阅读说明：本技术 液晶取向剂、液晶取向膜、液晶元件及液晶元件的制造方法 (Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, and method for producing liquid crystal element ) 是由 冈田敬 村上嘉崇 于 2018-12-19 设计创作，主要内容包括：使液晶取向剂中含有聚烯胺作为聚合体成分。在一个形态中,聚烯胺为在一分子内具有两个以上的式(1)或式(2)所表示的部分结构的一种的α,β-不饱和化合物、与二胺化合物的反应产物。式(1)及式(2)中,X<Sup>1</Sup>为羰基或磺酰基,L<Sup>1</Sup>为通过与二胺化合物的反应而脱离的脱离基,L<Sup>2</Sup>为氧原子或硫原子,R<Sup>5</Sup>为氢原子或碳数1以上的1价有机基。<Image he="212" wi="700" file="DDA0002521636840000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(In one embodiment, the polyvinylamine is a reaction product of an α -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, and in the formulae (1) and (2), X is represented by 1 Is carbonyl or sulfonyl, L 1 L is a leaving group to be removed by reaction with a diamine compound 2 Is an oxygen atom or a sulfur atom, R 5 Is hydrogen atom or C1 or more organic radical.)

1. A liquid crystal aligning agent contains a polyvinylamine.

2. The liquid crystal aligning agent according to claim 1, wherein the polyalkyleneamine is a reaction product of an α -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;

[ solution 1]

(in the formulae (1) and (2), X¹Is carbonyl or sulfonyl, L¹L is a leaving group to be removed by reaction with a diamine compound²Is an oxygen atom or a sulfur atom, R⁵Hydrogen atom or monovalent organic group having 1 or more carbon atoms; multiple X in one molecule¹、R⁵、L¹And L²Each independently has the definition; ") represents a bond.

3. The liquid crystal aligning agent according to claim 2, wherein the α -unsaturated compound is at least one selected from the group consisting of a compound having two or more partial structures represented by each of 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);

[ solution 2]

In (formulae (4-1) to (4-4), formulae (5) and (6), X¹Is carbonyl or sulfonyl, R¹～R⁵And R⁷～R¹⁰Each independently represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, R⁶Is an alkanediyl group having 2 to 5 carbon atoms or a carbon-carbon bond in the alkanediyl grouphaving-O-or-S-groups in between L¹L is a leaving group to be removed by reaction with a diamine compound²Is an oxygen atom or a sulfur atom; multiple X in one molecule¹、R¹～R¹⁰、L¹And L²Each independently has the definition; ") represents a bond.

4. The liquid crystal aligning agent according to any one of claims 1 to 3, 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;

[ solution 3]

(in the formula (d-1), X¹¹And X¹²Each independently being a single bond, -O-, -S-, -OCO-or-COO-, Y¹¹Is an oxygen atom or a sulfur atom, R¹¹And R¹²Each 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 where n1 is 0, and n2 and n3 are n2 ═ n3 ═ 1 in the case where n1 is 1; in the formula (d-2), X¹³Is a single bond, -O-or-S-, and m1 is an integer of 0-3; when m1 is 0, m2 is an integer of 1 to 12, and when m1 is an integer of 1 to 3, m2 is m2 is 2; in the formula (d-3), X¹⁴And X¹⁵Each independently is a single bond, -O-, -COO-or-OCO-, R¹⁷Is an alkanediyl group having 1 to 3 carbon atoms, A¹¹A 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), A¹²Represents a single bond, an alkanediyl group having 1 to 12 carbon atoms or a fluoroalkanediyl group having 1 to 6 carbon atoms, A¹³represents-O-, -COO-, -OCO-, -NHCO-, -CONH-or-CO-, A¹⁴Represents a monovalent organic group having a steroid skeleton).

5. The liquid crystal aligning agent according to any one of claims 1 to 4, 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;

[ solution 4]

(in the formula (9), R⁵¹And R⁵²Each independently is a divalent aromatic ring radical, R⁵³Hydrogen atom or monovalent organic group having 1 or more carbon atoms; ") represents a bond.

6. The liquid crystal aligning agent according to any one of claims 1 to 5, 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.

7. The liquid crystal aligning agent according to any one of claims 1 to 6, 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);

[ solution 5]

(in the formulae (7-1) and (7-2), A²¹Is a single bond or a divalent organic group having 1 or more carbon atoms, Y¹Is a protecting group, R²¹～R²³Each independently represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms; m is an integer of 0 to 6; ") represents a bond.

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

[ solution 6]

(in the formula (8), A³¹Is a divalent aromatic ring radical, R³¹Is C1-C5 alkanediyl, R³²A C1-4 monovalent hydrocarbon group).

9. The liquid crystal aligning agent according to any one of claims 1 to 8, 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.

10. The liquid crystal aligning agent according to any one of claims 1 to 9, which contains an organic solvent having a boiling point of 180 ℃ or less 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), respectively;

[ solution 7]

(in the formula (E-1), R⁴¹Is C1-4 alkyl or R⁴⁰-CO- (wherein, R⁴⁰An alkyl group having 1 to 3 carbon atoms); r⁴²Is C1-4 alkanediyl or- (R)⁴⁷-O)r-R⁴⁸- (wherein, R)⁴⁷And R⁴⁸Each independently is an alkanediyl group having 2 or 3 carbon atoms, and r is an integer of 1 to 4); r⁴³Hydrogen atom or C1-4 alkyl group);

[ solution 8]

(in the formula (E-2), R⁴⁴An alkanediyl group having 1 to 4 carbon atoms);

[ solution 9]

(in the formula (E-3), R⁴⁵And R⁴⁶Each independently an alkyl group having 1 to 8 carbon atoms);

[ solution 10]

R⁴⁹-R⁵⁰-OH (E-4)

(in the formula (E-4), R⁴⁹Is a hydrogen atom or a hydroxyl group, in R⁴⁹In the case of a hydrogen atom, R⁵⁰Is 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 is⁴⁹In the case of hydroxy, R⁵⁰A 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 11]

R⁵¹-COO-R⁵²(E-5)

(in the formula (E-5), R⁵¹R 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 group⁵²A C1-6 monovalent hydrocarbon group).

11. The liquid crystal aligning agent according to any one of claims 1 to 10, further comprising a polymer different from the polyalkene amine.

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

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

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

15. 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 11;

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.

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).

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, a large-screen and high-definition liquid crystal television is mainly used, and a demand for a high-quality liquid crystal panel has been further increased by the spread of small-sized display terminals such as a smart phone and a tablet personal computer (tablet PC). 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 element 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. In addition, the structure may not necessarily be composed of only an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in a part thereof.

Liquid crystal aligning agent

The liquid crystal aligning agent of the present disclosure contains a polyalkyleneamine 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 contains a polyalkyleneaminoketone, a polyalkyleneamino ester, a polyalkyleneaminonitrile, and a polyalkyleneaminosulfonyl group, and in terms of the availability of monomers or the ease of synthesis, the polyalkyleneamine used is preferably a reaction product of an α -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.

[ solution 1]

(in the formulae (1) and (2), X¹Is carbonyl or sulfonyl, L¹L is a leaving group to be removed by reaction with a diamine compound²Is an oxygen atom or a sulfur atom, R⁵Is hydrogen atom or C1 or more monovalent organic group. Multiple X in one molecule¹、R⁵、L¹And L²Each independently having the definition. "+" indicates a bond)

(α -unsaturated Compound)

In the above formulae (1) and (2), X is a high degree of freedom in the selection of the monomer¹Preferably a carbonyl group.

AsL of the formula (1)¹The 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 part of the heterocyclic ring, and the like, L¹In 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 -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), wherein the structures represented by the following formulae (4-1), (4-2), (4-4), (5), and (6) correspond to the structure having the partial structure represented by the formula (1), and the structure represented by the following formula (4-3) corresponds to the structure having the partial structure represented by the formula (2).

[ solution 2]

In (formulae (4-1) to (4-4), formulae (5) and (6), X¹Is carbonyl or sulfonyl, R¹～R⁵And R⁷～R¹⁰Each independently represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, R⁶L is C2-5 alkanediyl or a group having-O-or-S-between carbon-carbon bonds of the alkanediyl¹L is a leaving group to be removed by reaction with a diamine compound²Is an oxygen atom or a sulfur atom. Multiple X in one molecule¹、R¹～R¹⁰、L¹And L²Respectively and independently haveThere is the definition. "+" indicates a bond)

L in the formulae (4-1), (4-2), (4-4) and (5)¹Specific example of (3), L in the above formula (1) can be applied¹And (4) description.

R¹～R⁵And R⁷～R¹⁰The monovalent organic group is preferably a monovalent alkyl group, alkoxy group or cycloalkyl group having 1 to 20 carbon atoms.

α -unsaturated compound having 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, more preferably 2, and specifically, compounds represented by the formulae (M-1) to (M-4) are preferably used.

[ solution 3]

In (formulae (M-1) to (M-4), B¹～B⁴Is a single bond or a divalent organic group. X¹、R¹～R⁶、L¹And L²The same as the above formulae (4-1) to (4-4)

In the formulae (M-1) to (M-4), B is¹～B⁴Examples of the divalent organic group of (3) include: a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent group having-O-, -S-, -NH-, or the like, between carbon-carbon bonds of the hydrocarbon group, and the like. In B¹～B⁴In the case of a divalent organic radical, B¹～B⁴Preferably, 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 -unsaturated compound include compounds represented by the following formulae (A-1) to (A-14), respectively, and α -unsaturated compounds may be used singly or in combination of two or more kinds in the synthesis of the polyalkyleneamine.

[ solution 4]

[ solution 5]

In the present specification, in the "α -unsaturated compound", with respect to a compound showing tautomerism, the meaning of including a tautomer thereof is as follows.e., L of the formula (4-1)¹The partial structure which is a hydroxyl group is interconverted with the partial structure represented by the following formula (4-1A), and when synthesizing a polyvinylamine, a compound having two or more partial structures represented by the following formula (4-1A) in one molecule is allowed to exist L of the formula (4-2)¹Similarly, the partial structure of the hydroxyl group and the compound represented by the above formula (6) are also converted into each other with the partial structure represented by the following formula (4-2A) and the compound represented by the following formula (6A). Hereinafter, tautomers of the compounds represented by the formulae (A-5), (A-9) and (A-10), respectively, are shown.

[ solution 6]

[ solution 7]

In the exemplified α -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, the compounds represented by the formula (A-10) correspond to compounds having two or more partial structures represented by the formula (4-2) in one molecule, the compounds represented by the formula (A-13) correspond to compounds having two or more partial structures represented by the formula (4-3) in one molecule, 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 compounds represented by the formula (5), and the compounds represented by the formulae (A-5) and (A-6) correspond to compounds represented by the formula (A-6) and (A-3) in one molecule, respectively.

(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), X¹¹And X¹²Each independently being a single bond, -O-, -S-, -OCO-or-COO-, Y¹¹Is an oxygen atom or a sulfur atom, R¹¹And R¹²Each independently 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 where n1 is 0, and n2 and n3 are n2 ═ n3 ═ 1 in the case where n1 is 1. In the formula (d-2), X¹³Is a single bond, -O-or-S-, and m1 is an integer of 0-3. When m1 is 0, m2 is an integer of 1 to 12, and when m1 is an integer of 1 to 3, m2 is m2 is 2. In the formula (d-3), X¹⁴And X¹⁵Each independently is a single bond, -O-, -COO-or-OCO-, R¹⁷Is an alkanediyl group having 1 to 3 carbon atoms, A¹¹Is 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), A¹²Represents a single bond, an alkanediyl group having 1 to 12 carbon atoms or a fluoroalkanediyl group having 1 to 6 carbon atoms, A¹³represents-O-, -COO-, -OCO-, -NHCO-, -CONH-or-CO-, A¹⁴Represents a monovalent organic group having a steroid skeleton)

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

In the formula (d-1), as R¹¹And R¹²Examples of the C1-3 alkanediyl group 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 preferable.

X¹¹And X¹²Preferably a single bond, -O-or-S-.

Y¹¹Is an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

When n1 is 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 to the different benzene 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. In the case where there are two primary amino groups on the benzene ring, the bonding position to other groups includes, for example, the 2, 4-position and the 2, 5-position, and among these, the 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, 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), compounds in which n1 is 0 include, for example, 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 (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-aminophenylethyl) urea, 1, 3-bis (2- (2-aminobenzoyloxy) ethyl) urea, 1, 3-bis (3- (2-aminobenzoyloxy) propyl) urea and the like. 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), X¹³Is a single bond, -O-or-S-, preferably a single bond or-O-.

When m1 is 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 the application of the liquid crystal alignment film, from the viewpoint of maintaining good liquid crystal alignment properties and improving rubbing resistance, it is preferable that m1 be 0, and from the viewpoint of reducing the pretilt angle of the liquid crystal molecules, m1 be an integer of 1 to 3.

The bonding position of the primary amino group on the benzene ring is not particularly limited, and each primary amino group is preferably in the 3-position or 4-position, more preferably in the 4-position, with respect to other groups. Furthermore, 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.

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-aminophenoxy) heptane, 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 "-X¹⁴-(R¹⁷-X¹⁵)_kThe divalent group represented by- "is preferably an alkanediyl group having 1 to 3 carbon atoms, an-O-, -COO-group or an-O-C group₂H₄-O- (wherein the bond with the "-" is bonded to the diaminophenyl).

radical-C_cH_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 "X⁴"instead is the 2, 4-or 3, 5-position, more preferably the 2, 4-position. Furthermore, 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.

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), respectively.

[ solution 9]

[ solution 10]

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

A as said formula (d-4)¹²The C1-12 alkanediyl group in (1) is preferably a C1-4 alkanediyl group, and more preferably a methylene group, an ethylene group, a 1, 3-propanediyl group, or a 1, 4-butanediyl group. The fluorinated alkanediyl group having 1 to 6 carbon atoms is preferably a perfluoroalkanediyl group having 1 to 4 carbon atoms, and more preferably-CF₂-, perfluoroethylene, 1, 3-perfluoropropanediyl and 1, 4-perfluorobutanediyl.

A¹³preferably-O-.

So-called A¹⁴The 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 preferable example of the compound represented by the formula (d-4), in order to provide a high pretilt angle to a coating film in the use of a liquid crystal alignment film, it is preferable to use a compound selected from the group consisting of 1-cholesteryloxymethyl-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-diaminophenylmethoxy) -1, 1-difluoromethoxy) -4, 4-dimethylcholestane, hexadecyl 3- ((2, 4-diaminophenyl) methoxy) cholane-24-oate, stearyl 3- (2, 4-diaminophenylmethoxy) cholane-24-oate, stearyl 3- (1- (2, 4-diaminophenyl) -1, 1-difluoromethoxy) cholane-24-oate [ acid ] stearate, stearyl 3- (3, 5-diaminophenylmethoxy) cholane-24-oate, 1-cholesteryloxy-2, 4-diaminobenzene, cholesteryl 3, 5-diaminobenzoate, cholestanyl 1-cholanyl-2, 4-diaminobenzene and cholestanyl 3, 5-diaminobenzoate, 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, cholesterol ester of 3, 5-diaminobenzoate, 1-cholesteryloxy-2, 4-diaminobenzene, and cholesteryl ester of 3, 5-diaminobenzoate.

The ratio of the specific diamine to be used in the synthesis of the polyalkyleneamine can be arbitrarily set according to the diamine compound to be used. When the compound represented by the above formula (d-1) is used, the amount thereof to be used is preferably 1 mol% or more, more preferably 3 mol% or more, based on the total amount of the diamines. 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 proportion of the compound used (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-mentioned 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), R²⁰Is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, Z¹Is 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 the condition that r7+ r8 is 2. Wherein r3+ r5+ r7 ≦ 5, and r4+ r6+ r8 ≦ 5. In which a plurality of R are present²⁰In the case of (2), these R' s²⁰Independently of the definition)

As R, there may be mentioned the formulae (d-5-1) and (d-5-2)²⁰Examples of the alkyl group having 1 to 10 carbon atoms in (A) 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 Z¹Examples 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 compounds represented by the formula (d-5-1) such as 3, 5-diaminobenzoic acid, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, and the like; examples of the compound represented by the formula (d-5-2) include 4,4' -diaminobiphenyl-3, 3' -dicarboxylic acid, 4' -diaminobiphenyl-2, 2' -dicarboxylic acid, 3' -diaminobiphenyl-4, 4' -dicarboxylic acid, 3' -diaminobiphenyl-2, 4' -dicarboxylic acid, 4' -diaminodiphenylmethane-3, 3' -dicarboxylic acid, 4' -diaminobiphenyl-3-carboxylic acid, 4' -diaminodiphenylmethane-3-carboxylic acid, 4' -diaminodiphenylethane-3, 3' -dicarboxylic acid, 4' -diaminodiphenylethane-3-carboxylic acid, and mixtures thereof, 4,4' -diaminodiphenyl ether-3, 3' -dicarboxylic acid, 4' -diaminodiphenyl ether-3-carboxylic acid, and the like. Further, as the carboxyl group-containing diamine, one kind of these may be used alone or two or more kinds may be used.

When the carboxyl group-containing diamine 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 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 included in 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, 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 when the polyalkyleneamine is used in combination with other polymers. 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), A²¹Is a single bond or a divalent organic group having 1 or more carbon atoms, Y¹Is a protecting group, R²¹～R²³Each independently represents 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), Y¹The 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: t-butoxycarbonyl, benzyloxycarbonyl, 1-dimethyl-2-haloethyloxycarbonyl, 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.

R²¹And R²²The monovalent organic group(s) is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably carbonA number of 1 to 10 alkyl or cycloalkyl groups.

R²³The monovalent organic group (C) is preferably a C1-10 monovalent alkyl group or a protecting group. As A²¹Examples of the divalent organic group of (3) include: divalent hydrocarbon groups, groups having-O-, -CO-, -COO-, -NH-between carbon-carbon bonds of the hydrocarbon groups, and the like. A. the²¹Preferably 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 a 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), R⁵¹And R⁵²Each independently is a divalent aromatic ring radical, R⁵³Is hydrogen atom or C1 or more monovalent organic group. "+" indicates a bond)

In the formula (9), as R⁵¹And R⁵²Examples 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. R⁵¹And R⁵²Particularly preferred is phenylene.

As R⁵³Examples 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. R⁵³Preferably 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 polyalkyleneamine, a diamine compound represented by the following formula (8) (hereinafter, also referred to as "secondary amino group-containing diamine compound") 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), A³¹Is a divalent aromatic ring radical, R³¹Is C1-C5 alkanediyl, R³²A monovalent hydrocarbon group having 1 to 4 carbon atoms)

In the above formula (8), as A³¹Examples 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, an anthracene ring, etc. A. the³¹Preferably phenylene.

R³¹The alkanediyl group (b) may be linear or branched, and examples thereof include: methylene, ethylene, propanediyl, butanediyl and pentanediyl.

As R³²Examples of the monovalent hydrocarbon group of (2) include: alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; alkylene groups such as vinyl and propenyl. R³²Preferably 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.

[ solution 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: aliphatic diamines such as 1, 3-propanediamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine;

1, 4-diaminocyclohexane, 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' -diaminodiphenylsulfide, 2' -dimethyl-4, 4' -diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 4' - (p-phenylenediisopropylidene) dianiline, 1, 4-bis (4-aminophenoxy) benzene, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-inden-5-amine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diamino-N, N-diallylaniline, N-diphenylsulfide, N-methyl-4, 4' -diaminobiphenyl, N-bis (4-amino-4-phenyl) aniline, N-bis (4-amino-phenyl) aniline, N, 2, 5-diamino-N, N-diallylaniline, the following formulae (d-10-1) to (d-10-5)

[ solution 21]

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

diaminoorganosiloxanes such as 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, and the 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)

In the synthesis of the polyalkyleneamine, other monomers than the α -unsaturated compound and the diamine compound may be used, and examples of the other monomers include tetracarboxylic acid dianhydride, tetracarboxylic acid diester dihalide, and dilactone compound.

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-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 5- (2, 5-dioxotetrahydrofuran-3-yl) -8-methyl-3 a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 2,4,6, 8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, cyclopentanetetracarboxylic dianhydride, Alicyclic tetracarboxylic dianhydrides such as cyclohexanetetracarboxylic dianhydride;

and aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, p-phenylenebis (trimellitic acid monoester anhydride), ethyleneglycol bis (trimellitic acid anhydride), and 1, 3-propanediol bis (trimellitic acid anhydride), and tetracarboxylic dianhydrides described in japanese patent application laid-open 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 term "α -unsaturated compound and diamine compound reaction product" means that α -unsaturated compound and diamine compound, and other monomers except α -unsaturated compound and diamine compound are allowed to be used as monomers used for synthesis, as long as the effect of the present disclosure is not impaired, and the ratio of the other monomers (preferably tetracarboxylic dianhydride) to be used is preferably 40 mol% or less, more preferably 30 mol% or less, relative to the total amount of the monomers used for the synthesis of 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, and examples of the organic solvent used in the reaction include aprotic polar solvents (such as N-methyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide), phenolic solvents (such as phenol and cresol), alcohols, ketones, esters, ethers, halogenated hydrocarbons, and the ratio of the organic solvent is preferably from 0.1 to 50% by mass relative to the total amount of the reaction solution by the total amount of α -unsaturated compound and diamine compound, and the reaction temperature in this case is preferably from-20 to 150 ℃ and the reaction time is preferably from 0.1 to 24 hours.

In the case where a reaction solution in which the polyalkyleneamine 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 a known separation method may be used to separate the polyalkyleneamine contained in the reaction solution and then supply the separated polyalkyleneamine to the production of the liquid crystal aligning agent, for example, 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 in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) 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, α -unsaturated compounds represented by the following formulae (M-1) to (M-4), formula (5) or formula (6), and "NH" are shown below₂-Y²-NH₂"reaction scheme of the compound represented by the formula (I). In the following scheme, Y²A 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 aligning agent is used to impart liquid crystal aligning ability to an organic film formed using the liquid crystal aligning agent by rubbing treatment, the liquid crystal aligning agent of the present disclosure more preferably contains at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide as another 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.

(III) the polymer component is in the form of a polymer of the poly (enamine) and poly (styrene-phenylmaleimide) series.

(IV) the polymeric component 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)₂CH — O-), vinylene, maleimide, and the like, and cyclic carbonate groups, epoxy groups, or (meth) acryloyl groups are preferable in terms of high reactivity to 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-dibromoneopentyl glycol diglycidyl ether, N, n, N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, N-diglycidylcenzylamine, N-diglycidylaminomethylcyclohexane, 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, and more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total of the polymers 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.

The solvent component of the liquid crystal aligning agent of the present disclosure may be at least one selected from the group consisting of compounds represented by the following formulae (E-1) to (E-5), and may be a solvent having a boiling point of 180 ℃ or lower at 1 atm (hereinafter, also referred to as "specific solvent"). 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 (suppression of film thickness unevenness or pinholes, and securing of linearity or flatness at the end of a coated region) to a substrate, and is excellent in liquid crystal alignment property and electric characteristics.

[ solution 31]

(in the formula (E-1), R⁴¹Is C1-4 alkyl or R⁴⁰-CO- (wherein, R⁴⁰Alkyl group having 1 to 3 carbon atoms), R⁴²Is C1-4 alkanediyl or- (R)⁴⁷-O)r-R⁴⁸- (wherein, R)⁴⁷And R⁴⁸Each independently is an alkanediyl group having 2 or 3 carbon atoms, R is an integer of 1 to 4), R⁴³Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

[ solution 32]

(in the formula (E-2), R⁴⁴An alkanediyl group having 1 to 4 carbon atoms)

[ solution 33]

(in the formula (E-3), R⁴⁵And R⁴⁶Each independently an alkyl group having 1 to 8 carbon atoms)

[ chemical 34]

R⁴⁹-R⁵⁰-OH (E-4)

(in the formula (E-4), R⁴⁹Is a hydrogen atom or a hydroxyl group, in R⁴⁹In the case of a hydrogen atom, R⁵⁰Is 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 is⁴⁹In the case of hydroxy, R⁵⁰Is 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-R⁵²(E-5)

(in the formula (E-5), R⁵¹R 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 group⁵²A 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 can be mentioned: cyclobutanone, cyclopentanone, cyclohexanone;

as the compound represented by the formula (E-3), there can 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 solvent 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 singly or in combination of two or more. Among the other solvents, a highly polar solvent can be used for the purpose of further improving the 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 tends to increase to lower 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 is different depending on the desired operation mode. 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: containing tin oxide (SnO)₂) A film of (Nesa) (registered trademark of PPG Corp., USA) containing indium oxide-tin oxide (In)₂O₃-SnO₂) Indium Tin Oxide (ITO) film, and the like. In the case of manufacturing a TN-type, STN-type, or VA-type liquid crystal cell, 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 aligning agent is applied, it is preferable to perform preliminary heating (pre-baking) for the purpose of preventing dripping of the applied liquid crystal aligning 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 can 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), cotton (cotton), or the like 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, the ultraviolet light contains 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, from an oblique direction, or a combination of 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/m²～50,000J/m²More preferably 1,000J/m²～20,000J/m². After the light irradiation for imparting alignment ability, a treatment of cleaning the surface of the substrate with, for example, water, an organic solvent (for example, methanol, isopropanol, 1-methoxy-2-propanol acetate, or the like), or a mixture thereof, 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 case of manufacturing a liquid crystal cell, for example, the following methods can be cited: 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 liquid crystal into a cell gap surrounded by the substrate surfaces and the sealant, and sealing the filling hole, a method of using a liquid crystal 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. It is composed ofThen, the liquid crystal cell is irradiated with light while 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, and 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/m²～200,000J/m²More preferably 1,000J/m²～100,000J/m²。

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 timepiece, 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, an information display, a light adjusting film, a retardation 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.