CN111433665B

CN111433665B - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, and method for producing liquid crystal element

Info

Publication number: CN111433665B
Application number: CN201880078150.0A
Authority: CN
Inventors: 冈田敬; 村上嘉崇
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2018-01-25
Filing date: 2018-12-19
Publication date: 2023-02-28
Anticipated expiration: 2038-12-19
Also published as: JPWO2019146319A1; TWI786251B; CN111433665A; KR20200073285A; KR102349617B1; WO2019146319A1; TW201934609A; JP6962387B2

Abstract

The invention provides a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal element and a manufacturing method of the liquid crystal element, wherein the liquid crystal aligning agent has good coating performance on a substrate and can obtain the liquid crystal element with excellent liquid crystal aligning performance and voltage holding rate. The liquid crystal aligning agent contains a polyvinylamine as a polymer component. In one form, the polyvinylamine is a reaction product of an α, β -unsaturated compound having one of two or more partial structures represented by the formula (1) or the formula (2) in one molecule and a diamine compound. In the formulae (1) and (2), X ¹ Is carbonyl or sulfonyl, L ¹ Is a leaving group which is removed by reaction with a diamine compound, L ² Is an oxygen atom or a sulfur atom, R ⁵ Is hydrogen atom or C1 or more organic radical.

Description

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

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is filed based on japanese patent application No. 2018-10894 filed on No. 1/25 in 2018, and the contents of the description thereof are incorporated herein by reference.

Technical Field

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

Background

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

In general, a liquid crystal alignment film is formed by: a liquid crystal aligning agent in which a polymer component is dissolved in an organic solvent is applied to a substrate and heated. As a polymer component of the liquid crystal aligning agent, polyamic acid, soluble polyimide, polyamide, polyester, polyorganosiloxane, and the like are known, and particularly, polyamic acid and soluble polyimide have been used preferably since long since they are excellent in heat resistance, mechanical strength, affinity with liquid crystal molecules, and the like (see patent documents 1 to 3).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. Hei 4-153622

Patent document 2: japanese patent laid-open No. Sho 56-91277

Patent document 3: japanese patent laid-open publication No. Hei 11-258605

Disclosure of Invention

Problems to be solved by the invention

Polyamic acid and soluble polyimide have relatively low solubility in organic solvents, and as a solvent component of a liquid crystal aligning agent, a high boiling point solvent such as N-methyl-2-pyrrolidone (NMP) is generally used as an aprotic polar solvent. Here, in order to obtain a liquid crystal element having good electrical characteristics and reliability, it is necessary to reduce the residual solvent in the liquid crystal alignment film as much as possible. However, when a liquid crystal alignment film is formed, heating at a high temperature is required, and there are problems such as restrictions on the material of the substrate, and for example, there are cases where the film substrate is applied as a substrate of a liquid crystal device. In addition, in a color liquid crystal display element, a dye used as a colorant for a color filter is relatively weak against heat, and when heating at the time of film formation at a high temperature is required, the use of the dye may be limited.

As a method for solving such a problem, it is considered to reduce the amount of the high boiling point solvent used in the preparation of the liquid crystal aligning agent or to use a low boiling point solvent instead of the high boiling point solvent. However, there are practical cases as follows: the solvent having sufficiently high solubility in the polymer component of the liquid crystal aligning agent and sufficiently low boiling point is limited, and the selection range is narrow. Further, if the polymer component is not uniformly dissolved in the solvent, there is a concern that: the liquid crystal alignment film formed on the substrate has coating unevenness (film thickness unevenness) or pinholes, and linearity or a flat surface cannot be secured at the end of the coating region. In this case, the product yield may be reduced, and the display performance such as the liquid crystal alignment property and the electrical characteristics may be affected.

Further, although polyamic acid is more excellent in solubility than polyimide, heating at the time of device production needs to be performed at a relatively high temperature in order to cyclize polyamic acid to polyimide and secure excellent electrical characteristics.

Therefore, as a polymer component of a liquid crystal aligning agent, a new material is required which exhibits high solubility even in a low boiling point solvent, exhibits good coatability to a substrate, and is excellent in liquid crystal aligning properties and electrical characteristics when the liquid crystal aligning agent is produced. In particular, in recent years, liquid crystal televisions having a large screen and high definition have become the main units, and small display terminals such as smart phones and tablet personal computers (tablet PC) have become widespread, and demands for high quality liquid crystal panels have been further increased. Therefore, it is important to ensure excellent display quality.

The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal aligning agent which has good coatability to a substrate and can obtain a liquid crystal device having excellent liquid crystal alignment properties and voltage holding ratio.

Means for solving the problems

According to the present disclosure, the following methods are provided.

[1] A liquid crystal aligning agent contains polyalkyleneamine (Polyenamine).

[2] A liquid crystal alignment film formed by using the liquid crystal aligning agent of [1 ].

[3] A liquid crystal cell comprising the liquid crystal alignment film of [2 ].

[4] A method of manufacturing a liquid crystal element, comprising: a step of forming a coating film on each of the conductive films of a pair of substrates having the conductive films by using the liquid crystal aligning agent of [1 ]; a step of configuring a liquid crystal cell by disposing a pair of substrates on which the coating films are formed, in opposition to each other with the coating films facing each other through a liquid crystal layer; and a step of irradiating the liquid crystal cell with light in a state where a voltage is applied between the conductive films of the pair of substrates.

ADVANTAGEOUS EFFECTS OF INVENTION

By using a liquid crystal aligning agent containing a polyvinylamine as a polymer component, a liquid crystal device having excellent liquid crystal alignment properties and voltage holding ratio can be obtained. In addition, the liquid crystal aligning agent has excellent coating performance on a substrate.

Detailed Description

Hereinafter, each component contained in the liquid crystal aligning agent of the present disclosure and other components optionally blended as necessary will be described.

In the present specification, the term "hydrocarbon group" is intended to include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group having no cyclic structure in the main chain and consisting of only a chain structure. The polymer may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. The alicyclic hydrocarbon may not be composed of only the alicyclic hydrocarbon structure, but may have a chain structure in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not necessary to be composed of only an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof.

Liquid crystal aligning agent

The liquid crystal aligning agent of the present disclosure contains a polyvinylamine as a polymer component. The polyalkyleneamine is a polymer having a carbon-carbon double bond in the ortho position to the amino group of the polyamine, and includes a polyalkyleneaminoketone, a polyalkyleneaminoester, a polyalkyleneaminonitrile, and a polyalkyleneaminosulfonyl group. The polyalkene amine used is preferably a reaction product of an α, β -unsaturated compound having one of two or more partial structures represented by the following formula (1) or formula (2) in one molecule and a diamine compound, in terms of easy availability of the monomer or easy synthesis.

[ solution 1]

(in the formulae (1) and (2), X ¹ Is carbonyl or sulfonyl, L ¹ Is a leaving group which is removed by reaction with a diamine compound, L ² Is an oxygen atom or a sulfur atom, R ⁵ Is hydrogen atom or C1 or more monovalent organic group. Multiple X in one molecule ¹ 、R ⁵ 、L ¹ And L ² Each independently having the definition. "+" indicates a bond)

(alpha, beta-unsaturated Compound)

In the above formulae (1) and (2), X is a high degree of freedom in the selection of the monomer ¹ Preferably a carbonyl group.

L as said formula (1) ¹ The diamine compound is not particularly limited as long as it is a group which is eliminated by the reaction with the amino group of the diamine compound, and examples thereof include: an alkoxy group having 1 to 5 carbon atoms, a pyrrolidinyl group, a halogen atom, a hydroxyl group, a substituted or unsubstituted phenoxy group, a heterocyclic group, a monovalent group obtained by introducing a hydroxyl group or a thiol group into the ring portion of the heterocyclic ring, and the like. At L ¹ In the case of a substituted phenoxy group, examples of the substituent group of the phenoxy group include an alkyl group (for example, methyl group, ethyl group, etc.). The term "heterocyclic group" as used herein means an n-valent group obtained by removing n (n is an integer) hydrogen atoms from a ring of a heterocyclic ring (for example, a nitrogen-containing heterocyclic ring, an oxygen-containing heterocyclic ring, a sulfur-containing heterocyclic ring, etc.).

Preferred specific examples of the α, β -unsaturated compound include at least one selected from the group consisting of a compound having two or more partial structures represented by the following formulae (4-1) to (4-4) in one molecule, a compound represented by the following formula (5), and a compound represented by the following formula (6) (including tautomers). The structures represented by the following formulas (4-1), (4-2), (4-4), (5) and (6) correspond to the structures having the partial structures represented by the above formula (1), and the structures represented by the following formulas (4-3) correspond to the structures having the partial structures represented by the above formula (2).

[ solution 2]

In (formulae (4-1) to (4-4), formulae (5) and (6), X ¹ Is carbonyl or sulfonyl, R ¹ ～R ⁵ And R ⁷ ～R ¹⁰ Each independently represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, 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 is ¹ A leaving group which is removed by a reaction with a diamine compound, L ² Is an oxygen atom or a sulfur atom. Multiple X in one molecule ¹ 、R ¹ ～R ¹⁰ 、L ¹ And L ² Each independently having the definition. "+" indicates a bond)

With respect to L in the above-mentioned formula (4-1), formula (4-2), formula (4-4) and formula (5) ¹ Specific example of (2), L in the above formula (1) can be applied ¹ And (4) description.

R ¹ ～R ⁵ And R ⁷ ～R ¹⁰ The monovalent organic group (2) is preferably a monovalent alkyl group, alkoxy group or cycloalkyl group having 1 to 20 carbon atoms.

When the α, β -unsaturated compound has two or more partial structures represented by the formulae (4-1) to (4-4) in one molecule, the number of the partial structures in one molecule 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.

[ solution 3]

In (formulae (M-1) to (M-4), B ¹ ～B ⁴ Is a single bond or a divalent organic group. X ¹ 、R ¹ ～R ⁶ 、L ¹ And L ² The same as the above formulae (4-1) to (4-4)

In the formulae (M-1) to (M-4), B is ¹ ～B ⁴ Examples of the divalent organic group of (3) include: a divalent hydrocarbon group having 1 to 20 carbon atoms, having-O-or-O-between carbon-carbon bonds in the hydrocarbon group divalent groups such as-S-, -NH-, and the like. In B ¹ ～B ⁴ In the case of a divalent organic radical, B ¹ ～B ⁴ Preferably, the aromatic ring group is bonded to the groups represented by the formulae (4-1) to (4-4). The aromatic ring group is preferably phenylene or naphthylene, and particularly preferably phenylene. The aromatic ring group may have a methyl group, an ethyl group, an alkoxy group or the like as a substituent on the ring portion.

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

[ solution 4]

[ solution 5]

In the present specification, in the "α, β -unsaturated compound", a compound showing tautomerism is defined as including its tautomeric forms. For example, L of said formula (4-1) ¹ Is a partial structure of a hydroxyl group inThe partial structures represented by the following formula (4-1A) are converted with each other, and when the polyvinylamine is synthesized, a compound having two or more partial structures represented by the following formula (4-1A) in one molecule is allowed to exist. L of said formula (4-2) ¹ Similarly, the partial structure of the hydroxyl group and the compound represented by the above formula (6) are also converted into the partial structure represented by the following formula (4-2A) and the compound represented by the following formula (6A). The following shows tautomers of the compounds represented by the above formulae (A-5), (A-9) and (A-10), respectively.

[ solution 6]

[ solution 7]

In the exemplary α, β -unsaturated compounds, the compounds represented by the formulae (a-8), (a-9), (a-11), (a-12) and (a-14) correspond to compounds 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 a compound having two or more partial structures represented by the formula (4-2) in one molecule. 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, and the compounds represented by the formulae (a-6) and (a-7) correspond to compounds 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 compound represented by the formula (5), and the compounds represented by the formulae (A-4) and (A-5) correspond to the compound represented by the formula (6).

(diamine Compound)

The diamine compound used for the synthesis of the polyalkyleneamine is not particularly limited, and a known diamine compound can be used. Among these, the polyalkyleneamine preferably has a partial structure derived from at least one diamine compound (hereinafter, also referred to as "specific diamine") selected from the group consisting of compounds represented by the following formulae (d-1) to (d-4), respectively, in order to obtain a liquid crystal element having excellent liquid crystal alignment properties.

[ solution 8]

(in the formula (d-1), X ¹¹ And X ¹² Independently represents a single bond, -O-, -S-, -OCO-or-COO-, Y is ¹¹ Is an oxygen atom or a sulfur atom, R ¹¹ And R ¹² Each independently is an alkanediyl group having 1 to 3 carbon atoms. n1 is 0 or 1, n2 and n3 are integers satisfying n2+ n3=2 in the case of n1=0, and n2 and n3 are n2= n3=1 in the case of n1= 1. In the formula (d-2), X ¹³ Is a single bond, -O-or-S-, and m1 is an integer of 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 the formula (d-3), X ¹⁴ And X ¹⁵ Each independently is 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 an alkanediyl group having 1 to 3 carbon atoms. a is 0 or 1,b is an integer of 0 to 2, c is an integer of 1 to 20, and k is 0 or 1. Wherein a and b do not become 0 at the same time. In the formula (d-4), A ¹² Represents a single bond, an alkanediyl group having 1 to 12 carbon atoms or a fluoroalkanediyl group having 1 to 6 carbon atoms, A ¹³ <xnotran> -O-, -COO-, -OCO-, -NHCO-, -CONH- -CO-, A </xnotran> ¹⁴ Represents a monovalent organic group having a steroid skeleton)

(Compound represented by the formula (d-1))

In the formula (d-1), as R ¹¹ And R ¹² Examples of the alkanediyl group having 1 to 3 carbon atoms include: methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, propane-2,3-diyl, and the like. Of these, methylene, ethylene or propane-1,3-diyl is preferred.

X ¹¹ And X ¹² 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 amino 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 amino groups are each bound one by one to different phenyl rings.

The bonding position of the primary amino group on the benzene ring is not particularly limited. For example, in the case where one primary amino group is present on the benzene ring, the bonding position may be any of 2-, 3-and 4-positions, preferably 3-or 4-and more preferably 4-with respect to the other groups. When the number of primary amino groups on the benzene ring is two, the bonding position to other groups includes, for example, 2,4-position, 2,5-position, etc., and particularly, 2,4-position is preferable.

The hydrogen atom on the benzene ring to which the primary amino group is bonded may be substituted with 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 substituted with a fluorine atom, or a fluorine atom. Examples of the monovalent hydrocarbon group in such a 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, an aryl group having 5 to 10 carbon atoms (e.g., phenyl group, tolyl group, etc.), an aralkyl group having 5 to 10 carbon atoms (e.g., benzyl group, etc.), and the like.

As preferable specific examples of the compound represented by the formula (d-1), examples of the compound having n1=0 include 4,4' -diaminodiphenylamine, 2,4-diaminodiphenylamine, and the like; examples of the compound having n1=1 include 1,3-bis (4-aminobenzyl) urea, 1,3-bis (4-aminophenylethyl) urea, 1,3-bis (3-aminobenzyl) urea, 1- (4-aminobenzyl) -3- (4-aminophenylethyl) urea, 1,3-bis (2- (4-aminophenoxy) ethyl) urea, 1,3-bis (3- (4-aminophenoxy) propyl) urea, 1,3-bis (4-aminobenzyl) thiourea, 1,3-bis (2-aminobenzyl) urea, 1,3-bis (2-aminophenoxy) ethyl) urea, 1,3-bis (2- (2-aminobenzoyloxy) ethyl) urea, and 1,3-bis (3- (2-aminobenzoyloxy) propyl) urea. Further, as the compound represented by the formula (d-1), one kind of these compounds may be used alone or two or more kinds may be used in combination.

(Compound represented by the 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 to 12. In this case, m2 is preferably 1 to 10, more preferably 1 to 8, from the viewpoint of improving the heat resistance of the obtained polymer. In addition, in the application of the liquid crystal alignment film, m1=0 is preferable from the viewpoint of maintaining good liquid crystal alignment properties and improving rubbing resistance, and m1 is preferably an integer of 1 to 3 from the viewpoint of reducing the pretilt angle of the liquid crystal molecules.

The bonding position of the primary amino group on the benzene ring is not particularly limited, and each primary amino group is preferably at the 3-position or 4-position, more preferably at the 4-position, relative to other groups. Further, the hydrogen atom on the benzene ring to which the primary amino group is bonded may be substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent group in which at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom, or a fluorine atom.

Preferable specific examples of the compound represented by the formula (d-2) include: bis (4-aminophenoxy) methane, bis (4-aminophenoxy) ethane, bis (4-aminophenoxy) propane, bis (4-aminophenoxy) butane, bis (4-aminophenoxy) pentane, bis (4-aminophenoxy) hexane, bis (4-aminophenoxy) heptane, bis (4-aminophenoxy) octane, bis (4-aminophenoxy) nonane, bis (4-aminophenoxy) decane, bis (4-aminophenyl) methane, bis (4-aminophenyl) ethane, bis (4-aminophenyl) propane, bis (4-aminophenyl) butane, bis (4-aminophenyl) 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 the like. Further, as the compound represented by the formula (d-2), one kind of the compounds exemplified above may be used alone or two or more kinds may be used in combination.

(Compound represented by the formula (d-3))

In the formula (d-3)As "-X ¹⁴ -(R ¹⁷ -X ¹⁵ ) _k A divalent group represented by the above-mentioned-, preferably an alkanediyl group having 1 to 3 carbon atoms, an-O-, an-COO-or an-O-C group ₂ H ₄ -O- (wherein the bond with the "-" is bonded to the diaminophenyl).

radical-C _c H _2c+1 "is preferably linear, and specific examples thereof include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, 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 amino groups in the diaminophenyl radical are preferably relative to the radical "X ⁴ "instead is 2,4-position or 3,5-position, more preferably 2,4-position. Further, the hydrogen atom on the benzene ring to which the primary amino group is bonded may be substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent group in which at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom, or a fluorine atom.

Preferable specific examples of the compound represented by the formula (d-3) include compounds represented by the following formulae (d-3-1) to (d-3-12).

[ solution 9]

[ solution 10]

(Compound represented by the formula (d-4))

A as said formula (d-4) ¹² The alkanediyl group having 1 to 12 carbon atoms in (A) is preferably an alkanediyl group having 1 to 4 carbon atoms, and more preferably a methylene group, an ethylene group, a 1,3-propanediyl group, or a 1,4-butanediyl group. The fluoroalkanediyl group having 1 to 6 carbon atoms is preferably a perfluoroalkanediyl group having 1 to 4 carbon atoms, and more preferably-CF ₂ -、Perfluoroethylene, 1,3-perfluoropropanediyl, 1,4-perfluorobutanediyl.

A ¹³ preferably-O-.

So-called A ¹⁴ The steroid skeleton in (1) refers to a structure containing a cyclopentanoperhydrophenanthrene (cyclopentano-perhydrophenanthrene) core or a structure in which one 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 preferred specific example of the compound represented by the above formula (d-4), in the case where a coating film is provided with a high pretilt angle in the application to a liquid crystal alignment film, preferably, one or more selected from the group consisting of 1-cholesteryloxymethyl-2,4-diaminobenzene, 1- (1-cholesteryloxy-1,1-difluoromethyl) -2,4-diaminobenzene, 1- (1-cholesteryloxy-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-diaminophenylmethoxy) cholestane-24-hexadecyl-hexadecanoate, 3- (3734 zxft) methoxy) stearyl-24-cholestane, 3- (3757-diaminophenyl) stearyl-3527 zxft 3528-3527-diaminobenzene, 3- (3757-diaminophenyl) -3527 zxft-3527-cholesterol stearate, 3- (3-3527 zxft) stearyl-3528-3-diaminobenzoate, 3-3625-diaminobenzoate, 3-35zxft-3527-cholesterol-3527-3-diaminobenzoate, 3-355825-3-diaminobenzoates, of these, in terms of providing a high pretilt angle at a small use ratio, it is particularly preferable to use one or more selected from the group consisting of 1-cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl ester, 1-cholesteryloxy-2,4-diaminobenzene, and 3,5-diaminobenzoic acid cholesteryl ester.

The ratio of the specific diamine used in the synthesis of the polyvinylamine can be arbitrarily set according to the diamine compound used. When the compound represented by the above formula (d-1) is used, the amount thereof to be used is preferably 1 mol% or more, more preferably 3 mol% or more, based on the whole diamine. In the case of using the compound represented by the above formula (d-2), the amount thereof to be used is preferably 10 mol% or more, more preferably 30 mol% or more, and still more preferably 50 mol% or more, based on the total diamines, from the viewpoint of imparting a low tilt orientation angle to the liquid crystal molecules.

In the case where 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) is used, the use ratio thereof (the total amount thereof in the case where two or more compounds are used) is preferably 5 mol% or more, more preferably 10 mol% or more, with respect to the total diamine, from the viewpoint of imparting good orientation. Further, as the specific diamine, one of the above-exemplified compounds may be used alone or two or more thereof may be used in combination.

As the diamine compound used for the synthesis of the polyalkyleneamine, a diamine compound other than the specific diamine (hereinafter, also referred to as "other diamine") may be used. Specific examples of the other diamine include the compounds shown below. Further, when the diamine compounds shown below are used in the synthesis of the polyalkyleneamine, the polyalkyleneamine having a structural unit derived from the diamine compound can be obtained.

(diamine Compound having carboxyl group)

The diamine compound having a carboxyl group (hereinafter, also referred to as "carboxyl group-containing diamine") can be used for the purpose of improving the electrical characteristics (particularly, the effect of alleviating accumulated charges) of the obtained liquid crystal element. In order to further improve the effect of improving the electrical characteristics of the obtained liquid crystal element, the diamine containing a carboxyl group is preferably used in combination with a diamine compound having a nitrogen-containing aromatic heterocycle 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).

[ solution 11]

(in the formulae (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, 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 satisfying r7+ r8= 2. Wherein r3+ r5+ r7 ≦ 5, and r4+ r6+ r8 ≦ 5. In which a plurality of R are present ²⁰ In the case of (2), these R' s ²⁰ Independently of the definition)

As R, there may be mentioned the formulae (d-5-1) and (d-5-2) ²⁰ Examples of the alkyl group having 1 to 10 carbon atoms in (b) include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like, and these groups may be straight or branched. Examples of the alkoxy group having 1 to 10 carbon atoms include: methoxy, ethoxy, propoxy, butoxy, hexyloxy, and the like. As Z ¹ Examples of the alkanediyl group having 1 to 3 carbon atoms include: methylene, ethylene, trimethylene and the like. r1, r3 and r4 are preferably 0 or 1, more preferably 0.

Specific examples of the carboxyl group-containing diamine include the compounds represented by the formula (d-5-1) such as 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid; 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, 5623 zxft 23 '-diaminodiphenylethane-3,3' -dicarboxylic acid, 4,4 '-diaminodiphenylethane-3-carboxylic acid, 56 zxft 56' -diaminodiphenylether-383438 zxft 3838 '-diaminodiphenylether-5749' -diaminodiphenylcarboxylic acid, and the like. Further, as the carboxyl group-containing diamine, one of these may be used alone or two or more thereof may be used.

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

(diamine Compound having Nitrogen-containing aromatic heterocycle)

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

Specific examples of the diamine compound having a nitrogen-containing aromatic heterocycle include: 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, 3,6-diaminoacridine, and compounds represented by the following formulae (d-6-1) to (d-6-8), respectively, and the like. Further, as the diamine compound having a nitrogen-containing aromatic heterocycle, one kind of these may be used alone or two or more kinds may be used in combination.

[ solution 12]

The proportion of the diamine compound having a nitrogen-containing aromatic heterocycle used is preferably 2 mol% or more, more preferably 3 mol% to 50 mol%, and still more preferably 5 mol% to 40 mol% based on the total diamines.

(diamine Compound having protective group)

The diamine compound having a protecting group (hereinafter, also referred to as "protecting group-containing diamine") can be used for the purpose of improving the solubility of the polyalkyleneamine in a solvent and improving the affinity with other polymers in the case of using the polyalkyleneamine and other polymers in combination. The protecting group-containing diamine preferably has a partial structure in which a protecting group is bonded to a nitrogen atom, and specifically, a diamine compound having a group represented by the following formula (7-1) or formula (7-2) is exemplified.

[ solution 13]

(in the formulae (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, R ²¹ ～R ²³ Each independently a hydrogen atom or a monovalent organic group having 1 or more carbon atoms. m is an integer of 0 to 6. "+" indicates a bond)

In the above formulae (7-1) and (7-2), Y ¹ The protecting group (b) is preferably a group which is released by heat, and examples thereof include: urethane-based protecting groups, amide-based protecting groups, imide-based protecting groups, sulfonamide-based protecting groups, and the like. Among these, a carbamate-based protecting group is preferable, and specific examples thereof include: tert-butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethyloxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) ethoxycarbonyl and the like. Among these, tert-butoxycarbonyl is particularly preferable in terms of high releasability by heat and further reducing the remaining amount of deprotected portions in the film.

R ²¹ And R ²² The monovalent organic group (2) 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.

R ²³ The monovalent organic group (2) is preferably a monovalent alkyl group having 1 to 10 carbon atoms or a protecting group. As A ²¹ Examples of the divalent organic group of (3) include: a divalent hydrocarbon group having-O-between carbon-carbon bonds of the hydrocarbon group-CO-, -COO-, -NH-, etc. A. The ²¹ Preferably to an aromatic ring, particularly preferably 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). The protective group-containing diamine may be used alone or in combination of two or more.

[ solution 14]

[ solution 15]

(wherein TMS represents trimethylsilyl)

When the diamine containing a protecting group is used, the proportion thereof is preferably 2 mol% or more, more preferably 3 mol% to 80 mol%, and still more preferably 5 mol% to 70 mol% based on the total diamine.

(diamine containing secondary or tertiary amine structure/nitrogen-containing heterocyclic structure)

In the synthesis of the polyvinylamine, a diamine compound having at least one selected from the group consisting of a secondary amine or a tertiary amine structure represented by the following formula (9) and a nitrogen-containing heterocyclic structure (hereinafter, also referred to as "diamine containing a secondary amine or a tertiary amine structure/nitrogen-containing heterocyclic structure") may be used. The use of a diamine containing a secondary amine or tertiary amine structure/nitrogen-containing heterocyclic structure is preferable in that the effect of improving the reduction in burn marks due to direct current voltage can be enhanced.

[ solution 16]

(in the formula (9), R ⁵¹ And R ⁵² Each independently is a divalent aromatic ring radical, R ⁵³ Is hydrogen atom or C1 or more monovalent organic group. "+" indicates a bond)

In the formula (9), as R ⁵¹ And R ⁵² Examples of the divalent aromatic ring group in (b) include an aromatic hydrocarbon group and a nitrogen-containing aromatic heterocyclic group. Aromatic hydrocarbon groups are preferred, and examples thereof include: phenylene, naphthylene, and the like. R is ⁵¹ And R ⁵² Particularly preferred is phenylene.

As R ⁵³ Examples of the monovalent organic group include: alkyl groups such as methyl, ethyl, and propyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and methylphenyl, and protecting groups such as tert-butoxycarbonyl. R ⁵³ Preferably a hydrogen atom or a methyl group.

Examples of the nitrogen-containing heterocycle include: nitrogen-containing hetero alicyclic structures such as piperidine, piperazine, pyrrolidine and hexamethyleneimine, and the above-mentioned nitrogen-containing aromatic heterocycles. Of these, at least one selected from the group consisting of pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, and carbazole is preferable.

Specific examples of the diamine having a secondary amine structure or a tertiary amine structure/nitrogen-containing heterocyclic structure include: examples of the diamine compound include bis (4-aminophenyl) amine, 2,4-diaminopyrimidine, 1,4-bis- (4-aminophenyl) -piperazine, N ' -bis (4-aminophenyl) -benzidine, N ' -bis (4-aminophenyl) -N, N ' -dimethylbenzidine, diamine compounds having a nitrogen-containing aromatic heterocycle, and compounds represented by the following formulae (d-9-1) to (d-9-8). Further, the diamine having a secondary amine structure or a tertiary amine structure/nitrogen-containing heterocyclic structure may be used alone or in combination of two or more.

[ solution 17]

When a diamine containing a secondary amine or a tertiary amine structure/nitrogen-containing heterocyclic structure is used, the proportion thereof is preferably 2 mol% or more, more preferably 3 mol% to 60 mol%, and still more preferably 5 mol% to 50 mol% based on the total diamine.

(diamine Compound containing Secondary amino group)

In the synthesis of the polyvinylamine, a diamine compound represented by the following formula (8) (hereinafter, also referred to as "diamine compound containing a secondary amino group") may be used as the other diamine. When the diamine compound containing a secondary amino group is used, in the case of using the polyalkyleneamine and another polymer in combination as a polymer component of the liquid crystal aligning agent, the phase separation property from the other polymer can be controlled, and this is preferable in view of the above.

[ solution 18]

(in the formula (8), A ³¹ Is a divalent aromatic ring radical, R ³¹ Is alkanediyl having 1 to 5 carbon atoms, R ³² A monovalent hydrocarbon group having 1 to 4 carbon atoms)

In the above formula (8), as A ³¹ Examples of the divalent aromatic ring group of (2) include: a group obtained by removing two hydrogen atoms from the ring part of an aromatic ring such as a benzene ring, a naphthalene ring, or an anthracene ring. A. The ³¹ Preferably phenylene.

R ³¹ The alkanediyl group (b) may be linear or branched, and examples thereof include: methylene, ethylene, propanediyl, butanediyl and pentanediyl.

As R ³² The monovalent hydrocarbon group of (2) includes: alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; alkenyl groups such as vinyl and propenyl. R ³² Preferably methyl or ethyl.

Specific examples of the diamine compound having a secondary amino group include compounds represented by the following formulae (d-8-1) to (d-8-4). Further, the diamine compound containing a secondary amino group may be used alone or in combination of two or more.

[ formula 19]

When the diamine compound containing a secondary amino group is used, the proportion thereof is preferably 2 mol% or more, more preferably 3 mol% to 90 mol%, and still more preferably 5 mol% to 70 mol% based on the total diamines.

Examples of the other diamines other than the above-mentioned diamines include: 1,3-aliphatic diamines such as propylenediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine;

1,4-diaminocyclohexane, 4,4' -methylenebis (cyclohexylamine), the following formulae (d-11-1) to (d-11-6)

[ solution 20]

Alicyclic diamines such as the compounds represented by the above formulae;

p-phenylenediamine, 4,4 '-diaminodiphenylsulfide, 2,2' -dimethyl-4,4 '-diaminobiphenyl, 2,2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 4,4' - (p-phenylenediisopropylidene) dianiline, 1,4-bis (4-aminophenoxy) benzene, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 2,2-bis [4- (4-aminophenoxy) phenyl ] propane, 2,4-diamino-N, N-diallyl aniline, 2,5-diamino-N, N-diallyl aniline, of the formula (d-10-1-d-10-5-d-10-5-10-1)

[ solution 21]

Aromatic diamines such as the compounds represented by the above;

and diaminoorganosiloxanes such as 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, and diamines described in Japanese patent application laid-open No. 2010-97188 can be used. Further, other diamines may be used singly or in combination of two or more.

(other Single measuring body)

Monomers other than the α, β -unsaturated compound and the diamine compound may be used in the synthesis of the polyalkyleneamine. Examples of other monomers include: tetracarboxylic dianhydride, tetracarboxylic diester dihalide, dilactone compound, and the like. Among these, tetracarboxylic dianhydride can be preferably used.

Examples of tetracarboxylic dianhydrides include: aliphatic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride and ethylenediamine tetraacetic acid dianhydride;

1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a,4,5,9 b-tetralino [1,2-c ] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5, b-tetralino [1,2-c ] furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2;

pyromellitic dianhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, aromatic tetracarboxylic dianhydrides such as p-phenylene bis (trimellitic acid monoester anhydride), ethylene glycol bis (trimellitic anhydride), and 1,3-propylene glycol bis (trimellitic anhydride), etc., and tetracarboxylic dianhydrides described in japanese unexamined patent publication No. 2010-97188 can be used. Further, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

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

Examples of the bislactone compound include: cycloalkenol esters, exocyclic enol esters, cyclic acylimide esters, exocyclic acylimide esters, oxime esters, and the like. Specific examples of the dilactone compound used for the synthesis include compounds represented by the following formulas (b-1) to (b-11).

[ solution 22]

In the present specification, the "reaction product of an α, β -unsaturated compound and a diamine compound" may be used as a monomer used for synthesis in combination with other monomers than the α, β -unsaturated compound and the diamine compound, unless the effects of the present disclosure are impaired. The proportion of the other monomer (preferably tetracarboxylic dianhydride) used is preferably 40 mol% or less, more preferably 30 mol% or less, based on the total amount of the monomers used for synthesizing the polyalkyleneamine.

(Synthesis reaction of Polyenamine)

The method for synthesizing the polyalkyleneamine is not particularly limited, and the polyalkyleneamine can be synthesized by, for example, nucleophilic substitution polymerization of vinyl group. The synthesis reaction is preferably carried out in an organic solvent. Examples of the organic solvent used in the reaction include: aprotic polar solvents (e.g., N-methyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide), phenolic solvents (e.g., phenol and cresol), alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The ratio of the organic solvent used is preferably such that the total amount of the α, β -unsaturated compound and the diamine compound is 0.1 to 50% by mass relative to the total amount of the reaction solution. The reaction temperature in this case is preferably from-20 ℃ to 150 ℃ and the reaction time is preferably from 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 in which the polyallylamine is dissolved is obtained by the reaction, the reaction solution may be used as it is for the production of the liquid crystal aligning agent, or the polyallylamine contained in the reaction solution may be separated and then used for the production of the liquid crystal aligning agent by using a known separation method such as a method of drying a precipitate obtained by injecting the reaction solution into a large amount of a poor solvent under a reduced pressure, a method of distilling off the reaction solution under a reduced pressure using an evaporator, or the like.

The weight average molecular weight (Mw) of the obtained polyvinylamine as measured by Gel Permeation Chromatography (GPC) in terms of polystyrene is preferably 1,000 to 300,000, more preferably 2,000 to 100,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 5 or less, more preferably 3 or less. The amount of the polyvinylamine used in the production of the liquid crystal aligning agent may be only one, or two or more kinds may be combined.

From the viewpoint of sufficiently improving coatability to the substrate and improving liquid crystal alignment properties and voltage holding ratio of the liquid crystal device, the content ratio of the polyvinylamine in the liquid crystal aligning agent is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more, relative to the total amount of the polymer components contained in the liquid crystal aligning agent. The content of the polyvinylamine is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less, based on the total polymer contained in the liquid crystal aligning agent.

As an example of the synthesis of the polyalkyleneamine, the following α, β -unsaturated compounds represented by the following formulae (M-1) to (M-4), formula (5) or formula (6), and "NH" are shown ₂ -Y ² -NH ₂ "reaction scheme of the compound represented by the formula (I). In the following scheme, Y ² A divalent organic group obtained by removing two primary amino groups from a diamine compound.

[ solution 23]

[ solution 24]

[ solution 25]

[ solution 26]

[ solution 27]

[ solution 28]

< other ingredients >

The liquid crystal aligning agent of the present disclosure may contain other components than the polyalkyleneamine as necessary. 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: a polymer other than the polyalkyleneamine (hereinafter, also referred to as "other polymer"), a compound having a crosslinkable group (hereinafter, also referred to as "crosslinkable group-containing compound"), a functional silane compound, an antioxidant, a metal chelate compound, a curing accelerator, a surfactant, a filler, a dispersant, a photosensitizer, a solvent, and the like. The blending ratio of the other components may be appropriately selected depending on each compound within a range not impairing the effect of the present disclosure.

(other polymers)

Other polymers may be used for the purpose of improving solubility to a solvent or electrical characteristics, etc. Examples of the other polymer include polymers having a main skeleton such as polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, polystyrene derivative, (styrene-maleimide) polymer, and poly (meth) acrylate. Further, (meth) acrylate is meant to include both acrylate and methacrylate. When the liquid crystal aligning agent is prepared, one kind of other polymer may be used alone, or two or more kinds may be used in combination.

The other polymer is preferably at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, polyorganosiloxanes, and (styrene-maleimide) polymers, in view of having good affinity with the polyvinylamine and improving the liquid crystal alignment properties and electrical characteristics of the obtained liquid crystal device. Among these, when the liquid crystal alignment ability is imparted to the organic film formed using the liquid crystal alignment agent by the rubbing treatment, the liquid crystal alignment agent of the present disclosure more preferably contains at least one selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides as the other polymer. In the case where the organic film is given liquid crystal Alignment ability by photo-Alignment treatment or in the case where a liquid crystal element is obtained by Polymer Stabilized Alignment (PSA) treatment, the liquid crystal aligning agent of the present disclosure more preferably contains at least one selected from the group consisting of polyorganosiloxane and (styrene-maleimide) based Polymer as another Polymer. The (styrene-maleimide) polymer is preferably a (styrene-phenylmaleimide) polymer.

When another polymer is contained in the liquid crystal aligning agent, the blending ratio of the other polymer is preferably 10 to 1000 parts by mass, more preferably 30 to 500 parts by mass, relative to 100 parts by mass of the total amount of the polyvinylamines contained in the liquid crystal aligning agent.

Preferred examples of the polymer component of the liquid crystal aligning agent include the following (I) to (IV).

(I) The polymer component comprises a mixture of a polyvinylamine and at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.

(II) the polymeric component comprises a combination of a polyalkyleneamine and a polyorganosiloxane.

The polymer component (III) is in the form of a polymer of polyvinylamine and (styrene-phenylmaleimide).

(IV) the polymeric ingredient comprises a form of a polyvinylamine.

Among these, the (I) is particularly preferable in terms of obtaining a liquid crystal element having more excellent coatability, liquid crystal alignment properties, and electrical characteristics.

(Compound having crosslinkable group)

The liquid crystal aligning agent of the present disclosure may also contain a compound having at least one crosslinkable group selected from the group consisting of a cyclic carbonate group, an epoxy group, an isocyanate group, a blocked isocyanate group, an oxetanyl group, a trialkoxysilyl group, and a polymerizable unsaturated bonding group (hereinafter, also referred to as "crosslinkable group-containing compound"). The compound containing a crosslinkable group is preferable in that adhesion between the liquid crystal alignment film and the substrate, and electrical characteristics and reliability of the liquid crystal element can be improved.

When the crosslinkable group-containing compound has a polymerizable unsaturated bonding group, examples of the polymerizable unsaturated bonding group include a (meth) acryloyl group, an ethylenic carbon-carbon double bond, a vinylphenyl group, and a vinyloxy group (CH) ₂ = CH-O-), vinylene, maleimide group, and the like, and a cyclic carbonate group, epoxy group, or (meth) acryloyl group is preferable in terms of high reactivity by light or heat. The molecular weight of the crosslinkable group-containing compound is preferably 3,000 or less, more preferably 2,000 or less, from the viewpoint of storage stability.

Specific examples of the crosslinkable group-containing compound include a cyclocarbonate group-containing compound such as: a compound represented by the following formula (11-1), a compound represented by the following formula (11-2), and the like;

examples of the compound having an epoxy group include: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, triglycidyl isocyanurate, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl-4,4 ' -diaminodiphenylmethane, N, N-diglycidylbenzylamine, N, N-diglycidylaminomethylcyclohexane, N, N-diglycidylcyclohexylamine, and the like;

examples of the compound having a trialkoxysilyl group include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, a compound represented by the following formula (11-3), a compound represented by the following formula (11-4), and the like;

examples of the compound having a blocked isocyanate group include: a compound represented by the following formula (11-5), a compound represented by the following formula (11-6), and the like;

examples of the compound having a (meth) acryloyl group include: ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, a compound represented by the following formula (11-7), a compound represented by the following formula (11-8), and the like;

examples of the oxetanyl group-containing compound include: a compound represented by the following formula (11-9), a compound represented by the following formula (11-10), and the like. Further, as an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in international publication No. 2009/096598 can be used.

[ solution 29]

[ solution 30]

When the crosslinkable group-containing compound is blended in the liquid crystal aligning agent, the blending ratio of the crosslinkable group-containing compound is preferably 40 parts by mass or less, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total polymer contained in the liquid crystal aligning agent. The crosslinkable group-containing compound may be used singly or in combination of two or more.

(solvent)

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

As the solvent component of the liquid crystal aligning agent of the present disclosure, at least one selected from the group consisting of compounds represented by the following formulae (E-1) to (E-5), and a solvent having a boiling point of 180 ℃ or less at 1 atm (hereinafter, also referred to as "specific solvent") may be used. By using a specific solvent as at least a part of the solvent component, a liquid crystal element excellent in liquid crystal alignment properties and electric characteristics can be obtained even when heating is performed at low temperature (for example, 200 ℃ or lower) during film formation, which is preferable in view of the above. Further, the polyalkyleneamine is preferable in terms of excellent solubility in a solvent, and therefore, even when a solvent having a low boiling point such as a specific solvent is used as a solvent component, the liquid crystal device is excellent in coatability to a substrate (suppression of film thickness unevenness or pinholes, and assurance of linearity or flatness at an end portion of a coated region), and is excellent in liquid crystal alignment property and electric characteristics.

[ solution 31]

(in the formula (E-1), R ⁴¹ Is alkyl with 1 to 4 carbon atoms or R ⁴⁰ -CO- (wherein, R ⁴⁰ Alkyl with 1 to 3 carbon atoms) R ⁴² Is alkanediyl having 1 to 4 carbon atoms or- (R) ⁴⁷ -O)r-R ⁴⁸ - (wherein, R) ⁴⁷ And R ⁴⁸ Each independently is an alkanediyl group having 2 or 3 carbon atoms, R is an integer of 1 to 4), R ⁴³ Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

[ chemical No. 32]

(in the formula (E-2), R ⁴⁴ An alkanediyl group having 1 to 4 carbon atoms)

[ chemical formula 33]

(in the formula (E-3), R ⁴⁵ And R ⁴⁶ Each independently an alkyl group having 1 to 8 carbon atoms)

[ chemical 34]

R ⁴⁹ -R ⁵⁰ -OH (E-4)

(in the formula (E-4), R ⁴⁹ Is a hydrogen atom or a hydroxyl group, in R ⁴⁹ In the case of a hydrogen atom, R ⁵⁰ Is a divalent hydrocarbon group having 1 to 9 carbon atoms or a divalent group having-CO-between carbon-carbon bonds of a chain hydrocarbon group having 3 to 9 carbon atoms, wherein R is ⁴⁹ In the case of hydroxy, R ⁵⁰ Is a divalent hydrocarbon group having 1 to 9 carbon atoms or a divalent group having an oxygen atom between carbon-carbon bonds of a hydrocarbon group having 2 to 9 carbon atoms)

[ solution 35]

R ^5l -COO-R ⁵² (E-5)

(in the formula (E-5), R ⁵¹ R is a C1-6 monovalent hydrocarbon group, a monovalent group in which a hydrogen atom of a C1-6 hydrocarbon group is substituted with a hydroxyl group, or a monovalent group having-CO-between carbon-carbon bonds of a C2-6 hydrocarbon group ⁵² A monovalent hydrocarbon group having 1 to 6 carbon atoms)

Specific examples of the specific solvent include the compounds represented by the formula (E-1): partial ethers of polyhydric alcohols such as 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, and diethylene glycol dimethyl ether; partial esters of polyhydric alcohols such as ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate;

as the compound represented by the formula (E-2), there may be mentioned: cyclobutanone, cyclopentanone, cyclohexanone;

as the compound represented by the above formula (E-3), there may be mentioned: acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, and the like;

as the compound represented by the formula (E-4), there can be mentioned: methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, cyclohexanol, methylcyclohexanol, diacetone alcohol, etc.;

as the compound represented by the formula (E-5), there can be mentioned: methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, 3-methoxybutyl acetate, methyl acetoacetate, ethyl propionate, n-butyl propionate, isoamyl propionate, methyl lactate, ethyl lactate, and the like. Further, the specific solvent may be used alone or in combination of two or more.

The solvent component of the liquid crystal aligning agent may be a mixed solvent of a solvent other than the specific solvent and the specific solvent, or may be a solvent containing only the specific solvent. Examples of the other solvents include high-polarity solvents such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ -butyrolactone, γ -butyrolactam, N-dimethylformamide, and N, N-dimethylacetamide; further, there may be mentioned:

4-hydroxy-4-methyl-2-pentanone, butyl lactate, methylmethoxypropionate, ethylethoxypropionate, 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 may be used alone or in combination of two or more. Among the other solvents, a highly polar solvent can be used for the purpose of further improving solubility and leveling property. Further, the hydrocarbon solvent having no amide structure can be used for the purpose of application to a plastic substrate or low-temperature calcination.

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

The liquid crystal aligning agent of the present disclosure is preferable in that a liquid crystal element having excellent liquid crystal alignment properties and electrical characteristics can be obtained even when N-methyl-2-pyrrolidone (NMP) is not substantially contained. In the present specification, "substantially no NMP" means that the NMP content is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 0.5% by mass or less, relative to the total amount of the solvent contained in the liquid crystal aligning agent.

The concentration of the solid component in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) may be appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 1 to 10 mass%. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10 mass%, the film thickness of the coating film is too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases to decrease the coatability.

Liquid crystal alignment film and liquid crystal element

The liquid crystal alignment film of the present disclosure is formed of the liquid crystal aligning agent prepared as described. 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, and the liquid crystal can be applied to various modes such as a TN type, an STN type, a VA type (including a Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, a Vertical Alignment-pattern Vertical Alignment (VA-PVA) type, and the like), an In-Plane Switching (IPS) type, a Fringe Field Switching (FFS) type, an Optically Compensated Bend (OCB) type, and a Polymer stabilized Alignment (Polymer stabilized Alignment). The liquid crystal element can be manufactured by a method including, for example, the following steps 1 to 3. In step 1, the substrate used differs depending on the desired mode of operation. In step 2 and step 3, the operation modes are common.

< step 1: formation of coating film

First, a liquid crystal aligning agent is applied to a substrate, and preferably, the coated surface is heated, thereby forming a coating film on the substrate. As the substrate, for example, a transparent substrate including the following materials can be used: float glass, soda glass, and the like; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin). The transparent conductive film provided on one surface of the substrate may use: comprising tin oxide (SnO) ₂ ) A film of (Nesa) (registered trademark of PPG Corp., USA) containing indium oxide-tin oxide (In) ₂ O ₃ -SnO ₂ ) Indium Tin Oxide (ITO) film, and the like. In the case of manufacturing a TN type, STN type, or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, in the case of manufacturing an IPS-type or FFS-type liquid crystal element, a substrate provided with electrodes patterned into a comb-tooth shape and an opposing substrate provided with no electrodes are used. The application of the liquid crystal aligning agent to the substrate is preferably performed by offset printing (offset printing), flexography, spin coating, roll coater or inkjet printing on the electrode-formed surface.

After the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent, and the like. The pre-baking temperature is preferably 30-200 ℃, and the pre-baking time is preferably 0.25-10 minutes. Thereafter, a firing (post-baking) step is performed for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amic acid structure in the polymer component. The calcination temperature (post-baking temperature) in this case is preferably 80 to 250 ℃, more preferably 80 to 200 ℃. The post-baking time is preferably 5 minutes to 200 minutes. In particular, the polyallylamine has good solubility in a specific solvent, and even when the postbaking temperature is set to, for example, 200 ℃ or less, preferably 180 ℃ or less, and more preferably 160 ℃ or less, a liquid crystal element having excellent liquid crystal alignment properties and electrical characteristics can be obtained. The film thickness of the film thus formed is preferably 0.001 to 1 μm.

< step 2: orientation treatment

In the case of producing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal cell, a treatment (alignment treatment) is performed to impart liquid crystal alignment ability to the coating film formed in the above-described step 1. Thereby, the coating film is provided with the alignment ability of the liquid crystal molecules, and becomes a liquid crystal alignment film. As the orientation treatment, the following treatments may be used: rubbing treatment of rubbing a coating film formed on a substrate in a predetermined direction by a roller around which a cloth containing fibers such as nylon (nylon), rayon (rayon), or cotton (cotton) is wound; or photo-alignment treatment in which a coating film formed on a substrate is irradiated with light to impart liquid crystal alignment ability to the coating film. On the other hand, in the case of manufacturing a Vertical Alignment (VA) type liquid crystal cell, the coating film formed in the above step 1 may be directly used as a liquid crystal alignment film, but an alignment treatment may be applied to the coating film in order to further improve the liquid crystal alignment ability. The liquid crystal alignment film suitable for the vertical alignment type liquid crystal cell can also be suitably used for the PSA type liquid crystal cell.

Light irradiation for photo-alignment can be performed by the following method or the like: a method of irradiating a coating film after a post-baking step, a method of irradiating a coating film after a pre-baking step and before a post-baking step, and a method of irradiating a coating film while heating the coating film in at least any one of the pre-baking step and the post-baking step. As the radiation irradiated to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150nm to 800nm can be used. Preferably ultraviolet light containing light having a wavelength of 200nm to 400 nm. When the radiation is polarized light, the radiation may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction, or may be performed by combining these directions. The irradiation direction in the case of unpolarized radiation 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 irradiation dose of the radiation is preferably 400J/m ² ～50,000J/m ² More preferably 1,000J/m ² ～20,000J/m ² . After the light irradiation for imparting alignment ability, a treatment of cleaning the substrate surface with, for example, water, an organic solvent (for example, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, or the like) or a mixture of these, or a treatment of heating the substrate may be performed.

< step 3: construction of liquid Crystal cell

A liquid crystal cell was produced by preparing 2 substrates on which liquid crystal alignment films were formed as described above and disposing liquid crystal between the 2 substrates disposed opposite to each other. In the production of a liquid crystal cell, for example, the following methods are exemplified: a method of arranging 2 substrates facing each other with a gap therebetween so that liquid crystal alignment films face each other, bonding peripheral portions of the 2 substrates with a sealant, filling a cell gap surrounded by the substrate surfaces and the sealant with a liquid crystal, and sealing the filling hole, a method of an One Drop Fill (ODF) method, or the like. For the sealant, for example, an epoxy resin containing a hardener and alumina balls as spacers (spacers) can be used. The liquid crystal includes nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable. In the PSA mode, after the liquid crystal cell is constructed, the liquid crystal cell is subjected to light irradiation treatment in a state where a voltage is applied between conductive films provided on a pair of substrates.

When a PSA-type liquid crystal cell is manufactured, a liquid crystal cell is constructed in the same manner as described above, except that the photopolymerizable compound is injected or dropped together with the liquid crystal. Thereafter,the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates. The voltage applied here may be, for example, a direct current or an alternating current of 5V to 50V. The light to be irradiated may be, for example, ultraviolet light and visible light including light having a wavelength of 150nm to 800nm, preferably ultraviolet light including light having a wavelength of 300nm to 400 nm. Examples of the light source for irradiating light include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser. The dose of light irradiation is preferably 1,000J/m ² ～200,000J/m ² More preferably 1,000J/m ² ～100,000J/m ² 。

Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell as necessary to produce a liquid crystal cell. Examples of the polarizing plate include: a polarizing plate obtained by sandwiching a polarizing film called an "H film" obtained by stretching and orienting polyvinyl alcohol and absorbing iodine while absorbing it, or a polarizing plate including the H film itself, with a cellulose acetate protective film.

In a process for manufacturing a liquid crystal element, a liquid crystal alignment film may be formed on a substrate due to mechanical failure, pitch adjustment, or the like, and then the substrate may be placed (set) directly. At this time, moisture in the air may be adsorbed to or absorbed into the liquid crystal alignment film, and the electric characteristics may be degraded in the constructed liquid crystal element, resulting in display unevenness. In the above aspect, the liquid crystal alignment film obtained using the liquid crystal alignment agent is excellent in that a liquid crystal element having good electrical characteristics (good standing resistance) can be obtained even when a substrate is left to stand in a state in which the liquid crystal alignment film is formed.

The liquid crystal element of the present disclosure can be effectively applied to various applications, for example, to various display devices such as a clock, a portable game machine, a word processor, a notebook Personal computer, a car navigation system, a camcorder, a Personal Digital Assistant (PDA), a Digital camera, a mobile phone, a smartphone, various monitors, a liquid crystal television, and an information display, a light adjusting film, a phase difference film, and the like. In addition, the liquid crystal element of the present disclosure is also suitably used for a liquid crystal element using a dye as a colorant of a color filter layer. Here, as the dye, a known dye that can be used in a liquid crystal element can be used.

Examples

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) was calculated from the Mw and Mn thus obtained.

GPC column: TSKgelGRCXLII manufactured by Tosoh corporation

Mobile phase: n, N-dimethylformamide solution containing lithium bromide and phosphoric acid

Temperature of the pipe column: 40 deg.C

Flow rate: 1.0 mL/min

Pressure: 68kgf/cm ²

The following are abbreviations for compounds used in the following examples. Hereinafter, the "compound represented by the formula (X)" may be simply referred to as "compound (X)" for convenience.

(alpha, beta-unsaturated Compound)

[ solution 36]

(tetracarboxylic dianhydride)

[ solution 37]

(diamine Compound)

[ solution 38]

[ chemical 39]

(crosslinking agent)

[ solution 40]

< Synthesis of alpha, beta-unsaturated Compound >

Synthesis examples 1-1 to 1-8

Compounds (VL-1) to (VL-8) were synthesized according to the methods described in the following documents.

Compound (VL-1): zuotenghe, wu Zheyi Yan, yu Gong Kangyu, pianshan Dai, the university of Japan, ergonomic division of ergonomics, 16, A,113 (1975)

Compound (VL-2): m. shanghai (m.ueda), k. Wood field (k.kino), t. Guangdian field (t.hirono), y. Jin well (y.imai), journal of polymer science (j.poly.sci.), polymer chemistry (poly.chem.ed.), 14,931 (1976)

Compound (VL-3): s. woodmura (s.kimura), polymer chemistry (makromol. Chem.), 117,203 (1968)

Compound (VL-4): S.J. yellow (S.J. Huang), J.palisko (J.Pavlisko), E.Hong (E.hong), american society of chemistry Polymer preprints (am.chem.Soc.Polym.preprints), 19[2],57 (1978)

Compound (VL-5): j.a. moore (j.a.moore), t.d. michael (t.d.mitchell), american society of chemistry polymer preprints (am.chem.soc.polymer.preprints), 19[2],13 (1978)

Compound (VL-6): gu Benchong Fr, nagasaki-Navy, xiao Tian Liangping, organic Synthesis chemistry, 26,361 (1968)

Compound (VL-7): m. shang tian (m.ueda), m. navian (m.funayama), y. Jin well (y.imai), journal of polymer (ym.j., 11,491 (1979)

Compound (VL-8): y. jin well (y.imai), n. saka well (n.sakai), j. zotoca (j.sasaki), m. shang tian (m.ueda), polymer chemistry (makromol. Chem.), 180,1797 (1979)

< Synthesis of Polyenamine >

[ Synthesis examples 2-1]

In a 100mL two-necked flask under nitrogen, 1.68g (10 mmol) of the compound (VL-1) and 2.18g (10 mmol) of pyromellitic dianhydride were dissolved in 60g of N-methyl-2-pyrrolidone (NMP), and 0.60g (2 mmol) of the compound (DA-1) as a diamine compound and 4.39g (18 mmol) of the compound (DA-2) were added thereto, and a reaction was carried out at 60 ℃ for 4 hours to obtain a solution containing the polymer (P-1) as a polyalkyleneamine.

Synthesis examples 2-2 to 2-13, 2-20 and 2-21

A solution containing a polyalkyleneamine (each of polymer (P-2) to polymer (P-15)) was obtained in the same manner as in Synthesis example 2-1, except that the kind and amount of the monomer used were changed as shown in Table 1 below. In addition, in the polymerization, when the solubility of the monomer is insufficient, the polymer is diluted with NMP or m-cresol, and when the polymerization rate is slow, the polymer is heated to 60 ℃ or higher by an oil bath, thereby synthesizing the target polymer.

< Synthesis of Polyamic acid >

Synthesis examples 2-14 to 2-19

A solution containing polyamic acid (each polymer (C-1) to polymer (C-6)) was obtained in the same manner as in Synthesis example 2-1, except that the kind and amount of the monomer used were changed as shown in Table 1 below.

In synthesis examples 2-1 to 2-21, the α, β -unsaturated compound and the tetracarboxylic dianhydride were referred to as "monomer group a" and the diamine compound was referred to as "monomer group B", and in the case where two or more monomers were used as the monomer group a, the total amount of the monomers in the monomer group a was 20mmol, and in the case where two or more diamine compounds were used as the monomer group B, the total amount of the diamine compound was 20 mmol. Table 1 shows the molar ratio of the α, β -unsaturated compound and the tetracarboxylic dianhydride in the monomer group a, and the molar ratio of the diamine compound in the monomer group B.

In table 1, the solid content concentration of the liquid crystal aligning agent was the same (4.0 mass%) in all cases. "-" means that the compounds of the column are not used.

< Synthesis of polyorganosiloxane

[ Synthesis example 3-1]

Polymer (C-7) was synthesized according to the following scheme 1.

[ solution 41]

A1000 ml three-necked flask was charged with 90.0g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500g of methyl isobutyl ketone and 10.0g of triethylamine, and mixed at room temperature. Then, 100g of deionized water was added dropwise over 30 minutes from the addition funnel, mixed under reflux and reacted at 80 ℃ for 6 hours. After the reaction was completed, the organic layer was taken out, 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. A proper amount of methyl isobutyl ketone was added to obtain a 50 mass% solution of polyorganosiloxane (E-1) having an epoxy group.

A500 ml three-necked flask was charged with 26.69g (0.3 mol equivalent) of a side chain carboxylic acid (ca-1) shown below, 2.00g of tetrabutylammonium bromide, 80g of a polyorganosiloxane (E-1) -containing solution, and 239g of methyl isobutyl ketone, and stirred at 110 ℃ for 4 hours. After cooling to room temperature, the liquid-separation washing operation was repeated 10 times with distilled water. Thereafter, the organic layer was recovered, and concentration and dilution with NMP were repeated 2 times by a rotary evaporator to obtain a 15 mass% NMP solution of the polymer (C-7) intermediate. To 50g of the intermediate solution, 0.45g (0.1 mol equivalent) of trimellitic anhydride was added, and then the mixture was prepared using NMP so that the solid content concentration became 10 mass%, and then stirred at room temperature for 4 hours, thereby obtaining an NMP solution of a polymer (C-7).

[ solution 42]

[ Synthesis examples 3 and 2]

A NMP solution containing a polymer (C-8) was obtained in the same manner as in Synthesis example 3-1, except that in Synthesis example 3-1, a side-chain carboxylic acid (ca-2) shown below was used in place of the side-chain carboxylic acid (ca-1).

[ solution 43]

Synthesis examples 3 to 3

A NMP solution containing a polymer (C-9) was obtained in the same manner as in Synthesis example 3-1, except that in Synthesis example 3-1, a side-chain carboxylic acid (ca-3) shown below was used in place of the side-chain carboxylic acid (ca-1).

[ solution 44]

< Synthesis of styrene-maleimide interpolymer >

Synthesis examples 3 to 4

1. Synthesis of Compound (MI-1)

Compound (MI-1) was synthesized according to the following scheme 2.

[ solution 45]

In a 100mL eggplant-shaped flask equipped with a stirrer were charged 11.8g of (E) -3- (4- ((4- (4,4,4-trifluorobutoxy) benzoyl) oxy) phenyl) acrylic acid, 20g of thionyl chloride, and 0.01g of N, N-dimethylformamide, and stirred at 80 ℃ for 1 hour. Thereafter, excess thionyl chloride was removed by a membrane pump, and 100g of tetrahydrofuran was added to prepare a solution a. A500 mL three-necked flask equipped with a stirrer was charged with 5.67g of 4-hydroxyphenylmaleimide, 200g of tetrahydrofuran, and 12.1g of triethylamine again, and subjected to ice-bath. Solution a was added dropwise thereto and stirred at room temperature for 3 hours. The reaction solution was reprecipitated with 800mL of water, and the obtained white solid was dried under vacuum to obtain 13.3g of compound (MI-1).

2. Synthesis of Polymer

5.00g (8.6 mmol) of the obtained compound (MI-1) as a polymerization monomer, 0.64g (4.3 mmol) of 4-vinylbenzoic acid, 2.82g (13.0 mmol) of 4- (2,5-dioxo-3-pyrrolin-1-yl) benzoic acid, and 3.29g (17.2 mmol) of 4- (glycidyloxymethyl) styrene, 2,2' -azobis (2,4-dimethylpentanenitrile) as a radical polymerization initiator, 0.31g (1.3 mmol), 2,4-diphenyl-4-methyl-1-pentene (2.2 mmol) as a chain transfer agent, and 25mL of tetrahydrofuran as a solvent were charged in a 100mL two-necked flask under nitrogen, and polymerization was carried out at 70 ℃ for 5 hours. After reprecipitation in n-hexane, the precipitate was filtered and vacuum-dried at room temperature for 8 hours, thereby obtaining the objective polymer (C-10). The weight-average molecular weight Mw, as measured in terms of polystyrene by GPC, was 30000 and the molecular weight distribution Mw/Mn was 2.

Production and evaluation of < Friction level type liquid Crystal display element >

[ example 1]

1. Preparation of liquid Crystal Aligning agent (AL-1)

To 100 parts by mass of the polymer (P-1) obtained in synthesis example 2-1, 200 parts by mass of the polymer (C-4) and NMP and Butyl Cellosolve (BC) as solvents were added to prepare a solution having a solvent composition of NMP/BC =50/50 (mass ratio) and a solid content concentration of 4.0 mass%. The solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal aligning agent (AL-1).

2. Evaluation of coatability (film thickness unevenness, pinhole, edge shape and film thickness uniformity)

The prepared liquid crystal aligning agent (AL-1) was applied to a glass substrate using a spinner, prebaked for 1 minute by a hot plate at 80 ℃ and then heated (postbaked) for 30 minutes in an oven at 230 ℃ in which a chamber was replaced with nitrogen gas, thereby forming a coating film having an average film thickness of 0.1. Mu.m. The coating film was observed with a microscope at a magnification of 100 times and 10 times to examine the presence or absence of film thickness unevenness and pinholes. For the evaluation, "good (a)" is set in the case where both the film thickness unevenness and the pinholes are not observed even when observed with a microscope of 100 times, "ok (B)" is set in the case where at least either the film thickness unevenness or the pinholes is observed with a microscope of 100 times but both the film thickness unevenness and the pinholes are not observed with a microscope of 10 times, and "bad (C)" is set in the case where at least either the film thickness unevenness or the pinholes is clearly observed with a microscope of 10 times. In the examples, both film thickness unevenness and pinholes were not observed even with a microscope at a magnification of 100 times, and the coatability was evaluated as "good (a)".

As a more detailed evaluation of the coatability, the coatability of the edge portion (outer edge portion of the formed coating film) was evaluated. The prepared liquid crystal aligning agent (AL-1) was applied to a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a liquid crystal alignment film coating printer, and dried in the same manner as described above. When the shape and flatness of the edge portion are observed, the "good" state is assumed when the edge portion has high linearity and is a flat surface, the "ok" state is assumed when the edge portion has high linearity and has irregularities, and the "bad" state is assumed when the edge portion has irregularities and has a liquid returning from the edge (the linearity is low). As a result, "good (a)" was judged in the example.

Further, the film thickness was measured at 4 points in the surface of the coating film using a stylus type film thickness meter, and the uniformity of the film thickness was evaluated by the deviation of the measured value (difference from the average film thickness δ (δ =0.1 μm in example 1)). For the evaluation, the measured values at 4 points were in the range of the average film thickness δ

In the range of (1), and in the case of obtaining a uniform film thickness, "good (A)" is set, and the average film thickness δ is out of the range

The measured values at 4 points are all in the range of

In the case where the film thickness is within the range of (d), the film thickness is set to "acceptable (B)", and the film thickness is out of the range of the average film thickness δ

And a case where the measured value in the range of (1) is large and the variation in the measured value is large is defined as "failure (C)". As a result, the evaluation of "good (A)" in the examples was conducted.

3. Manufacture of friction horizontal type liquid crystal display element

The prepared liquid crystal aligning agent (AL-1) was coated on the transparent electrode surface of the glass substrate with the transparent electrode including the ITO film using a spinner, and pre-baked for 1 minute using a hot plate at 80 ℃. Thereafter, the resultant was heated at 230 ℃ for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen gas, thereby forming a coating film having a thickness of 0.1 μm. The coating film was rubbed by a rubbing machine having a roll around which rayon cloth was wound at a roll rotation speed of 400rpm, a table moving speed of 3 cm/sec, and a length of Mao Yaru of 0.1 mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, followed by drying in a clean oven at 100 ℃ for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. These series of operations were repeated to produce a pair (2 pieces) of substrates having liquid crystal alignment films.

An epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied to the outer periphery of the surface having the liquid crystal alignment film of 1 of the substrates by screen printing, and then the surfaces of the liquid crystal alignment films were stacked and pressure bonded so as to face each other, and the adhesive was cured. Then, 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 photo-curing adhesive, and polarizing plates were attached to both outer surfaces of the substrates, thereby manufacturing a horizontal alignment type liquid crystal display element.

4. Evaluation of liquid Crystal alignment Properties

In the thus manufactured liquid crystal display element of the rubbing horizontal type, the presence or absence of an abnormal domain (domain) in a light and dark change at the time of turning ON and OFF (ON and OFF) of a voltage of 5V (applied and released) was observed by an optical microscope, the case where no abnormal domain was present was referred to as "a", the case where a part of abnormal domains were present was referred to as "B", and the case where abnormal domains were present as a whole was referred to as "C", and the liquid crystal alignment property was evaluated. As a result, the liquid crystal alignment property in the example was "a".

5. Evaluation of Voltage Holding Ratio (VHR)

The thus produced liquid crystal display element of the rubbing horizontal type was applied with a voltage of 5V for an application time of 60 microseconds and a span of 167 milliseconds, and then a voltage holding ratio after 167 milliseconds from the release of the application was measured. The measurement apparatus was VHR-1 manufactured by TOYO Technical (TOYO). In this case, "a" is used when the voltage holding ratio is 95% or more, "B" is used when 80% or more and less than 95%, and "C" is used when 50% or more and less than 80%, and "D" is used when less than 50%. As a result, the voltage holding ratio in the example was evaluated as "a".

6. Evaluation of Placement resistance

By performing the same operation as in the above "3. Manufacturing of a rubbing horizontal type liquid crystal display element", 2 sets (4 pieces in total) of a pair of substrates having liquid crystal alignment films were prepared.

A pair of substrates (2 sheets) among the prepared substrates and a petri dish containing NMP were placed in a stainless steel tank (vat) (about 20 cm. Times.about 30 cm), the stainless steel tank containing the substrates and the petri dish was covered with aluminum foil, and the substrates were taken out after standing at 25 ℃ for 2 hours. By this operation, a pair of substrates (2 pieces) was exposed to an NMP environment. Thereafter, a liquid crystal display element (referred to as "element a") was manufactured using the pair of substrates by the same method as "manufacturing of a rubbing horizontal type liquid crystal display element" described above.

Further, a liquid crystal display element (referred to as "element B") was manufactured by the same method as in the above "3. Manufacturing of a rubbing horizontal type liquid crystal display element" without exposing the pair of substrates (2 sheets) of the other set to NMP environment.

Then, the pretilt angles of the two liquid crystal display elements were measured by a crystal rotation method using a He — Ne laser according to a method described in non-patent literature (t.j. Scheffer, et al, journal of applied physics (j.appl.phys.) -19 (vo.19.) -p 2013 (1980)), and the difference Δ θ [% ] in the tilt was obtained by the following equation (2).

Δθ＝((θ1-θ2)/θ1)×100…(2)

(in equation (2), θ 1 is the pretilt angle of element B, and θ 2 is the pretilt angle of element A.)

"a" is used when Δ θ is 5% or less, "B" is used when Δ θ is 5% or more and less than 10%, and "C" is used when Δ θ is 10% or more. As a result, the standing resistance in the examples was evaluated as "a".

Examples 5 to 7, 14 to 20 and comparative example 1

Liquid crystal aligning agents were obtained in the same solid content concentrations as in example 1, except that the formulation compositions were changed as shown in table 2 below. Further, the coatability of the liquid crystal aligning agent was evaluated in the same manner as in example 1 using each liquid crystal aligning agent, and a rubbing horizontal type liquid crystal display element was produced in the same manner as in example 1 and subjected to various evaluations. These results are shown in table 3 below. In table 3 below, the observation results of film thickness unevenness and pinholes are shown in the column "coatability", the observation results of edge portions are shown in the column "edge shape", and the evaluation results based on variations in film thickness are shown in the column "film thickness uniformity". In examples 6 and 7, a polymer component and a crosslinking agent were blended. In Table 2, "-" indicates that the polymer in the column was not used.

< production and evaluation of optical FFS type liquid Crystal display element >

[ example 2]

1. Preparation of liquid Crystal Aligning agent (AL-2)

Liquid crystal aligning agent (AL-2) was prepared in the same solvent composition and solid content concentration as in example 1, except that the polymer used was changed to 100 parts by mass of polymer (P-2) and 50 parts by mass of polymer (C-9).

2. Evaluation of coatability

The coatability was evaluated in the same manner as in example 1, except that (AL-2) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in the above examples, the evaluation results of film thickness unevenness, pinholes, edge shape, and film thickness uniformity were all "a".

3. Manufacture of optical FFS type liquid crystal display element

The prepared liquid crystal aligning agent (AL-2) was applied to the surfaces of a glass substrate having a plate electrode, an insulating layer, and a comb-teeth electrode laminated in this order on one surface and an opposing glass substrate having no electrode, respectively, using a spinner, and heated (prebaked) for 1 minute using a hot plate at 80 ℃. Thereafter, the resultant was dried (post-baked) for 30 minutes in an oven at 230 ℃ in which the inside of the chamber was replaced with nitrogen, to form a coating film having an average film thickness of 0.1. Mu.m. Irradiating the surface of the coating film with ultraviolet ray 1,000J/m containing linearly polarized 254nm bright line from the substrate normal direction by using Hg-Xe lamp ² And a liquid crystal alignment film is formed on the substrate by performing photo-alignment treatment.

Then, a pair of substrates having liquid crystal alignment films were subjected to screen printing coating of an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm, with a liquid crystal injection port provided at the edge of the surface on which the liquid crystal alignment films were formed, and then the substrates were stacked and pressure bonded so that the polarization axes at the time of light irradiation were antiparallel to the projection direction of the substrate surface, and the adhesive was thermally cured at 150 ℃ for 1 hour. Then, nematic liquid crystal (MLC-7028 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 epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal cell was manufactured by heating the liquid crystal at 120 ℃ and then gradually cooling the liquid crystal to room temperature. Then, polarizing plates were bonded to both outer surfaces of the substrate so that the polarization directions of the polarizing plates were orthogonal to each other and that an angle of 90 ° was formed between the optical axis of the ultraviolet ray of the liquid crystal alignment film and the projection direction of the substrate surface, thereby producing a liquid crystal display element.

4. Evaluation of liquid Crystal alignment Properties

The produced optical FFS type liquid crystal display device was evaluated for liquid crystal alignment properties in the same manner as in example 1. As a result, the liquid crystal alignment property in the example was "a".

5. Evaluation of Voltage Holding Ratio (VHR)

The voltage holding ratio of the produced optical FFS mode liquid crystal display device was evaluated in the same manner as in example 1. As a result, the voltage holding ratio in the example was evaluated as "a".

6. Evaluation of standing resistance

By performing the same operation as in the above "3. Manufacturing of the optical FFS type liquid crystal display element", 2 sets (4 pieces in total) of the pair of substrates having the liquid crystal alignment film were manufactured. Of these, a pair of substrates was exposed to an NMP atmosphere in the same manner as in example 1, and then a liquid crystal display element (referred to as "element a") was manufactured by the same method as in the above "3. Manufacturing of an optical FFS type liquid crystal display element" using the pair of substrates. Further, a liquid crystal display element (referred to as "element B") was produced by the same method as in the above "production of optical FFS type liquid crystal display element" without exposing the pair of substrates (2 sheets) of the other set to NMP atmosphere. Using the above-mentioned elements a and B, the standing resistance was evaluated in the same manner as in example 1. As a result, the standing resistance in the examples was evaluated as "a".

Comparative example 2

A liquid crystal aligning agent (BL-2) was prepared at the same solid content concentration as in example 1, except that the formulation composition was changed as shown in table 2 below. Further, the coatability of the liquid crystal aligning agent was evaluated using the liquid crystal aligning agent (BL-2) in the same manner as in example 1, and an optical FFS type liquid crystal display device was produced in the same manner as in example 2 and subjected to various evaluations. These results are shown in table 3 below.

Production and evaluation of < VA type liquid Crystal display element

[ example 3]

1. Preparation of liquid Crystal Aligning agent (AL-3)

A liquid crystal aligning agent (AL-3) was prepared in the same solvent composition and solid content concentrations as in example 1, except that the polymer used was changed to 100 parts by mass of polymer (P-3) and 300 parts by mass of polymer (C-6).

2. Evaluation of coatability

The coatability was evaluated in the same manner as in example 1, except that (AL-3) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in the above examples, the evaluation results of film thickness unevenness, pinholes, edge shape, and film thickness uniformity were all "a".

Production of VA type liquid Crystal display element

The prepared liquid crystal aligning agent (AL-3) was coated on the transparent electrode surface of the glass substrate with the transparent electrode including the ITO film using a spinner, and pre-baked for 1 minute using a hot plate at 80 ℃. Thereafter, the resultant was heated at 230 ℃ for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen gas, thereby forming a coating film having a thickness of 0.1 μm. The operation was repeated, thereby producing a pair (2 pieces) of substrates having liquid crystal alignment films.

An epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied to the outer periphery of the surface having the liquid crystal alignment film of 1 of the substrates by screen printing, and then the surfaces of the liquid crystal alignment films were stacked and pressure bonded so as to face each other, and the adhesive was cured. Then, a VA liquid crystal display element was manufactured by filling a negative type liquid crystal (MLC-6608 manufactured by Merck) between a pair of substrates from a liquid crystal injection port, sealing the liquid crystal injection port with an acrylic photo-curing adhesive, and bonding polarizing plates to both outer surfaces of the substrates.

4. Evaluation of liquid Crystal alignment Properties

The VA liquid crystal display device manufactured as described above was evaluated for liquid crystal alignment properties in the same manner as in example 1. As a result, the liquid crystal alignment property in the example is "a".

5. Evaluation of Voltage Holding Ratio (VHR)

The VA liquid crystal display device thus manufactured was evaluated for voltage holding ratio in the same manner as in example 1. As a result, the voltage holding ratio in the example was evaluated as "a".

6. Evaluation of Placement resistance

By performing the same operation as in the above-mentioned "manufacturing of 3.Va mode liquid crystal display element", 2 sets (4 pieces in total) of a pair of substrates having liquid crystal alignment films were prepared. Of these, a pair of substrates was exposed to an NMP atmosphere in the same manner as in example 1, and then a liquid crystal display element (referred to as "element a") was manufactured by the same method as the above "manufacturing of a 3.Va liquid crystal display element" using the pair of substrates. In addition, a liquid crystal display element (referred to as "element B") was manufactured by the same method as that of the above-described "manufacturing of 3.Va mode liquid crystal display element" without exposing a pair of substrates (2 sheets) of the other set to NMP environment. Using the elements a and B, the standing resistance was evaluated in the same manner as in example 1. As a result, the standing resistance in the examples was evaluated as "a".

Example 4 and comparative example 3

Liquid crystal aligning agents were obtained in the same solid content concentrations as in example 1, except that the formulation compositions were changed as shown in table 2 below. Further, using each liquid crystal aligning agent, the coatability of the liquid crystal aligning agent was evaluated in the same manner as in example 1, and a VA-type liquid crystal display element was produced in the same manner as in example 3, and various evaluations were performed. These results are shown in table 3 below.

< production and evaluation of PSA type liquid Crystal display element >

[ example 9]

1. Preparation of liquid Crystal Aligning agent (AL-9)

A liquid crystal aligning agent (AL-9) was prepared in the same solvent composition and solid content concentration as in example 1, except that the polymer used was changed to 200 parts by mass of the polymer (P-6) and 50 parts by mass of the polymer (C-7).

2. Evaluation of coatability

The coatability was evaluated in the same manner as in example 1, except that (AL-9) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in the above examples, the evaluation results of film thickness unevenness, pinholes, edge shape, and film thickness uniformity were all "a".

3. Preparation of liquid Crystal composition

A liquid crystal composition LC1 was obtained by adding 5 mass% of a liquid crystalline compound represented by the following formula (L1-1) and 0.3 mass% of a photopolymerizable compound represented by the following formula (L2-1) to 10g of a nematic liquid crystal (MLC-6608 manufactured by Merck).

[ solution 46]

Production of PSA type liquid Crystal display element

The thus prepared liquid crystal aligning agent (AL-9) was applied to each electrode surface of 2 glass substrates each having a conductive film including an ITO electrode using a liquid crystal alignment film printer (manufactured by japan portrait printing (stock)), and after heating (pre-baking) for 2 minutes on a hot plate at 80 ℃ and removing the solvent, heating (post-baking) for 10 minutes on a hot plate at 230 ℃ was performed to form a coating film having an average film thickness of 0.06 μm. These coating films were ultrasonically cleaned in ultrapure water for 1 minute, and then dried in a clean oven at 100 ℃ for 10 minutes, thereby obtaining a pair of (2) substrates having liquid crystal alignment films. The electrode pattern used is the same kind of pattern as the electrode pattern in the PSA mode.

Then, an epoxy adhesive containing alumina balls having a diameter of 5.5 μm was applied to the outer edge of the surface of one of the pair of substrates having the liquid crystal alignment film, and then the substrates were stacked and pressure bonded so that the liquid crystal alignment film surfaces were opposed to each other, and the adhesive was cured. Then, the prepared liquid crystal group is filled between a pair of substrates from a liquid crystal injection portAfter the compound LC1, the liquid crystal injection port was sealed with an acrylic photo-curing adhesive, thereby producing a liquid crystal cell. Thereafter, an alternating current of 10V at a frequency of 60Hz was applied between the conductive films of the liquid crystal cell and, in a state of liquid crystal driving, 100,000J/m was used as an ultraviolet irradiation apparatus using a metal halide lamp as a light source ² The irradiation amount of (2) is irradiated with ultraviolet rays. The irradiation dose is a value measured by using a light meter that measures with a wavelength of 365nm as a reference. Then, polarizing plates were bonded to both outer surfaces of the substrate so that the polarization directions of the polarizing plates were orthogonal to each other and that an angle of 45 ° was formed between the optical axis of the ultraviolet ray of the liquid crystal alignment film and the projection direction of the substrate surface, thereby producing a liquid crystal display element.

5. Evaluation of liquid Crystal alignment Properties

The PSA liquid crystal display device manufactured as described above was evaluated for liquid crystal alignment properties in the same manner as in example 1. As a result, the liquid crystal alignment property in the example was "a".

6. Evaluation of Voltage Holding Ratio (VHR)

The PSA liquid crystal display device thus produced was evaluated for voltage holding ratio in the same manner as in example 1. As a result, the voltage holding ratio in the example was evaluated as "a".

7. Evaluation of standing resistance

By performing the same operation as in the above-mentioned "manufacturing of 4.psa type liquid crystal display element", 2 sets (4 pieces in total) of a pair of substrates having liquid crystal alignment films were prepared. Of these, a pair of substrates was exposed to an NMP atmosphere in the same manner as in example 1, and then a liquid crystal display element (referred to as "element a") was manufactured by the same method as the "manufacturing of 4.psa type liquid crystal display element" using the pair of substrates. Note that, the liquid crystal display element (referred to as "element B") was manufactured by the same method as in the above "manufacturing of 4.psa type liquid crystal display element" without exposing the pair of substrates (2 sheets) of the other set to NMP environment. Using the elements a and B, the standing resistance was evaluated in the same manner as in example 1. As a result, the standing resistance in the examples was evaluated as "a".

[ example 10, example 11 and comparative example 5]

Liquid crystal aligning agents were obtained in the same solid content concentrations as in example 1, except that the formulation compositions were changed as shown in table 2 below. The obtained liquid crystal aligning agent was used to evaluate the coatability of the liquid crystal aligning agent in the same manner as in example 1, and a PSA-type liquid crystal display device was produced in the same manner as in example 9 and subjected to various evaluations 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.

< production and evaluation of optical vertical liquid Crystal display element >

[ example 8]

1. Preparation of liquid Crystal Aligning agent (AL-8)

A liquid crystal aligning agent (AL-8) was prepared in the same solvent composition and solid content concentrations as in example 1, except that the polymer used was changed to 200 parts by mass of the polymer (P-7) and 50 parts by mass of the polymer (C-8).

2. Evaluation of coatability

The coatability was evaluated in the same manner as in example 1, except that (AL-8) was used instead of (AL-1) as the liquid crystal aligning agent. As a result, in the above examples, the evaluation results of the film thickness unevenness, the pinhole, the edge shape, and the film thickness uniformity were all "a".

3. Manufacture of optical vertical liquid crystal display element

The prepared liquid crystal aligning agent (AL-8) was coated on the transparent electrode surface of the glass substrate with the transparent electrode including the ITO film using a spinner, and pre-baked for 1 minute using a hot plate at 80 ℃. Thereafter, the resultant was heated at 230 ℃ for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen, thereby forming a coating film having a thickness of 0.1. Mu.m. Then, the surface of the coating film was irradiated with 1,000J/m containing 313nm bright lines from a direction inclined at 40 ° from the substrate normal line using an Hg-Xe lamp and a Glan-Taylor prism (glan-taylor prism) ² The polarizing ultraviolet ray of (2) to impart the liquid crystal alignment ability. The same operation was repeated to produce a pair (2 sheets) of substrates having liquid crystal alignment films.

An epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied to the outer periphery of the surface having the liquid crystal alignment film of one of the substrates by screen printing, and then the liquid crystal alignment film surfaces of the pair of substrates were opposed to each other, and pressure-bonded so that the projection directions of the optical axes of ultraviolet rays of the respective substrates on the substrate surfaces became antiparallel to each other, and the adhesive was heat-cured at 150 ℃ for 1 hour. Then, a gap between the substrates was filled with negative type liquid crystal (MLC-6608 manufactured by Merck) from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, the mixture was heated at 130 ℃ and then gradually cooled to room temperature. Then, polarizing plates were bonded to both outer surfaces of the substrate so that the polarization directions of the polarizing plates were orthogonal to each other and that an angle of 45 ° was formed between the optical axis of the ultraviolet ray of the liquid crystal alignment film and the projection direction of the substrate surface, thereby producing a liquid crystal display element.

4. Evaluation of liquid Crystal alignment Properties

The manufactured optical homeotropic liquid crystal display device was evaluated for liquid crystal alignment properties in the same manner as in example 1. As a result, the liquid crystal alignment property in the example is "a".

5. Evaluation of Voltage Holding Ratio (VHR)

The voltage holding ratio of the manufactured optical homeotropic mode liquid crystal display device was evaluated in the same manner as in example 1. As a result, the voltage holding ratio in the example was evaluated as "a".

6. Evaluation of Placement resistance

By performing the same operation as in the above "3. Manufacturing of optical vertical liquid crystal display element", 2 sets (4 pieces in total) of a pair of substrates having liquid crystal alignment films were prepared. Of these, a pair of substrates was exposed to an NMP atmosphere in the same manner as in example 1, and then a liquid crystal display element (referred to as "element a") was manufactured by the same method as in the above "3. Manufacturing of an optical vertical liquid crystal display element" using the pair of substrates. Further, a liquid crystal display element (referred to as "element B") was produced by the same method as in the above "production of optical vertical liquid crystal display element" of "3" without exposing the pair of substrates (2 sheets) of the other set to NMP atmosphere. Using the elements a and B, the standing resistance was evaluated in the same manner as in example 1. As a result, the standing resistance in the examples was evaluated as "a".

Example 12 and example 13, and comparative example 4 and comparative example 6

Liquid crystal aligning agents were obtained in the same solid content concentrations as in example 1, except that the formulation compositions were changed as shown in table 2 below. Further, the coatability of the liquid crystal aligning agent was evaluated in the same manner as in example 1 using each liquid crystal aligning agent, and an optical homeotropic liquid crystal display device was produced in the same manner as in example 8 and subjected to various evaluations. These results are shown in table 3 below. In examples 12 and 13, polymer components and a crosslinking agent were blended.

[ Table 2]

[ Table 3]

Evaluation process

Coatability

Edge shape

Uniformity of film thickness

Liquid crystal alignmentProperty of (2)

VHR

Standing property

Example 1

Friction of

A

Example 2

Light FFS

A

Example 3

VA

A

Example 4

VA

A

Example 5

Friction of

A

Example 6

Friction by friction

A

Example 7

Friction of

A

Example 8

Light VA

A

Example 9

PSA

A

Example 10

PSA

A

Example 11

PSA

A

Example 12

Optical VA

A

Example 13

Light VA

A

Example 14

Friction by friction

A

Example 15

Friction of

A

Example 16

Friction by friction

A

Example 17

Friction of

A

Example 18

Friction of

A

Example 19

Friction by friction

A

Example 20

Friction of

A

Comparative example 1

Friction of

A

B

A

Comparative example 2

Light FFS

A

B

A

C

A

Comparative example 3

VA

A

B

A

Comparative example 4

Light VA

A

B

A

B

Comparative example 5

PSA

A

B

ComparisonExample 6

Light VA

A

B

A

B

[ examples 21 to 23]

Liquid crystal aligning agents (AL-21) to (AL-23) were 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) in example 9. Further, the coatability of the liquid crystal aligning agent was evaluated in the same manner as in example 1 except that the liquid crystal aligning agent to be used was changed and the post-baking temperature was changed from 230 ℃ to 200 ℃, and a PSA-type liquid crystal display element was produced in the same manner as in example 9 and subjected to various evaluations. These results are shown in table 5 below.

Comparative examples 7 to 9

Liquid crystal aligning agents (BL-7) to (BL-9) were prepared in the same manner as in examples 21 to 23 except that in examples 21 to 23, 300 parts by mass of the polymer (C-5) was used in place of 200 parts by mass of the polymer (P-6) (see Table 4 below). Further, the coatability of the liquid crystal aligning agent was evaluated in the same manner as in example 1 except that the liquid crystal aligning agent to be used was changed and the post-baking temperature was changed from 230 ℃ to 200 ℃, and a PSA-type liquid crystal display element was produced in the same manner as in example 9 and subjected to various evaluations. These results are shown in table 5 below. In table 5, it is observed that the solubility of the polymer in the solvent is insufficient, and thus, it is represented by "-" in the items that could not be evaluated (the same applies to comparative examples 10 and 11).

[ example 24]

A liquid crystal aligning agent (AL-24) was prepared in the same manner as in example 8, except that in example 8, the solvent composition was changed as shown in table 4 below instead of NMP/BC =50/50 (mass ratio). In addition, the coatability of the liquid crystal aligning agent was evaluated in the same manner as in example 1 except that the obtained liquid crystal aligning agent was used and that the post-baking temperature was changed from 230 ℃ to 200 ℃, and a light VA liquid crystal display device was manufactured in the same manner as in example 8 and subjected to various evaluations. The results are shown in table 5 below.

Comparative example 10

A liquid crystal aligning agent (BL-10) was prepared in the same manner as in example 24, except that in example 24, the polymer composition was changed as shown in Table 4 below. In addition, the coatability of the liquid crystal aligning agent was evaluated in the same manner as in example 1 except that the obtained liquid crystal aligning agent was used and that the post-baking temperature was changed from 230 ℃ to 200 ℃, and a light VA liquid crystal display device was manufactured in the same manner as in example 8 and subjected to various evaluations. The results are shown in table 5 below.

[ example 25]

A liquid crystal aligning agent (AL-25) was prepared in the same manner as in example 2, except that the solvent composition was changed as shown in table 4 below instead of NMP/BC =50/50 (mass ratio) in example 2. In addition, the coatability of the liquid crystal aligning agent was evaluated in the same manner as in example 1 except that the obtained liquid crystal aligning agent was used and that the post-baking temperature was changed from 230 ℃ to 200 ℃, and an optical FFS type liquid crystal display element was manufactured in the same manner as in example 2 and subjected to various evaluations. The results are shown in table 5 below.

Comparative example 11

A liquid crystal aligning agent (BL-11) was prepared in the same manner as in example 25, except that in example 25, the polymer composition was changed as shown in Table 4 below. In addition, the coatability of the liquid crystal aligning agent was evaluated in the same manner as in example 1 except that the obtained liquid crystal aligning agent was used and that the post-baking temperature was changed from 230 ℃ to 200 ℃, and an optical FFS type liquid crystal display element was manufactured in the same manner as in example 2 and subjected to various evaluations. The results are shown in table 5 below.

[ Table 4]

In table 4, the numerical value of the solvent composition represents a mass ratio (mass%) with respect to the total amount of the solvent used in the preparation of the liquid crystal aligning agent. The solvent is abbreviated as follows.

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 using the liquid crystal aligning agent containing the polyvinylamine, the coatability (including the edge shape and the film thickness uniformity) was evaluated as "a". In examples 1 to 20, the liquid crystal alignment properties and the voltage holding ratios of the obtained liquid crystal display devices were also good, and the evaluation was "a" in all examples.

Further, as shown in table 4, the solubility of the polyalkyleneamine was sufficiently high even in the solvent composition not containing the amide-based polar solvent (NMP), and good results were obtained in the evaluation of "a" or "B" in coatability (including edge shape and film thickness uniformity), liquid crystal alignment property, and voltage holding ratio (examples 21 to 25). From the above results, it can be said that the dye having poor heat resistance can be suitably used even in the case of using the dye having poor heat resistance as a colorant to form a color filter layer of a liquid crystal element.

On the other hand, in comparative examples using a liquid crystal aligning agent containing no polyvinylamine as a polymer component, in comparative examples 1 to 4 and 6 in examples using an amide-based polar solvent (NMP), the edge shape was evaluated as "B" and was inferior to that of the examples. Further, comparative example 1 also evaluated the film thickness uniformity as "B". In comparative example 2, the voltage holding ratio was evaluated as "C", and in comparative example 4, as "B". As shown in table 5, in the comparative examples, the solubility was insufficient for the solvent composition containing no amide-based polar solvent (NMP), and no good results were obtained (comparative examples 7 to 11).

These results show that the liquid crystal aligning agent containing the polyallylamine is excellent in coatability, liquid crystal alignment properties, and voltage holding ratio. Further, the liquid crystal aligning agent containing the polyvinylamine is also excellent in standing resistance.

Claims

1. A liquid crystal aligning agent contains a polyalkyleneamine, wherein the polyalkyleneamine is a reaction product of an α, β -unsaturated compound having one of two or more partial structures represented by the following formula (1) or formula (2) in one molecule and a diamine compound;

in the formulae (1) and (2), X ¹ Is carbonyl or sulfonyl, L ¹ A leaving group which is removed by a reaction with a diamine compound, L ² Is an oxygen or sulfur atom, R ⁵ Hydrogen atom or monovalent organic group having 1 or more carbon atoms; multiple X in one molecule ¹ 、R ⁵ 、L ¹ And L ² Each independently have the X ¹ 、R ⁵ 、L ¹ And L ² The definition of (1); "" indicates a bond.

2. The liquid crystal aligning agent according to claim 1, wherein the α, β -unsaturated compound is at least one selected from the group consisting of a compound having one of two or more partial structures represented by the following formulae (4-1) to (4-4) respectively in one molecule and a tautomer thereof, a compound represented by the following formula (5) and a tautomer thereof, and a compound represented by the following formula (6) and a tautomer thereof;

in the formulae (4-1) to (4-4), the formulae (5) and (6), X ¹ Is carbonyl or sulfonyl, R ¹ ～R ⁵ And R ⁷ ～R ¹⁰ Each independently represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, 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 is a radical of an alcohol ¹ Is a leaving group which is removed by reaction with a diamine compound, L ² Is an oxygen atom or a sulfur atom; multiple X in one molecule ¹ 、R ¹ ～R ¹⁰ 、L ¹ And L ² Each independently have the X ¹ 、R ¹ ～R ¹⁰ 、L ¹ And L ² The definition of (1); "" indicates a bond.

3. The liquid crystal aligning agent according to claim 1 or 2, wherein the polyalkene amine has a partial structure derived from at least one diamine compound selected from the group consisting of compounds represented by the following formulae (d-1) to (d-4), respectively;

in the formula (d-1), X ¹¹ And X ¹² Independently represents a single bond, -O-, -S-, -OCO-or-COO-, Y is ¹¹ Is an oxygen atom or a sulfur atom, R ¹¹ And R ¹² Each independently is an alkanediyl group having 1 to 3 carbon atoms; n1 is 0 or 1, n2 and n3 are integers satisfying n2+ n3=2 in the case of n1=0, and n2 and n3 are n2= n3=1 in the case of n1= 1; in the formula (d-2), X ¹³ Is a single bond, -O-or-S-, and m1 is an integer of 0 to 3; m2 is an integer of 1 to 12 when m1=0, and m2 is an integer of 1 to 3 when m1 ism2=2; in the formula (d-3), X ¹⁴ And X ¹⁵ Are respectively and 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 an alkanediyl group having 1 to 3 carbon atoms; a is 0 or 1,b is an integer of 0-2, c is an integer of 1-20, and k is 0 or 1; wherein a and b do not become 0 at the same time; in the formula (d-4), A ¹² Represents a single bond, an alkanediyl group having 1 to 12 carbon atoms or a fluoroalkanediyl group having 1 to 6 carbon atoms, A ¹³ <xnotran> -O-, -COO-, -OCO-, -NHCO-, -CONH- -CO-, A </xnotran> ¹⁴ Represents a monovalent organic group having a steroid skeleton.

4. The liquid crystal aligning agent according to claim 1 or 2, wherein the polyalkyleneamine has a partial structure derived from a diamine compound having at least one selected from the group consisting of a secondary amine or a tertiary amine structure represented by the following formula (9) and a nitrogen-containing heterocyclic structure;

in the formula (9), R ⁵¹ And R ⁵² Each independently is a divalent aromatic ring radical, R ⁵³ Hydrogen atom or monovalent organic group having 1 or more carbon atoms; "" indicates a bond.

5. The liquid crystal aligning agent according to claim 1 or 2, wherein the polyalkyleneamine has a partial structure derived from a diamine compound having a carboxyl group and a partial structure derived from a diamine compound having a nitrogen-containing aromatic heterocycle.

6. The liquid crystal aligning agent according to claim 1 or 2, wherein the polyalkene amine has a partial structure derived from a diamine compound having a group represented by the following formula (7-1) or formula (7-2);

in the formulae (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, R ²¹ ～R ²³ Each independently a hydrogen atom or a monovalent organic group having 1 or more carbon atoms; m is an integer of 0 to 6; "" indicates a bond.

7. The liquid crystal aligning agent according to claim 1 or 2, wherein the polyalkyleneamine has a partial structure derived from a diamine compound represented by the following formula (8);

in the formula (8), A ³¹ Is a divalent aromatic ring radical, R ³¹ Is alkanediyl having 1 to 5 carbon atoms, R ³² Is a monovalent hydrocarbon group having 1 to 4 carbon atoms.

8. The liquid crystal aligning agent according to claim 1 or 2, further comprising a compound having at least one crosslinkable group selected from the group consisting of a cyclic carbonate group, an epoxy group, an isocyanate group, a blocked isocyanate group, an oxetanyl group, a trialkoxysilane group, and a polymerizable unsaturated bonding group.

9. The liquid crystal aligning agent according to claim 1 or 2, which comprises an organic solvent having a boiling point of 180 ℃ or lower at 1 atm, the organic solvent being at least one selected from the group consisting of compounds represented by the following formulae (E-1) to (E-5);

in the formula (E-1), R ⁴¹ Is alkyl with 1 to 4 carbon atoms or R ⁴⁰ -CO-, wherein R ⁴⁰ Is alkyl with 1 to 3 carbon atoms; r ⁴² Is alkanediyl having 1 to 4 carbon atoms or- (R) ⁴⁷ -O)r-R ⁴⁸ -, in which R ⁴⁷ And R ⁴⁸ Are respectively provided withIndependently an alkanediyl group having 2 or 3 carbon atoms, r is an integer of 1 to 4; r ⁴³ Hydrogen atom or alkyl group having 1 to 4 carbon atoms;

in the formula (E-2), R ⁴⁴ Is an alkanediyl group having 1 to 4 carbon atoms;

in the formula (E-3), R ⁴⁵ And R ⁴⁶ Each independently is an alkyl group having 1 to 8 carbon atoms;

R ⁴⁹ -R ⁵⁰ -OH (E-4)

in the formula (E-4), R ⁴⁹ Is a hydrogen atom or a hydroxyl group, in R ⁴⁹ In the case of a hydrogen atom, R ⁵⁰ Is a divalent hydrocarbon group having 1 to 9 carbon atoms or a divalent group having-CO-between carbon-carbon bonds of a chain hydrocarbon group having 3 to 9 carbon atoms, wherein R is ⁴⁹ In the case of hydroxy, R ⁵⁰ A divalent hydrocarbon group having 1 to 9 carbon atoms or a divalent group having an oxygen atom between carbon-carbon bonds of a hydrocarbon group having 2 to 9 carbon atoms;

R ⁵¹ -COO-R ⁵² (E-5)

in the formula (E-5), R ⁵¹ R is a C1-6 monovalent hydrocarbon group, a monovalent group in which a hydrogen atom of a C1-6 hydrocarbon group is substituted with a hydroxyl group, or a monovalent group having-CO-between carbon-carbon bonds of a C2-6 hydrocarbon group ⁵² Is a monovalent hydrocarbon group having 1 to 6 carbon atoms.

10. The liquid crystal aligning agent according to claim 1 or 2, further comprising a polymer different from the polyalkene amine.

11. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 10.

12. A liquid crystal cell comprising the liquid crystal alignment film according to claim 11.

13. The liquid crystal element according to claim 12, comprising a color filter layer containing a dye.

14. A method of manufacturing a liquid crystal element, comprising:

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 aligning agent according to any one of claims 1 to 10;

a step of configuring a liquid crystal cell by disposing a pair of substrates on which the coating films are formed, in opposition to each other with the coating films facing each other through a liquid crystal layer; and

and irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates.