TW201943844A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, and production method for liquid crystal element - Google Patents

Abstract

This liquid crystal alignment agent contains a polymer component and a heterocycle-containing compound that includes, in each molecule thereof, at least two substructures that are the result of removing n hydrogen atoms from a structure represented by formula (1) (n being an integer that is equal to or greater than 1). In formula (1), X1 is -CR1=CR2- or the like, and A1 is a bivalent organic group and may be bonded to another ring structure to form a fused ring with the other ring structure. Each of the multiple X1s and A1s in each molecule are independently as defined above.

Description

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

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

The liquid crystal element includes a liquid crystal alignment film having a function of aligning liquid crystal molecules in a certain direction. Generally, a liquid crystal alignment film is formed by applying a liquid crystal alignment agent obtained by dissolving a polymer component in an organic solvent on a substrate surface, and preferably by heating it. In addition, for an organic film formed on a substrate using a liquid crystal alignment agent, a rubbing treatment or a photo alignment treatment is performed as needed, thereby giving the liquid crystal alignment ability.

In recent years, large-screen and high-definition LCD TVs have become the mainstay. In addition, the popularity of small display terminals such as smart phones or tablet personal computers (tablet PCs) has progressed. Previously and further improved. According to this background, in order to improve the performance of the liquid crystal alignment film and make various characteristics of the liquid crystal element (for example, liquid crystal alignment or voltage retention, afterimage characteristics, etc.) more excellent, various liquid crystal alignment agents have been proposed (for example, refer to Patent Document 1 ~ Patent Document 3).

Patent Document 1 discloses an epoxy compound containing polyfluorene imine and a nitrogen atom (for example, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane) , 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane, etc.). According to the liquid crystal alignment agent described in Patent Document 1, it is possible to obtain a liquid crystal alignment film capable of suppressing display defects due to friction damage and having excellent liquid crystal alignment properties. In addition, Patent Document 2 discloses a compound (for example, a monoallyl diglycidyl group) in which a polyamic acid or polyimide is contained in a liquid crystal alignment agent and a polyamine bond and two or more epoxy groups are contained. Isocyanuric acid, triglycidyl isocyanuric acid, etc.). Patent Document 3 discloses a polyfunctional epoxy compound in which a polyamic acid or polyimide is contained in a liquid crystal alignment agent and two or more 3,4-epoxycyclohexane rings. When a liquid crystal alignment film is formed using a liquid crystal alignment agent containing a cross-linking agent, the film is usually crosslinked by heating (post-baking) during film formation to promote curing of the film.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 10-333153
[Patent Document 2] Japanese Patent Laid-Open No. 2007-139949
[Patent Document 3] Japanese Patent Laid-Open No. 2016-170409

[Problems to be Solved by the Invention]
In order to sufficiently harden the film and increase the hardness of the film by adding a crosslinking agent, it is desirable to perform heating during film formation at a high temperature (for example, 200 ° C. or higher). However, if heating at a high temperature is required when forming a liquid crystal alignment film, problems such as restrictions on the material of the substrate may occur, and the use of a film base material as a substrate of a liquid crystal element is limited. In addition, in a color liquid crystal display element, a dye used as a coloring agent for a color filter is relatively heat-resistant, and there is a concern that the use of the dye is limited when heating during film formation at a high temperature is required. On the other hand, if the curing of the film is insufficient, the hardness of the film is insufficient, and there is a concern that the alignment of the liquid crystal and the voltage holding ratio are lowered.

In addition, when the solubility of the polymer component is reduced by the addition of the crosslinking agent or the crosslinking agent is precipitated in the alignment agent, the coatability of the liquid crystal alignment agent to the substrate is deteriorated. In addition, there is a concern that the liquid crystal alignment of the obtained liquid crystal element, the voltage holding ratio, or the product yield may decrease.

This invention is made in view of the said situation, and one of the objective is to provide the liquid crystal aligning agent which has favorable coating property to a board | substrate, has high film hardness, and can obtain a liquid crystal even when film formation is performed at low temperature. A liquid crystal element with excellent alignment and voltage retention.

[Means for solving problems]
According to the present invention, the following means are provided.
[1] A liquid crystal alignment agent comprising: a polymer component; and having two or more molecules in one molecule from which n (n is an integer of 1 or more) hydrogen atoms are removed from a structure represented by the following formula (1) A heterocyclic compound containing a partial structure.
[Chemical 1]


(In formula (1), X ¹ is any one of the groups represented by the following formula (2-1) to formula (2-5). A ¹ is a divalent organic group, and may be bonded to Other ring structures together with the other ring structures to form a condensed ring. A plurality of A ¹ and X ^{1 in a} molecule each independently have the definition.)
[Chemical 2]



(In Formulas (2-1) to (2-5), R ¹ to R ⁷ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having a carbon number of 1. Formulas (2-3) and ( "*" In 2-5) represents a bonding bond with an oxygen atom in formula (1).)
[2] A liquid crystal alignment film formed using the liquid crystal alignment agent of [1].
[3] A liquid crystal element including the liquid crystal alignment film of [2].
[4] A method for manufacturing a liquid crystal element, comprising: applying the liquid crystal alignment agent of [1] to each substrate surface of a pair of substrates, and irradiating the coated substrate surfaces with light, thereby imparting A step of forming a liquid crystal alignment film by liquid crystal alignment capability; and a step of constructing a liquid crystal cell by arranging a pair of substrates on which the liquid crystal alignment film is formed so as to face each other with a coating surface of the substrate through a liquid crystal layer.
[5] A method for manufacturing a liquid crystal element, comprising: a step of applying the liquid crystal alignment agent of [1] on each of the conductive films of a pair of substrates having a conductive film; and coating the conductive film with the A step of constructing a liquid crystal cell by arranging a pair of substrates of a liquid crystal alignment agent opposite to each other with a coating surface of the substrate through a liquid crystal layer; and performing the liquid crystal cell in a state where a voltage is applied between the conductive films Steps of light irradiation.

[Effect of the invention]
According to the liquid crystal alignment agent of the present invention, a liquid crystal element having excellent liquid crystal alignment and voltage retention can be obtained even when heating during film formation at a low temperature (for example, a temperature of 170 ° C. or lower). In addition, the liquid crystal alignment agent of the present invention is excellent in applicability to a substrate, and therefore, it is possible to suppress a decrease in product yield.

＜ Liquid crystal alignment agent ＞＞
The liquid crystal alignment agent of the present disclosure contains a polymer component and an additive component. In addition, as the additive component, a heterocyclic ring containing a partial structure having two or more partial structures obtained by removing n (n is an integer of 1 or more) hydrogen atoms from the structure represented by the formula (1) in one molecule is included. Compound (hereinafter, also referred to as "compound [W]"). Hereinafter, each component contained in the liquid crystal aligning agent of this disclosure, and other components arbitrarily mix | blended as needed are demonstrated.
In addition, in this specification, a "hydrocarbon group" means the meaning which includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that have only a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it does not need to be comprised only of the structure of an alicyclic hydrocarbon, and it is also included in the part which has a chain structure. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof.

＜ Polymer composition ＞
The main component of the polymer component contained in the liquid crystal alignment agent is not particularly limited as long as it is crosslinked by the compound [W]. Specific examples of the polymer component include polyamic acid, polyamidate, polyimide, polyamine, polyenamine, polyorganosiloxane, polyester, and polyamine. , Polyfluorene imine, polystyrene, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, polymaleimide, styrene-maleimide Polymers based on a copolymer or a poly (meth) acrylate as a main skeleton and having a functional group that reacts with the compound [W] (crosslinking reaction). In addition, (meth) acrylate means an acrylate and a methacrylate. The so-called polyenamine is a polymer having a carbon-carbon double bond in the ortho position of the amine group of a polyamine, and examples thereof include polyenamino ketone, polyenamino ester, polyenamino nitrile, and polyene. Aminosulfonyl and the like.

As the polymer component, among these, in terms of sufficiently improving the performance of the obtained liquid crystal element (for example, liquid crystal alignment or electrical characteristics, mechanical strength, weather resistance, etc.), it is preferably selected from polyamic acid , Polyamidate, polyamidoimide, polyamine, polyenamine, polyamidoamine, polystyrene, poly (meth) acrylate, polymaleimide, styrene-maleimide It is at least one selected from the group consisting of an interpolymer and a polyorganosiloxane. In terms of a higher improvement effect by the compound [W], it is preferable to include a polymer having a structural unit derived from a diamine, and more specifically to include a polymer selected from polyamine At least one of the group consisting of polyamine, polyimide, polyamine, polyenamine, and polyamine.

The polymer component preferably includes a polymer having a primary amine group at a terminal. In this case, it is preferable in that the crosslinking by the compound [W] is further promoted, and the voltage retention of the obtained liquid crystal element is further improved. The polymer having a primary amine group at the terminal is preferably at least one selected from the group consisting of polyamic acid, polyamidate, polyimide, polyamine, polyenamine, and polyamine, From the viewpoint of further improving the effect of improving liquid crystal alignment and voltage retention by the compound [W], and in terms of ease of synthesis, the polymer component is particularly preferably at least partly selected from polyamines, At least one of the group consisting of polyamidate and polyimide.

(Polyamic acid)
Polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

Tetracarboxylic dianhydride The tetracarboxylic dianhydride used in the synthesis of polyamic acid includes, for example, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Anhydride, etc. As specific examples of these, examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and the like;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid. Acid dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1 , 2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1 , 2-c] furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, cyclopentanetetracarboxylic acid Dianhydride, cyclohexanetetracarboxylic dianhydride, etc .; Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, In addition to ethylene glycol bistrimellitic anhydride, 4,4'-carbonyldiphthalic anhydride, and the like, tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. 2010-97188 can also be used. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

Diamine compound As a diamine compound used in the synthesis of a polyamic acid, a known diamine compound can be used, and examples thereof include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine groups. Organosiloxanes, etc. In terms of high reactivity with the compound [W] when heated, and further promoting cross-linking, and improving the solubility of the polymer in a solvent, the following formula (7-1 ) To a diamine compound having a partial structure represented by a formula (7-3) (hereinafter, also referred to as a "protecting group-containing diamine").
[Chemical 3]


(In formula (7-1), A ²¹ is a single bond or a divalent organic group having a carbon number of 1 or more, Y ¹ is a protecting group, and R ²¹ to R ²³ are each independently a hydrogen atom or a monovalent number of 1 or more carbon atoms. Organic group. M is an integer from 0 to 6. In formula (7-2), Y ² is a protecting group. In formula (7-3), R ²⁴ and R ²⁵ are each independently a divalent hydrocarbon group, and Y ³ is a protection group. Base. "*" Indicates a bond.)

In the formulae (7-1) to (7-3), the protecting group of Y ¹ to Y ³ is preferably a group that is removed by heat, and examples thereof include a urethane-based protecting group, Amidamine-based protecting group, amidine-based protecting group, a sulfonamide-based protecting group, and the like. As the protecting group, a urethane-based protecting group is preferred, and specific examples thereof include a third butoxycarbonyl group, a benzyloxycarbonyl group, and 1,1-dimethyl-2-haloethyl group. Oxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) ethoxy Carbonyl, etc. Among these, a third butoxycarbonyl group is particularly preferred in terms of a high releasability by heat and a point that the remaining amount of the deprotected portion in the film can be further reduced.
The monovalent organic group of R ²¹ and R ²² is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably an alkyl group or cycloalkyl group having 1 to 10 carbon atoms.
The monovalent organic group of R ²³ is preferably a monovalent alkyl group or protecting group having 1 to 10 carbon atoms.
The divalent hydrocarbon group of R ²⁴ and R ²⁵ is preferably a divalent chain hydrocarbon group having 1 to 10 carbon atoms, and more preferably an alkanediyl group having 1 to 10 carbon atoms.
Examples of the divalent organic group of A ²¹ include a divalent hydrocarbon group and a group having -O-, -CO-, -COO-, -NH- between carbon-carbon bonds of the hydrocarbon group. A ^{21 is} preferably bonded to an aromatic ring, and more preferably bonded to a benzene ring.

Specific examples of the protective group-containing diamine include, for example, compounds represented by the following formulae (d-7-1) to (d-7-14).
[Chemical 4]



(In the formula, TMS stands for trimethylsilyl.)

When a diamine containing a protective group is used, its use ratio is preferably 2 mol% or more, more preferably 3 mol, relative to the total amount of the diamine compound used in the synthesis of the polymer. Ear% to 80 mole%, and more preferably 5 to 70 mole%. Moreover, the diamine containing a protective group may be used individually by 1 type, and may use 2 or more types together.

Examples of the diamine used in the synthesis of polyamic acid include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, and pentaimine. Methyldiamine, hexamethylenediamine, etc .; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), etc .;
Examples of the aromatic diamine include dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, and hexadecyloxy-2,4-diamine. Benzene, octadecyloxy-2,4-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholesterol Alkoxy-3,5-diaminobenzene, cholestoxy-3,5-diaminobenzene, cholesteroxy-2,4-diaminobenzene, cholestoxy-2 1,4-Diaminobenzoic acid, Cholesteryl 3,5-diaminobenzoate, Cholesteryl 3,5-diaminobenzoate, Lanostane 3,5-diaminobenzoate Ester, 3,6-bis (4-aminobenzyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 2,4-diamino- N, N-diallylaniline, 4- (4'-trifluoromethoxybenzyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4- ((Aminophenyl) methyl) phenyl) -4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestane-3-yl, the following formula (E-1)
[Chemical 5]



(In formula (E-1), X ^I and X ^II are each independently a single bond, -O-, * -COO-, or * -OCO- (where "*" represents a bonding bond with X ^I ), R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^II is a single bond or alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, and c is an integer of 1 to 20, d is 0 or 1. Among them, a and b will not become 0 at the same time.)
A compound represented by the formula, a diamine having a cinnamic acid structure in a side chain, and a compound represented by the following formula (d-1) to formula (d-7), respectively, such as a side chain diamine:

P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 3,5- Diaminobenzoic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 1,5-bis (4-aminophenoxy) pentane, 1,2-bis (4 -Aminophenoxy) ethane, 1,6-bis (4-aminophenoxy) hexane, bis [2- (4-aminophenyl) ethyl] adipic acid, N, N ' -Bis (4-aminophenyl) -1,4-phenylenediamine, N, N'-bis (4-aminophenyl) -N, N'-dimethyl-1,4-phenylenediamine , Bis (4-aminophenyl) amine, bis (4-aminophenyl) methylamine, 2,6-diaminopyridine, 1,4-bis- (4-aminophenyl) -piper Hydrazine, N, N'-bis (4-aminophenyl) -benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) Group) -4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(phenylene diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4 '-[4,4'-propane-1,3-diylbis (piperidine-1,4-diyl)] Diphenylamine, 4,4'-diaminobenzidineaniline, 4,4'-diaminostilbene, 4,4 '-Diaminodiphenylamine, 1,3-bis (4-aminophenethyl) urea, 1,3-bis (4-aminobenzyl) urea, 1,4-bis (4-amine Phenyl) -piperazine, N- (4-aminophenylethyl) -N-methylamine, and the following formulae (d-8-8) to (d-8-16) Main chain-type diamines such as compounds; examples of the diamine-based organosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisilaxane, etc. In addition, Japan can also be used The diamine described in Japanese Patent Application Laid-Open No. 2010-97188.
[Chemical 6]


[Chemical 7]

-Synthesis of Polyamines Polyamines can be obtained by reacting a tetracarboxylic dianhydride and a diamine compound as described above together with a molecular weight adjuster as necessary. The ratio of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine compound and the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 equivalent to 2 Equivalent ratio. Examples of the molecular weight regulator include acid anhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; phenyl isocyanate, and isocyanate Monoisocyanate compounds such as acid naphthyl esters and the like. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less with respect to 100 parts by mass of the total of the tetracarboxylic dianhydride and the diamine compound used.

Furthermore, in order to obtain a polymer having polyamino acid as a terminal having a primary amine group, (1) in the reaction of tetracarboxylic dianhydride with a diamine compound, the amount of diamine is increased compared to tetracarboxylic dianhydride A method of using the amount of the amine compound (for example, 1.1 mol to 1.5 mol equivalent of the amount of tetracarboxylic dianhydride used); (2) a method of reacting the monoamine compound as a molecular weight modifier;

The synthesis reaction of the polyamic acid is preferably performed in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and the reaction time is preferably 0.1 hour to 24 hours.
Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. A particularly preferred organic solvent is preferably one selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylmethylene, One or more of the group consisting of γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol and halogenated phenol are used as a solvent, or one or more of these are used in combination with Mixture of other organic solvents (eg, butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount (a) of the organic solvent is preferably such that the total amount of the tetracarboxylic dianhydride and diamine (b) is 0.1% to 50% by mass with respect to the total amount (a + b) of the reaction solution. the amount.
As described above, a reaction solution obtained by dissolving polyamic acid can be obtained. The reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or the polyamidic acid contained in the reaction solution can be separated and used for the preparation of the liquid crystal alignment agent.

(Polyurethane)
The polyamidate can be obtained, for example, by the following methods: [I] a method of reacting a polyamino acid obtained by the synthesis reaction with an esterifying agent; [II] a tetracarboxylic acid diester A method of reacting with a diamine compound; [III] A method of reacting a tetracarboxylic diester dihalide with a diamine compound. The polyamidate contained in the liquid crystal alignment agent may have only a pseudoamidate structure, or may be a partial esterified product in which a pseudoamidate structure and a pseudoamidate structure coexist. In addition, the reaction solution obtained by dissolving the polyfluorene ester may be directly used for the preparation of the liquid crystal alignment agent, or the polyphosphonium acid contained in the reaction solution may be separated and used for the preparation of the liquid crystal alignment agent.

(Polyimide)
The polyfluorene imine can be obtained, for example, by dehydrating and closing the polyphosphonium acid synthesized as described above and subjecting it to imidization. The polyamidoimide may be a complete phosphonium imide obtained by dehydrating and ring-closing all of the polyamino acid structures of the polyamidic acid as a precursor thereof, or may be dehydrating and cyclically closing only a part of the polyamino acid structure. In addition, a part of the phosphonium imine compound in which the phosphonium acid structure and the phosphonium imine ring structure coexist. The polyfluorene imine used in the reaction preferably has a hydrazone imidization rate of 20% to 99%, and more preferably 30% to 90%. This fluorene imidization ratio represents the ratio of the number of fluorene imine ring structures with respect to the sum of the number of fluorene acid structures and the number of fluorene imine ring structures of a polyfluorene imine, as a percentage. Here, a part of the fluorene imine ring may be an isofluorene ring.

Dehydration ring closure of polyamic acid is preferably performed by dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. In this method, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The used amount of the dehydrating agent is preferably 0.01 mol to 20 mol with respect to 1 mol of the fluoric acid structure of the polyamic acid. Examples of the dehydration ring-closing catalyst include tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine. The used amount of the dehydration closed-loop catalyst is preferably set to 0.01 to 10 mol based on 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closing reaction include organic solvents exemplified as users used in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 ° C to 180 ° C. The reaction time is preferably from 1.0 to 120 hours. The reaction solution containing the polyfluorene imine thus obtained may be directly used for the preparation of the liquid crystal alignment agent, or the polyfluorene imide may be separated and then used for the preparation of the liquid crystal alignment agent. Polyfluorene imine can also be obtained by fluorination of a polyfluorene ester.

When the liquid crystal alignment ability is provided to the organic film formed using a liquid crystal alignment agent using a photo-alignment method, it is preferable that at least a part of a polymer component is a polymer which has a photo-alignment group. The photo-alignment group refers to an anisotropy that can be imparted to a film by a light reaction such as photo-isomerization reaction, photo-dimerization reaction, photo-Fries rearrangement reaction, or photo-decomposition reaction using light irradiation. Functional group.

Specific examples of the photo-alignment group include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, and a containing cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton. A cinnamic acid structure group, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, Coumarin-containing groups having a coumarin or a derivative thereof as a basic skeleton, cyclobutane-containing structures containing a cyclobutane or a derivative thereof as a basic skeleton, A stilbene-containing group, a phenyl benzoate-containing group containing phenyl benzoate or a derivative thereof as a basic skeleton, and the like. Among these, the photo-alignment group is preferably selected from the group consisting of an azobenzene-containing group, a cinnamic acid structure-containing group, a chalcone-containing group, a stilbene-containing group, and a cyclobutane-containing group. At least one of a structure and a group consisting of a phenyl benzoate-containing group is preferably a cinnamic acid-containing structure in terms of high sensitivity to light and easy introduction into a polymer. Group or cyclobutane-containing structure.

A polymer having a photo-alignment group can be obtained by, for example, the following methods: (1) a method obtained by polymerizing a monomer having a photo-alignment group; (2) synthesis of a polymer having an epoxy group in a side chain; A method of polymerizing an epoxy group-containing polymer with a carboxylic acid having a photo-alignment group. The content ratio of the photo-alignment group in the polymer is appropriately set depending on the type of the photo-alignment group so as to impart the required liquid crystal alignment ability to the coating film. For example, in the case of a group containing a cinnamic acid structure, For all the constituent units of the polymer having a photo-alignment group, the content ratio of the photo-alignment group is preferably 5 mol% or more, and more preferably 10 mol% to 60 mol%. In the case where the photo-alignment group has a cyclobutane-containing structure, the content ratio of the photo-alignment group is preferably 50 mol% or more with respect to all the constituent units of the polymer having the photo-alignment group. More preferably, it is set to 80 mol% or more. Moreover, the polymer which has a photo-alignment group may be used individually by 1 type, and may be used in combination of 2 or more type.

The polymer component contained in the liquid crystal alignment agent may be a single kind, or may be a blend system of two or more kinds. For example, the liquid crystal alignment agent contains a first polymer and a second polymer having a higher polarity than the first polymer. In this case, it is preferable that the second polymer having a high polarity is present in the lower layer, and the first polymer is present in the upper layer, and phase separation can occur. Preferred embodiments of the polymer component of the liquid crystal alignment agent include the following (I) to (III).
(I) The aspect in which the first polymer and the second polymer are polymers selected from the group consisting of polyamic acid, polyamidate, and polyimide.
(II) One of the first polymer and the second polymer is a polymer selected from the group consisting of polyamic acid, polyamidate, and polyimide, and the other is poly The appearance of organosiloxane.
(III) One of the first polymer and the second polymer is at least one polymer selected from the group consisting of polyamic acid, polyamidate, and polyimide, and the other is An aspect of a polymer (hereinafter, also referred to as "polymer (Q)") having a structural unit derived from a monomer having a polymerizable unsaturated bond.

(Polyorganosiloxane)
The polyorganosiloxane contained in the liquid crystal alignment agent can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. Examples of the hydrolyzable silane compound include alkane such as tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldiethoxysilane. Oxysilane compounds; 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (3-cyclohexylamino) propyltrimethoxy Nitrogen and sulfur-containing alkoxysilane compounds such as alkylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Epoxy-containing silane compounds such as dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane; 3- (meth) propenyloxypropyltrimethoxy Silane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltriethoxysilane, Unsaturated bond-containing alkoxysilane compounds such as p-styryltrimethoxysilane; trimethoxysilylpropylsuccinic anhydride and the like. The hydrolyzable silane compound may be used alone or in combination of two or more thereof. In addition, "(meth) acryl fluorenyloxy" means including "acryl fluorenyloxy" and "methacryl fluorenyloxy".

The hydrolysis / condensation reaction is performed by reacting one or two or more of the silane compounds as described above with water, preferably in the presence of a suitable catalyst and an organic solvent. When the reaction is performed, the use ratio of water is preferably 1 mole to 30 moles relative to the silane compound (total amount). Examples of the catalyst to be used include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and should be appropriately set. For example, it is preferably 0.01 times to 3 times mole relative to the total amount of the silane compound. Examples of the organic solvent to be used include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, it is preferable to use an organic solvent that is not water-soluble or hardly water-soluble. The use ratio of the organic solvent is preferably 10 parts by mass to 10,000 parts by mass with respect to 100 parts by mass of the total of the silane compound used in the reaction.

The hydrolysis / condensation reaction is preferably carried out by heating in an oil bath or the like, for example. In this case, the heating temperature is preferably 130 ° C. or lower, and the heating time is preferably 0.5 to 12 hours. After the reaction is completed, if necessary, the organic solvent layer separated from the reaction solution is dried with a desiccant, and the solvent is removed to obtain a target polyorganosiloxane. The method for synthesizing the polyorganosiloxane is not limited to the hydrolysis / condensation reaction. For example, the method can be performed by a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and an alcohol.

In the case where the polyorganosiloxane is a polymer having a photo-alignment group, the method for synthesizing the polyorganosiloxane is not particularly limited, and examples thereof include the following methods. An epoxy group-containing silane compound is used for at least a part of the raw materials, and the synthesis side Polyorganosiloxane having an epoxy group (hereinafter also referred to as "epoxy-containing polyorganosiloxane"), and then the polyorganosiloxane containing an epoxy group and a photo-alignable group Carboxylic acid reaction. This method is simple and preferable in terms of improving the introduction rate of the photosensitive group and the liquid crystal structure. In addition, a polyorganosiloxane having a photo-alignment group in a side chain can also be synthesized by a reaction including a hydrolyzable silane compound having a photo-alignment group in a monomer. As for polyorganosiloxane, the polystyrene-equivalent weight average molecular weight (Mw) measured by Gel Permeation Chromatography (GPC) is preferably in the range of 100 to 50,000, and more preferably 200. The range is ~ 10,000.

(Aggregate (Q))
Examples of the monomer having a polymerizable unsaturated bond used in the synthesis of the polymer (Q) include compounds having a (meth) acrylfluorenyl group, a vinyl group, a styryl group, and a maleimide group. . Specific examples of such compounds include unsaturated carboxylic acids such as (meth) acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and vinyl benzoic acid: alkyl (meth) acrylates , Cycloalkyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4- Unsaturated carboxylic acid esters such as hydroxybutyl glycidyl ether: Unsaturated polycarboxylic acid anhydrides such as maleic anhydride: iso (meth) acrylic compounds; aromatic vinyl compounds such as styrene, methylstyrene, and divinylbenzene ; Conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene; N-methylmaleimide, N-cyclohexylmaleimide, N- Compounds containing maleimide imine, such as phenylmaleimide; etc. When the polymer (Q) is a polymer having a photo-alignment group, a compound having a photo-alignment group may be used as a monomer having a polymerizable unsaturated bond. The monomer having a polymerizable unsaturated bond may be used alone or in combination of two or more.

The polymer (Q) can be obtained, for example, by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator. As the polymerization initiator used, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2 are preferred. Azo compounds such as' -azobis (4-methoxy-2,4-dimethylvaleronitrile). The use ratio of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of all the monomers used in the reaction. The polymerization reaction is preferably performed in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amidines, esters, and hydrocarbon compounds. Diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate are preferred. The reaction temperature is preferably 30 ° C to 120 ° C, and the reaction time is preferably 1 hour to 36 hours. The amount (a) of the organic solvent used is preferably a total amount (b) of the monomers used in the reaction of 0.1 to 60% by mass based on the total amount (a + b) of the reaction solution. Regarding the polymer (Q), the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 250 to 500,000, and more preferably 500 to 100,000.

In the aspects (II) and (III), regarding the total content ratio of polyamic acid, polyamidate, and polyimide, the film hardness of the obtained liquid crystal alignment film is sufficiently increased, In terms of sufficiently increasing the liquid crystal alignment property and voltage holding ratio of the liquid crystal element, it is preferably set to 20% by mass or more, and more preferably set to 20% by mass relative to the total amount of the polymer component contained in the liquid crystal alignment agent. 30 mass% or more, and more preferably 50 mass% to 90 mass%. When the liquid crystal alignment ability is imparted to the organic film formed using the liquid crystal alignment agent by a photo-alignment method, a polyorganosiloxane, a poly (meth) acrylate, or a styrene-maleimide system is used. The copolymer is preferably a polymer having a photo-alignment group, and an alignment film having better liquid crystal alignment can be obtained, which is preferable in this respect.

＜ Compound [W] ＞
Next, the compound [W] will be described. The compound [W] is an intra-enol ester, an exo-enol ester, an in-loop fluorenyl ammonium ester, an ex-exo-fluorenyl amine, or an oxime ester. Specifically, examples of the divalent organic group of A ¹ in the formula (1) include a hydrocarbon group having 2 to 20 carbon atoms, a group having -O- between carbon-carbon bonds of the hydrocarbon group, and the like. . A ^{1 is} preferably a hydrocarbon group having 2 to 20 carbon atoms.
Examples of the monovalent organic group of R ¹ to R ⁷ in the formulae (2-1) to (2-5) include a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a carbon-carbon of the hydrocarbon group. There are groups such as -O- between the bonds. The monovalent organic group of R ¹ to R ⁷ is preferably a monovalent hydrocarbon group.

The compound [W] has, for example, a partial structure in which n (n is preferably 1 or 2) arbitrary hydrogen atoms are removed from the structure represented by the formula (1), and a plurality of compounds are bonded directly or via a linking group, and Into a compound. The linking group is, for example, a hydrocarbon group having 1 to 30 carbon atoms, and a group having -O-, -S-, -NH-, -CO- between carbon-carbon bonds of the hydrocarbon group. From the viewpoint of monomer synthesis and polymerization reactivity, X ^{1 is} preferably a group represented by the formula (2-3) to formula (2-5), respectively.

Specific examples of the partial structure represented by the formula (1) include a partial structure represented by the following formula (3-1) to formula (3-9), and the like. The following formulae (3-1) and (3-2) correspond to a case where X ¹ in the formula (1) is the formula (2-1), and the following formula (3-3) Corresponding to the case where X ¹ in the formula (1) is the formula (2-2), the following formulae (3-4), (3-5), and (3-6) correspond to the In the case where X ¹ in the formula (1) is the formula (2-3). In addition, the following formulae (3-7) and (3-8) correspond to a case where X ¹ in the formula (1) is the formula (2-4), and the following formula (3-9) corresponds In the case where X ¹ in the formula (1) is the formula (2-5).
[Chemical 8]



(In the formulae (3-1) to (3-9), R ⁵¹ to R ⁷¹ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 24 carbon atoms. Among them, R ⁵¹ to R ⁵⁴ Any one of R ⁵⁵ to R ⁵⁷ , any one of R ⁶⁰ to R ⁶² , any one of R ⁶³ and R ⁶⁴ , any one of R ⁶⁶ to R ⁶⁸ , and R ⁶⁹ and R ⁷⁰ Any one of them is a bonding bond. A plurality of R ⁵¹ to R ^{71 in} one molecule have the above definitions independently. "*" Represents a bonding bond.)

In the formulae (3-1) to (3-9), the monovalent organic group of R ⁵¹ to R ⁷¹ is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably an alkane having 1 to 10 carbon atoms. Or phenyl.

Specific examples of the compound [W] include, for example, compounds represented by the following formulae (b-1) to (b-11).
[Chemical 9]



(In the formula, "Ph" is phenyl.)

From the viewpoint of sufficiently obtaining the effect of improving the liquid crystal alignment and voltage retention of the obtained liquid crystal element, the content ratio of the compound [W] is preferably 100 with respect to the total amount of the polymer component contained in the liquid crystal alignment agent. It is 0.001 parts by mass or more, more preferably 0.003 parts by mass or more, and even more preferably 0.005 parts by mass or more. In addition, regarding the upper limit value of the content ratio of the compound [W], from the viewpoint of suppressing the decrease in the electrical characteristics caused by the compound [W] remaining in the film after the post-baking, it is preferably compared with the liquid crystal alignment agent. The total amount of the polymer components contained is 100 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less. The compound [W] may be used singly or in combination of two or more kinds.

＜ Other additive ingredients ＞
The liquid crystal alignment agent of the present disclosure may contain other additive components other than the compound [W] as necessary. The other additive components are not particularly limited as long as the effects of the present disclosure are not impaired. Specific examples of the other additive component include a compound different from the compound [W] and having a crosslinkable group (hereinafter, also referred to as a “crosslinkable group-containing compound”), a functional silane compound, Antioxidants, metal chelate compounds, hardening accelerators, surfactants, fillers, dispersants, photosensitizers, solvents, etc. The blending ratio of other additive components may be appropriately selected depending on each compound within a range that does not impair the effects of the present disclosure.

(Crosslinkable compound)
The compound containing a crosslinkable group can also be used in order to further improve the adhesion between the liquid crystal alignment film and the substrate, and the reliability of the liquid crystal element. Examples of the compound having a crosslinkable group include a compound selected from a cyclic carbonate group, an epoxy group, an isocyanate group, a block isocyanate group, an oxetanyl group, a trialkoxysilyl group, and a polymerizable unsaturated group. A compound of at least one crosslinkable group in a group consisting of a bonding group, and the like. Examples of the polymerizable unsaturated bonding group include a (meth) acrylfluorenyl group, an ethylenic carbon-carbon double bond, a vinylphenyl group, a vinyloxy group (CH ₂ = CH-O-), a vinylidene group, The maleimidine group and the like are preferably a cyclic carbonate group, an epoxy group, or a (meth) acrylfluorenyl group in terms of high reactivity by light or heat.

Specific examples of the crosslinkable group-containing compound include 1,6-hexanediol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1 , 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-aminomethylcyclohexane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, compounds represented by the following formulae (11-1) to (11-10), and the like. Furthermore, the crosslinkable group-containing compound may be used singly or in combination of two or more kinds.
[Chemical 10]

When a compound containing a crosslinkable group is formulated in a liquid crystal alignment agent, the cross-linking reaction is sufficiently advanced even when the post-baking temperature is set to a low temperature (for example, 170 ° C. or lower), and the low temperature From the viewpoint of obtaining a liquid crystal element with high liquid crystal alignment and voltage retention by firing, the compounding ratio of the crosslinkable group-containing compound is better than 100 parts by mass of the compound [W] contained in the liquid crystal alignment agent. It is 150 mass parts or less, More preferably, it is 120 mass parts or less. The blending ratio of the crosslinkable group-containing compound is preferably 100 parts by mass of the total amount of the compound [W] and the crosslinkable group-containing compound relative to the total amount of the polymer contained in the liquid crystal alignment agent. It is more preferably 10 parts by mass or less, and more preferably 0.001 to 5 parts by mass.

<Solvent component>
The liquid crystal alignment agent of the present disclosure is prepared in the form of a solution-like composition in which a polymer component, a compound [W], and a component arbitrarily blended as required are preferably dissolved in an organic solvent and to make. Examples of the organic solvent include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The solvent component may be one of these or a mixed solvent of two or more.

Examples of the solvent component of the liquid crystal alignment agent of the present disclosure include solvents having high polymer solubility and leveling properties (hereinafter, also referred to as "first solvents"), and solvents having good wetting and spreading properties (hereinafter, also It is called "second solvent") and these mixed solvents.
Specific examples of the solvent include, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamidamine, 4-hydroxy-4-methyl-2-pentanone, diisobutyl ketone, ethylene carbonate, propylene carbonate, N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (third butyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 1,3-dimethyl -2-imidazolidinone, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, etc .;
Examples of the second solvent include ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, and diethylene glycol dimethyl ether. , Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, cyclopentanone, butyl lactate, Butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, isoamyl propionate, isoamyl isobutyrate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol monobutyl ether Ether, diisoamyl ether, etc. The solvents may be used singly or in combination of two or more kinds.

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

<< Liquid crystal alignment film and liquid crystal element >>
The liquid crystal alignment film of the present disclosure is formed of a liquid crystal alignment agent prepared as described above. The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. For example, it can be applied to a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, or a Vertical Alignment (VA) type. (Including Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), coplanar switching (In-Plane Switching, IPS), Fringe Field Switching (FFS), Optically Compensated Bend (OCB), Polymer Sustained Alignment (PSA) and other modes. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate to be used differs depending on the required operation mode. Steps 2 and 3 are common in each operation mode.

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

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing dripping of the applied liquid crystal alignment agent. The pre-baking temperature is preferably 30 ° C to 200 ° C, and the prebaking time is preferably 0.25 minutes to 10 minutes. Thereafter, a calcination (post-baking) step is performed for the purpose of completely removing the solvent and thermally imidizing the amido acid structure in the polymer component as necessary. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 250 ° C, and more preferably 80 ° C to 200 ° C. In addition, as for the liquid crystal alignment agent using the compound [W] as a cross-linking agent, even after post-baking at a low temperature of 170 ° C or lower, a liquid crystal alignment agent exhibiting good liquid crystal alignment and voltage retention can be obtained. A liquid crystal element is preferable in this respect. The post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the thus formed film is preferably 0.001 μm to 1 μm.

<Step 2: Alignment Processing>
When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, a process (alignment process) of imparting liquid crystal alignment ability to the coating film formed in the step 1 is performed. Thereby, the alignment ability of liquid crystal molecules is given to a coating film, and it becomes a liquid crystal alignment film. As the alignment process, a process in which a coating film formed on a substrate is rubbed in a certain direction by a roller wound with a cloth including fibers such as nylon, rayon, and cotton can be used. A rubbing treatment, or a light alignment treatment in which a coating film formed on a substrate is irradiated with light to give a liquid crystal alignment ability to the coating film. On the other hand, in the case of manufacturing a vertical alignment (VA) type liquid crystal element, the coating film formed in the step 1 may be directly used as a liquid crystal alignment film, but in order to further improve the liquid crystal alignment capability, the coating film may also be used. Implement alignment processing. A liquid crystal alignment film suitable for a vertical alignment type liquid crystal element can also be suitably used for a PSA type liquid crystal element.

The light irradiation for light alignment can be performed by a method such as a method of irradiating a coating film after the post-baking step, a method of irradiating a coating film after the pre-baking step and before the post-baking step, A method of irradiating the coating film during heating of the coating film in at least one of the pre-baking step and the post-baking step. As radiation to be applied to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. Ultraviolet light including light having a wavelength of 200 nm to 400 nm is preferred. When the radiation is polarized, linearly polarized light or partially polarized light may be used. When the radiation used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction, or a combination of these directions may be used. In the case of non-polarized radiation, the irradiation direction is an oblique direction.

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

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

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

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

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

Hereinafter, specific examples will be described, but the content of the present disclosure is not limited to the following examples.
In the following examples, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymer were measured by the following methods.
<Weight average molecular weight, number average molecular weight, and molecular weight distribution>
Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) is calculated from the obtained Mw and Mn.
GPC column: made by Tosoh Corporation, TSKgelGRCXLII
Mobile phase: N, N-dimethylformamide solution containing lithium bromide and phosphoric acid Column temperature: 40 ° C
Flow rate: 1.0 mL / min Pressure: 68 kgf / cm ²

The abbreviations of the compounds used in the following examples are shown below. In addition, in the following, the "compound represented by formula (X)" may be simply expressed as "compound (X)" for convenience.

(Tetracarboxylic dianhydride)
[Chemical 11]

(Diamine compound)
[Chemical 12]

(Compound [W])
[Chemical 13]

(Other crosslinkers)
[Chemical 14]

<Synthesis of compound [W]>
[Synthesis Example 1-1 to Synthesis Example 1-8]
Compound (BL-1) to compound (BL-8) were synthesized separately according to the methods described in the following documents.
· Compound (BL-1): Endo-enol ester; M. Ueda, M. Yabuuchi, Y. Imai, Polymer J. Polym. Sci., Polym. Chem. Ed., 15, 323 (1977)
· Compound (BL-2): Endo-acyl imidate; M. Ueda, Y. Imai, J. Polym. Sci. ), Polymer Chemistry (Polym. Chem. Ed.), 17, 1163 (1979)
· Compound (BL-3): Endo-acyl imidate; M. Ueda, K. Kino, Y. Imai, Polymer J. Polym. Sci., Polym. Chem. Ed., 13, 659 (1975)
· Compound (BL-4): Endo-enol ester; M. Ueda, T. Takahashi, Y. Imai, Polymer Science J. Polym. Sci., Polym. Chem. Ed., 15, 2641 (1977)
· Compound (BL-5): Exo-enol ester; M. Ueda, T. Takahashi, Y. Imai, Polymer Science J. Polym. Sci., Polym. Chem. Ed., 14 591 (1976)
· Compound (BL-6): Endo-acyl imidate; M. Ueda, K. Kino, K. Yamaki, Y. Y. Imai, J. Polym. Sci., Polym. Chem. Ed., 16, 155 (1978)
· Compound (BL-7): Oxime ester; M. Ueda, H. Hazome, Y. Imai, J. Polym Sci.), Polym. Chem. Ed., 14, 1127 (1976)
· Compound (BL-8): Exo-acyl omidate; M. Ueda, S. Kanno, Y. Imai, Polymer J. Polym. Sci., Polym. Chem. Ed., 14, 663 (1976)

<Synthesis of Polymer>
[Synthesis Example 2-1: Synthesis of Polyamic Acid]
In a 100 mL two-necked flask under nitrogen, 50 mol of 2,3,5-tricarboxycyclopentylacetic dianhydride and 50 mol of 1,2,3,4-cyclobutanetetracarboxylic dianhydride were added. The ears were dissolved in N-methyl-2-pyrrolidone (NMP), and then 10 mols of compound (DA-1) and 90 mols of compound (DA-2) were added. The reaction was performed at 60 ° C for 4 hours to obtain a solution containing 20% by mass of the polymer (P-1). A small amount of the obtained polyamic acid solution was divided, and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass, and the measured solution viscosity was 1020 mPa · s.

[Synthesis Example 2-2 to Synthesis Example 2-14]
Except that the type and amount of the monomers used were changed as shown in Table 1 below, the same operation as in Synthesis Example 2-1 was performed to obtain a polyamine-containing acid (respectively, a polymer (P-2) to a polymer Body (P-14)). In addition, "-" in Table 1 means the compound which does not use this column.

[Table 1]

[Synthesis example 2-15]
Under nitrogen, 100 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride (compound (AH-2)) were dissolved in N-methyl-2-pyrrolidine in a 100 mL two-necked flask. Ketone (NMP), followed by (E) -4- (3- (2,4-diaminophenethoxy) -3-oxoprop-1-en-1-yl) phenyl 4- ( 100 mol parts of 4,4,4-trifluorobutoxy) benzoate was reacted at 60 ° C for 24 hours to obtain a solution containing 30% by mass of a polymer (P-15). A small amount of the obtained polyamic acid solution was divided, and NMP was added to prepare a solution having a polyamic acid concentration of 10% by mass, and the measured solution viscosity was 640 mPa · s.

[Synthesis Example 3-1: Synthesis of polyorganosiloxane]
The polymer (ES-1) was synthesized according to the following scheme 1.
[Chemical 15]

A 1000 ml three-necked flask was charged with 90.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine, and mixed at room temperature. . Then, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then mixed under reflux and reacted at 80 ° C. for 6 hours. After the reaction was completed, the organic layer was taken out, and the organic layer was washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure. An appropriate amount of methyl isobutyl ketone was added to obtain a 50% by mass solution of the polyorganosiloxane (E-1) having an epoxy group.
A 500 ml three-necked flask was charged with 26.69 g (0.3 mol equivalent) of side chain carboxylic acid (ca-1), 2.00 g of tetrabutylammonium bromide, and polyorganosiloxane (E-1) 80 g of the solution and 239 g of methyl isobutyl ketone were stirred at 110 ° C. for 4 hours. After cooling to room temperature, the liquid separation and washing operation was repeated 10 times with distilled water. Thereafter, the organic layer was recovered, and repeatedly concentrated and diluted with NMP by a rotary evaporator to obtain a 15% by mass NMP solution of the polymer (ES-1) intermediate. 0.45 g (0.1 mol equivalent) of trimellitic anhydride was added to 50 g of the intermediate solution, and NMP was used to prepare a solid content concentration of 10% by mass, followed by stirring at room temperature for 4 hours, whereby An NMP solution of the polymer (ES-1) was obtained.
[Chemical 16]

[Synthesis example 3-2]
In Synthesis Example 3-1, the same operation as in Synthesis Example 3-1 was performed except that the side chain carboxylic acid (ca-2) shown below was used instead of the side chain carboxylic acid (ca-1), thereby obtaining NMP solution containing polymer (ES-2).
[Chemical 17]

[Synthesis Example 4-1: Synthesis of styrene-maleimide-based copolymer]
1. Synthesis of Compound (MI-1) Compound (MI-1) was synthesized according to the following scheme 2.
[Chemical 18]

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

2. Synthesis of Polymer Under nitrogen, a 100 mL two-necked flask was charged with 5.00 g (8.6 mmol) of the obtained compound (MI-1) as a polymerization monomer, and 0.64 g of 4-vinylbenzoic acid (4.3 mmol), 4- (2,5-dioxo-3-pyrrolinolin-1-yl) benzoic acid 2.82 g (13.0 mmol), and 4- (glycidyloxymethyl) styrene 3.29 g (17.2 mmol), 2,1'-azobis (2,4-dimethylvaleronitrile) 0.31 g (1.3 mmol) as a radical polymerization initiator, and 2,4-diphenyl- 0.52 g (2.2 mmol) of 4-methyl-1-pentene and 25 ml of tetrahydrofuran as a solvent were polymerized at 70 ° C for 5 hours. After reprecipitation in n-hexane, the precipitate was filtered and vacuum-dried at room temperature for 8 hours to obtain the target polymer (StMI-1). The weight average molecular weight Mw measured by polystyrene conversion by GPC was 30,000, and the molecular weight distribution Mw / Mn was 2.

[Synthesis example 4-2]
In Synthesis Example 4-1, polymerization was obtained by performing the same operation as in Synthesis Example 4-1, except that the following maleimide compound (MI-2) was used instead of compound (MI-1). Body (StMI-2). The weight average molecular weight Mw measured by polystyrene conversion by GPC was 35,000, and the molecular weight distribution Mw / Mn was 2.
[Chemical 19]

<Manufacturing and Evaluation of Friction FFS Liquid Crystal Display Elements>
[Example 1]
1. Preparation of Liquid Crystal Alignment Agent (AL-1) To a solution containing 100 parts by mass of a polymer (P-1) obtained in Synthesis Example 2-1 was added the solution obtained in Synthesis Example 2-1. 200 parts by mass of polymer (P-11), 5 parts by mass of compound (BL-1), and NMP and butylcellosolve (BC) as solvents. The solvent composition is NMP / BC = 50/50 (mass) Ratio), a solution with a solid content concentration of 4.0% by mass. This solution was filtered through a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (AL-1).

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

3. Evaluation of film hardness The prepared liquid crystal alignment agent (AL-1) was coated on a glass substrate using a spinner, and pre-baked for 1 minute using a heating plate at 80 ° C. Then, it heated at 150 degreeC for 1 hour in the oven which replaced the inside of the chamber with nitrogen, and the coating film with a film thickness of 0.1 micrometer was formed. The obtained coating film was evaluated for pencil hardness (surface hardness) in accordance with Japanese Industrial Standards (JIS) -K5400. A case where the pencil hardness is 4H or more is evaluated as "A", a case where the pencil hardness is 2H or 3H is evaluated as "B", a case where the pencil hardness is H is evaluated as "C", and a case where the pencil hardness is less than H The evaluation was "D". As a result, the pencil hardness of the liquid crystal alignment film was "A".

4. Manufacture of Friction Horizontal Liquid Crystal Display Elements (1)
The prepared liquid crystal alignment agent (AL-1) was coated on a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a spinner, and pre-baked for 1 minute using a heating plate at 80 ° C. Then, it heated at 230 degreeC for 1 hour in the oven which replaced the inside of the chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. This coating film was subjected to a rubbing treatment using a friction machine having a roll around which a cloth was wound, at a roll rotation speed of 400 rpm, a table moving speed of 3 cm / sec, and a gross press-in length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then it was dried in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. This series of operations is repeated to make a pair (two pieces) of substrates having a liquid crystal alignment film.
On the outer periphery of the surface of the substrate having the liquid crystal alignment film of one of the substrates, an epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied by screen printing, and then the liquid crystal alignment film surfaces were applied. The opposing methods are overlapped and crimped to harden the adhesive. Next, a nematic liquid crystal (MLC-6221 manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic light curing adhesive, and the polarizing plates were bonded together. On both surfaces on the outside of the substrate, a friction horizontal liquid crystal display element A is manufactured.

5. Manufacture of friction horizontal liquid crystal display elements (2)
A rubbing-type liquid crystal display element B was produced by performing the same operation as described in 4. above, except that the post-baking temperature was changed from 230 ° C to 150 ° C.

6. Evaluation of liquid crystal alignment For each of the above-mentioned friction horizontal type liquid crystal display element A and friction horizontal type liquid crystal display element B manufactured, the voltage of 5 V was turned on and off (ON and OFF) with an optical microscope. ) The presence or absence of anomalous domains during light and dark changes during (apply and release), the case where there is no anomalous domains is set to "A", the part with the anomalous domains is set to "B", and the entire anomalous domain In the case of "C", the liquid crystal alignment was evaluated. As a result, in this example, the liquid crystal alignment was “A” for any of the element A having a post-baking temperature of 230 ° C. and the element B having a post-baking temperature of 150 ° C.

7. Evaluation of voltage holding ratio (VHR) For each of the manufactured friction horizontal liquid crystal display element A and the friction horizontal liquid crystal display element B, the application time of 60 microseconds and the span of 167 milliseconds After a voltage of 5 V was applied, the voltage retention rate after 167 milliseconds after the release of the voltage was measured. The measuring device used was VHR-1 manufactured by TOYO Technica. At this time, it is set to "S" when the voltage retention is 98% or more, "A" when it is 95% or more and less than 98%, and 80% or more and 95% or less. Set "B", "C" when it is 50% or more and less than 80%, and "D" when it is less than 50%. As a result, in this example, the voltage holding ratio was evaluated as “A” for any of the component A having the post-baking temperature of 230 ° C. and the component B of 150 ° C.

[Example 5, Example 8 and Example 9]
A liquid crystal alignment agent was obtained at the same solid content concentration as in Example 1 except that the formulation composition was changed as shown in Table 2 below. In addition, the applicability of the liquid crystal alignment agent and the film hardness were evaluated in the same manner as in Example 1 using each liquid crystal alignment agent. In the same manner as in Example 1, a rubbed horizontal liquid crystal display element A and a rubbed horizontal liquid crystal display element B were produced. And carry out various evaluations. These results are shown in Table 3 below.

<Manufacturing and Evaluation of Optical FFS Liquid Crystal Display Elements>
[Example 2]
1. Preparation of Liquid Crystal Alignment Agent (AL-2) The same solvent composition and solid content as those of Example 1 except that the types and amounts of the polymer and crosslinking agent used were changed as described in Table 2 below. Concentration to prepare a liquid crystal alignment agent (AL-2).
2. Evaluation of applicability The evaluation of applicability was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-2) instead of (AL-1). As a result, this example is "A".
3. Evaluation of Film Hardness The evaluation of film hardness was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-2) instead of (AL-1). As a result, this example is "A".

4. Manufacturing of optical FFS liquid crystal display elements (1)
Using a spinner, the prepared liquid crystal alignment agent (AL-2) was applied to each of a glass substrate having a flat electrode, an insulating layer, and a comb-shaped electrode laminated in this order on one side, and an opposite glass substrate without an electrode. The surface was heated (pre-baked) for 1 minute using a heating plate at 80 ° C. Thereafter, it was dried (post-baking) in an oven at 230 ° C. in which nitrogen was substituted in the cavity for 30 minutes to form a coating film having an average film thickness of 0.1 μm. An Hg-Xe lamp was used to irradiate the surface of the coating film from the normal direction of the substrate with ultraviolet light 1,000 J / m ² including a linearly polarized 254 nm bright line to perform photo-alignment treatment, thereby forming a liquid crystal alignment film on the substrate.
Then, for a pair of substrates having a liquid crystal alignment film, a liquid crystal injection port is left at the edge of the surface where the liquid crystal alignment film is formed, and an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm is added for screen printing. The substrates were overlapped and crimped so that the projection direction of the polarization axis toward the substrate surface during light irradiation became antiparallel, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a nematic liquid crystal (MLC-7028 manufactured by Merck) was filled from the liquid crystal injection port between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it was heated at 120 ° C. and then slowly cooled to room temperature to manufacture a liquid crystal cell. Then, the polarizing plates were laminated on the two outer surfaces of the substrate so that the polarizing directions of the polarizing plates were orthogonal to each other and were at an angle of 90 ° to the projection direction of the ultraviolet axis of the liquid crystal alignment film on the substrate surface, thereby manufacturing a light FFS type. Liquid crystal display element A.
5. Manufacturing of optical FFS liquid crystal display elements (2)
Except for changing the post-baking temperature from 230 ° C. to 150 ° C., the same operation as in 4. was performed to manufacture a light FFS-type liquid crystal display element B.

6. Evaluation of Liquid Crystal Alignment About the manufactured optical FFS liquid crystal display element A and optical FFS liquid crystal display element B, the liquid crystal alignment was evaluated in the same manner as in Example 1. As a result, in this embodiment, the liquid crystal alignment of the light FFS liquid crystal display element A and the light FFS liquid crystal display element B are both “A”.
7. Evaluation of voltage holding ratio (VHR) The light holding ratio of the manufactured FFS liquid crystal display element A and light FFS liquid crystal display element B were evaluated in the same manner as in Example 1. As a result, in this embodiment, the voltage retention ratios of the light FFS liquid crystal display element A and the light FFS liquid crystal display element B were both evaluated as “A”.

[Example 10 to Example 12]
A liquid crystal alignment agent was obtained at the same solid content concentration as in Example 1 except that the formulation composition was changed as shown in Table 2 below. In addition, the applicability and film hardness of the liquid crystal alignment agent were evaluated in the same manner as in Example 1 using each liquid crystal alignment agent, and a light FFS liquid crystal display element A and a light FFS liquid crystal display element B were produced in the same manner as in Example 2. And carry out various evaluations. These results are shown in Table 3 below.

<Manufacturing and Evaluation of VA-type Liquid Crystal Display Elements>
[Example 3]
1. Preparation of the liquid crystal alignment agent (AL-3) except that the types and amounts of the polymer and the cross-linking agent used were changed as described in Table 2 below, the same solvent composition and solid content as in Example 1 were used. Concentration to prepare a liquid crystal alignment agent (AL-3).
2. Evaluation of Coating Properties The evaluation of coating properties was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-3) instead of (AL-1). As a result, this example is "A".
3. Evaluation of Film Hardness The evaluation of film hardness was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-3) instead of (AL-1). As a result, this example is "A".

4. Manufacturing of VA-type liquid crystal display elements (1)
The prepared liquid crystal alignment agent (AL-3) was coated on a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a spinner, and pre-baked for 1 minute using a heating plate at 80 ° C. Then, it heated at 230 degreeC for 1 hour in the oven which replaced the inside of the chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. This operation is repeated, thereby producing a pair (two pieces) of substrates having a liquid crystal alignment film.
On the outer periphery of the surface of the substrate having the liquid crystal alignment film of one of the substrates, an epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied by screen printing, and then the liquid crystal alignment film surfaces were applied. The opposing methods are overlapped and crimped to harden the adhesive. Next, a negative type liquid crystal (MLC-6608 manufactured by Merck) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light curing adhesive, and the polarizing plates are bonded together. VA-type liquid crystal display elements A are manufactured on both surfaces on the outside of the substrate.
5. Manufacturing of VA-type liquid crystal display elements (2)
A VA-type liquid crystal display element B was manufactured by performing the same operation as described in 4. except that the post-baking temperature was changed from 230 ° C to 150 ° C.

6. Evaluation of Liquid Crystal Alignment About the manufactured VA-type liquid crystal display element A and VA-type liquid crystal display element B, the liquid crystal alignment was evaluated in the same manner as in Example 1. As a result, in this embodiment, the liquid crystal alignment of the VA-type liquid crystal display element A and the VA-type liquid crystal display element B are both "A".
7. Evaluation of Voltage Holding Ratio (VHR) The voltage holding ratio was evaluated in the same manner as in Example 1 with respect to the manufactured VA-type liquid crystal display element A and VA-type liquid crystal display element B. As a result, in this example, the voltage retention ratios of the VA-type liquid crystal display element A and the VA-type liquid crystal display element B were both evaluated as “A”.

[Example 4]
A liquid crystal alignment agent was obtained at the same solid content concentration as in Example 1 except that the formulation composition was changed as shown in Table 2 below. In addition, using the obtained liquid crystal alignment agent, the applicability of the liquid crystal alignment agent and the film hardness were evaluated in the same manner as in Example 1, and VA-type liquid crystal display elements A and VA-type liquid crystal display elements B were produced in the same manner as in Example 3. And carry out various evaluations. The results are shown in Table 3 below.

<Manufacturing and Evaluation of PSA-type Liquid Crystal Display Elements>
[Example 6]
1. Preparation of the liquid crystal alignment agent (AL-6) except that the types and amounts of the polymer and the cross-linking agent used were changed as described in Table 2 below, and the same solvent composition and solid content were used as in Example 1. Concentration to prepare a liquid crystal alignment agent (AL-6).
2. Evaluation of Coating Properties The evaluation of coating properties was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-6) instead of (AL-1). As a result, this example is "A".
3. Evaluation of film hardness The evaluation of film hardness was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-6) instead of (AL-1). As a result, this example is "A".

4. Preparation of Liquid Crystal Composition To 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck), 5 mass% of a liquid crystal compound represented by the following formula (L1-1) and 0.3 mass were added. % The photopolymerizable compound represented by the following formula (L2-1) is mixed and mixed to obtain a liquid crystal composition LC1.
[Chemical 20]

5. Manufacturing of PSA type liquid crystal display element (1)
The prepared liquid crystal alignment agent (AL-6) was applied to each electrode surface of two glass substrates each having a conductive film including an ITO electrode using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), After heating (pre-baking) on a hot plate at 80 ° C. for 2 minutes to remove the solvent, heating (post-baking) on a hot plate at 230 ° C. for 10 minutes to form a coating film having an average film thickness of 0.06 μm. These coating films were subjected to ultrasonic cleaning in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes, thereby obtaining a pair (two pieces) of substrates having a liquid crystal alignment film. The pattern of the electrodes used is the same pattern as the electrode pattern in the PSA mode.
Then, the outer edge of the surface of the substrate having the liquid crystal alignment film on one of the pair of substrates was coated with an epoxy resin adhesive having alumina balls having a diameter of 5.5 μm, and the liquid crystal alignment film faces were opposite to each other. Overlap and crimp to harden the adhesive. Then, the prepared liquid crystal composition LC1 is filled between a pair of substrates from a liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light-curing adhesive, thereby manufacturing a liquid crystal cell. Thereafter, an alternating current of 10 Hz at a frequency of 60 Hz was applied between the conductive films of the liquid crystal cell and the liquid crystal was driven, and an ultraviolet irradiation device using a metal halide lamp as a light source was used to irradiate ultraviolet rays at an irradiation amount of 100,000 J / m ² . In addition, this irradiation amount is a value measured using the light quantity meter which measured based on the wavelength of 365 nm. Thereafter, the polarizing plates were laminated on the two outer surfaces of the substrate such that the polarization directions of the polarizing plates were orthogonal to each other and were at an angle of 45 ° to the projection direction of the ultraviolet axis of the liquid crystal alignment film on the substrate surface, thereby manufacturing a PSA type Liquid crystal display element A.
6. Manufacturing of PSA type liquid crystal display element (2)
A PSA-type liquid crystal display element B was produced by performing the same operation as described in 5. except that the post-baking temperature was changed from 230 ° C to 150 ° C.

7. Evaluation of Liquid Crystal Alignment About the manufactured PSA-type liquid crystal display element A and PSA-type liquid crystal display element B, the liquid crystal alignment was evaluated in the same manner as in Example 1. As a result, in this embodiment, the liquid crystal alignment of both the PSA-type liquid crystal display element A and the PSA-type liquid crystal display element B is "A".
8. Evaluation of Voltage Holding Ratio (VHR) The PSA-type liquid crystal display element A and PSA-type liquid crystal display element B manufactured as described above were evaluated in the same manner as in Example 1. As a result, in this embodiment, the voltage retention ratios of the PSA-type liquid crystal display element A and the PSA-type liquid crystal display element B were both evaluated as “A”.

[Example 7, Example 13, Example 14]
A liquid crystal alignment agent was obtained at the same solid content concentration as in Example 1 except that the formulation composition was changed as shown in Table 2 below. In addition, using the obtained liquid crystal alignment agent, the applicability of the liquid crystal alignment agent and film hardness were evaluated in the same manner as in Example 1, and PSA-type liquid crystal display elements A and PSA-type liquid crystal display elements B were produced in the same manner as in Example 6. Various evaluations were performed in the same manner as in Example 1. The evaluation results are shown in Table 3 below.

<Manufacturing and Evaluation of Optical Vertical Liquid Crystal Display Elements>
[Example 15]
1. Preparation of the liquid crystal alignment agent (AL-15) except that the types and amounts of the polymer and the cross-linking agent used were changed as described in Table 2 below, the solvent composition and solid content were the same as those of Example 1 Concentration to prepare a liquid crystal alignment agent (AL-15).
2. Evaluation of applicability The evaluation of applicability was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was used instead of (AL-1) (AL-15). As a result, this example is "A".
3. Evaluation of film hardness The evaluation of film hardness was performed in the same manner as in Example 1 except that the liquid crystal alignment agent was replaced with (AL-15) instead of (AL-1). As a result, this example is "A".

4. Manufacturing of light vertical liquid crystal display elements (1)
The prepared liquid crystal alignment agent (AL-15) was coated on a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a spinner, and pre-baked for 1 minute using a heating plate at 80 ° C. Then, it heated at 230 degreeC for 1 hour in the oven which replaced the inside of the chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. Then, using a Hg-Xe lamp and a glan-taylor prism, the coating film surface was irradiated with polarized ultraviolet light including a bright line at 313 nm from a direction inclined by 40 ° from the substrate normal 1,000 J / m ² And give the liquid crystal alignment ability. The same operation was repeated to form a pair (two pieces) of substrates having a liquid crystal alignment film.
On one of the substrates, the outer periphery of the surface of the substrate having the liquid crystal alignment film is coated with an epoxy resin adhesive having alumina balls having a diameter of 3.5 μm by screen printing, and then the liquid crystal alignment of the pair of substrates is performed. The film surfaces face each other, and compression bonding is performed so that the projection direction of the optical axis of the ultraviolet rays of each substrate on the substrate surface becomes antiparallel, and the adhesive is thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (MLC-6608 manufactured by Merck) is filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it was gradually cooled to room temperature after being heated at 130 ° C. Next, the polarizing plates were laminated on the two outer surfaces of the substrate so that the polarizing directions of the polarizing plates were orthogonal to each other and were at an angle of 45 ° to the projection direction of the ultraviolet axis of the liquid crystal alignment film on the substrate surface, thereby manufacturing an optical vertical type. Liquid crystal display element A.
5. Manufacturing of light vertical liquid crystal display elements (2)
A light vertical liquid crystal display element B was manufactured by performing the same operation as described in 4. above except that the post-baking temperature was changed from 230 ° C to 150 ° C.

6. Evaluation of Liquid Crystal Alignment About the manufactured light vertical liquid crystal display element A and light vertical liquid crystal display element B, the liquid crystal alignment was evaluated in the same manner as in Example 1. As a result, in this embodiment, the liquid crystal alignment of the light vertical liquid crystal display element A and the light vertical liquid crystal display element B are both "A".
7. Evaluation of Voltage Holding Ratio (VHR) The light vertical liquid crystal display element manufactured as described above was evaluated in the same manner as in Example 1. As a result, in this embodiment, the voltage retention ratios of the light vertical liquid crystal display element A and the light vertical liquid crystal display element B were both evaluated as “A”.

[Examples 16 to 25 and Comparative Examples 1 to 6]
A liquid crystal alignment agent was obtained at the same solid content concentration as in Example 1 except that the formulation composition was changed as shown in Table 2 below. In addition, the applicability and film hardness of the liquid crystal alignment agent were evaluated in the same manner as in Example 1 using each liquid crystal alignment agent, and a light vertical liquid crystal display element A and a light vertical liquid crystal display element B were produced in the same manner as in Example 15. And carry out various evaluations. These results are shown in Table 3 below. In addition, in Table 2, "-" means the compound which does not use this column.

[Table 2]

[table 3]

As shown in Table 3, in Examples 1 to 25 using a liquid crystal alignment agent containing the compound [W] as a cross-linking agent, the applicability was evaluated as "A" except for Example 14. Example 14 is the evaluation of "B". In addition, in Examples 1 to 25, the liquid crystal alignment properties and voltage retention of the obtained liquid crystal display elements were also good, and were evaluated as "S", "A", or "B". In particular, in Example 17 in which a diamine rich polymer (P-12) was used, when the post-baking temperature was set to 150 ° C, the voltage retention was evaluated as "S", and in particular, Excellent. On the other hand, in Example 22 using the anhydride-enriched polymer (P-13), when the post-baking temperature was set to 150 ° C., the voltage retention was evaluated as “B”.
In contrast, in Comparative Example 1 which does not include a crosslinking agent and Comparative Examples 2 to 6 which only include a crosslinking agent different from the compound [W], when the post-baking temperature is set to 230 ° C The evaluation of liquid crystal alignment and voltage retention is "A" or "B", but if the post-baking temperature is set to 150 ° C, the evaluation is "C" or "B", which is a worse result than the examples .
From these results, it is understood that the liquid crystal alignment film and the liquid crystal element formed using the liquid crystal alignment agent containing the compound [W] are excellent in coatability, film hardness, liquid crystal alignment, and voltage retention.

no

no

Claims (9)

A liquid crystal alignment agent comprising: a polymer component; and a heterocyclic ring-containing compound having a partial structure obtained by removing n hydrogen atoms from a structure represented by the following formula (1) in one molecule , Where n is an integer of 1 or more; In formula (1), X ¹ is any one of the groups represented by the following formulas (2-1) to (2-5); A ¹ is a divalent organic group, and may be bonded to other groups A ring structure together with the other ring structures to form a condensed ring; a plurality of A ¹ and X ^{1 in a} molecule each independently have the definition of the A ¹ and X; In Formulas (2-1) to (2-5), R ¹ to R ⁷ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having a carbon number of 1 or more; Formulas (2-3) and (2) "*" In -5) represents a bonding bond with the oxygen atom in Formula (1). The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the heterocyclic-containing compound is represented by the following formulae (3-1) to (3-9) having two or more molecules in one molecule. A compound of any of the partial structures; In the formulae (3-1) to (3-9), R ⁵¹ to R ⁷¹ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 24 carbon atoms; wherein, among R ⁵¹ to R ⁵⁴ Any one of R ⁵⁵ to R ⁵⁷ , any one of R ⁶⁰ to R ⁶² , any one of R ⁶³ and R ⁶⁴ , any one of R ⁶⁶ to R ⁶⁸ , and any of R ⁶⁹ and R ⁷⁰ Any one of is a bonding bond; a plurality of R ⁵¹ to R ^{71 in} one molecule each independently have the definition of R ⁵¹ to R ⁷¹ ; “*” represents a bonding bond. The liquid crystal alignment agent according to claim 1 or claim 2, wherein the polymer component includes a polymer having a partial structure represented by the following formulae (7-1) to (7-3), respectively. ; In Formula (7-1), A ²¹ is a single bond or a divalent organic group having 1 or more carbon atoms, Y ¹ is a protecting group, and R ²¹ to R ²³ are each independently a hydrogen atom or a monovalent organic group having 1 or more carbon atoms. M is an integer from 0 to 6; in formula (7-2), Y ² is a protecting group; in formula (7-3), R ²⁴ and R ²⁵ are each independently a divalent hydrocarbon group, and Y ³ is a protecting group ; "*" Indicates a bonding key. The liquid crystal alignment agent according to claim 1 or claim 2, wherein the polymer component includes a polymer having a primary amine group at a terminal. The liquid crystal alignment agent according to item 1 or item 2 of the patent application scope, wherein the polymer component includes at least one selected from the group consisting of polyamidic acid, polyamidate, and polyimide One. A liquid crystal alignment film is formed by using the liquid crystal alignment agent according to any one of claims 1 to 5 of a patent application scope. A liquid crystal element includes the liquid crystal alignment film according to item 6 of the patent application scope. A method for manufacturing a liquid crystal element includes: The liquid crystal alignment agent according to any one of claims 1 to 5 is applied to each substrate surface of a pair of substrates, and the coated substrate surfaces are irradiated with light, thereby providing A liquid crystal alignment capability and a step of forming a liquid crystal alignment film; and A step of constructing a liquid crystal cell by arranging a pair of substrates on which the liquid crystal alignment film is formed so as to face each other with a coating surface of the substrate facing each other through a liquid crystal layer. A method for manufacturing a liquid crystal element includes: A step of applying the liquid crystal alignment agent according to any one of claims 1 to 5 of the scope of the patent application on each of the conductive films of a pair of substrates having a conductive film; A step of constructing a liquid crystal cell by arranging a pair of substrates coated with the liquid crystal alignment agent so as to face each other with a coating surface of the substrate facing each other via 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.