rubbing treatment, the liquid crystal alignment agent of the present disclosure more preferably contains a material selected from the group consisting of polyamic acid, polyamic acid, and At least one of the groups consisting of polyimide serves as another polymer. In the case where a liquid crystal alignment ability is imparted to the organic film by a photo-alignment process or a liquid crystal element is obtained by polymer-sustained alignment (PSA) treatment, the liquid crystal alignment agent of the present disclosure preferably contains At least one selected from the group consisting of a polyorganosiloxane and a (styrene-maleimide) -based polymer as another polymer. The (styrene-maleimide imide) -based polymer is preferably a (styrene-phenylmaleimide) -based polymer.

When the liquid crystal alignment agent contains other polymers, the blending ratio of the other polymers is preferably set to 10 parts by mass to 1,000 parts by mass relative to 100 parts by mass of the total amount of the polyenamine contained in the liquid crystal alignment agent. Parts, more preferably 30 to 500 parts by mass.

Preferred embodiments of the polymer component of the liquid crystal alignment agent include the following (I) to (IV).
(I) An aspect in which the polymer component contains polyenamine and at least one selected from the group consisting of polyamidic acid, polyamidate, and polyimide.
(II) A state in which the polymer component contains polyenamine and polyorganosiloxane.
(III) The polymer component contains a polyenamine and a (styrene-phenylmaleimide) -based polymer.
(IV) A state in which the polymer component contains polyenamine.
Among these, (I) is particularly preferable from the viewpoint of obtaining a liquid crystal element having more excellent coatability, liquid crystal alignment, and electrical characteristics.

(Crosslinkable compound)
The liquid crystal alignment agent of the present disclosure may also have a material selected from the group consisting of a cyclic carbonate group, an epoxy group, an isocyanate group, a block isocyanate group, an oxetanyl group, a trialkoxysilyl group, and a polymerizable compound. A compound (hereinafter, also referred to as a "crosslinkable group-containing compound") of at least one type of crosslinkable group in a group consisting of a saturated bond group. By including a compound containing a crosslinkable group, adhesion between the liquid crystal alignment film and the substrate, electrical characteristics and reliability of the liquid crystal element can be improved, and it is preferable in this respect.
When the compound having a crosslinkable group has a polymerizable unsaturated bond group, examples of the polymerizable unsaturated bond group include a (meth) acrylfluorenyl group, an ethylenic carbon-carbon double bond, and a vinyl group. Phenyl, vinyloxy (CH ₂ = CH-O-), vinylidene, maleimide, and the like are preferably cyclic carbonates from the viewpoint of high reactivity by light or heat. Radical, epoxy or (meth) acrylfluorenyl. In terms of storage stability, the molecular weight of the compound containing a crosslinkable group is preferably 3,000 or less, and more preferably 2,000 or less.

As specific examples of the compound having a crosslinkable group, examples of the compound containing a cyclic carbonate group include a compound represented by the following formula (11-1) and a compound represented by the following formula (11-2) Wait;
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, and isocyanuric acid triglycidyl ester. , 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, N, N, N ' , N'-Tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-Tetraglycidyl Glyceryl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N- Diglycidyl-cyclohexylamine, etc .;
Examples of the compound having a trialkoxysilyl group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3 -Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, a compound represented by the following formula (11-3), and a compound represented by the following formula (11-4) Represented compounds, etc .;
Examples of the compound having a block isocyanate group include a compound represented by the following formula (11-5), a compound represented by the following formula (11-6), and the like;
Examples of the compound having a (meth) acrylfluorenyl group include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and pentaerythritol tri (meth) acrylate. A compound represented by the following formula (11-7), a compound represented by the following formula (11-8), and the like;
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. As an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.
[Chemical 29]



[Chemical 30]

When a compound containing a crosslinkable group is formulated in a liquid crystal alignment agent, the compounding ratio of the compound containing a crosslinkable group is preferably relative to 100 parts by mass of a total amount of a polymer contained in the liquid crystal alignment agent. It is 40 mass parts or less, More preferably, it is 0.1-30 mass parts. Furthermore, the crosslinkable group-containing compound may be used singly or in combination of two or more kinds.

(Solvent)
The liquid crystal alignment agent of the present disclosure is prepared in the form of a solution-like composition, which is preferably obtained by dissolving a polymer component and a component arbitrarily blended as necessary in an organic solvent. Examples of the organic solvent include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The solvent component may be one of these or a mixed solvent of two or more.

As a solvent component of the liquid crystal alignment agent of the present disclosure, at least one pressure selected from the group consisting of compounds represented by the following formulae (E-1) to (E-5) can be used. A solvent having a boiling point of 180 ° C or lower (hereinafter, also referred to as a "specific solvent"). By using a specific solvent as at least a part of the solvent component, a liquid crystal element having excellent liquid crystal alignment and electrical characteristics can be obtained even when heating during film formation at a low temperature (for example, 200 ° C. or lower). Speak better. In addition, polyenamine has excellent solubility in solvents. Therefore, even when a low-boiling solvent such as a specific solvent is used as a solvent component, the coating property (non-uniformity in film thickness or pinhole suppression, coating, etc.) on a substrate is used. The end of the cloth region is also excellent in ensuring the linearity or flatness), and a liquid crystal element having good liquid crystal alignment and electrical characteristics can be obtained, which is preferable in this respect.
[Chemical 31]



(In the 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 1 to 4 carbon atoms. Alkanediyl or-(R ⁴⁷ -O) rR ^48- (wherein R ⁴⁷ and R ⁴⁸ are each independently alkanediyl having 2 or 3 carbon atoms, and r is an integer of 1 to 4), and R ⁴³ is hydrogen Atomic or carbon number 1-4 alkyl group)
[Chemical 32]



(In formula (E-2), R ⁴⁴ is an alkanediyl group having 1 to 4 carbon atoms)
[Chemical 33]



(In formula (E-3), R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 8 carbon atoms.)
[Chem 34]



(In the formula (E-4), R ⁴⁹ is a hydrogen atom or a hydroxyl group. When R ⁴⁹ is a hydrogen atom, R ⁵⁰ is a divalent hydrocarbon group having 1 to 9 carbon atoms or a chain having 3 to 9 carbon atoms. A divalent group having -CO- between carbon-carbon bonds of a hydrocarbon group. When R ⁴⁹ is a hydroxyl group, R ⁵⁰ is a divalent hydrocarbon group having 1 to 9 carbons, or a carbon of a hydrocarbon group having 2 to 9 carbons. -A divalent group having an oxygen atom between carbon bonds)
[Chemical 35]



(In the formula (E-5), R ⁵¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, a monovalent group in which a hydrogen atom in a hydrocarbon group having 1 to 6 carbon atoms is substituted with a hydroxyl group, or 2 carbon atoms A monovalent group having -CO- between carbon-carbon bonds of a hydrocarbon group of ～ 6, and R ⁵² is a monovalent hydrocarbon group of 1 to 6 carbon atoms)

Specific examples of the specific solvent include, as the compound represented by the formula (E-1), propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, 3-methoxy-1-butanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. Partial ethers of alcohols; ethylene glycol ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Partial esters of alcohols, etc .;
Examples of the compound represented by the formula (E-2) include cyclobutanone, cyclopentanone, and cyclohexanone;
Examples of the compound represented by the formula (E-3) include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, and methyl-iso Butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, etc .;
Examples of the compound represented by the formula (E-4) include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, cyclohexanol, methylcyclohexanol, and diacetone alcohol. ;
Examples of the compound represented by the formula (E-5) include methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, third butyl acetate, and 3-methoxy acetate. Butyl ester, methyl ethyl acetate, ethyl ethyl acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, methyl lactate, ethyl lactate and the like. The specific solvents may be used singly or in combination of two or more kinds.

The solvent component of the liquid crystal alignment agent may include only a specific solvent, or a mixed solvent of a solvent other than the specific solvent and the specific solvent. Examples of other solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidone, γ-butyrolactone, and γ -Highly polar solvents such as butyromethamine, N, N-dimethylformamide, N, N-dimethylacetamide, and others:
4-hydroxy-4-methyl-2-pentanone, butyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, cyclohexane, octanol, tetrahydrofuran and the like. These can be used alone or in combination of two or more. Furthermore, among the other solvents, a highly polar solvent may be used for the purpose of further improving solubility and leveling property. In addition, a hydrocarbon-based solvent that does not contain an amidine structure can be used for the purpose of application to a plastic substrate or low-temperature firing.

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

The liquid crystal alignment agent of the present disclosure is preferable in that a liquid crystal element having excellent liquid crystal alignment and electrical characteristics can be obtained even when N-methyl-2-pyrrolidone (NMP) is not substantially contained. . The term "substantially does not include NMP" in this specification means that the content of NMP is preferably 5 mass% or less, and more preferably 3 mass% or less, with respect to the total amount of the solvent contained in the liquid crystal alignment agent. It is further preferably 0.5% by mass or less.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) may be appropriately selected in consideration of viscosity and volatility, and is preferably 1 mass % To 10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small, and it is 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 is too large, and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent tends to increase and the coatability tends to decrease.

<< Liquid crystal alignment film and liquid crystal element >>
The liquid crystal alignment film of the present disclosure is formed of a liquid crystal alignment agent prepared as described above. 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, it can be applied to TN type, STN type, and VA type (including Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA), etc.), In-Plane Switching (IPS), Fringe Field Switching (FFS), optically compensated bending (Optically Compensated Bend (OCB)), polymer stabilized alignment (Polymer Sustained Alignment) and other modes. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate to be used differs depending on the required operation mode. In step 2 and step 3, each operation mode is common.

<Step 1: Formation of a coating film>
First, a liquid crystal alignment agent is coated on a substrate, and it is preferable to heat a coating surface to form a coating film on the substrate. As the substrate, for example, a transparent substrate including glass such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polycarbonate, poly ( Alicyclic olefins) and other plastics. The transparent conductive film provided on one surface of the substrate can be used: a NESA film (registered trademark of the United States PPG) containing tin oxide (SnO ₂ ), and an indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Indium Tin Oxide (ITO) film. 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 an electrode patterned into a comb-tooth type and an opposing substrate provided with no electrode are used. The application of the liquid crystal alignment agent to the substrate is preferably performed by an offset printing method, a flexographic printing method, a spin coating method, a roll coater method, or an inkjet printing method on the electrode formation surface.

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing dripping of the applied liquid crystal alignment agent. The pre-baking temperature is preferably 30 ° C to 200 ° C, and the prebaking time is preferably 0.25 minutes to 10 minutes. Thereafter, a calcination (post-baking) step is performed for the purpose of completely removing the solvent and thermally imidizing the ammonium acid structure in the polymer component as necessary. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 250 ° C, and more preferably 80 ° C to 200 ° C. The post-baking time is preferably 5 minutes to 200 minutes. In particular, polyeneamine has good solubility in a specific solvent, and a liquid crystal can be obtained even when the post-baking temperature is set to, for example, 200 ° C or lower, preferably 180 ° C or lower, and more preferably 160 ° C or lower. A liquid crystal element with excellent alignment and electrical characteristics. The film thickness of the thus formed film is preferably 0.001 μm to 1 μm.

<Step 2: Alignment Processing>
When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, a process (alignment process) of imparting liquid crystal alignment ability to the coating film formed in the step 1 is performed. Thereby, the alignment ability of liquid crystal molecules is given to a coating film, and it becomes a liquid crystal alignment film. As the alignment process, a process in which a coating film formed on a substrate is rubbed in a certain direction by a roller wound with a cloth including fibers such as nylon, rayon, and cotton can be used. Rubbing treatment; or light alignment treatment such as applying light irradiation to a coating film formed on a substrate to give the coating film liquid crystal alignment ability. On the other hand, in the case of manufacturing a vertical alignment (VA) type liquid crystal element, the coating film formed in the step 1 may be directly used as a liquid crystal alignment film, but in order to further improve the liquid crystal alignment capability, the coating film may also be used. Implement alignment processing. 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 light alignment can be performed by a method such as a method of irradiating a coating film after the post-baking step, a method of irradiating a coating film after the pre-baking step and before the post-baking step, and A method of irradiating a coating film while heating the coating film in at least one of the pre-baking step and the post-baking step. As radiation to be applied to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. Ultraviolet light including light having a wavelength of 200 nm to 400 nm is preferred. When the radiation is polarized, linearly polarized light or partially polarized light may be used. When the radiation used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction, or a combination of these directions may be used. In the case of non-polarized radiation, the irradiation direction is an oblique direction.

Examples of the light source used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and the like. The radiation dose is preferably 400 J / m ² to 50,000 J / m ² , and more preferably 1,000 J / m ² to 20,000 J / m ² . After the light irradiation for imparting the alignment ability, the surface of the substrate may be subjected to, for example, water, an organic solvent (for example, methanol, isopropanol, 1-methoxy-2-propanol acetate, or the like) or these The mixture is cleaned, or the substrate is heated.

<Step 3: Construction of the liquid crystal cell>
The two substrates on which the liquid crystal alignment film is formed as described above are prepared, and the liquid crystal is arranged between the two substrates disposed opposite to each other, thereby manufacturing a liquid crystal cell. When manufacturing a liquid crystal cell, for example, the following methods can be cited: the two substrates are arranged facing each other with a gap between the liquid crystal alignment films, the peripheral portions of the two substrates are bonded with a sealant, and the substrate surface is sealed with the sealant. A method of injecting liquid crystal into the enclosed cell gap and sealing the injection hole, a method using a liquid crystal drip (ODF) method, and the like. As the sealant, for example, an epoxy resin containing a hardener and alumina balls as a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferred. In the PSA mode, after the liquid crystal cell is constructed, a light irradiation process is performed on the liquid crystal cell in a state where a voltage is applied between the conductive films included in the pair of substrates.

When manufacturing 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. Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films included in the pair of substrates. The voltage applied here may be, for example, 5 V to 50 V DC or AC. In addition, as the light to be irradiated, for example, ultraviolet rays including visible light with a wavelength of 150 to 800 nm and visible rays may be used, and ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable. As a light source of the irradiation light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the like can be used. The light irradiation amount is preferably 1,000 J / m ² to 200,000 J / m ² , and more preferably 1,000 J / m ² to 100,000 J / m ² .

Then, if necessary, a polarizing plate is laminated on the outer surface of the liquid crystal cell to form a liquid crystal element. Examples of the polarizing plate include a polarizing plate called a "H film" obtained by extending a polyvinyl alcohol with a protective film of cellulose acetate and aligning it with one side to absorb iodine, or a polarizing plate containing the H film itself. Polarizer.

In the manufacturing process of a liquid crystal element, a substrate may be directly placed (positioned) after a liquid crystal alignment film is formed on the substrate due to a mechanical failure or a beat adjustment. At this time, the moisture in the air may be adsorbed on the liquid crystal alignment film or absorbed into the liquid crystal alignment film, and the electrical characteristics of the constructed liquid crystal element may be reduced, which may cause display unevenness. In this regard, the liquid crystal alignment film obtained by using the liquid crystal alignment agent can obtain a liquid crystal element with good electrical characteristics (good resistance to placement) even when the substrate is left in a state where the liquid crystal alignment film is formed. Excellent.

The liquid crystal element disclosed herein can be effectively used in various applications, such as clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, and personal digital assistants (PDAs). ), Digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays and other display devices, or dimming films, retardation films, etc. In addition, the liquid crystal element of the present disclosure is also suitably used for a liquid crystal element using a dye as a coloring agent for a color filter layer. Here, as the dye, a known dye that can be used in a liquid crystal element can be used.
[Example]

Hereinafter, specific descriptions will be made through examples, but the content of the present disclosure is 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. The molecular weight distribution (Mw / Mn) is calculated from the obtained Mw and Mn.
GPC column: made by Tosoh Corporation, TSKgelGRCXLII
Mobile phase: N, N-dimethylformamide solution containing lithium bromide and phosphoric acid 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 addition, in the following, the "compound represented by formula (X)" may be simply expressed as "compound (X)" for convenience.
(Α, β-unsaturated compounds)
[Chemical 36]

(Tetracarboxylic dianhydride)
[Chemical 37]

(Diamine compound)
[Chemical 38]



[Chemical 39]

(Crosslinking agent)
[Chemical 40]

＜ Synthesis of α, β-unsaturated compounds ＞
[Synthesis Example 1-1 to Synthesis Example 1-8]
Compounds (VL-1) to (VL-8) were synthesized by the methods described in the following documents, respectively.
· Compounds (VL-1): Sato Ryowa, Takeshi Yoshihiko, Amemiya Yasuhiro, Katayama General Road, Minutes of Engineering, Nihon University, 16, A, 113 (1975)
· Compound (VL-2): M. Ueda, K. Kino, T. Hirono, Y. Imai, Journal of Polymer Science ( J. Polym. Sci.), Polym. Chem. Ed., 14, 931 (1976)
· Compound (VL-3): S. Kimura, Makromol. Chem., 117, 203 (1968)
Compound (VL-4): SJ Huang (SJ Huang), J. Pavlisko, E. Hong (E. Hong), American Chemical Society Polymer Preprint (Am. Chem. Soc. Polym. Preprints), 19 [2], 57 (1978)
· Compound (VL-5): JA Moore, TD Mitchell, American Chemical Society Polymer Preprints (Am. Chem. Soc. Polym. Preprints), 19 [2], 13 (1978)
· Compound (VL-6): Takamoto Tanimoto, Masao Kurosaki, Ryota Oda, Organic Synthetic Chemistry, 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, Polymer Chemistry (Makromol. Chem.), 180, 1797 (1979)

<Synthesis of Polyenamine>
[Synthesis Example 2-1]
Under nitrogen, 1.68 g (10 mmol) of compound (VL-1) and 2.18 g (10 mmol) of pyromellitic dianhydride were dissolved in N-methyl-2-pyrrolidone in a 100 mL two-necked flask. (NMP) 60 g, compound (DA-1) 0.60 g (2 mmol) and compound (DA-2) 4.39 g (18 mmol) were added as diamine compounds, and reacted at 60 ° C for 4 hours to obtain A solution containing a polymer (P-1) as a polyenamine.

[Synthesis Example 2-2 to Synthesis Example 2-13 to Synthesis Example 2-20, Synthesis Example 2-21]
Except changing the type and amount of the monomers used as shown in Table 1 below, the same operations as in Synthesis Example 2-1 were performed to obtain polyeneamine-containing (respectively, polymers (P-2) to Polymer (P-15)). In addition, during the 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 oil is heated to 60 ° C or higher to synthesize the target polymer. .

＜ Synthesis of Polyamic Acid ＞
[Synthesis Example 2-14 to Synthesis Example 2-19]
Except changing the type and amount of the monomers used as shown in Table 1 below, the same operation as in Synthesis Example 2-1 was performed to obtain a polyamine-containing acid (respectively, a polymer (C-1) ~ Polymer (C-6)) solution.

In addition, in Synthesis Examples 2-1 to 2-21, α, β-unsaturated compounds and tetracarboxylic anhydrides were designated as “single body group A”, and diamine compounds were designated as “single body group B”. ”, When two or more monomers are used as the singular body group A, the total amount of the monomers of the singular body group A is 20 mmol, and two or more diamine compounds are used as a single amount In the case of the group B, it is used so that the total of the diamine compound becomes 20 mmol. In addition, Table 1 shows the molar ratios of the α, β-unsaturated compounds and tetracarboxylic dianhydrides in the singlet group A, and the molar ratios of the diamine compounds in the singlet group B.

[Table 1]

In Table 1, the solid content concentration of the liquid crystal alignment agent was set to be the same (4.0% by mass) in any of the examples. "-" Means compounds that do not use this column.

＜ Synthesis of polyorganosiloxanes ＞
[Synthesis Example 3-1]
The polymer (C-7) was synthesized according to the following scheme 1.
[Chemical 41]

A 1000 ml three-necked flask was charged with 90.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine, and mixed at room temperature. . Then, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then mixed under reflux and reacted at 80 ° C. for 6 hours. After completion of the reaction, the organic layer was taken out, and the organic layer was washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water 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 the polyorganosiloxane (E-1) having an epoxy group.
A 500 ml three-necked flask was charged with 26.69 g (0.3 mol equivalent) of side chain carboxylic acid (ca-1), 2.00 g of tetrabutylammonium bromide, and polyorganosiloxane (E-1) 80 g of the solution and 239 g of methyl isobutyl ketone were stirred at 110 ° C. for 4 hours. After cooling to room temperature, the liquid separation and washing operation was repeated 10 times with distilled water. Thereafter, the organic layer was recovered, and repeatedly concentrated and diluted with NMP by a rotary evaporator to obtain a 15% by mass NMP solution of the polymer (C-7) intermediate. 0.45 g (0.1 mol equivalent) of trimellitic anhydride was added to 50 g of the intermediate solution, and then prepared using NMP so that the solid content concentration became 10% by mass, and then stirred at room temperature for 4 hours to obtain Polymer (C-7) in NMP solution.
[Chemical 42]

[Synthesis example 3-2]
In Synthesis Example 3-1, the same operation as in Synthesis Example 3-1 was performed except that the side chain carboxylic acid (ca-2) shown below was used instead of the side chain carboxylic acid (ca-1). This obtained an NMP solution containing a polymer (C-8).
[Chemical 43]

[Synthesis example 3-3]
In Synthesis Example 3-1, the same operation as in Synthesis Example 3-1 was performed except that the side chain carboxylic acid (ca-3) shown below was used instead of the side chain carboxylic acid (ca-1). This obtained an NMP solution containing a polymer (C-9).
[Chemical 44]

<Synthesis of styrene-maleimide imide copolymer>
[Synthesis Example 3-4]
1. Synthesis of Compound (MI-1) Compound (MI-1) was synthesized according to the following scheme 2.
[Chemical 45]

A 100 mL eggplant-shaped flask equipped with a stirrer was charged with (E) -3- (4-((4- (4,4,4-trifluorobutoxy) benzylidene) oxy) phenyl) 11.8 g of acrylic acid, 20 g of thionyl chloride, and 0.01 g of N, N-dimethylformamide were stirred at 80 ° C for 1 hour. Thereafter, the excess thionyl chloride was removed by a diaphragm pump, and 100 g of tetrahydrofuran was added to prepare a solution A. Into a 500 mL three-necked flask equipped with a stirrer, 5.67 g of 4-hydroxyphenylmaleimide, 200 g of tetrahydrofuran, and 12.1 g of triethylamine were added, and an ice bath was performed. Solution A was added dropwise thereto and stirred at room temperature for 3 hours. The reaction solution was reprecipitated with 800 mL of water, and the obtained white solid was vacuum-dried to obtain 13.3 g of a compound (MI-1).

2. Synthesis of Polymer Under nitrogen, a 100 mL two-necked flask was charged with 5.00 g (8.6 mmol) of the obtained compound (MI-1) as a polymerization monomer, and 0.64 g of 4-vinylbenzoic acid (4.3 mmol), 4- (2,5-dioxo-3-pyrrolidin-1-yl) benzoic acid 2.82 g (13.0 mmol), and 4- (glycidyloxymethyl) styrene 3.29 g (17.2 mmol), 2,1'-azobis (2,4-dimethylvaleronitrile) 0.31 g (1.3 mmol) as a radical polymerization initiator, and 2,4-diphenyl- 0.52 g (2.2 mmol) of 4-methyl-1-pentene and 25 ml of tetrahydrofuran as a solvent were 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.

<Manufacturing and Evaluation of Friction Horizontal Liquid Crystal Display Elements>
[Example 1]
1. Preparation of Liquid Crystal Alignment Agent (AL-1) To a solution containing 100 parts by mass of a polymer (P-1) obtained in Synthesis Example 2-1, 200 parts by mass of a polymer (C-4), And NMP and butylcellosolve (BC) as a solvent, a solution having a solvent composition of NMP / BC = 50/50 (mass ratio) and a solid content concentration of 4.0% by mass was prepared. This solution was filtered through a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (AL-1).

2. Evaluation of coating properties (uneven film thickness, pinhole, edge shape, and film thickness uniformity) The prepared liquid crystal alignment agent (AL-1) was coated on a glass substrate using a spinner, and the temperature was 80 ° C. After preheating for 1 minute on a hot plate, heat (post-bake) for 30 minutes in a 230 ° C oven with nitrogen replacement in the cavity to form a coating film with an average film thickness of 0.1 μm. This coating film was observed with a microscope with a magnification of 100 times and 10 times, and the presence or absence of uneven film thickness and pinholes was investigated. Regarding the evaluation, when both film thickness unevenness and pinholes were not observed even when observed with a 100-fold microscope, it was set to "good (A)", and film thickness unevenness and When at least one of the pinholes is observed with a 10-fold microscope and both film thickness unevenness and pinholes are not observed, it is set to "OK (B)", and the film thickness is clearly observed with a 10-fold microscope In the case of at least one of the pinholes, it is set to "defective (C)". In this example, even with a 100-fold microscope, both film thickness unevenness and pinholes were not observed, and the applicability was evaluated as "good (A)".

As a more detailed evaluation of the applicability, the applicability of the edge portion (the outer edge portion of the formed coating film) was evaluated. The prepared liquid crystal alignment agent (AL-1) was applied to a transparent electrode surface on a glass substrate with a transparent electrode containing an ITO film by using a liquid crystal alignment film coating printer, and dried in the manner described above. Observe the shape and flatness of the edge portion, and set it to "good (A)" when the linearity is high and flat, and "possible (B)" when the linearity is high but there are unevenness. It is set as "defective (C)" when there is unevenness and liquid return from the edge (low linearity). As a result, it was judged as "good (A)" in this embodiment.
In addition, the thickness of the film was measured at four points in the plane of the coating film using a stylus-type film thickness meter, and the deviation of the measured value (difference from the average film thickness δ (δ = 0.1 μm in Example 1)) Evaluation of film thickness uniformity. Regarding the evaluation, when the measured values at 4 points were within the range of ± 25 Å with respect to the average film thickness δ, and when a uniform film thickness was obtained, it was set to "good (A)", and compared with the average film thickness δ, There are measured values outside the range of ± 25 Å, but when the measured values at 4 points are within the range of ± 50 Å with respect to the average film thickness δ, it is set to "allowable (B)", compared to the average film thickness. δ When there is a measured value outside the range of ± 50 Å, and the deviation of the measured value is large, it is regarded as "defective (C)". As a result, the evaluation was "good (A)" in this example.

3. Manufacture of friction horizontal type liquid crystal display element On the transparent electrode surface of a glass substrate with a transparent electrode including an ITO film, the prepared liquid crystal alignment agent (AL-1) was applied using a spinner, and a heating plate at 80 ° C. was used. Pre-bake for 1 minute. Then, it heated at 230 degreeC for 1 hour in the oven which replaced the inside of the chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. This coating film was subjected to a rubbing treatment using a friction machine having a roll around which a cloth was wound, at a roll rotation speed of 400 rpm, a table moving speed of 3 cm / sec, and a gross press-in length of 0.1 mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. These series of operations were repeated to form a pair (2 sheets) of substrates having a liquid crystal alignment film.
The outer periphery of the surface of the substrate having the liquid crystal alignment film of one of the substrates was coated with an epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm by screen printing, and then each liquid crystal alignment film was applied. Faces are superimposed so as to be crimped, and the adhesive is hardened. Next, a nematic liquid crystal (MLC-6221 manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic light-curing adhesive, and the polarizing plate was bonded to the substrate. On both sides of the substrate, a horizontal alignment type liquid crystal display element is manufactured.

4. Evaluation of Liquid Crystal Orientation With respect to the produced friction horizontal type liquid crystal display device, the light and dark changes when the voltage of 5 V was turned on and off (ON and OFF) (applied and released) were observed with an optical microscope. The presence or absence of an abnormal domain is evaluated as "A" when there is no abnormal domain, "B" is used for some abnormal domains, and "C" is evaluated for the entire abnormal domain. . As a result, the liquid crystal alignment in this example is "A".

5. Evaluation of voltage holding ratio (VHR) For the manufactured friction-level liquid crystal display device, a voltage of 5 V was applied at an application time of 60 microseconds and a span of 167 milliseconds, and then the self-release was measured. Voltage retention after 167 milliseconds. The measuring device used was VHR-1 manufactured by TOYO Technica. At this time, it is set to "A" when the voltage holding ratio is 95% or more, "B" when it is 80% or more and less than 95%, and 50% or more and 80% or less. Set to "C" and "D" if it is less than 50%. As a result, the voltage holding ratio in this example was evaluated as "A".

6. Evaluation of placement resistance The same operation as the above-mentioned "3. Production of a rubbing horizontal type liquid crystal display element" was performed to prepare two sets (a total of 4 pieces) of a pair of substrates having a liquid crystal alignment film.
Place a pair of substrates (2 pieces) among the prepared substrates in a stainless steel vat (approximately 20 cm × approximately 30 cm), and put a Petri dish with NMP, cover with aluminum foil and place The substrate and the petri dish were made of stainless steel. After being left at 25 ° C for 2 hours, the substrate was taken out. With this operation, a pair of substrates (two pieces) are exposed to the NMP environment. Thereafter, a liquid crystal display element was manufactured by using the pair of substrates by the same method as described in "3. Manufacturing of a friction horizontal liquid crystal display element" (this is referred to as "element A").
In addition, for a pair of substrates (two pieces) of another group, a liquid crystal display element was manufactured by the same method as described in "3. Production of a friction horizontal type liquid crystal display element" without exposing it to an NMP environment ( Set it to "Component B").
Then, according to the method described in the non-patent literature (TJ Scheffer et al. "J. Appl. Phys." Vol. 19 (vo. 19.) p2013 (1980)) and by The pretilt angles of the two liquid crystal display elements were measured using a crystal rotation method using He-Ne laser light, and the tilt difference Δθ [%] was obtained by the following formula (2).

Δθ = ((θ1-θ2) / θ1) × 100… (2)

(In Equation (2), θ1 is the pretilt angle of element B, and θ2 is the pretilt angle of element A)
It is set to "A" when Δθ is 5% or less, "B" when it is 5% or more and less than 10%, and "C" when it is 10% or more. As a result, the placement resistance in this example was evaluated as "A".

[Example 5 to Example 7, Example 14 to Example 20, and Comparative Example 1]
Except that the preparation composition was changed as shown in Table 2 below, it was prepared at the same solid content concentration as in Example 1 to obtain a liquid crystal alignment agent. In addition, the applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1 using each liquid crystal alignment agent, and a rubbing horizontal liquid crystal display element was produced in the same manner as in Example 1 and various evaluations were performed. These results are shown in Table 3 below. In addition, in Table 3 below, the observation results of uneven film thickness and pinholes are shown in the "coatability" column, and the observation results of the edge portions are shown in the "edge shape" column. The evaluation results of the thickness deviation are shown in the column of "film thickness uniformity". In Examples 6 and 7, a polymer component and a crosslinking agent were blended. In addition, in Table 2, "-" means a polymer which does not use this column.

<Manufacturing and Evaluation of Optical FFS Liquid Crystal Display Elements>
[Example 2]
1. Preparation of liquid crystal alignment agent (AL-2) The polymer used was changed to 100 parts by mass of polymer (P-2) and 50 parts by mass of polymer (C-9). A liquid crystal alignment agent (AL-2) was prepared in the same solvent composition and solid content concentration as in Example 1.
2. Evaluation of applicability The evaluation of applicability was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-2) instead of (AL-1). As a result, in this example, the evaluation results of uneven film thickness, pinhole, edge shape, and film thickness uniformity were all "A".

3. Manufacturing of optical FFS type liquid crystal display element The prepared liquid crystal alignment agent (AL-2) was applied to a glass substrate having a flat electrode, an insulating layer and a comb-shaped electrode laminated in this order on one side by a rotator, and The respective surfaces of the glass substrates facing each other without electrodes were heated (pre-baked) with a heating plate at 80 ° C. for 1 minute. After that, it was dried (post-baking) in an oven at 230 ° C. in which nitrogen was substituted in the cavity for 30 minutes to form a coating film having an average film thickness of 0.1 μm. An Hg-Xe lamp was used to irradiate the surface of the coating film from the normal direction of the substrate with ultraviolet light 1,000 J / m ² including 254 nm bright lines that were linearly polarized to perform photo-alignment treatment, thereby forming a liquid crystal alignment film on the substrate.
Next, for a pair of substrates having a liquid crystal alignment film, a liquid crystal injection port is left at the edge of the surface on which the liquid crystal alignment film is formed, and an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm is added for screen printing and coating. Thereafter, the substrates were superimposed and compression-bonded so that the projection direction of the polarization axis toward the substrate surface during light irradiation became antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, a nematic liquid crystal (MLC-7028 manufactured by Merck) was filled from the liquid crystal injection port between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it was heated at 120 ° C. and then slowly cooled to room temperature to manufacture a liquid crystal cell. Then, the polarizing plates were laminated on the two outer surfaces of the substrate such that the polarizing directions of the polarizing plates were orthogonal to each other and were at an angle of 90 ° to the projection direction of the ultraviolet axis of the liquid crystal alignment film on the substrate surface, thereby manufacturing a liquid crystal display element. .

4. Evaluation of Liquid Crystal Alignment About the manufactured optical FFS liquid crystal display element, the liquid crystal alignment was evaluated in the same manner as in Example 1. As a result, the liquid crystal alignment in this example is "A".
5. Evaluation of Voltage Holding Ratio (VHR) The light holding ratio of the manufactured FFS liquid crystal display device was evaluated in the same manner as in Example 1. As a result, the voltage holding ratio in this example was evaluated as "A".
6. Evaluation of placement resistance The same operation as described in "3. Production of optical FFS liquid crystal display element" was performed to prepare two groups (total 4 pieces) of a pair of substrates having a liquid crystal alignment film. Among these, a pair of substrates was exposed to an NMP environment in the same manner as in Example 1, and thereafter, the pair of substrates were used and the same as described in "3. Manufacturing of optical FFS liquid crystal display elements""To produce a liquid crystal display element (this is referred to as" element A "). In addition, for a pair of substrates (two pieces) of another group, a liquid crystal display element was manufactured by the same method as described in "3. Manufacturing of optical FFS liquid crystal display elements" without exposing them to the NMP environment ( Set it to "Component B"). Using the element A and the element B, the evaluation of the placement resistance was performed in the same manner as in Example 1. As a result, the placement resistance in this example was evaluated as "A".

[Comparative Example 2]
A liquid crystal alignment agent (BL-2) was obtained at the same solid content concentration as in Example 1 except that the blending composition was changed as shown in Table 2 below. In addition, the applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1 using the liquid crystal alignment agent (BL-2), and a light FFS liquid crystal display element was produced in the same manner as in Example 2 and various evaluations were performed. These results are shown in Table 3 below.

<Manufacturing and Evaluation of VA-type Liquid Crystal Display Elements>
[Example 3]
1. Preparation of liquid crystal alignment agent (AL-3) The polymer used was changed to 100 parts by mass of polymer (P-3) and 300 parts by mass of polymer (C-6). A liquid crystal alignment agent (AL-3) was prepared with the same solvent composition and solid content concentration in Example 1.
2. Evaluation of Coating Properties The evaluation of coating properties was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-3) instead of (AL-1). As a result, in this example, the evaluation results of uneven film thickness, pinhole, edge shape, and film thickness uniformity were all "A".

3. Production of VA type liquid crystal display element On the transparent electrode surface of a glass substrate with a transparent electrode including an ITO film, the prepared liquid crystal alignment agent (AL-3) was applied using a spinner, and a heating plate was used at 80 ° C. Pre-bake for 1 minute. Then, it heated at 230 degreeC for 1 hour in the oven which replaced the inside of the chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. This operation was repeated, thereby producing a pair (2 sheets) of substrates having a liquid crystal alignment film.
The outer periphery of the surface of the substrate having the liquid crystal alignment film of one of the substrates was coated with an epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm by screen printing, and then each liquid crystal alignment film was applied. Faces are superimposed so as to be crimped, and the adhesive is hardened. Next, a negative type liquid crystal (MLC-6608 manufactured by Merck) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light-curing adhesive, and the polarizing plate is bonded to On both sides of the substrate, a VA-type liquid crystal display element is manufactured.

4. Evaluation of Liquid Crystal Alignment About the manufactured VA-type liquid crystal display element, the liquid crystal alignment was evaluated in the same manner as in Example 1. As a result, the liquid crystal alignment in this example is "A".
5. Evaluation of Voltage Holding Ratio (VHR) The VA-type liquid crystal display element manufactured as described above was evaluated in the same manner as in Example 1. As a result, the voltage holding ratio in this example was evaluated as "A".
6. Evaluation of Placement Resistance The same operation as described in "3. Manufacture of VA-type liquid crystal display elements" was performed to produce two groups (total of four) of a pair of substrates having a liquid crystal alignment film. Among these, a pair of substrates were exposed to an NMP environment in the same manner as in Example 1. Thereafter, the pair of substrates were used in accordance with the above-mentioned "3. VA-type liquid crystal display element manufacturing" The same method is used to manufacture a liquid crystal display element (this is referred to as "element A"). In addition, a pair of substrates (two pieces) of the other group were not exposed to the NMP environment, and a liquid crystal display element was manufactured by the same method as described in "3. VA-type liquid crystal display element manufacturing" ( Set it to "Component B"). Using the element A and the element B, the evaluation of the placement resistance was performed in the same manner as in Example 1. As a result, the placement resistance in this example was evaluated as "A".

[Example 4 and Comparative Example 3]
Except that the preparation composition was changed as shown in Table 2 below, it was prepared at the same solid content concentration as in Example 1 to obtain a liquid crystal alignment agent. In addition, the applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1 using each liquid crystal alignment agent. In the same manner as in Example 3, a VA-type liquid crystal display element was produced and various evaluations were performed. These results are shown in Table 3 below.

<Manufacturing and Evaluation of PSA-type Liquid Crystal Display Elements>
[Example 9]
1. Preparation of liquid crystal alignment agent (AL-9) The polymer used was changed to 200 parts by mass of polymer (P-6) and 50 parts by mass of polymer (C-7). 1. Prepare liquid crystal alignment agent (AL-9) with the same solvent composition and solid content concentration.
2. Evaluation of applicability The evaluation of applicability was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-9) instead of (AL-1). As a result, in this example, the evaluation results of uneven film thickness, pinhole, edge shape, and film thickness uniformity were all "A".

3. Preparation of liquid crystal composition To 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck), 5 mass% of a liquid crystal compound represented by the following formula (L1-1) and 0.3 mass were added. % The photopolymerizable compound represented by the following formula (L2-1) is mixed and mixed to obtain a liquid crystal composition LC1.
[Chemical 46]

4. Manufacture of PSA type liquid crystal display element The prepared liquid crystal alignment agent (AL-9) was applied to a liquid crystal alignment film printer (manufactured by Japan Photo Printing (Stock)) on 2 each having a conductive film including an ITO electrode. Each electrode surface of the glass substrate was heated (pre-baked) on a hot plate at 80 ° C for 2 minutes to remove the solvent, and then heated (post-baked) on a hot plate at 230 ° C for 10 minutes to form an average film thickness. 0.06 μm coating film. The coating 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, thereby obtaining a pair (2 sheets) of substrates having a liquid crystal alignment film. The pattern of the electrodes used is the same pattern as the electrode pattern in the PSA mode.
Then, the outer edge of the surface of the substrate having the liquid crystal alignment film on one of the pair of substrates was coated with an epoxy resin adhesive having alumina balls having a diameter of 5.5 μm, and the liquid crystal alignment film faces were opposite to each other. Overlap and crimp to harden the adhesive. Then, the prepared liquid crystal composition LC1 is filled between a pair of substrates from a liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light-curing adhesive, thereby manufacturing a liquid crystal cell. Thereafter, an alternating current of 10 Hz at a frequency of 60 Hz was applied between the conductive films of the liquid crystal cell and the liquid crystal was driven, and an ultraviolet irradiation device using a metal halide lamp as a light source was used to irradiate ultraviolet rays at an irradiation amount of 100,000 J / m ² . In addition, the said irradiation amount is a value measured using the light quantity meter which measured based on the wavelength of 365 nm. Thereafter, the polarizing plates were laminated on the two outer surfaces of the substrate such that the polarization directions of the polarizing plates were orthogonal to each other and were at an angle of 45 ° to the projection direction of the ultraviolet axis of the liquid crystal alignment film on the substrate surface, thereby manufacturing a liquid crystal display. element.

5. Evaluation of Liquid Crystal Alignment The PSA liquid crystal display device manufactured as described above was evaluated for liquid crystal alignment as in Example 1. As a result, the liquid crystal alignment in this example is "A".
6. Evaluation of Voltage Holding Ratio (VHR) The PSA-type liquid crystal display device manufactured as described above was evaluated in the same manner as in Example 1. As a result, the voltage holding ratio in this example was evaluated as "A".
7. Evaluation of placement resistance The same operation as described in "3. Manufacture of PSA-type liquid crystal display element" was performed to prepare two groups (total of 4 pieces) of a pair of substrates having a liquid crystal alignment film. Among these, a pair of substrates was exposed to an NMP environment in the same manner as in Example 1, and thereafter, the pair of substrates were used in accordance with the "4. Manufacturing of PSA-type liquid crystal display element" The same method is used to manufacture a liquid crystal display element (this is referred to as "element A"). In addition, for a pair of substrates (two pieces) of another group, a liquid crystal display element was manufactured by the same method as described in "4. Manufacturing of PSA-type liquid crystal display elements" without exposing them to the NMP environment. It is set to "Component B"). Using the element A and the element B, the evaluation of the placement resistance was performed in the same manner as in Example 1. As a result, the placement resistance in this example was evaluated as "A".

[Example 10, Example 11 and Comparative Example 5]
Except that the preparation composition was changed as shown in Table 2 below, it was prepared at the same solid content concentration as in Example 1 to obtain a liquid crystal alignment agent. The applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1 using the obtained liquid crystal alignment agent, and a PSA-type liquid crystal display element was produced in the same manner as in Example 9 and various evaluations were performed in the same manner as in Example 1. The evaluation results are shown in Table 3 below. In Examples 10 and 11, a polymer component and a crosslinking agent were blended.

<Manufacturing and Evaluation of Optical Vertical Liquid Crystal Display Elements>
[Example 8]
1. Preparation of the liquid crystal alignment agent (AL-8) is performed in the same way as the polymer used is changed to 200 parts by mass of the polymer (P-7) and 50 parts by mass of the polymer (C-8). In Example 1, a liquid crystal alignment agent (AL-8) was prepared with the same solvent composition and solid content concentration.
2. Evaluation of Coating Properties The evaluation of coating properties was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-8) instead of (AL-1). As a result, in this example, the evaluation results of uneven film thickness, pinhole, edge shape, and film thickness uniformity were all "A".

3. Manufacture of light vertical liquid crystal display element On the transparent electrode surface of a glass substrate with a transparent electrode containing an ITO film, the prepared liquid crystal alignment agent (AL-8) was applied using a spinner, and heated at 80 ° C. The plate was pre-baked for 1 minute. Then, it heated at 230 degreeC for 1 hour in the oven which replaced the inside of the chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. Next, a Hg-Xe lamp and a glan-taylor prism were applied to the surface of the coating film, and a polarized light of 1,000 J / m ² including a bright line of 313 nm was irradiated from a direction inclined by 40 ° from the substrate normal. Ultraviolet rays give liquid crystal alignment ability. The same operation was repeated to form a pair (two sheets) of substrates having a liquid crystal alignment film.
On one of the substrates, the outer periphery of the surface of the substrate having the liquid crystal alignment film is coated with an epoxy resin adhesive having alumina balls having a diameter of 3.5 μm by screen printing, and then the liquid crystal alignment of the pair of substrates is performed. The film surfaces face each other, and compression bonding is performed so that the projection direction of the optical axis of the ultraviolet rays of each substrate on the substrate surface becomes antiparallel, and the adhesive is thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (MLC-6608 manufactured by Merck) is filled into the gap between the liquid crystal injection ports and the substrate, and then the liquid crystal injection port is sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it was gradually cooled to room temperature after heating at 130 ° C. Then, the polarizing plates were laminated on the two outer surfaces of the substrate so that the polarizing directions of the polarizing plates were orthogonal to each other and were at an angle of 45 ° to the projection direction of the ultraviolet axis of the liquid crystal alignment film on the substrate surface. .

4. Evaluation of Liquid Crystal Alignment As for the manufactured optical vertical liquid crystal display element, the liquid crystal alignment was evaluated in the same manner as in Example 1. As a result, the liquid crystal alignment in this example is "A".
5. Evaluation of Voltage Holding Ratio (VHR) The light vertical liquid crystal display element manufactured as described above was evaluated in the same manner as in Example 1. As a result, the voltage holding ratio in this example was evaluated as "A".
6. Evaluation of placement resistance The same operation as described in "3. Production of optical vertical liquid crystal display elements" was performed to produce two groups (total of four) of a pair of substrates having a liquid crystal alignment film. Among these, a pair of substrates was exposed to an NMP environment in the same manner as in Example 1, and thereafter, the pair of substrates were used and the same as described in "3. Manufacturing of a light vertical liquid crystal display element""To produce a liquid crystal display element (this is referred to as" element A "). In addition, for a pair of substrates (two pieces) of another group, a liquid crystal display element was manufactured by the same method as described in "3. Manufacturing of a light vertical liquid crystal display element" without exposing it to an NMP environment ( Set it to "Component B"). Using the element A and the element B, the evaluation of the placement resistance was performed in the same manner as in Example 1. As a result, the placement resistance in this example was evaluated as "A".

[Example 12, Example 13 and Comparative Example 4, Comparative Example 6]
Except that the preparation composition was changed as shown in Table 2 below, it was prepared at the same solid content concentration as in Example 1 to obtain a liquid crystal alignment agent. In addition, the applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1 using each liquid crystal alignment agent, and a light vertical liquid crystal display element was produced in the same manner as in Example 8 and various evaluations were performed. These results are shown in Table 3 below. In Example 12 and Example 13, a polymer component and a crosslinking agent were blended.

[Table 2]

[table 3]

[Example 21 to Example 23]
In Example 9, a liquid crystal alignment agent (AL-21) was prepared in the same manner as in Example 9 except that the solvent composition was changed as shown in Table 4 below instead of NMP / BC = 50/50 (mass ratio). Liquid crystal alignment agent (AL-23). The applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1, except that the liquid crystal alignment agent used was changed and the post-baking temperature was changed from 230 ° C to 200 ° C. 9 Similarly, a PSA-type liquid crystal display device was produced and various evaluations were performed. These results are shown in Table 5 below.
[Comparative Example 7 to Comparative Example 9]
In Examples 21 to 23, liquid crystals were prepared in the same manner as in Examples 21 to 23 except that 300 parts by mass of the polymer (C-5) was used instead of 200 parts by mass of the polymer (P-6). Alignment agent (BL-7) to liquid crystal alignment agent (BL-9) (refer to Table 4 below). The applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1, except that the liquid crystal alignment agent used was changed and the post-baking temperature was changed from 230 ° C to 200 ° C. 9 Similarly, a PSA-type liquid crystal display device was produced and various evaluations were performed. These results are shown in Table 5 below. In addition, in Table 5, it was observed that the solubility of the polymer with respect to the solvent was insufficient. As a result, it was expressed as "-" in the items that could not be evaluated (the same applies to Comparative Example 10 and Comparative Example 11).

[Example 24]
A liquid crystal alignment 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). The applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1 except that the obtained liquid crystal alignment agent was used and the post-baking temperature was changed from 230 ° C to 200 ° C. 8 Similarly, an optical VA-type liquid crystal display device was produced and various evaluations were performed. The results are shown in Table 5 below.

[Comparative Example 10]
A liquid crystal alignment 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. The applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1 except that the obtained liquid crystal alignment agent was used and the post-baking temperature was changed from 230 ° C to 200 ° C. 8 Similarly, an optical VA-type liquid crystal display device was produced and various evaluations were performed. The results are shown in Table 5 below.

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

[Comparative Example 11]
A liquid crystal alignment agent (BL-11) was prepared in the same manner as in Example 25 except that the polymer composition was changed as shown in Table 4 below. The applicability of the liquid crystal alignment agent was evaluated in the same manner as in Example 1 except that the obtained liquid crystal alignment agent was used and the post-baking temperature was changed from 230 ° C to 200 ° C. 2 An optical FFS-type liquid crystal display element was produced in the same manner and various evaluations were performed. The results are shown in Table 5 below.

[Table 4]

In Table 4, the numerical value of the solvent composition represents the mass ratio (mass%) with respect to the total amount of the solvent used in the preparation of the liquid crystal alignment agent. The abbreviation of the solvent has the following meanings.
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

[table 5]

As shown in Table 3, in Examples 1 to 20 in which a polyenamine-containing liquid crystal alignment agent was used, the applicability (including edge shape and film thickness uniformity) was evaluated as "A". In addition, in Examples 1 to 20, the liquid crystal alignment properties and voltage retention of the obtained liquid crystal display elements were also good, and they were evaluated as "A" in all the examples.
Furthermore, as shown in Table 4, polyenamine has a sufficiently high solubility with respect to a solvent composition that does not include a fluorene-based polar solvent (NMP), and has good applicability (including edge shape and film thickness uniformity), The evaluation of "A" or "B" in the liquid crystal alignment and voltage holding ratio yielded good results (Example 21 to Example 25). From this result, it can be said that it can be used suitably even when the color filter layer of a liquid crystal element is produced using the dye with inferior heat resistance as a coloring agent.
In contrast, in Comparative Examples using a liquid crystal alignment agent that does not contain polyenamine as a polymer component, and Comparative Examples 1 to 4 and Comparative Example 6 in the case of using a fluorene-based polar solvent (NMP) The evaluation of the edge shape is "B", which is inferior to the examples. Furthermore, in Comparative Example 1, the evaluation of the film thickness uniformity was also "B". In Comparative Example 2, the evaluation of the voltage holding ratio was "C", and Comparative Example 4 was "B". Moreover, as shown in Table 5, in the comparative example, the solubility with respect to the solvent composition which does not contain the amidine type | system | group polar solvent (NMP) was insufficient, and the favorable result was not obtained (comparative example 7 to comparative example 11).
From these results, it turns out that the liquid crystal aligning agent containing a polyenamine is excellent in the coating property, liquid crystal alignment property, and voltage retention. In addition, the liquid crystal alignment agent containing polyenamine is also excellent in placement resistance.

no

no

Claims (15)

A liquid crystal alignment agent containing polyenamine. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the polyenamine is an α having one or more partial structures represented by the following formula (1) or formula (2) in one molecule. β-unsaturated compounds, reaction products with diamine compounds; In the formulae (1) and (2), X ¹ is a carbonyl group or a sulfofluorenyl group, L ¹ is a leaving group which is released by reaction with a diamine compound, L ² is an oxygen atom or a sulfur atom, and R ⁵ is hydrogen An atom or a monovalent organic group having a carbon number of 1 or more; a plurality of X ¹ , R ⁵ , L ^1, and L ^{2 in} one molecule each independently have the definition; “*” represents a bonding bond. The liquid crystal alignment agent according to item 2 of the scope of patent application, wherein the α, β-unsaturated compound is selected from the following formulae (4-1) to (4-4) having two or more molecules in one molecule. ) In the group consisting of a compound having one type of partial structure, a compound represented by the following formula (5), and a compound represented by the following formula (6) (including tautomers) At least one In the formulae (4-1) to (4-4), (5), and (6), X ¹ is a carbonyl group or a sulfonyl group, and R ¹ to R ⁵ and R ⁷ to R ¹⁰ are each independently hydrogen. An atom or a monovalent organic group having 1 or more carbon atoms, and R ⁶ is an alkanediyl group having 2 to 5 carbon atoms or a group having -O- or -S- between carbon-carbon bonds of the alkanediyl group; L ¹ is a leaving group which is released by a reaction with a diamine compound, and L ² is an oxygen atom or a sulfur atom; a plurality of X ¹ , R ¹ to R ¹⁰ , L ¹ and L ^{2 in} one molecule each have a The definition; "*" means a bond. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the polyenamine has a source selected from the group consisting of the following formulae (d-1) to (d-4). A partial structure of at least one diamine compound in the group consisting of the represented compounds; In formula (d-1), X ¹¹ and X ¹² are each independently a single bond, -O-, -S-, -OCO-, or -COO-, Y ¹¹ is an oxygen atom or a sulfur atom, and R ¹¹ and R ¹² Each independently is an alkanediyl group having 1 to 3 carbon atoms; n1 is 0 or 1; in the case of n1 = 0, n2 and n3 are integers satisfying n2 + n3 = 2; in the case of n1 = 1, n2 And n3 is n2 = n3 = 1; in formula (d-2), X ¹³ is a single bond, -O- or -S-, m1 is an integer of 0 to 3; when m1 = 0, m2 is 1 An integer of -12, when m1 is an integer of 1 to 3, m2 is m2 = 2; in formula (d-3), X ¹⁴ and X ¹⁵ are each independently a single bond, -O-, -COO- Or -OCO-, R ¹⁷ is an alkanediyl group having 1 to 3 carbon atoms, A ¹¹ is a single bond or alkanediyl group having 1 to 3 carbon atoms; a is 0 or 1, b is an integer of 0 to 2, and c is An integer from 1 to 20, where k is 0 or 1, wherein a and b do not become 0 at the same time; in formula (d-4), A ¹² represents a single bond, an alkanediyl group having 1 to 12 carbon atoms, or a carbon number 1 Fluoroalkanediyl of ~ 6, A ¹³ represents -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -CO-, and A ¹⁴ represents a monovalent organic group having a steroid skeleton. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the polyenamine has a derivative derived from a compound having a secondary amine or a tertiary amine selected from the group consisting of the following formula (9) A structure and a partial structure of at least one diamine compound in the group consisting of a nitrogen-containing heterocyclic structure; In formula (9), R ⁵¹ and R ⁵² are each independently a divalent aromatic ring group, R ⁵³ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more; "*" represents a bonding bond. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the polyenamine has a partial structure derived from a diamine compound having a carboxyl group, and is derived from a nitrogen-containing aromatic heterocyclic compound. Partial structure of a cyclic diamine compound. The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the polyenamine has a derivative derived from a compound having the following formula (7-1) or (7-2) Partial structure of a diamine compound of a group; In the formulae (7-1) and (7-2), A ²¹ is a single bond or a divalent organic group having a carbon number of 1 or more, Y ¹ is a protecting group, and R ²¹ to R ²³ are each independently a hydrogen atom or a carbon A monovalent organic group having a number of 1 or more; m is an integer from 0 to 6; "*" represents a bonding bond. The liquid crystal alignment 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 formula (8), A ³¹ is a divalent aromatic ring group, R ³¹ is an alkanediyl group having 1 to 5 carbon atoms, and R ³² is a monovalent hydrocarbon group having 1 to 4 carbon atoms. The liquid crystal alignment agent according to any one of claims 1 to 8 of the patent application scope, further comprising a liquid crystal alignment agent selected from the group consisting of a cyclic carbonate group, an epoxy group, an isocyanate group, a block isocyanate group, and an oxetane. A compound of at least one type of crosslinkable group in the group consisting of an alkyl group, a trialkoxysilyl group, and a polymerizable unsaturated bonding group. The liquid crystal alignment agent according to any one of claims 1 to 9 of the patent application scope, which contains a compound selected from the group consisting of compounds represented by the following formulae (E-1) to (E-5), respectively. At least one organic solvent in the group and having a boiling point at 180 ° C or lower at 1 atmosphere; In formula (E-1), R ⁴¹ is an alkyl group having 1 to 4 carbon atoms or R ⁴⁰ -CO- (where R ⁴⁰ is an alkyl group having 1 to 3 carbon atoms); R ⁴² is an alkyl group having 1 to 4 carbon atoms Alkanediyl or-(R ⁴⁷ -O) rR ^48- (wherein R ⁴⁷ and R ⁴⁸ are each independently alkanediyl having 2 or 3 carbon atoms, and r is an integer of 1 to 4); 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; In formula (E-4), R ⁴⁹ is a hydrogen atom or a hydroxyl group. When R ⁴⁹ is a hydrogen atom, R ⁵⁰ is a divalent hydrocarbon group having 1 to 9 carbon atoms or a chain hydrocarbon group having 3 to 9 carbon atoms. The carbon-carbon bond has a -CO- divalent group. When R ⁴⁹ is a hydroxyl group, R ⁵⁰ is a divalent hydrocarbon group having 1 to 9 carbon atoms, or a carbon-2 to a hydrocarbon group having 2 to 9 carbon atoms. Divalent groups with oxygen atoms between carbon bonds; In the formula (E-5), R ⁵¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, a monovalent group in which a hydrogen atom in a hydrocarbon group having 1 to 6 carbon atoms is substituted with a hydroxyl group, or 2 to 6 carbon atoms. The hydrocarbon group of 6 has a monovalent group of -CO- between carbon-carbon bonds, and R ⁵² is a monovalent hydrocarbon group having 1 to 6 carbon atoms. The liquid crystal alignment agent according to any one of claims 1 to 10 of the scope of patent application, which further contains a polymer different from the polyenamine. A liquid crystal alignment film is formed by using the liquid crystal alignment agent according to any one of claims 1 to 11 of a patent application range. A liquid crystal element includes the liquid crystal alignment film according to item 12 of the scope of patent application. The liquid crystal element according to item 13 of the patent application scope, which includes a color filter layer containing a dye. A method for manufacturing a liquid crystal element includes: A step of forming a coating film on each of the conductive films of a pair of substrates having a conductive film using the liquid crystal alignment agent according to any one of claims 1 to 11 of the scope of patent application; A step of constructing a liquid crystal cell by arranging a pair of substrates on which the coating film is formed so as to face each other via the liquid crystal layer; and And a step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films included in the pair of substrates.