TWI676644B - Liquid crystal alignment agent, liquid crystal alignment film, method for producing liquid crystal alignment film, liquid crystal display element, polymer, diamine compound, acid dianhydride, and carboxylic acid - Google Patents

Abstract

In the present invention, the liquid crystal alignment agent contains a compound (X) having a partial structure represented by the following formula (1).

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group, and R ³ is a substituent; wherein at least one of R ¹ and R ² is a halogen atom , Cyano, or monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (where R ⁴ is a hydrogen atom, a hydroxyl group, or a monovalent organic group, and R ⁴ may also be bonded to other groups to form a nitrogen atom. And form a ring structure). R ³ can also be bonded to other groups to form a ring structure; n is an integer from 0 to 4; "*" represents a bonding bond)

Description

Liquid crystal alignment agent, liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display element, polymer, diamine compound, acid dianhydride, and carboxylic acid

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

Liquid crystal display elements are widely used in televisions, mobile devices, and various monitors. In addition, in a liquid crystal display element, a liquid crystal alignment film is used in order to control the alignment of liquid crystal molecules in a liquid crystal cell. As a method for obtaining an organic film having a liquid crystal alignment restriction force, a method of rubbing an organic film, a method of obliquely vaporizing silicon oxide, a method of forming a monomolecular film having a long-chain alkyl group, and a method of obtaining light A method (light alignment method) and the like of a flexible organic film for light irradiation.

The photo-alignment method not only suppresses the generation of static electricity or dust, but also imparts uniform liquid crystal alignment to a photosensitive organic film, and it can also precisely control the liquid crystal alignment direction. Therefore, various studies have been conducted in recent years (for example, refer to patent documents 1). Patent Document 1 discloses that a liquid crystal alignment film is formed using a liquid crystal alignment agent containing a polyfluorene imide precursor having a cinnamon fluorene group in the main chain, a polyfluorene imine, or a polyfluorene.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2013/161984

In recent years, large-screen and high-definition liquid crystal televisions have become the main body. In addition, the spread of small-sized display terminals such as smart phones and tablet PCs has further increased the demand for high-definition liquid crystal panels. Specifically, in order to improve the display quality of a liquid crystal display element, it is important that afterimages (afterimage characteristics) and good contrast (contrast characteristics) are not generated, and these various characteristics are required to be further improved.

The present invention has been made in view of the problems described above, and an object of the present invention is to provide a liquid crystal alignment agent capable of obtaining a liquid crystal display element having excellent afterimage characteristics and contrast characteristics.

The present inventors conducted intensive studies in order to achieve the above-mentioned problems of the prior art, and as a result, found that the above-mentioned problems can be solved by including a compound having a specific structure in the liquid crystal alignment agent, thereby completing the present invention. Specifically, the following liquid crystal alignment agent, liquid crystal alignment film, method for producing liquid crystal alignment film, liquid crystal display element, polymer, and compound are provided.

[1] A liquid crystal alignment agent containing a compound (X) having a partial structure represented by the following formula (1),

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group, and R ³ is a substituent; wherein at least one of R ¹ and R ² is a halogen atom , Cyano, or monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (where R ⁴ is a hydrogen atom, a hydroxyl group, or a monovalent organic group, and R ⁴ may also be bonded to other groups to form a nitrogen atom. And forms a ring structure); R ³ may also be bonded to other groups to form at least a part of the ring; n is an integer from 0 to 4; when n is 2 or more, multiple R ³ may be the same or different ; "*" Indicates a bonding key).

[2] A method for manufacturing a liquid crystal alignment film, comprising: a step of applying the liquid crystal alignment agent of [1] on a substrate to form a coating film; and a step of irradiating the coating film with light.

[3] A liquid crystal alignment film formed using the liquid crystal alignment agent of the above [1].

[4] A liquid crystal display element including the liquid crystal alignment film according to the above [3].

[5] A polymer selected from the group consisting of polyamic acid, polyimide, polyamidate, polyamidoamine, polyorganosiloxane, and poly (meth) acrylate Polymer having a partial structure represented by the formula (1).

[6] A diamine compound represented by the following formula (2-1) or (2-2): [Chem 2] H ₂ NR ⁵ -A ¹ -R ⁶ -A ² -R ^7- NH ₂ (2-1)

(In formula (2-1), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula ( A group represented by 1-1) or a group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ⁵ is divalent An organic group, when A ¹ is a group represented by the following formula (1-2), R ⁵ is a single bond or a divalent organic group; and A ² is a group represented by the following formula (1-1) In the case of a group, R ⁷ is a divalent organic group, and when A ² is a group or a single bond represented by the following formula (1-2), R ⁷ is a single bond or a divalent organic group; R ⁶ is a divalent organic group; wherein "* 1" in the following formulae (1-1) and (1-2) is bonded to R ⁶ )

[Chemical 3] R ⁸ -A ¹ -R ⁹ -A ² -R ¹⁰ (2-2)

(In formula (2-2), A ¹ and A ² have the same meaning as the formula (2-1); and when A ¹ is a group represented by the following formula (1-1), R ⁸ Is a monovalent organic group, and when A ¹ is a group represented by the following formula (1-2), R ⁸ is a hydrogen atom or a monovalent organic group; and when R ⁸ is a hydrogen atom, A ¹ has a diaminophenyl group, and when R ⁸ is a monovalent organic group, R ⁸ has a diamine phenyl group; and when A ² is a group represented by the following formula (1-1) R ¹⁰ is a monovalent organic group. When A ² is a group or a single bond represented by the following formula (1-2), R ¹⁰ is a hydrogen atom or a monovalent organic group; R ⁹ is a divalent organic group. Group; "* 1" in the following formulae (1-1) and (1-2) is bonded to R ⁹ )

(In formulas (1-1) and (1-2), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group, and R ³ is a substituent; wherein R ¹ and R ² At least one of R ² is a halogen atom, a cyano group, or a monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (where R ⁴ is a hydrogen atom, a hydroxyl group, or a monovalent organic group, and R ⁴ may also be bonded Together with the nitrogen atom in other groups to form a ring structure); n is an integer from 0 to 4; when n is 2 or more, a plurality of R ³ may be the same or different; "* 1" represents a bonding bond ).

[7] An acid dianhydride represented by the following formula (5-1) or (5-2),

(In formula (5-1), A ³ is a group represented by the formula (1-1) or a group represented by the formula (1-2), A ⁴ is a single bond, and the formula ( A group represented by 1-1) or a group represented by the formula (1-2); R ¹⁵ and R ¹⁷ are each independently an aromatic ring group, an alicyclic group or a heterocyclic group, and R ¹⁶ is Divalent organic groups, X ³ and X ⁴ are each independently a single bond or a divalent linking group; wherein "* 1" in the formula (1-1) and formula (1-2) is bonded to R ¹⁶ )

(In formula (5-2), R ¹⁸ is a divalent organic group, R ¹⁹ is an aromatic ring group, an alicyclic group, or a heterocyclic group; R ¹ , R ^2, and X ^{1 are the} same as those in the formula (5-1 ) Have the same meaning).

[8] A carboxylic acid represented by the following formula (3),

(In formula (3), A ¹ is a group represented by the formula (1-1) or a group represented by the formula (1-2), A ² is a single bond, and the formula (1- A group represented by 1) or a group represented by the formula (1-2); when A ¹ is a group represented by the formula (1-1), R ¹¹ is a monovalent organic group In the case where A ¹ is a group represented by the formula (1-2), R ¹¹ is a hydrogen atom or a monovalent organic group; R ¹² is a divalent organic group; and A ² is the formula (1) In the case of a group represented by -1), R ¹³ is a divalent organic group, and when A ² is a group represented by the formula (1-2), R ¹³ is a single bond or a divalent organic group S and r are each independently 0 or 1; wherein, there is one carboxyl group in formula (3); "* 1" in formula (1-1) and formula (1-2) is bonded to R ¹² ).

By using the liquid crystal alignment agent containing the compound (X), a liquid crystal display element having a low contrast (especially an afterimage caused by an AC voltage) and a high contrast can be obtained.

10‧‧‧FFS type liquid crystal display element

11a‧‧‧ glass substrate

11b‧‧‧ Opposite glass substrate

13‧‧‧top electrode

14‧‧‧ Insulation

15‧‧‧ bottom electrode

d1‧‧‧ electrode line width

d2‧‧‧Distance between electrodes

C1‧‧‧ part enclosed by dotted line

A, B, C, D, E‧‧‧ electrodes

F‧‧‧ Pixel edge

FIG. 1 is a schematic configuration diagram of a Fringe Field Switching (FFS) type liquid crystal display element.

2 (a) and 2 (b) are schematic plan views of a top electrode for manufacturing a liquid crystal display element by a photo-alignment process. FIG. 2 (a) is a top view of the top electrode, and FIG. 2 (b) is a partially enlarged view of the top electrode.

FIG. 3 is a diagram showing drive electrodes of a four-system system.

Hereinafter, each component contained in the liquid crystal aligning agent of this disclosure, and other components arbitrarily mix | blended as needed are demonstrated.

<Compound (X)>

The liquid crystal alignment agent of the present disclosure contains a compound having a partial structure represented by the following formula (1) (hereinafter also referred to as "compound (X)").

[Chemical 8]

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group, and R ³ is a substituent; wherein at least one of R ¹ and R ² is a halogen atom , Cyano, or monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (where R ⁴ is a hydrogen atom, a hydroxyl group, or a monovalent organic group, and R ⁴ may also be bonded to other groups to form a nitrogen atom. And forms a ring structure); R ³ may also be bonded to other groups to form at least a part of the ring; n is an integer from 0 to 4; when n is 2 or more, multiple R ³ may be the same or different ; "*" Means a bond)

Examples of the monovalent organic group of R ¹ and R ² in the formula (1) include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a fluoroalkyl group having 1 to 20 carbon atoms. , Cycloalkyl having 3 to 20 carbons, aryl having 6 to 20 carbons, aralkyl having 7 to 20 carbons, epoxy, alkylsilyl, alkoxysilyl, and the like.

Here, the alkyl group having 1 to 20 carbon atoms may be linear or branched. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl. , Octyl, nonyl, decyl, etc. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentyloxy; examples of the fluoroalkyl group having 1 to 20 carbon atoms include: all Fluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, etc .; Cycloalkyl groups having 3 to 20 carbon atoms include, for example: cyclopentyl, cyclohexyl, methylcyclohexyl, etc .; carbon number 6 Examples of the aryl group of ~ 20 include phenyl and tolyl; examples of the aralkyl group of 6 to 20 carbon include benzyl and the like.

Examples of the halogen atom of R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom is preferred.

Regarding R ¹ and R ² , although at least one of these is a halogen atom, a cyano group, or a monovalent organic group, it is preferably at least at least from the viewpoint that the alignment restriction force of the liquid crystal is sufficiently expressed by light irradiation. R ² is a halogen atom, a cyano group, or a monovalent organic group. Specifically, in the group, R ^{1 is} preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a fluorine atom, or a methyl group, and even more preferably a hydrogen atom. In addition, R ^{2 is} preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms, more preferably a fluorine atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. Among them, a combination in which R ¹ is a hydrogen atom and R ² is a methyl group is particularly preferred.

R ⁴ in -NR ⁴ -is preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or a protecting group. Examples of the protective group include a urethane-based protective group, a fluorenyl-based protective group, a fluorenimine-based protective group, and a sulfonamide-based protective group. A urethane-based protecting group is preferred, and specific examples thereof include a third butoxycarbonyl group, a benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, 1 , 1-dimethyl-2-cyanoethyloxycarbonyl, 9-fluorenylmethylcarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) ethoxycarbonyl and the like. The third butoxycarbonyl group is preferable in terms of being easily deprotected by heat, or being easily discharged as a gas to the outside of the membrane as a gas.

Among these groups, R ^{4 is} preferably a hydrogen atom, a methyl group, a hydroxyl group, or a third butoxycarbonyl group, and more preferably a hydrogen atom or a methyl group. R ⁴ may be bonded to other groups to form a ring structure together with the nitrogen atom. Examples of the ring structure include piperidine and piperazine. X ^{1 is} preferably an oxygen atom.

Examples of the substituent of R ³ include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an amine group, a cyano group, an alkylsilyl group, and an alkoxysilane. Group, ester group, etc. Examples of the ring formed by bonding R ³ to another group include a sulfonimine ring and the like. n is preferably 0 to 2, more preferably 0 or 1. The "*" in formula (1) may be bonded to a hydrogen atom, or to an organic group, or may be bonded to R ³ to form a ring structure (for example, an imine ring, etc.).

The compound (X) may be a polymer component capable of being a main component of the liquid crystal alignment film, or may be an additive component formulated separately from the polymer component. Among these compounds, in terms of the high effect of the anisotropy expression by the photo-alignment method, it is preferable that the compound is contained in the liquid crystal alignment agent as at least a part of the polymer component. The chain has a partial structure represented by the formula (1).

Here, the "main chain" of a polymer in this specification means the "dry" part which contains the longest atomic chain in a polymer. In addition, the "dry" part is allowed to include a ring structure. Therefore, "having a partial structure represented by the formula (1) in the main chain of the polymer" means that the partial structure constitutes a part of the main chain. However, it is not excluded that the partial structure represented by the formula (1) also exists in a portion other than the main chain, for example, a side chain (a portion branched from the “dry” of the polymer). The "organic group" refers to a group containing a hydrocarbon group, and may include a hetero atom in the structure.

The main skeleton in the case where the compound (X) is a polymer is not particularly limited, and examples thereof include polyamic acid, polyimide, polyamidate, polyorganosiloxane, polyester, and polyamine , Cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylcis butylene diimide) derivatives, and poly (meth) acrylates.

Among these polymers, in terms of heat resistance, mechanical strength, and affinity with liquid crystal, etc. From the point of view, it is preferably at least one selected from the group consisting of polyamic acid, polyimide, polyamidate, polyamidoamine, polyorganosiloxane, and poly (meth) acrylate. A polymer (hereinafter also referred to as "polymer (A)"), more preferably selected from the group consisting of polyamidic acid, polyamidoimide, polyamidate, and polyorganosiloxane The at least one polymer is particularly preferably at least one polymer selected from the group consisting of polyamidic acid, polyimide, and polyamidate. In addition, the polymer used in the preparation of the liquid crystal alignment agent may be only one kind, or two or more kinds. (Meth) acrylate means including an acrylate and a methacrylate.

[Polyamic acid]

The polyamidic acid as the compound (X) is a polyamidic acid having a partial structure represented by the formula (1), and can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. Specifically, [1] a method of polymerizing a monomer including a tetracarboxylic dianhydride (hereinafter also referred to as a "specific acid dianhydride") having a partial structure represented by the formula (1); [2] A method of polymerizing a monomer including a diamine (hereinafter also referred to as a "specific diamine") having a partial structure represented by the formula (1); [3] including the specific acid dianhydride And a method for polymerizing the monomer of the specific diamine. Among these methods, a specific diamine is preferably used, and the method of the above-mentioned [2] is more preferable because it is relatively easy to synthesize a monomer.

(Tetracarboxylic dianhydride)

As long as the specific acid dianhydride used in the synthesis of the polyamic acid has a partial structure represented by the formula (1), the remaining structure is not particularly limited. Preferred specific examples include the following formula (5-1 ), A compound represented by the following formula (5-2) Things.

(In formula (5-1), A ³ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ⁴ is a single bond, and the following formula ( A group represented by 1-1) or a group represented by the following formula (1-2); R ¹⁵ and R ¹⁷ are each independently an aromatic ring group, an alicyclic group or a heterocyclic group, and R ¹⁶ is Divalent organic groups, X ³ and X ⁴ are each independently a single bond or a divalent linking group; wherein "* 1" in the following formula (1-1) and formula (1-2) is bonded to R ¹⁶ )

(In the formula (1-1) and formula (1-2), R ¹ , R ² , R ³ , X ¹ and n have the same meaning as the formula (1); “* 1” represents a bonding bond)

[Chemical 11]

(In formula (5-2), R ¹⁸ is a divalent organic group, R ¹⁹ is an aromatic ring group, an alicyclic group, or a heterocyclic group; R ¹ , R ^2, and X ¹ and the formula (1) are (Same meaning)

In the formula (5-1), R ¹⁵ and R ¹⁷ are groups obtained by removing three hydrogen atoms from a ring portion of an aromatic ring, an aliphatic ring, or a heterocyclic ring. An aromatic ring group or an alicyclic group is preferable, and a group obtained by removing three hydrogen atoms from a ring portion of a benzene ring, a naphthalene ring, a cyclopentane ring, or a cyclohexane ring is more preferable. A group obtained by removing three hydrogen atoms from a ring portion of a benzene ring or a cyclohexane ring.

Regarding the divalent organic group of R ¹⁶ , examples of R ⁵ to R ⁷ of the following formula (2-1) can be applied. From the viewpoint of making the afterimage characteristics and contrast characteristics of the liquid crystal display element better, a substituted or unsubstituted aromatic ring group or an alicyclic group is preferred, and a substituted or unsubstituted aromatic group is more preferred. Family ring base.

Examples of the divalent linking group of X ³ and X ⁴ include: -O-, -CO-, -COO-, -CONR ^4- (R ⁴ has the same meaning as the formula (1)), and the following formula (2- 1) Divalent organic groups and the like exemplified for R ⁵ to R ⁷ .

Regarding R ¹ , R ² , R ³ and X ^{1 in} the formulas (1-1) and (1-2), the description of the formula (1) can be applied.

From the viewpoint of ease of synthesis, the compound represented by the formula (5-1) is preferably A ³ is a compound represented by the formula (1-2), and more preferably A ⁴ is a single bond.

Regarding the divalent organic group of R ¹⁸ in the formula (5-2), an exemplary description of R ⁵ to R ⁷ of the following formula (2-1) can be applied. Regarding R ¹⁹ , the illustrations of R ¹⁵ and R ¹⁷ in the formula (5-1) can be applied, and descriptions of preferred specific examples can be applied. In the compound represented by the formula (5-2), at least a part of R ¹⁸ may be bonded to R ¹⁹ to further form a partial structure represented by the formula (1).

As a preferable specific example of a specific acid dianhydride, the compound represented by the following formula (t-1)-formula (t-31), etc. are mentioned, for example. Moreover, a specific acid dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.

[Chemical 13]

(In formulas (t-1) to (t-4) and (t-11) to (t-15), R is an alkyl group having 1 to 5 carbon atoms, and k and j are each independently 0 to (Integer of 2)

[Chemical 14]

In addition, in the formulae (t-1) to (t-4) and (t-11) to (t-15), the R bonded to the ring portion of 1,4-phenylene is The position is not particularly limited. Specifically, in the case of 1 substitution, it may be 2-, 3-, 5-, or 6-position. In the case of 2 substitution, 2,4- or 3,5- is preferred. Bit. R is preferably methyl.

The specific acid dianhydride can be synthesized by appropriately combining ordinary methods in organic chemistry. For example, it can be obtained by reacting a compound having "-C (R ¹ ) = C (R ² ) -CO-X ^1- ""with a phthalic acid derivative to synthesize a compound having the formula ( The tetracarboxylic acid having a partial structure represented by 1) is then acid-anhydrided. However, the synthesis method of a specific acid dianhydride is not limited to the said.

In the case of the method [1] and the method [3], the tetracarboxylic dianhydride used in the synthesis of the polyamic acid as the compound (X) may be only a specific acid dianhydride, or it may be used in combination without having any The tetracarboxylic dianhydride (hereinafter also referred to as "other acid dianhydride") having a partial structure represented by the formula (1). In the method [2], when synthesizing the polyamic acid as the compound (X), another acid dianhydride is used as the tetracarboxylic dianhydride.

Examples of other acid dianhydrides include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As specific examples of these tetracarboxylic dianhydrides, examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride, the following formula (AN-2) or formula (AN-3)

(In the formula (AN-2), X ¹³ and X ¹⁴ are each independently a group or a nitrogen atom obtained by removing one hydrogen atom from a methylene group, and R ⁴¹ is an alkanediyl group having 1 to 10 carbon atoms; In (AN-3), X ¹⁵ and X ¹⁶ are each independently a group or nitrogen atom obtained by removing a hydrogen atom from a methylene group, and B ¹ and B ² are each independently a phenylene group or a pyridylene group. , R ⁴² is an alkanediyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 3; wherein, when m is 2 or 3, a plurality of R ⁴² may be the same as or different from each other)

Represented compounds and the like; Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4 -Cyclobutane tetracarboxylic 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, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran -2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3 , 5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid-2 : 4,6: 8-dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] Undecane-3,5,8,10-tetraketone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7- Ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), 1,3- Propylene glycol bis (anhydrotrimellitic acid ester), the following Formula (AN-4)

[Chemical 16]

Represented compounds and the like; Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, and the following formula (AN- 1)

(In the formula (AN-1), X ¹¹ and X ¹² are each independently a single bond, an oxygen atom, a sulfur atom, -CO-, * -COO-, * -OCO-, * -CO-NR ^21- , * -NR ²¹ -CO- (wherein R ²¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; "*" represents a bonding bond with R ²⁰ ); R ²⁰ is a single bond and two carbon atoms having 1 to 20 carbon atoms Valent hydrocarbon group, a divalent group containing -O- between carbon-carbon bonds of the hydrocarbon group, or a divalent group having a nitrogen-containing heterocyclic ring)

The compound represented by the following formula (AN-5-1) to (AN-5-4)

[Chemical 18]

Respective compounds and the like; in addition to this, tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. 2010-97188 can be used.

Examples of the alkylene group having 1 to 10 carbon atoms in R ⁴¹ and R ⁴² in the formula (AN-2) include methylene, ethylidene, propylidene, butylenediyl, glutaryl, and hexane. Diyl, heptyl, octyl, nonyl, decanedi, etc. These groups may be linear or branched. B ¹ and B ^{2 are} preferably 1,4-phenylene or 2,5-pyridylene.

Specific examples of the compound represented by the formula (AN-2) include, for example, a compound represented by the following formula (a-2), and specific examples of the compound represented by the formula (AN-3) Examples include compounds represented by the following formulae (AN-3-1) to (AN-3-28).

[Chemical 20]

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms of R ²⁰ in the formula (AN-1) include, for example, methylene, ethylidene, propylidene, butadiyl, and glutaryl. , Hexadiyl, heptyl, octyl, nonyl, decanediyl and other alkanediyl groups; divalent cycloaliphatic hydrocarbon groups such as cyclohexyl; divalent aromatic hydrocarbon groups such as phenylene and diphenylene Wait. The number of oxygen atoms that can be introduced into the carbon-carbon bond of the hydrocarbon group may be one, or may be two or more. When R ²⁰ is a divalent group having a nitrogen-containing heterocyclic ring, examples of the nitrogen-containing heterocyclic ring include a pyrrole ring, an imidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a piperidine ring, and a piperazine ring , Pyrrolidine ring and so on.

Specific examples of the compound represented by the formula (AN-1) include, for example, a compound represented by the following formula (AN-1-1) to (AN-1-27), and the following formula (AN a-1) and a compound represented by the following formula (a-3) Things.

[Chemical 24]

In the synthesis of polyamic acid, one tetracarboxylic dianhydride may be used alone or two or more thereof may be used in combination.

From the viewpoint of electrical characteristics, the other acid dianhydride preferably contains at least one selected from the group consisting of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride, and more preferably Is selected from the group consisting of a compound represented by the formula (a-2), bicyclic [2.2.1] heptane-2,3,5,6-tetracarboxylic acid-2: 3,5: 6-dianhydride, 1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxy ring Amylacetic 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 At least one of the groups consisting of bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid-2: 4,6: 8-dianhydride and cyclohexanetetracarboxylic dianhydride A compound. Relative to the total amount of other acid dianhydrides used in the synthesis of polyamic acid, it is preferable that the amount of these compounds used (the total amount in the case of using two or more kinds) is 10 mol. More than ear mole%, more preferably at least 20 mole%, and even more preferably at least 50 mole%.

From the viewpoint of sufficiently obtaining the afterimage characteristics and the improvement effect of the contrast characteristics of the liquid crystal display element, the specific method in the method [1] is specific to the total amount of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid. The use ratio of the acid dianhydride is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more.

(Diamine)

The specific diamine used in the synthesis of the polyamic acid is not particularly limited as long as it has a partial structure represented by the formula (1), and examples thereof include compounds represented by the following formula (2-1) And a compound represented by the following formula (2-2).

H ₂ NR ⁵ -A ¹ -R ⁶ -A ² -R ⁷ -NH ₂ (2-1)

(In formula (2-1), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula ( A group represented by 1-1) or a group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ⁵ is divalent the organic group in the following formula (1-2) in the case of a group represented by, R ⁵ is a single bond or a divalent organic group; a ² in the group represented by the following formula (1-1) is represented by In the case, R ⁷ is a divalent organic group, and in the case of a group or a single bond represented by the following formula (1-2), R ⁷ is a single bond or a divalent organic group; R ⁶ is a divalent organic group )

R ⁸ -A ¹ -R ⁹ -A ² -R ¹⁰ (2-2)

(In formula (2-2), A ¹ and A ² have the same meaning as the formula (2-1); and when A ¹ is a group represented by the following formula (1-1), R ⁸ Is a monovalent organic group, and in the case of a group represented by the following formula (1-2), R ⁸ is a hydrogen atom or a monovalent organic group; and when R ⁸ is a hydrogen atom, A ¹ has A diaminophenyl group, when R ⁸ is a monovalent organic group, R ⁸ has a diamino phenyl group; and when A ² is a group represented by the following formula (1-1), R ¹⁰ Is a monovalent organic group, and in the case of a group or a single bond represented by the following formula (1-2), R ¹⁰ is a hydrogen atom or a monovalent organic group; R ⁹ is a divalent organic group)

(In formulas (1-1) and (1-2), "* 1" represents a bonding bond bonded to R ⁹ ; R ¹ , R ² , R ³ , X ¹ and n and the formula (1) For the same meaning)

Examples of the divalent organic group of R ⁵ to R ⁷ in the formula (2-1) include a divalent hydrocarbon group having 1 to 20 carbon atoms; a part of the methylene group of the hydrocarbon group is represented by -O-, -CO-, -COO- or -NR ^33- (R ³³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a divalent group, a divalent heterocyclic group, etc .; these groups may also have Substituents. Here, the "hydrocarbon group" in the present specification means a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these groups, the "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that are composed only of a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure, and not including an aromatic ring structure. However, it does not need to be comprised only of the structure of an alicyclic hydrocarbon, and it also includes those which have a chain structure in a part. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not need to consist only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in part.

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in R ⁵ to R ⁷ include, for example, a methylene group, an ethylidene group, a propanediyl group, a butadiyl group, a pentadiyl group, and an hexamethylene group. Group, heptadiyl group, octyl group, nonane group, decanedyl group, etc .; Examples of the alicyclic hydrocarbon group include cyclohexyl group, -R ³⁰ -R ^31- (where R ³⁰ is cyclohexyl group, R ³¹ Is an alkanediyl group having 1 to 3 carbon atoms) and the like; examples of the aromatic hydrocarbon group include: phenylene, alkylene substituted phenylene, phenylene, naphthyl, -Ar ³ -R ^32- ( Among them, Ar ³ is a phenylene group, a biphenylene group, or a naphthyl group, and R ³² is an alkyldiyl group or a cyclohexyl group having 1 to 3 carbon atoms.

Examples of the divalent heterocyclic group in R ⁵ to R ⁷ include a group obtained by removing two hydrogen atoms from a nitrogen-containing heterocyclic ring such as pyridine, piperazine, and piperidine. Examples of the substituent that R ⁵ to R ⁷ may have include a halogen atom, an alkoxy group, and the like, a hydroxyl group, a carboxyl group, and a cyano group.

Among R ⁵ to R ⁷ , the divalent organic group of R ⁵ and R ⁷ is preferably a substituted or unsubstituted phenylene group, a biphenylene group, a naphthyl group, a cyclohexyl group, Pyridylene, or -Ar ⁴ -COO- * ³ (Ar ⁴ is substituted or unsubstituted phenylene, phenylene, naphthyl, or cyclohexyl. "* ³ " represents the Key combination). R ^{6 is} preferably an alkyldiyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenylene group, a biphenylene group, or a naphthyl group.

Examples of the monovalent organic group of R ⁸ and R ¹⁰ in the formula (2-2) include: a monovalent hydrocarbon group having 1 to 20 carbon atoms; a part of the methylene group of the hydrocarbon group is -O-, -CO-, -COO- or -NR ^33- (R ³³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a monovalent group, a monovalent heterocyclic group, etc .; these groups may also have Substituents. Specific examples of the monovalent organic group of R ⁸ and R ¹⁰ include, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and cyclohexyl group. , Phenyl, tolyl, benzyl, biphenyl, naphthyl, pyridyl, piperidinyl, and the like.

Regarding R ⁹ , the description of R ⁶ in the formula (2-1) can be applied. In the diaminophenyl group which the said formula (2-2) has, two amino groups are preferably located at the 2,4-position or the 3,5-position with respect to another group.

The descriptions of R ¹ , R ² , R ^3, and X ¹ in the formulas (1-1) and (1-2) can be applied to the description of the formula (1).

The specific diamine is preferably a compound having a partial structure represented by the following formula (4) in the molecule. By having a partial structure represented by the following formula (4), it is preferable to improve the reduction effect of the afterimage (alternating current (AC) afterimage) caused by the AC voltage in the liquid crystal display element.

(In formula (4), Ar ¹ and Ar ² are independently substituted or unsubstituted phenylene or cyclohexyl, and X ² is a single bond, -COO- or -CONR ^20- (R ²⁰ is hydrogen Atom or monovalent organic group); wherein Ar ¹ may also constitute the benzene ring in the formula (1); t is 1 or 2; when t = 2, Ar ² and X ² each independently have the definition; (`` * '' Indicates a bonding key)

Examples of the monovalent organic group of R ²⁰ in the formula (4) include an alkyl group having 1 to 6 carbons, a protecting group, and the like. Specific examples of the protective group include a third butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, and an allyloxycarbonyl group.

X ^{2 is} preferably a single bond or -COO-.

The substituent of the ring portion of Ar ¹ and Ar ² is preferably an alkyl group having 1 to 5 carbon atoms or a halogen atom, and more preferably a methyl group or a fluorine atom.

Preferred specific examples of the partial structure represented by the formula (4) include, for example, 4,4'-biphenylene, 4,4'-biscyclohexyl, and the following formula (4-1 ) To groups represented by formula (4-4), groups having a methyl group or a fluorine atom in a ring portion of these groups, and the like.

(In the formula, "*" indicates a bonding key)

A coating film formed using a liquid crystal alignment agent is applied by a photo-alignment method. In the case of the preorientation restricting force, it is preferable to use the compound represented by the formula (2-1) as the specific diamine in terms of reduction in AC afterimage of the liquid crystal display element and improvement in contrast. By using the compound represented by the formula (2-1) as the specific diamine, a polymer having a partial structure represented by the formula (1) in the main chain can be obtained.

As specific examples of the specific diamine, the compound represented by the formula (2-1) includes, for example, the following formulae (b-1) to (b-17), (b-26) to (b- 56) Compounds represented by the respective ones; Examples of the compounds represented by the formula (2-2) include compounds represented by the following formulae (b-18) to (b-59).

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chem 34]

Moreover, when synthesizing a polyamidic acid, a specific diamine may be used individually by 1 type, and may use 2 or more types together. In the formulae (b-1) to (b-59), the formulae (b-1), (b-3), (b-5) to (b-7), and (b-11) ), Formula (b-18), formula (b-20), formula (b-22) ~ formula (b-26), formula (b-28), formula (b-41) ~ formula (b-45) ,formula (b-47), formula (b-54), formula (b-56), and formula (b-57) correspond to a compound having a partial structure represented by the formula (4).

Specific diamines can be synthesized by appropriately combining common methods in organic chemistry. One example thereof is a method of synthesizing a dinitro intermediate having a nitro group instead of the primary amine group of the compound represented by the formula (2-1) or the formula (2-2), and then using a suitable reducing system. The nitro group of the obtained dinitro intermediate was aminated.

The method for synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. Specifically, for example, a compound represented by "O ₂ NR ⁵ -A ¹ -H" and a compound represented by "HO-R ⁶ -A ² -R ⁷ -NO ₂ " can be used, and more preferably The organic solvent is obtained by performing a reaction in the presence of a catalyst as necessary.

The reduction reaction of the dinitro intermediate is preferably performed in an organic solvent, for example, using a catalyst such as palladium on carbon, platinum oxide, zinc, iron, tin, or nickel. Examples of the organic solvent used herein include ethyl acetate, toluene, tetrahydrofuran, and alcohols. However, the synthesis order of a specific diamine is not limited to the said method.

When synthesizing the polyamic acid as the compound (X), a specific diamine may be used alone, or a diamine (other diamine) having no partial structure represented by the formula (1) may be used in combination.

Examples of the other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine organosiloxanes. As specific examples of these diamines, examples of the aliphatic diamine include m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Amine, 1,3-bis (aminomethyl) cyclohexane, 1,2-bis (2-aminoethoxy) ethane, etc .; Examples of the alicyclic diamine include 1,4-diaminocyclohexane and 4,4'-methylenebis (cyclohexylamine). Examples of the aromatic diamine include dodecyloxydi Aminobenzene, Tetradecyloxydiaminobenzene, Pentadecyloxydiaminobenzene, Hexadecyloxydiaminobenzene, Octadecyloxydiaminobenzene, Cholesteryloxy Diaminobenzene, cholesteryloxydiaminobenzene, cholesteryl diaminobenzoate, cholesteryl diaminobenzoate, lanosteryl diaminobenzoate, 3 , 6-bis (4-aminobenzyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1-bis (4-((amino Phenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1, 1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) 4- (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4- (4-heptylcyclohexyl) benzamide, the following formula (E- 1)

(In the formula (E-1), X ^I and X ^II are each independently a single bond, -O-, * ⁴ -COO-, or * ⁴ -OCO- (wherein "* ⁴ " is bonded to a benzene ring (Bonding bond), 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 1 An integer of ~ 20, where d is 0 or 1; where a and b do not become 0 at the same time)

The compound represented by the following formula (da-1) or (da-2)

Diamines with an orientation group such as the compounds shown: p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-di Amino diphenyl sulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis (4-aminophenoxy ) Pentane, 1,7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl] adipic acid, N, N-bis (4-amino Phenyl) methylamine, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4 , 4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane , 4,4 '-(p-phenylene diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) ) Biphenyl, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6 -Diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine 1,4-bis- (4-amine Phenyl) -piperazine, 3,5-diaminobenzoic acid, the following formulae (da-3) to (da-17)

Respective compounds and the like; Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisilaxane; in addition to this, Japanese patents can also be used The diamine described in Japanese Patent Application Laid-Open No. 2010-97188.

The divalent group represented by "-X ^I- (R ^I -X ^II ) _d- " in the formula (E-1) is preferably an alkanediyl group having 1 to 3 carbon atoms, * -O-, * -COO- or * -OC ₂ H ₄ -O- (wherein the bond with "*" is bonded to the diaminophenyl group). Examples of the "-C _c H _{2c + 1} " group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tridecyl Alkyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, dodecyl, etc., these groups are preferably linear. The two amino groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (E-1) include compounds represented by the following formulae (E-1-1) to (E-1-4).

In addition, the diamine used in the synthesis of polyamic acid can be used alone or in combination of two or more of them.

When it is applied to a liquid crystal alignment agent for a liquid crystal display element of a twisted nematic (TN) type, a super twisted nematic (STN) type, or a vertical alignment type, it can also be used in a polyamic acid A functional group (liquid crystal alignment) that exhibits a liquid crystal alignment restriction force regardless of whether or not light is irradiated on the side chain Sex-based). Examples of the liquid crystal alignment group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, and a group having a steroid skeleton having 17 to 51 carbon atoms. A group, a group having a polycyclic structure (for example, a group having a partial structure represented by the formula (4)), and the like. The polyamidic acid having a liquid crystal alignment group can be obtained, for example, by polymerization of a diamine containing the alignment group-containing diamine in a monomer composition. When a diamine containing an alignment group is used, it is preferable to set the ratio of the alignment of the diamine containing an alignment group with respect to all the diamines used in the synthesis from the viewpoint of improving the alignment of the liquid crystal. It is 3 mol% or more, and more preferably 5 mol% to 70 mol%.

In the case of synthesizing polyamic acid by the method [2], from the viewpoint of sufficiently obtaining the afterimage characteristics and the improvement effect of the contrast characteristic of the liquid crystal display element, compared with those used in the synthesis of polyamic acid The total amount of the diamine is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more.

In addition, in the case of using the method [3] to synthesize polyamidic acid, the specific acid dianhydride and the specific diamine are preferably compared to the total amount of the tetracarboxylic dianhydride and diamine used in the synthesis. The total amount is 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more.

(Synthesis of Polyamic Acid)

Polyamic acid can be obtained by reacting the tetracarboxylic dianhydride and diamine as described above together with a molecular weight adjuster as necessary. The use ratio of the tetracarboxylic dianhydride and diamine provided for the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine, and the anhydride group of the tetracarboxylic dianhydride becomes a ratio of 0.2 to 2 equivalents. Better It is a ratio of 0.3 to 1.2 equivalents.

Examples of the molecular weight adjusting agent include maleic anhydride, phthalic anhydride, itaconic anhydride, and the following formulae (F-1) to (F-4)

Examples of the respective compounds include acid monoanhydrides, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate.

As the molecular weight modifier, a monofunctional compound having a partial structure represented by the formula (1) may be used. The compound is preferably a monoamine compound and an acid monoanhydride. Specific examples include compounds represented by the following formulae (ma-1) to (ma-15), and compounds represented by the following formulae (mt-1) to (mt-10), and the like.

[Chemical 40]

[Chemical 41]

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used. Moreover, a molecular weight adjuster can be used individually by 1 type or in combination of 2 or more types.

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 more preferably 0 ° C to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, and more preferably from 0.5 to 12 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. Among these organic solvents, Preferably, one or more members selected from the group consisting of an aprotic polar solvent and a phenol-based solvent (organic solvent of the first group), or one or more members selected from the organic solvent of the first group and selected from the group consisting of A mixture of one or more of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (the organic solvent of the second group). In the latter case, the ratio of the organic solvent in the second group to the total amount of the organic solvent in the first group and the second group is preferably 50% by weight or less, and more preferably 40% by weight. % Or less, particularly preferably 30% by weight or less.

Particularly preferred organic solvents are preferably those selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylmethane, 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 used within the range of the ratio A mixture of one or more of these solvents with other organic solvents. The used amount of the organic solvent (a) is preferably an amount in which the total amount (b) of the tetracarboxylic dianhydride and diamine is 0.1% to 50% by weight relative to the total amount (a + b) of the reaction solution. .

In this manner, a reaction solution obtained by dissolving polyamidic acid can be obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the polyamic acid contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated polyamino acid can be purified and then provided to Preparation of liquid crystal alignment agent. In the case where the polyamidic acid is subjected to dehydration and ring closure to prepare a polyimide, the reaction solution may be directly provided to the dehydration and ring closure reaction, or the polyamidate contained in the reaction solution may be separated and then provided. For the dehydration ring-closing reaction, or the isolated polyamidic acid can be purified and then provided to the dehydration ring-closing reaction. Isolation and purification of polyamic acid can be performed according to known methods. Row.

[Polyurethane]

The polyamic acid ester as the compound (X) can be obtained, for example, by the following method: [I] A method of reacting a polyamino acid having a partial structure represented by the formula (1) with an esterifying agent. [II] A method of reacting a tetracarboxylic acid diester with a diamine; [III] A method of reacting a tetracarboxylic acid diester dihalide with a diamine, and the like.

The term "tetracarboxylic acid diester" as used herein refers to a compound in which two of the four carboxyl groups of a tetracarboxylic acid are esterified, and the remaining two are carboxyl groups. The "tetracarboxylic acid diester dihalide" refers to a compound in which two of the four carboxyl groups of a tetracarboxylic acid are esterified, and the remaining two are halogenated.

Examples of the esterifying agent used in the method [I] include a hydroxyl-containing compound, an acetal-based compound, a halide, and an epoxy-containing compound. As specific examples of these compounds, examples of the hydroxyl-containing compounds include alcohols such as methanol, ethanol, and propanol; phenols such as phenol and cresol; and acetal compounds such as N, N-dimethyl. Formamidine diethyl acetal, N, N-diethylformamide diethyl acetal, and the like; examples of the halide include: bromomethane, bromoethane, stearyl bromide, and methyl chloride , Chlorooctadecane, 1,1,1-trifluoro-2-iodoethane, chloromethyl methyl ether, 2-chloromethoxy-1,1,1-trifluoroethane, chloromethyl carbonate Isopropyl ester, chloromethyl trimethyl acetate, chloro methyl acetate, chloro methyl butyrate, chloromethyl methyl sulfide, and the like; examples of the epoxy group-containing compound include propylene oxide and the like.

The tetracarboxylic acid diester used in the method [II] can, for example, ring-open the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid by using alcohols such as methanol or ethanol. And get. Examples of the diamine used include the diamines exemplified in the synthesis of polyamic acid. The reaction of the method [II] is preferably performed in an organic solvent in the presence of a suitable dehydrating catalyst. Examples of the organic solvent include organic solvents exemplified as users of the synthesis of polyamic acid. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, and phosphorus-based condensation agent. Wait. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, and more preferably from 0.5 to 12 hours.

The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. Examples of the diamine used include the diamines exemplified in the synthesis of polyamic acid. The reaction of the method [III] is preferably performed in an organic solvent in the presence of a suitable base. Examples of the organic solvent include organic solvents exemplified as users of the synthesis of polyamic acid. Examples of the base that can be preferably used include tertiary amines such as pyridine and triethylamine; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, and potassium. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, and more preferably from 0.5 to 12 hours.

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 polyamidate can be directly provided to the preparation of the liquid crystal alignment agent, or the polyamidate contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or The isolated polyamidate can also be purified and then provided to the preparation of the liquid crystal alignment agent. Isolation and purification of polyamidate can be carried out according to known methods. Row.

[Polyimide]

The polyfluorene imide as the compound (X) can be obtained, for example, by dehydrating and ring-closing the polyfluorenic acid that is the compound (X) synthesized in the manner described above, and then performing imidization.

The polyamidoimide may be a complete phosphonium imide obtained by dehydrating and ring-closing all of the polyamidoamine structures that are the precursors of the polyamidoacid, or may be dehydrated and closed-loop by dehydrating only a part of the polyamidostructure. In addition, a part of the sulfonium imide compound in which the sulfonium acid structure and the sulfonium ring structure coexist. The polyfluorene imine used in the reaction preferably has a hydrazone imidization rate of more than 20%, more preferably 30% to 99%, and even more preferably 40% to 99%. This fluorene imidization ratio is a total of the number of fluorene imine structures and the number of fluorene imine rings with respect to the total number of fluorene imine rings and the number of fluorene imine rings. Here, a part of the fluorene imine ring may be an isofluorene ring.

The dehydration ring closure of the polyamic acid is preferably performed by the following method: heating the polyamic acid; or dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and dehydration ring closure to the solution Medium, if necessary, a method of heating. Among these methods, the latter method is preferred.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of a polyamic acid, for example, an acid anhydride such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. The use amount of the dehydrating agent is preferably set to 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. 1 Mo with respect to the dehydrating agent used The use amount of the dehydrated closed-loop catalyst is preferably 0.01 mol to 10 mol. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified as users of the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 ° C to 180 ° C, and more preferably 10 ° C to 150 ° C. The reaction time is preferably 1.0 to 120 hours, and more preferably 2.0 to 30 hours.

In this manner, a polyimide-containing reaction solution can be obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the dehydrating agent and the dehydration ring-closed catalyst can be removed from the reaction solution and then provided to the preparation of the liquid crystal alignment agent, or the polyimide can be separated and then provided to the liquid crystal. The preparation of the alignment agent, or the isolated polyfluorene imide can also be purified and then provided to the preparation of the liquid crystal alignment agent. These purification operations can be performed according to a known method. In addition, polyfluorene imine can also be obtained by hydrazone imidization of a polyfluorene ester.

It is preferable that the polyamidic acid, polyamidate, and polyimide as the compound (X) obtainable in the above manner are selected from the group consisting of the following formulae (6-1) to (6-10). At least one of the groups of the represented partial structure.

In addition, when the compound (X) is synthesized, when the compound represented by the formula (5-1) in the specific acid dianhydride is used, it is possible to obtain a compound selected from the following formula (6-1): And a polymer having at least one partial structure in a group consisting of a partial structure of the compound and a partial structure represented by the following formula (6-2). When the compound represented by the formula (5-2) in the specific acid dianhydride is used, it is possible to obtain a compound having a partial structure selected from the following formula (6-3) and the following formula (6) -4) A polymer having at least one partial structure in a group consisting of the partial structures represented by (4). another In addition, when a compound represented by the formula (2-1) in the specific diamine is used, a compound having a partial structure selected from the following formula (6-5) and the following formula ( 6-6) A polymer having at least one partial structure in a group consisting of the partial structures represented by 6-6). When the compound represented by the formula (2-2) in the specific diamine is used, it is possible to obtain a compound having a moiety selected from the group represented by the following formulae (6-7) to (6-10). At least one partially structured polymer in a group of structures.

(In formulas (6-1) and (6-2), A ³ , A ⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , X ³ and X ⁴ have the same meanings as the formula (5-1), respectively; (R ²⁰ and R ²¹ are each independently a hydrogen atom or a monovalent organic group)

[Chemical 43]

(In formulas (6-3) and (6-4), R ¹ , R ^2, and X ¹ have the same meanings as the formula (1), and R ¹⁸ and R ¹⁹ are respectively the same as the formula (5-2). ) Are the same meaning; R ²⁰ and R ²¹ are each independently a hydrogen atom or a monovalent organic group)

(In formulas (6-5) and (6-6), A ¹ , A ² , R ⁵ , R ^6, and R ⁷ have the same meanings as the formula (2-1), respectively; R ²⁰ and R ²¹ respectively Independently a hydrogen atom or a monovalent organic group, and R ²² and R ²³ are each independently a trivalent organic group)

[Chemical 45]

(In the formulae (6-7) to (6-10), A ¹ , A ² , R ⁹ and R ¹⁰ have the same meanings as the formula (2-2); R ²⁰ and R ²¹ are each independently A hydrogen atom or a monovalent organic group, and R ²² and R ²³ are each independently a trivalent organic group)

Regarding the formulae (6-1) to (6-8), examples of the monovalent organic group of R ²⁰ and R ²¹ include a monovalent hydrocarbon group having 1 to 10 carbon atoms, a group having a cinnamic acid structure, and the like. Examples of the trivalent organic group of R ²² and R ²³ include a chain hydrocarbon group, an alicyclic group, an aromatic ring group, and a heterocyclic group. An alicyclic group or an aromatic cyclic group is preferred. For specific examples thereof, the description of R ¹⁵ and R ¹⁷ of the formula (5-1) can be applied.

The polyamidic acid, the polyamidate, and the polyamidate as the compound (X) preferably have 10 mPa when they are made into a solution having a concentration of 10% by weight. s ~ 800mPa. The solution viscosity of s is more preferably 15 mPa. s ~ 500mPa. Solution viscosity of s. In addition, the solution viscosity (mPa.s) of the polymer is a concentration of 10 weights prepared using a good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) % Polymer solution, measured at 25 ° C using an E-type viscometer (the same applies to the following polymers).

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (Gel Penetration Chromatography, GPC) of polyamidic acid, polyamidate and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, and more preferably 10 or less. When the molecular weight is within the above range, good alignment and stability of the liquid crystal display element can be ensured.

[Polyamine]

The polyfluorene as the compound (X) can be obtained, for example, by a method in which a dicarboxylic acid and a diamine are reacted. Here, it is preferred that the dicarboxylic acid is subjected to arsine chlorination using a suitable chlorinating agent such as thionyl chloride, and is then provided to the reaction with the diamine.

The dicarboxylic acid used in the synthesis of polyamide is not particularly limited, and examples thereof include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, and 2-formaldehyde. Adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, Aliphatic dicarboxylic acids such as fumaric acid and muconic acid; cyclobutanedicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid Dicarboxylic acids with alicyclic structures such as carboxylic acids; phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 2, 5-dimethyl terephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid Acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid, 3,3 '-[4,4'-( Methylene di-p-phenylene)] dipropionic acid, 4,4 '-[4,4'-(oxybis-p-phenylene)] dibutyric acid, 3,4-diphenyl-1, Dicarboxylic acids and the like having an aromatic ring such as 2-cyclobutanedicarboxylic acid. Moreover, a dicarboxylic acid may be used individually by 1 type, and may use 2 or more types together.

The diamine used when synthesizing polyamine as the compound (X) includes a specific diamine. If necessary, other diamines may be used in combination. The proportion of the specific diamine used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 for the total amount of diamines used in the synthesis of polyamide. More than%. The diamines may be used singly or in combination of two or more.

The ratio of the dicarboxylic acid and the diamine to be used in the synthesis reaction of the polyamine is preferably 1 equivalent to the amine group of the diamine, and the carboxyl group of the dicarboxylic acid is a ratio of 0.2 to 2 equivalents, and more preferably 0.3. Equivalent to 1.2 equivalent.

The reaction of a dicarboxylic acid (preferably a fluorinated dicarboxylic acid) and a diamine is preferably performed in an organic solvent in the presence of a base. The reaction temperature at this time is preferably set to 0 ° C to 200 ° C, and more preferably set to 10 ° C to 100 ° C. The reaction time is preferably 0.5 to 48 hours, and more preferably 1 to 36 hours.

As the organic solvent used in the reaction, for example, tetrahydrofuran and dioxin can be preferably used. Alkane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylmethylene, N-methyl-2-pyrrolidone and the like. The used amount of the organic solvent is preferably 400 to 900 parts by weight, and more preferably 500 to 700 parts by weight based on 100 parts by weight of the total amount of dicarboxylic acid and diamine.

As the base used in the reaction, for example, a tertiary amine such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine can be preferably used. The amount of alkali used is preferably 2 to 4 mol, and more preferably 2 to 3 mol relative to 1 mol of the diamine.

In this manner, a reaction solution obtained by dissolving polyfluorene is obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the polyamide contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated polyamine can be purified and then provided to the liquid crystal alignment agent. Preparation of liquid crystal alignment agent. Isolation and purification of polyamine can be performed according to a known method.

The solution viscosity of the polyamidoamine as the compound (X) is preferably 10 mPa when it is made into a solution having a concentration of 10% by weight. s ~ 800mPa. The solution viscosity of s is more preferably 15 mPa. s ~ 500mPa. Solution viscosity of s. Moreover, about polyamine, the weight average molecular weight (Mw) of polystyrene conversion measured by GPC is preferably 1,000 to 500,000, and more preferably 5,000 to 300,000.

[Polyorganosiloxane]

The polyorganosiloxane (hereinafter also referred to as "polymer (S)") as the compound (X) can be hydrolyzed by, for example, a hydrolyzable silane compound. Obtained by condensation. Specific examples include the following [1] or [2]: [1] a hydrolyzable silane compound (ms-1) having an epoxy group, or the silicon An alkane compound (ms-1) is hydrolyzed and condensed with a mixture of other silane compounds to synthesize an epoxy-group-containing polyorganosiloxane, and then the obtained epoxy-group-containing polyorganosiloxane is (1) A method for reacting a carboxylic acid having a partial structure (hereinafter also referred to as a "specific carboxylic acid") represented by [1]; [2] a hydrolyzable silane compound having a partial structure represented by the formula (1) ( ms-2), or a method of hydrolyzing and condensing a mixture of the silane compound (ms-2) and another silane compound. Among these methods, the method of [1] is simple and preferable in terms of improving the introduction rate of the partial structure represented by the formula (1) in the polymer (S). In the method of [1], a reaction product of a polyorganosiloxane having an epoxy group and a carboxylic acid is used as the compound (X).

Specific examples of the hydrolyzable silane compound (ms-1) having an epoxy group include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane , 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyl Oxyethylmethyldimethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyldimethylethoxysilane, 4-glycidyloxy Butyltrimethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 4-glycidyloxybutyldimethylmethoxysilane , 4-glycidyloxybutyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane and the like. As the silane compound (ms-1), one of these compounds can be used Use alone or in combination of two or more.

The other silane compounds are not particularly limited as long as they are hydrolyzable silane compounds, and examples thereof include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Alkoxysilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane; 3-mercaptopropyltrimethoxysilane, 3- Mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , N- (3-cyclohexylamino) propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and other nitrogen-containing materials. Sulfur atom alkoxysilane; 3- (meth) propenyloxypropyltrimethoxysilane, 3- (meth) propenyloxypropyltriethoxysilane, 6- (methyl ) Acrylic fluorenyloxyhexyltrimethoxysilane, 3- (meth) acryl methoxypropylmethyldimethoxysilane, 3- (meth) acryl methoxypropylmethyldiethoxy Unsaturated hydrocarbon-containing alkoxysilanes such as silane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane; in addition, trimethoxysilylpropyl Succinic anhydride and so on. The other silane compounds may be used singly or in combination of two or more kinds.

Hydrolysis of silane compounds. The condensation reaction can be 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.

In the method of [1], not only a sufficient amount of the formula (1) can be expressed. From the viewpoint of introducing part of the structure into the side chain of the polymer and suppressing side reactions caused by an excessive amount of epoxy group, the epoxy equivalent of the polyorganosiloxane containing epoxy group is preferably 100 g / Mohr ~ 10,000g / mol, more preferably 150g / mol ~ 1,000g / mol. Therefore, when synthesizing an epoxy-group-containing polyorganosiloxane, it is preferable to adjust the use ratio of the silane compound (ms-1) so that the epoxy equivalent of the obtained polyorganosiloxane is within the range.

hydrolysis. In the condensation reaction, the use ratio of water is preferably 0.5 mol to 100 mol, and more preferably 1 mol to 30 mol, relative to 1 mol of the silane compound (total amount).

hydrolysis. Examples of the catalyst used in the condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. As the catalyst, in terms of suppressing side reactions such as ring opening of epoxy groups, speeding up hydrolysis and condensation, and excellent storage stability, the compounds are preferably alkali metal compounds or The organic base is particularly preferably a third- or fourth-grade organic base.

The amount of organic base used varies according to the type of organic base, reaction conditions such as temperature, etc., and can be appropriately set. It is preferably 0.01 to 3 times mole, more preferably 0.05 times mole to all silane compounds. ~ 1 mol.

hydrolysis. Examples of the organic solvent used in the condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. As specific examples of these organic solvents, examples of the hydrocarbon include toluene and xylene; examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, Cyclohexanone, cyclopentanone, etc .; Examples of the ester include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate. Examples of the ether include ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc. Examples of alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoethyl ether. -N-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like. Among these, a water-insoluble organic solvent is preferably used. These organic solvents may be used singly or in combination of two or more.

The use ratio of the organic solvent in the hydrolysis condensation reaction is preferably 10 parts by weight to 10,000 parts by weight, and more preferably 50 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of the entire silane compound used in the reaction.

hydrolysis. The condensation reaction is preferably carried out by dissolving the silane compound as described above in an organic solvent, mixing the solution with an organic base and water, and heating the solution with an oil bath or the like, for example. hydrolysis. In the condensation reaction, the heating temperature is preferably 130 ° C or lower, and more preferably 40 ° C to 100 ° C. The heating time is preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During the heating process, the mixed solution can be stirred or placed under reflux. After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt (for example, about 0.2% by weight of an aqueous ammonium nitrate solution, etc.) is preferred in terms of ease of washing operation. The washing is performed until the washed water layer becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieve as needed, and then the solvent is removed to obtain a polyorganosiloxane.

In the method of [1], the epoxy-containing polyorganosiloxane obtained by the reaction is reacted with a specific carboxylic acid. This allows the epoxy group-containing polyorganosiloxane to react with the carboxylic acid to obtain The polymer (S) whose chain has a partial structure represented by the formula (1).

Specific examples of the specific carboxylic acid include a compound represented by the following formula (3).

(In formula (3), A ¹ and A ² have the same meanings as the formula (2-1), respectively; wherein "* 1" in the formula (1-1) and formula (1-2) represents A bond to R ¹² ; when A ¹ is a group represented by the following formula (1-1), R ¹¹ is a monovalent organic group, and A ¹ is the following formula (1-2) In the case of the represented group, R ¹¹ is a hydrogen atom or a monovalent organic group; R ¹² is a divalent organic group; and when A ² is a group represented by the following formula (1-1), R is ¹³ is a divalent organic group, and when A ² is a group represented by the following formula (1-2), R ¹³ is a single bond or a divalent organic group; s and r are each independently 0 or 1; (Wherein the formula (3) has a carboxyl group)

In the formula (3), as examples of the monovalent organic group of R ¹¹ , the descriptions of R ⁸ and R ¹⁰ in the formula (2-2) can be applied. In addition, as examples of the divalent organic group of R ¹² and R ¹³ , the description of R ⁵ to R ⁷ in the formula (2-1) can be applied. The descriptions of R ¹ , R ² , R ^3, and X ¹ of A ¹ and A ² can be applied to the description of the formula (1).

From the viewpoint of improving the reduction effect of the AC afterimage, the specific carboxylic acid preferably has not only a partial structure represented by the formula (1) in the molecule, but also has A partial structure represented by the formula (4). In addition, the description of the case where a specific diamine is applied as a preferable specific example of the partial structure represented by said formula (4) can be used. In addition, a part of the structure represented by the formula (4) may be constituted by a benzene ring in the formula (1) in the same manner as the specific diamine.

Specific examples of the specific carboxylic acid include compounds represented by the following formulae (g-1) to (g-13).

Moreover, when synthesizing a polymer (S), a specific carboxylic acid may be used individually by 1 type, and may use 2 or more types together. In the formulas (g-1) to (g-13), the formulas (g-1), (g-2), (g-4) to (g-8), and (g- 11) ~ Formula (g-13) is equivalent A compound having a partial structure represented by the formula (4).

From the viewpoint of improving the sensitivity to light, the content ratio of the partial structure represented by the formula (1) in one molecule of the polymer (S) is preferably relative to the silicon contained in the polymer (S). It is set to 3 mol% to 100 mol%, more preferably 5 mol% to 95 mol%, and even more preferably 10 mol% to 90 mol%. Therefore, when synthesizing the polymer (S), the use ratio of the specific carboxylic acid is preferably selected such that the content ratio of the partial structure represented by the formula (1) falls within the range.

In addition, specific carboxylic acids can be synthesized by appropriately combining common methods in organic chemistry. As an example, it can be obtained, for example, by a method represented by "R ¹¹ -A ¹ -H" and "HO-R ¹² -A ² -R ¹³ -COOM (where M is a carboxyl group) The compound represented by "protecting group" is preferably in an organic solvent, and is reacted in the presence of a catalyst, if necessary, and then deprotected. However, the synthesis order of a specific carboxylic acid is not limited to the said method.

When synthesizing the polymer (S), the carboxylic acid used in the reaction with the epoxy-group-containing polyorganosiloxane may be only a specific carboxylic acid, or a carboxylic acid other than the specific carboxylic acid may be used in combination.

The other carboxylic acid is not particularly limited as long as it is a carboxylic acid that does not have a partial structure represented by the formula (1), and examples thereof include a carboxylic acid having the liquid crystal alignment group. Specific examples of other carboxylic acids include hexanoic acid, lauric acid, pentadecanoic acid, palmitic acid, stearic acid, oleic acid, 11-octadecenoic acid, linoleic acid, Fatty acids having 6 to 20 carbons such as linolenic acid and arachidic acid, compounds represented by the following formulae (C-2-1) to (C-2-10), and the like.

(Where j is an integer from 0 to 12 and h is an integer from 1 to 10)

In addition, other carboxylic acids may be used singly or in combination of two or more kinds.

The use ratio of the carboxylic acid to be reacted with the polyorganosiloxane containing an epoxy group is preferably 0.001 to 1.5 mol relative to a total of 1 mol of the epoxy group contained in the polyorganosiloxane. It is more preferably set to 0.01 mol to 1.0 mol.

From the viewpoint of sufficiently obtaining the effects of the present invention, the use ratio of other carboxylic acids is preferably 80 mol% or less based on the total amount of the carboxylic acid reacted with the epoxy-containing polyorganosiloxane. It is more preferable to set it to 50 mol% or less.

The reaction of the epoxy-containing polyorganosiloxane with a carboxylic acid is preferably performed in the presence of a catalyst and an organic solvent.

The catalyst used in the reaction of an epoxy-containing polyorganosiloxane with a carboxylic acid may be, for example, A compound known as an organic base or a so-called hardening accelerator that accelerates the reaction of an epoxy compound is used. Here, examples of the organic base include primary organic amines to secondary organic amines such as ethylamine, piperazine, and piperidine; tertiary organic amines such as triethylamine, pyridine; and tetramethylammonium hydroxide. Grade organic amines and so on. Among these compounds, the organic base is preferably a tertiary organic amine or a quaternary organic amine.

Examples of the hardening accelerator include tertiary amines, imidazole compounds, organic phosphorus compounds, quaternary phosphonium salts, diazabicyclic olefins, organometallic compounds such as tin octoate, quaternary ammonium salts, boron compounds, and tin chloride. Metal halide compounds and the like. Among these compounds, a quaternary ammonium salt is preferable, and specific examples thereof include tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butyl chloride. Ammonium, etc.

The catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and even more preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the epoxy-containing polyorganosiloxane. To use.

Examples of the organic solvent used in the reaction include hydrocarbons, ethers, esters, ketones, amidines, and alcohols. Among these agent solvents, ethers, esters, and ketones are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of the products. Specific examples of particularly preferred solvents include 2-butanone , 2-hexanone, methyl isobutyl ketone and butyl acetate. This organic solvent is preferably used at a solid content concentration (a ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) of 0.1% by weight or more, more preferably 5% by weight. % ~ 50% by weight.

The reaction temperature in the reaction is preferably 0 ° C to 200 ° C, and more preferably 50 ° C. ~ 150 ℃. The reaction time is preferably from 0.1 to 50 hours, and more preferably from 0.5 to 20 hours. After the reaction is completed, the organic solvent layer separated from the reaction solution is preferably washed with water. After washing with water, the organic solvent layer is dried with an appropriate desiccant if necessary, and then the solvent is removed to obtain a polymer (S). In addition, the synthesis method of polyorganosiloxane is not limited to the hydrolysis as described above. For the condensation reaction, for example, a method in which a hydrolyzable silane compound is reacted in the presence of oxalic acid and an alcohol can be adopted.

The polymer (S) obtained in the manner described above preferably includes a partial structure formed by the reaction of a polyorganosiloxane having an epoxy group with a carboxylic acid, and specifically, preferably includes the following formula ( 7) Partial structure shown.

(In formula (7), A ¹ , A ² , R ¹¹ , R ¹² , R ¹³ , s, and r have the same meanings as in formula (3), respectively; Z ¹ is a divalent organic group; “*” indicates that (Silicon atom bond)

Examples of the divalent organic group of Z ¹ include the groups exemplified by R ⁵ to R ⁷ in the formula (2-1).

The polymer (S) contained in the liquid crystal alignment agent of the present disclosure preferably has 1 mPa when it is made into a solution having a concentration of 10% by weight. s ~ 500mPa. The solution viscosity of s is more preferably 3 mPa. s ~ 200mPa. Solution viscosity of s. turn off In the polymer (S), the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and even more preferably 3,000 to 20,000.

[Poly (meth) acrylate]

The poly (meth) acrylate as the compound (X) can be obtained, for example, by (meth) acrylic monomer (m-1) having an epoxy group, or the (meth) acrylic acid A mixture of the monomer (m-1) and other (meth) acrylic monomers is polymerized in the presence of a polymerization initiator, and the obtained polymer (hereinafter also referred to as "ring-containing Poly (meth) acrylate ") and a specific carboxylic acid.

Examples of the (meth) acrylic monomer (m-1) include an unsaturated carboxylic acid ester having an epoxy group. Specific examples thereof include glycidyl (meth) acrylate, glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, (methyl ) 3,4-epoxybutyl acrylate, 3,4-epoxybutyl α-ethyl acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, (meth) acrylic acid 6 , 7-epoxyheptyl, α-ethylheptyl 6,7-epoxyheptyl, 4-hydroxybutyl glycidyl acrylate, (3-ethyloxetane- (meth) acrylic acid- 3-yl) methyl ester and the like. In addition, the (meth) acrylic monobasic body (m-1) may be used alone or in combination of two or more kinds.

Examples of other (meth) acrylic monomers include (meth) acrylic acid, (meth) acrylic ω-carboxy polycaprolactone, butenoic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butyl acrylic acid, maleic acid, fumaric acid, lemon Unsaturated carboxylic acids such as folic acid, mesaconic acid, itaconic acid, vinyl benzoic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic acid Allyl ester, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , Trimethoxysilylpropyl (meth) acrylate, methoxyethyl (meth) acrylate, -N, N-dimethylaminoethyl (meth) acrylate, -N (meth) acrylate N-diethylaminoethyl, methoxypolyethylene glycol (meth) acrylate, octyloxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (methyl (Meth) acrylates such as 2-hydroxyethyl acrylate, etc .; α-alkoxy acrylates such as α-methoxymethyl acrylate, α-ethoxy methyl acrylate; methyl butenoate, butene Unsaturated carboxylic acid esters such as ethyl methacrylate, etc .; unsaturated maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride Polycarboxylic anhydrides and the like. In addition, other (meth) acrylic monoliths can be used individually by 1 type or in combination of 2 or more types.

When synthesizing poly (meth) acrylate, the total amount (mole number) of epoxy groups per 1 g of epoxy group-containing poly (meth) acrylate is preferably 5.0 × 10 ^-5 mole / g or more, more preferably 1.0 × 10 ^-4 mole /g~1.0×10 ^-2 mole / g, particularly preferably 5.0 × 10 ^-4 mole /g~5.0×10 ^-3 mole / g. Therefore, as for the usage ratio of the (meth) acrylic monomer (m-1), it is preferable that the total molar number of epoxy groups per 1 g of the epoxy group-containing poly (meth) acrylate is To adjust the value range.

In addition, during the polymerization, other monomers than the (meth) acrylic monomer may be used. Examples of other monomers include: 1,3-butadiene, 2-methyl-1,3-butadiene, etc. Conjugated diene compounds; aromatic vinyl compounds such as styrene, methylstyrene, and divinylbenzene. The use ratio of the other monomers is preferably 30 mol% or less, and more preferably 20 mol% or less with respect to the total of the monomers used in the synthesis of the poly (meth) acrylate.

The polymerization reaction using a (meth) acrylic monomer is preferably performed by radical polymerization. Examples of the polymerization initiator used in the polymerization reaction include initiators generally used in radical polymerization, and examples thereof include 2,2'-azobis (isobutyronitrile), 2,2'-azobis ( 2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzamidine peroxide, lauryl peroxide醯, organic peroxides such as tributyl peroxy trimethylacetate, 1,1'-bis (third butyl peroxy) cyclohexane; hydrogen peroxide; those containing these peroxides and reducing agents Redox-type initiators and the like. Among these compounds, an azo compound is preferable, and 2,2'-azobis (isobutyronitrile) is more preferable. The polymerization initiator may be used alone or in combination of two or more of these compounds.

The use ratio of the polymerization initiator is preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 40 parts by weight, with respect to 100 parts by weight of all the monomers used in the reaction.

The polymerization of the (meth) acrylic monomer is preferably carried out in an organic solvent. Examples of the organic solvent used in this reaction include alcohols, ethers, ketones, amidines, esters, and hydrocarbon compounds. Among these compounds, it is preferable to use at least one selected from the group consisting of alcohols and ethers, and it is more preferable to use partial ethers of polyhydric alcohols. Preferred examples thereof include diethylene glycol methyl ether and propylene glycol monomethyl ether acetate. In addition, organic solvents can be used alone or in combination Use in combination.

In the polymerization reaction of the (meth) acrylic monomer, the reaction temperature is preferably 30 ° C to 120 ° C, and more preferably 60 ° C to 110 ° C. The reaction time is preferably 1 hour to 36 hours, and more preferably 2 hours to 24 hours. In addition, the amount (a) of the organic solvent used is preferably an amount of 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution, and the total amount (b) of the monomers used in the reaction .

The epoxy group-containing poly (meth) acrylate obtained by the reaction is then reacted with a specific carboxylic acid. Specific examples of the specific carboxylic acid can be applied to the description of the polymer (S). In this reaction, a specific carboxylic acid may be used alone, or a carboxylic acid other than the specific carboxylic acid may be used in combination.

The use ratio of the carboxylic acid to be reacted with the epoxy group-containing poly (meth) acrylate is preferably 1 mole relative to the total epoxy group of the epoxy group-containing poly (meth) acrylate. It is set to 0.001 mol to 0.95 mol. More preferably, it is 0.01 mol to 0.9 mol, and more preferably, it is set to 0.05 mol to 0.8 mol.

The reaction of the epoxy group-containing poly (meth) acrylate with a carboxylic acid is preferably performed in the presence of a catalyst and an organic solvent. Examples of the catalyst used in the reaction include compounds exemplified as the catalyst usable in the synthesis of the polymer (S). Among these compounds, a quaternary ammonium salt is preferable. The amount of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and even more preferably 0.1 parts by weight to 100 parts by weight of the epoxy-containing poly (meth) acrylate. 20 parts by weight.

Examples of the organic solvent used in the reaction include organic solvents that can be used in the polymerization of a (meth) acrylic monomer, and an ester is preferred among them. The organic solvent is The solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably used at a ratio of 0.1% by weight or more, and more preferably 5% to 50% by weight. % To use. The reaction temperature is preferably set to 0 ° C to 200 ° C, and more preferably set to 50 ° C to 150 ° C. The reaction time is preferably 0.1 to 50 hours, and more preferably 0.5 to 20 hours.

In this way, a solution containing a poly (meth) acrylate as the compound (X) was obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the poly (meth) acrylate contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated poly (methyl) ) After the acrylate is purified, it is provided to the preparation of the liquid crystal alignment agent. Isolation and purification of poly (meth) acrylate can be performed according to a known method.

The method of synthesizing the poly (meth) acrylate as the compound (X) is not limited to the method described above. For example, it can also be obtained by a method or the like in which a (meth) acrylic singular body having a partial structure represented by the formula (1) is obtained, or the (meth) acrylic singular body and another (meth) ) A mixture of acrylic monomers is polymerized in the presence of a polymerization initiator.

From the viewpoint of not only improving the liquid crystal alignment of the formed liquid crystal alignment film, but also ensuring the stability of the liquid crystal alignment over time, polystyrene is converted to polystyrene in terms of polystyrene by GPC. The number average molecular weight (Mn) is preferably 250 to 500,000, more preferably 500 to 100,000, and even more preferably 1,000 to 50,000.

<Other ingredients>

The liquid crystal alignment agent of the present invention contains the compound (X) as described above, and if necessary, May contain other ingredients. Examples of other components that can be added to the liquid crystal alignment agent include polymers other than the compound (X) and compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy-containing compounds"). , A functional silane compound, a compound having a photopolymerizable group (hereinafter referred to as a "photopolymerizable group-containing compound"), a photosensitizer, and the like.

[Other polymers]

The other polymers may be used for improving solution characteristics or electrical characteristics. The other polymer is a polymer that does not have a partial structure represented by the formula (1), and the main skeleton thereof is not particularly limited. Specific examples include derivatives derived from polyamic acid, polyimide, polyamidate, polyorganosiloxane, polyester, polyamine, cellulose derivatives, polyacetal, and polystyrene. Polymers, polymers such as poly (styrene-phenylcis butene diimide) derivatives, poly (meth) acrylates, and the like as main skeletons. Among these polymers, it is preferable to be selected from the group consisting of polyamidic acid, polyamidate, polyamidoimide, polyorganosiloxane, poly (meth) acrylate, and polyamidoamine. At least one polymer.

When other polymers are added to the liquid crystal alignment agent, the blending ratio of the other polymers is preferably 90 parts by weight or less with respect to 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent. It is more preferably set to 0.1 to 80 parts by weight, and even more preferably set to 0.1 to 70 parts by weight.

[Epoxy-containing compound]

The epoxy group-containing compound can be used in order to improve the adhesiveness or electrical characteristics of the liquid crystal alignment film to the substrate surface. The epoxy-containing compound as described above can be listed, for example. Examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 -Hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, N, N, N ', N'- Tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4 , 4'-Diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl -Cyclohexylamine and the like are preferred. Other examples of the epoxy group-containing compound include an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598.

When these epoxy compounds are added to the liquid crystal alignment agent, the blending ratio of the epoxy compound is preferably set to 40 parts by weight relative to 100 parts by weight of the total polymer contained in the liquid crystal alignment agent. Hereinafter, it is more preferably set to 0.1 to 30 parts by weight.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the printability of a liquid crystal alignment agent. Examples of the functional silane compound described above include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-amino group. Propyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldi Methoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethyl Oxysilylpropyltriethylene triamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl-3 Methyl 6,6-diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidyloxymethyltrimethyl Oxysilane, 2-glycidyloxyethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and the like.

When these functional silane compounds are added to the liquid crystal alignment agent, the ratio of the functional silane compound to the total amount of the polymer contained in the liquid crystal alignment agent is preferably set to 2 It is more preferably 0.02 parts by weight to 0.2 parts by weight.

[Photopolymerizable group-containing compound]

When the liquid crystal alignment ability is imparted by irradiating a coating film formed using a liquid crystal alignment agent with a light, a compound containing a photopolymerizable group can be used for the purpose of improving the alignment limiting force of the liquid crystal alignment film. Here, examples of the photopolymerizable group include a group having a polymerizable unsaturated bond, and specific examples thereof include (meth) acrylfluorenyloxy, styryl, and (meth) acrylamide Group, vinyl, vinylidene, vinyloxy (CH ₂ = CH-O-), maleimide and the like.

In terms of high photoreactivity, the photopolymerizable group-containing compound is preferably a (meth) acrylate compound, and specifically, for example, (meth) acrylate, (meth) ) Ethyl acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (methyl Monofunctional (meth) acrylic acid, such as acrylate, methoxytriethylene glycol (meth) acrylate, glycidyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate Acid esters; ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, polyether (meth) acrylate, ethoxy Polyfunctional (meth) acrylates such as bisphenol A di (meth) acrylate and the like.

When the photopolymerizable group-containing compound is added to the liquid crystal alignment agent, the compounding ratio of the photopolymerizable group-containing compound is preferably relative to 100 parts by weight of the total polymer contained in the liquid crystal alignment agent. It is 30 parts by weight or less, and more preferably 1 to 20 parts by weight.

[Photo sensitizer]

As the photosensitizer, various compounds having a photosensitizing function can be used. Here, the so-called "light sensitization function" refers to the fact that, after being irradiated with light, it becomes a singlet excited state, and as a result, an intersystem crossing is generated. If it collides with other molecules, it will change the other party to an excited state and itself The function of returning to the ground state. Specific examples of the photosensitizer include compounds represented by the following formulae (H-1) to (H-6).

In the case of using a photosensitizer, it is compared with the polymerization contained in the liquid crystal alignment agent. 100 parts by weight of the product, the blending ratio of the photosensitizer is preferably set to 0.01 to 50 parts by weight, and more preferably set to 0.1 to 20 parts by weight.

In addition, for other components, additives generally used in the preparation of liquid crystal alignment agents can be used. Examples of the additives other than the above include compounds having at least one oxetanyl group in the molecule, antioxidants, surfactants, dispersants, and the like.

<Solvent>

The liquid crystal alignment agent of the present invention is prepared in the form of a liquid composition in which the specific compound and other components used as necessary are preferably dispersed or dissolved in an appropriate solvent.

Examples of the organic solvent used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, and N, N-dimethylformamide. Acetylamine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate Ester, glycol methyl ether, glycol ether, glycol-n-propyl ether, glycol-isopropyl ether, glycol-n-butyl ether (butyl cellosolve), glycol dimethyl ether, ethyl Glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethyl ether Diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate and the like. These organic solvents may be used alone or in combination of two or more.

The liquid crystal alignment agent of the present invention may contain only one polymer as a polymer component, or may contain two or more polymers. The preferable aspect in the case of containing two or more types of polymers includes the following [1] to [3] and the like.

[1] Containing a polymer (hereinafter also referred to as "specific polymer") and other polymers as compound (X), and the specific polymer and other polymers are selected from the group consisting of polyamic acid, polyamic acid ester, A form of at least one of polyimide and polyimide.

[2] It contains a plurality of specific polymers, and the plurality of specific polymers are in the form of at least one selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyamido.

[3] Contains a specific polymer and other polymers, and the specific polymer is polyorganosiloxane, and the other polymers are selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyamido At least one form.

In addition, in the form of [1], it is presumed that by using a specific polymer as a polymer having a fluorine atom or a silicon atom, the specific polymer having a fluorine atom or a silicon atom is located in the upper layer, and does not have a fluorine atom and Other polymers of silicon atoms are located in the lower layer, so deviations in polymer distribution can be generated in the liquid crystal alignment film.

In addition, when the liquid crystal alignment agent containing the compound (X) is used, the reason for obtaining the effect of improving the afterimage characteristics and the contrast characteristic of the liquid crystal display element is not certain. As one of the hypotheses, consider the following. That is, it is considered that the compound (X) introduces a monovalent organic group into at least one of the α carbon and the β carbon of the carbonyl group, preferably the α carbon of the carbonyl group, in the partial structure represented by the formula (1), when the light is irradiated, and having (1) of the formula in which R ¹ and R ² is a hydrogen atom, a partial structure compound (cinnamyl acyl) as compared to photo-dimerization reaction is suppressed, a priority photoisomerization get on. Thereby, the alignment restricting force of the liquid crystal in the liquid crystal alignment film formed using the liquid crystal alignment agent containing the compound (X) is improved. As a result, it is estimated that the effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element is obtained.

The solid content concentration (the ratio of the total weight of components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) in the liquid crystal alignment agent of the present invention is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably from 1% by weight to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of a substrate by a method described later, and preferably is heated to form a coating film as a liquid crystal alignment film or a coating film as a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes 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 weight, the film thickness of the coating film becomes too large, and it is difficult to obtain a good liquid crystal alignment film. In addition, there are cases where the viscosity of the liquid crystal alignment agent increases and the coating property decreases. tendency.

A particularly preferable range of the solid content concentration varies depending on a method used when the substrate is coated with a liquid crystal alignment agent. For example, when the spinner method is used, the solid content concentration (the ratio of the total weight of all components except the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is in the range of 1.5% to 4.5% by weight . In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% to 9% by weight, thereby setting the solution viscosity to 12 mPa. s ~ 50mPa. The range of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% to 5% by weight, thereby setting the solution viscosity to 3 mPa. s ~ 15mPa. The range of s. The temperature when preparing the liquid crystal alignment agent of the present invention is preferably 10 ° C to 50 ° C, and more preferably 20 ° C to 30 ° C.

<Liquid crystal alignment film and liquid crystal display element>

Liquid crystal alignment can be produced by using the liquid crystal alignment agent of the present invention described above membrane. The liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited, and it can be applied to, for example, TN type, STN type, and Vertical Alignment (VA) type (including Vertical Alignment-Multi-domain Vertical) Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), In-Plane Switching (IPS) type, Fringe Field Switching , FFS) type, Optically Compensatory Bend (OCB) type and other action modes.

The liquid crystal display element of the present invention can be produced by, for example, a step including the following steps (1-1) to (1-3). Step (1-1) uses different substrates depending on the required operation mode. Steps (1-2) and (1-3) are shared in each operation mode.

[Step (1-1): Formation of Coating Film]

First, the liquid crystal alignment agent of the present invention is coated on a substrate, and then the coated surface is heated to form a coating film on the substrate.

(1-1A) In the case of manufacturing a TN type, STN type, or VA type liquid crystal display element, first, two substrates provided with a patterned transparent conductive film are used as a pair, and The transparent conductive film formation surface is preferably coated with the liquid crystal alignment agent of the present invention by a lithographic method, a spin coating method, a roll coater method, or an inkjet printing method, respectively. For the substrate, for example, glass such as float glass and soda glass; plastics including polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, and poly (alicyclic olefin) can be used. Transparent substrate. The transparent conductive film is provided on one surface of the substrate may be used: containing tin oxide (SnO ₂₎ of Naisai (a NESA) film (trademark of PPG Corporation), indium oxide - tin oxide (In ₂ O ₃ -SnO ₂₎ of Indium tin oxide (ITO) film and the like. In order to obtain a patterned transparent conductive film, for example, the following method may be used: After forming a transparent conductive film without a pattern, light is used. A method of forming a pattern by etching; a method of forming a transparent conductive film using a mask having a desired pattern; and the like. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface on which the coating film is formed may be coated with a functional silane compound or a functional titanium compound in advance. And so on.

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing the applied liquid crystal alignment agent from sagging or the like. The pre-baking temperature is preferably 30 ° C to 200 ° C, more preferably 40 ° C to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-baking time is preferably 0.25 minutes to 10 minutes, and more preferably 0.5 minutes to 5 minutes. Then, the solvent is completely removed, and if necessary, a calcination (post-baking) step is performed for the purpose of subjecting the ammonium acid structure present in the polymer to thermal ammonization. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and more preferably 120 ° C to 250 ° C. The post-baking time is preferably 5 minutes to 200 minutes, and more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this manner is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(1-1B) In the case of manufacturing an IPS-type or FFS-type liquid crystal display element, the electrode formation surface of a substrate provided with the following electrodes, and The liquid crystal alignment agent of the present invention is coated on one side of the substrate, and then each coated surface is heated to form a coating film. The electrode includes a transparent conductive film or a metal film patterned into a comb-tooth shape. Regarding the material, coating method, heating conditions after coating, the patterning method of the transparent conductive film or metal film, the substrate pretreatment, and the preferred coating film, the materials of the substrate and the transparent conductive film used at this time The film thickness is the same as that of (1-1A). As the metal film, for example, a film containing a metal such as chromium can be used.

In any of the cases (1-1A) and (1-1B), after the liquid crystal alignment agent is coated on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. At this time, the polyamidic acid, the polyamidate and the polyamidoimide prepared in the liquid crystal alignment agent of the present invention can be further heated after the coating film is formed to perform a dehydration ring-closing reaction to form a further compound.醯 imidized coating.

[Step (1-2): Alignment Capability Provisioning Process]

When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, a process of imparting a liquid crystal alignment ability to the coating film formed in the step (1-1) is performed. Thereby, the alignment ability of a liquid crystal molecule is given to a coating film, and it becomes a liquid crystal alignment film. Examples of the alignment ability imparting process include: rubbing treatment in which a coating film is rubbed in a certain direction by a roller wound with a cloth containing fibers such as nylon, rayon, and cotton; and optical alignment of the coating film with polarized or non-polarized radiation Processing, etc. On the other hand, in the case of manufacturing a VA-type liquid crystal display element, the coating film formed in the step (1-1) may be directly used as a liquid crystal alignment film, and an alignment ability imparting treatment may be performed on the coating film.

The light irradiation in the photo-alignment process can be obtained by the following methods: [1] After The method of irradiating the coating film after the baking step; [2] The method of irradiating the coating film after the pre-baking step and before the post-baking step; [3] at least the pre-baking step and the post-baking step In either step, a method of irradiating the coating film while heating the coating film, and the like. Among these methods, the method using [2] is preferable in terms of the high effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element.

As the radiation irradiating the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized, it may be linearly polarized or partially polarized. In addition, when the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction, or a combination of these irradiations may be performed. In the case of irradiating the non-polarized light, the direction of the irradiation is an oblique direction.

The light source used may be, 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. Ultraviolet rays in a preferable wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, and the like. Radiation irradiation amount is preferably ^{100J / m 2 ~ 50,000J / m} 2, more preferably ^{300J / m 2 ~ 20,000J / m} 2. In addition, in order to improve the reactivity, the coating film may be irradiated with light while being heated. The temperature during heating is usually 30 ° C to 250 ° C, preferably 40 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C.

In addition, the liquid crystal alignment film after the rubbing treatment may be further processed to make the liquid crystal alignment film have a different liquid crystal alignment ability in each region: a part of the liquid crystal alignment film is irradiated with ultraviolet rays to a part of the liquid crystal alignment film. Treatment of changing the pretilt angle; or forming a resist on a part of the surface of the liquid crystal alignment film After the film, a rubbing treatment is performed in a direction different from the rubbing treatment just before, and then the resist film is removed. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be used suitably for a polymer sustained alignment (PSA) type liquid crystal display element.

[Step (1-3): Construction of liquid crystal cell]

(1-3A) A liquid crystal cell is produced by preparing two substrates on which a liquid crystal alignment film is formed in the manner described above, and arranging liquid crystal between the two substrates disposed opposite to each other. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a previously known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together with a sealant, and the cells are divided by the substrate surface and the sealant. After the liquid crystal is injected into the gap, the injection hole is sealed to manufacture a liquid crystal cell. The second method is a method called a One Drop Fill (ODF) method. A predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, a UV-curable sealant, and the liquid crystal is added dropwise to predetermined locations on the liquid crystal alignment film. The liquid crystal alignment film is bonded to another substrate in a facing manner, and the liquid crystal is spread on the entire surface of the substrate. Then, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, thereby manufacturing a liquid crystal cell. In the case of using any of the methods, it is preferable that the liquid crystal cell manufactured as described above is further heated to a temperature at which the used liquid crystal obtains an isotropic phase, and then cooled to room temperature gradually, thereby removing the liquid crystal filling. Mobile alignment.

As the sealant, for example, a hardening agent and oxidation as a spacer can be used. Aluminum ball of epoxy resin, etc.

Examples of the liquid crystal include nematic liquid crystals and dish liquid crystals. Among them, nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, and phenyl rings can be used. Hexane-based liquid crystals, ester-based liquid crystals, bitriphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubic-based liquid crystals, and the like. In addition, these liquid crystals can also be used by adding the following substances: for example, cholesterol-type liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate; "C-15", "CB-15" (manufactured by Merck), chiral agents sold; iron such as p-decyloxymethylene-p-amino-2-methylbutyl cinnamate Electric liquid crystal and so on.

(1-3B) In the case of manufacturing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as described in (1-3A) except that a photopolymerizable compound is injected or dropped together with the liquid crystal. 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 can be, for example, 5V to 50V DC or AC. In addition, as the irradiated light, for example, ultraviolet rays including light having a wavelength of 150 to 800 nm and visible rays 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. In addition, the ultraviolet rays in the preferable wavelength region can be obtained by a method in which a light source is used in combination with a filter, a diffraction grating, and the like. The light irradiation amount is preferably 1,000 J / m ² or more and less than 200,000 J / m ² , and more preferably 1,000 J / m ² to 100,000 J / m ² .

(1-3C) In the case where a coating film is formed on a substrate using a liquid crystal alignment agent containing a compound (polymer or additive) having a photopolymerizable group, the following method may be adopted: ) A liquid crystal cell is constructed in the same manner, and a liquid crystal display element is manufactured by subjecting the liquid crystal cell to light irradiation in a state where a voltage is applied between the conductive films provided on a pair of substrates. According to this method, the advantages of the PSA mode can be realized with a small amount of light irradiation. The description of (1-3B) can be applied to the applied voltage or the conditions of the applied light.

Next, a liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include a polarizing plate sandwiching a polarizing film called "H film" with a cellulose acetate protective film or a polarizing plate including the H film itself. "It is made by absorbing iodine while extending the orientation of polyvinyl alcohol.

The liquid crystal display element of the present invention can be effectively applied to a variety of devices, such as: clocks, portable game consoles, word processors, notebook personal computers, car navigation, camcorders, and personal digital assistants (Personal Digital Assistant, Various display devices such as PDA), digital cameras, mobile phones, smart phones, various monitors, LCD televisions, and information displays.

[Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these examples.

In the following examples, the weight average score of a polymer was measured by the following method Sub-quantity Mw and epoxy equivalent. In addition, the compound represented by Formula A may be represented only as "compound A" below.

[Polymer average molecular weight Mw]

Mw is a polystyrene conversion value measured by GPC under the following conditions.

Column: Made by Tosoh, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ° C

Pressure: 68k gf / cm ²

[Epoxy equivalent]

The epoxy equivalent is measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

<Synthesis of Compound>

[Example 1-1: Synthesis of compound (b-1)]

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

9.6 g of 4-nitrobenzaldehyde and 15.0 g of methylmalonic acid were dissolved in 100 ml of pyridine, 12.5 ml of piperidine was added thereto, and the mixture was stirred at 80 ° C. for 5 hours. After the reaction solution was left to cool to room temperature, 100 ml of ethyl acetate was added, and then 100 ml of hydrochloric acid was added to separate the liquid. After pure water was separated again, it was concentrated to obtain 10.5 g of an intermediate (b-1-1) as a white solid with a purity of 99%.

10 g of the obtained intermediate (b-1-1) was added to 30 ml of thionyl chloride, and a catalytic amount of N, N-dimethylformamide was added, followed by stirring at 80 ° C for 1 hour. The reaction solution was concentrated, and the residue was dissolved in 100 ml of tetrahydrofuran. This solution was used as a reaction liquid (A). 9.4 g of 4-hydroxy-4'-nitrobiphenyl and 8.9 g of triethylamine were added to 60 ml of tetrahydrofuran, and the mixture was cooled to 0 ° C and stirred for 5 minutes. Then, the reaction solution (A) was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature for 4 hours to complete the reaction. 300 ml of ethyl acetate and 100 ml of tetrahydrofuran (THF) were added, and the solution was separated with hydrochloric acid, an aqueous sodium carbonate solution, and pure water, and then concentrated to obtain 19.0 g of a white solid intermediate with a purity of 99%. Body (b-1-2).

Next, 18.0 g of the intermediate (b-1-2) and 14.5 g of zinc powder were added to 150 ml of tetrahydrofuran, and 5.4 g of acetic acid was further added. Then, it stirred at 60 degreeC for 5 hours. After the reaction solution was left to cool to room temperature, 150 ml of ethyl acetate was added, and the mixture was separated with pure water. The solution was concentrated to obtain 13.5 g of a compound (b-1) as a yellow solid with 99% purity.

[Example 1-2: Synthesis of Compound (b-2)]

Except for the second stage of Scheme 1 of Example 1-1, 4-hydroxy-4'-nitro A compound (b-2) was obtained in the same manner as in Example 1-1 except that benzene was changed to 4-nitrophenol.

[Example 1-3: Synthesis of compound (b-3)]

Except that in the second stage of Scheme 1 of Example 1-1, 4-hydroxy-4'-nitrobiphenyl was changed to 4-amino-4'-nitrobiphenyl. It was synthesized by the same method to obtain compound (b-3).

[Example 1-4: Synthesis of compound (g-1)]

Except for changing 4-nitrobenzaldehyde to 4-phenylbenzaldehyde in the first stage of Scheme 1 of Example 1-1, the same operation as in the first stage of Scheme 1 was performed to obtain the compound in one stage ( g-1).

[Example 1-5: Synthesis of compound (b-27)]

The same procedure as in Example 1-1 was used except that 4-hydroxy-4'-nitrobiphenyl was changed to 2-methyl-4-nitroaniline in the second stage of Scheme 1 of Example 1-1. Method to synthesize to obtain compound (b-27).

[Example 1-6: Synthesis of compound (t-5)]

Compound (t-5) was synthesized according to the following scheme 2.

[Chemical 52]

5.0 g of piperazine and 12.3 g of triethylamine were dissolved in 100 ml of tetrahydrofuran, and the mixture was cooled to 0 ° C and stirred for 5 minutes. To this, a solution prepared by adding 12.1 g of methacrylic acid chloride to 100 ml of tetrahydrofuran was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature for 4 hours to complete the reaction. 300 ml of ethyl acetate was added, and the solution was separated with hydrochloric acid, sodium carbonate aqueous solution, and pure water, and then concentrated to obtain 11.6 g of an intermediate (t-5-1) as a white solid with a purity of 99%.

10 g of the obtained intermediate (t-5-1), 22.0 g of 4-bromophthalic acid, 1.0 g of palladium acetate, 2.7 g of tri (o-tolyl) phosphine, and 36.4 g of triethyl The base amine was added to 120 ml of N, N-dimethylacetamide. Then, it stirred at 60 degreeC for 6 hours. After the reaction solution was left to cool to room temperature, 300 ml of ethyl acetate was added, and the solution was separated with pure water. Hydrochloric acid was added to the obtained aqueous layer to form an acidic aqueous solution, and then ethyl acetate was added for liquid separation. Finally, the organic layer was separated with pure water and concentrated to obtain 20.0 g of an intermediate (t-5-2) as a pale yellow solid with a purity of 99%.

Then, 18.0 g of the intermediate (t-5-2) was added to 100 ml of acetic anhydride. Then, it stirred at 60 degreeC for 12 hours. After the reaction solution was left to cool to room temperature, the precipitated solid was filtered, washed with hexane, and dried to obtain 15.5 g of a compound (t-5) as a pale yellow solid with a purity of 99%.

<Synthesis of Polymer>

[Example 2-1: Synthesis of Polymer (A-1)]

100 mol parts of the compound represented by the formula (a-1) as a tetracarboxylic dianhydride and 100 mol parts of the compound (b-1) as a diamine were dissolved in N-methyl-2 -Pyrrolidone (N-methyl-2-pyrrolidone, NMP) was reacted at 60 ° C for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The weight average molecular weight Mw of the obtained polyamic acid (polymer (A-1)) was 45,000.

[Example 2-2 to Example 2-9 and Synthesis Example 1 to Synthesis Example 3]

Except that the types and amounts of the tetracarboxylic dianhydrides and diamines used were changed to those described in Table 1 below, polyamino acids (polymer (A -2) ~ polymer (A-9) and polymer (B-1) ~ polymer (B-3)).

In Table 1, the numerical values in parentheses of tetracarboxylic dianhydride and diamine represent the use ratio [mole part] with respect to the total of 100 mol parts of tetracarboxylic dianhydride used for polymer synthesis. The abbreviations in Table 1 have the following meanings.

<Tetracarboxylic dianhydride>

a-1: the compound represented by the formula (a-1)

a-2: the compound represented by the formula (a-2)

a-3: 1,3-propanediol bis (anhydrotrimellitate) (the compound represented by the formula (a-3))

a-4: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

a-5: 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride

a-6: pyromellitic dianhydride

t-5: the compound represented by the formula (t-5)

<Diamine>

b-1: a compound represented by the formula (b-1)

b-2: the compound represented by the formula (b-2)

b-3: a compound represented by the formula (b-3)

b-27: a compound represented by the formula (b-27)

c-1: Compound represented by the following formula (c-1)

c-2: Compound represented by the following formula (c-2)

c-3: p-phenylenediamine

c-4: N, N-bis (4-aminophenyl) methylamine

c-5: 4,4'-diamino-2,2'-dimethylbiphenyl

[Synthesis Example 4: Synthesis of Polymer (ES-1)]

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine were mixed at room temperature. Then, 100 g of pure water was slowly added dropwise, and then stirred at 80 ° C. for 6 hours. Then, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the washed water became neutral, and then it was concentrated to obtain a polyorganosiloxane having an epoxy group in the form of a thick transparent liquid. (ES-1). The epoxy-containing polyorganosiloxane (ES-1) The Mw was 2,200 and the epoxy equivalent was 186 g / mole.

[Example 2-10: Synthesis of polymer (S-1)]

9.3 g of the polyorganosiloxane (ES-1) having an epoxy group obtained in the Synthesis Example 4, 26 g of methyl isobutyl ketone, and 3 g of the compound obtained in the Examples 1-4 (g-1) and 0.10 g of UCAT 18X (trade name, quaternary amine salt manufactured by San-Apro Co., Ltd.) were mixed and stirred at 80 ° C. for 12 hours. Then, the precipitate produced by adding the reaction mixture to methanol was filtered, and the precipitate was dissolved in ethyl acetate to form a solution. The solution was separated with pure water and concentrated to obtain a white powder. 6.3 g of polyorganosiloxane (polymer (S-1)) was obtained as compound (X). The weight average molecular weight Mw of the polymer (S-1) was 4,000.

[Example 3-1]

1. Preparation of liquid crystal alignment agent

In a solution containing the polymer (A-1) obtained in Example 2-1 as a polymer component, NMP and a butyl cellosolve (BC) were added, and the mixture was sufficiently stirred to form a solvent composition of NMP: BC = 70: 30 (weight ratio) and a solid content concentration of 3.0% by weight. This solution was filtered using a filter having a pore size of 0.45 μm, thereby preparing a liquid crystal alignment agent.

2. Manufacturing of optical FFS liquid crystal display elements

An FFS-type liquid crystal display element 10 shown in FIG. 1 was produced. First, a glass substrate 11a having the following electrode pairs on one side and a counter glass substrate 11b not provided with an electrode are used as a pair on the surface of the glass substrate 11a having a transparent electrode and the counter glass. On one side of the substrate 11b, a spinner was used to apply the liquid crystal alignment agent prepared in 1. to form a coating film. The electrode pair was sequentially formed with a bottom electrode 15 without a pattern and silicon nitride as an insulating layer 14. A film, and a top electrode 13 patterned into a comb-tooth shape.

A schematic plan view of the used top electrode 13 is shown in FIGS. 2 (a) and 2 (b), where E represents an electrode and F represents a pixel edge portion. 2 (a) is a plan view of the top electrode 13, and FIG. 2 (b) is an enlarged view of a portion C1 surrounded by a dotted line in FIG. 2 (a). In this embodiment, the line width d1 of the electrodes is set to 4 μm, and the distance d2 between the electrodes is set to 6 μm. In addition, the top electrode 13 is a driving electrode of four systems using an electrode A, an electrode B, an electrode C, and an electrode D (FIG. 3). In addition, the bottom electrode 15 functions as a common electrode that functions for all the drive electrodes of the four systems, and the areas of the drive electrodes of the four systems each become a pixel area.

After the coating film was formed using a spinner, the coating film was pre-baked for 1 minute under a hot plate at 80 ° C. Then, on each surface of the coating film, a Hg-Xe lamp and a Glan-Taylor prism were used to irradiate polarized ultraviolet rays of 5,000 J / m ² to obtain a pair of substrates having a liquid crystal alignment film. At this time, the irradiation direction of the polarized ultraviolet rays is set from the normal direction of the substrate, and the direction of the line segment projected on the substrate by the polarized surface of the polarized ultraviolet rays is set to the direction of the double-sided arrow in FIG. Light irradiation treatment is performed. After light irradiation, it was heated (post-baked) at 230 ° C. for 1 hour in an oven in which nitrogen was replaced in the warehouse to form a coating film having an average film thickness of 0.1 μm.

Then, an alumina having a diameter of 3.5 μm was applied to the outer periphery of the surface of the substrate having a liquid crystal alignment film on one of the substrates by screen printing. After the epoxy resin adhesive of the ball, the liquid crystal alignment films of a pair of substrates are faced to each other, and the direction of projecting the polarized surface of the polarized ultraviolet rays to the substrate is parallel and superposed, and it is pressed for one hour at 150 ° C. The adhesive is thermally hardened. Then, the liquid crystal injection port was filled with a liquid crystal "MLC-7028" manufactured by Merck, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to eliminate the flow alignment during the liquid crystal injection, it was heated to 150 ° C. and then slowly cooled to room temperature.

Next, FPS liquid crystal display elements were manufactured by laminating polarizing plates on both surfaces of the substrate. At this time, one of the polarizing plates is attached so that the polarizing direction becomes parallel to the projection direction of the polarizing surface of the polarized ultraviolet rays of the liquid crystal alignment film on the substrate surface, and the other is such that the polarizing direction is parallel to the polarizing plate just now. The polarizing directions are attached in an orthogonal manner.

In addition, the above-mentioned series of operations are performed by changing the ultraviolet irradiation amount before the post-baking in the range of 100 J / m ² to 10,000 J / m ² to manufacture three or more liquid crystal display elements having different ultraviolet irradiation amounts. .

3. Evaluation of liquid crystal display elements

The following evaluation (1) was performed using the liquid crystal display element manufactured in said 2 .. A liquid crystal display element (a liquid crystal cell without a polarizing plate bonded) was manufactured by performing the same operation as in 2. except that the polarizing plate was not bonded, and the following (2) was evaluated. In addition, as for the evaluation result, an optimal result was selected from three or more liquid crystal display elements having different amounts of ultraviolet irradiation, and the results were provided for evaluation of the liquid crystal display element.

(1) Evaluation of AC afterimage characteristics

The FFS-type liquid crystal display element manufactured in 2. described above was placed in an environment of 25 ° C and 1 atmosphere. The bottom electrode is a common electrode for all the driving electrodes of the four systems, and the potential of the bottom electrode is set to a potential of 0 V (ground potential). The electrodes B and D were short-circuited to a common electrode to be in a 0V application state, and a combined voltage including an AC voltage of 5V was applied to the electrodes A and C for 100 hours. Immediately after 100 hours, a voltage of 1.5 V AC was applied to all of the electrodes A to D. Next, from the moment when the voltage of AC 1.5V was applied to all of the electrodes A to D, the driving stress application area (pixel area of electrode A and electrode C) and the driving stress unapplied area could no longer be confirmed visually. (The pixel area of the electrode B and the electrode D). In addition, the shorter this time, the more difficult it is to generate an afterimage. A case where the afterimage erasing time Ts is less than 30 seconds is evaluated as "good (○)", a case where 30 seconds or more is less than 120 seconds is evaluated as "OK (△)", and a case where 120 seconds or more is evaluated as "bad (○) ×) ", as a result, the liquid crystal display element of this example was evaluated as having" good "afterimage characteristics.

(2) Evaluation of contrast after driving stress

After the liquid crystal display element manufactured in 2. was driven at an AC voltage of 10V for 30 hours, a device in which a polarizer and an analyzer were arranged between a light source and a light amount detector was used to measure the expression represented by the following formula (1) Minimum relative transmittance (%).

Minimum relative transmittance (%) = (β-B ⁰ ) / (B ¹⁰⁰ -B ⁰ ) × 100 ... (1)

(In Mathematical Formula (1), B ⁰ is the amount of light transmitted under the cross Nicol in the blank sample; B ¹⁰⁰ is the amount of light transmitted under the parallel Nicol in the blank sample; β is orthogonal (Nicole clamps the liquid crystal display element between the polarizer and the analyzer to minimize the transmission)

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element. The smaller the black level in the dark state, the better the contrast; those with a minimum relative transmittance of less than 0.5% are regarded as "good (○)" and 0.5 % Or more and less than 1.0% are regarded as "possible (△)", and those with 1.0% or more are regarded as "bad (×)". As a result, the contrast evaluation of this liquid crystal display element was judged as "good."

[Examples 3-2 to 3-10 and Comparative Example 1]

A liquid crystal alignment agent was prepared at the same solvent ratio and solid content concentration as those of Example 3-1 except that the type of the polymer used was changed to that shown in Table 2 below. In addition, using each liquid crystal alignment agent, a liquid crystal display element was manufactured in the same manner as in Example 3-1, and various evaluations were performed using the obtained liquid crystal display element. The results are shown in Table 2 below.

In a liquid crystal display element manufactured using a liquid crystal alignment agent containing the compound (X), the evaluation of the AC afterimage characteristics and the contrast characteristics were "good" or "may" in any of the examples. (Examples 3-1 to 3-10). In particular, in Examples 3-1 to 3-7 and 3-9 to 3-10, which have a partial structure represented by the formula (1) in the main chain of the polymer, and Good results were obtained in Examples 3-8 in which the side chain of the polysiloxane skeleton had this partial structure. In addition, it was found that by using a diamine having a polycyclic structure such as a biphenyl structure, the effect of improving the afterimage characteristics of AC is improved.

On the other hand, in the liquid crystal alignment agent of the comparative example which does not contain the compound (X), AC afterimage characteristics and contrast characteristics are worse than the liquid crystal alignment agent of an Example.

Claims (14)

A liquid crystal alignment agent containing a compound (X) having a partial structure represented by the following formula (1), and containing a compound selected from the group consisting of polyamic acid, polyimide, polyamidate, and polyorganosiloxane As the compound (X), at least one polymer (A) in the formed group, (In the formula (1), R ¹ is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms, R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and R ³ is a substituent; wherein R ¹ And at least one of R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms; X ¹ is an oxygen atom; R ³ may also be bonded to other groups to form at least a part of a ring; n is an integer of 0 to 4 ; In the case where n is 2 or more, a plurality of R ³ may be the same or different; "*" represents a bonding bond). The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the polymer (A) is at least one polymer selected from the group consisting of polyamidic acid, polyamidate, and polyimide And a partial structure derived from a specific diamine selected from the group consisting of a compound represented by the following formula (2-1) and a compound represented by the following formula (2-2) At least one of the groups: H ₂ NR ⁵ -A ¹ -R ⁶ -A ² -R ⁷ -NH ₂ (2-1) (In formula (2-1), A ¹ is the following formula (1-1 ) Or a group represented by the following formula (1-2), and A ² is a single bond, a group represented by the following formula (1-1), or a group represented by the following formula (1-2) When A ¹ is a group represented by the following formula (1-1), R ⁵ is a divalent organic group, and A ¹ is a group represented by the following formula (1-2) In the case of a group, R ⁵ is a single bond or a divalent organic group; when A ² is a group represented by the following formula (1-1), R ⁷ is a divalent organic group, and when A ² is When the group or single bond represented by formula (1-2) is described, R ⁷ is a single bond or a divalent organic group; R ⁶ is a divalent organic group; wherein, the following formula (1-1) and formula (1-2) The "* 1" bonded to R ⁶⁾ in ^{R 8 -A 1 -R 9 -A 2} -R 10 (2-2) ( the formula (2-2), A ¹ and A ² in the formula (2 -1) have the same meaning; when A ¹ is a group represented by the following formula (1-1), R ⁸ is a monovalent organic group, and A ¹ is represented by the following formula (1-2) When R ⁸ is a hydrogen atom or a monovalent organic group, in the case where R ⁸ is a hydrogen atom, A ¹ has a diaminophenyl group, and when R ⁸ is a monovalent organic group R ⁸ has a diaminophenyl group; when A ² is a group represented by the following formula (1-1), R ¹⁰ is a monovalent organic group, and A ² is the following formula (1-2 In the case of a group or a single bond represented by), R ¹⁰ is a hydrogen atom or a monovalent organic group; R ⁹ is a divalent organic group; * 1 '' is bonded to R ⁹ ) (In the formula (1-1) and formula (1-2), R ¹ , R ² , R ³ , X ¹ and n have the same meaning as the formula (1); “* 1” represents a bonding bond). The liquid crystal alignment agent according to item 2 of the scope of patent application, wherein the specific diamine has a partial structure represented by the following formula (4) in the molecule, (In formula (4), Ar ¹ and Ar ² are each independently substituted or unsubstituted phenylene or substituted or unsubstituted cyclohexyl, and X ² is a single bond, -COO-, or- CONR ^20- (R ²⁰ is a hydrogen atom or a monovalent organic group); wherein, Ar ¹ may also constitute a benzene ring in the formula (1); t is 1 or 2; when t = 2, Ar ² and X ² Have the definitions independently; "*" indicates a bond). The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the polymer (A) is at least one polymer selected from the group consisting of polyamidic acid, polyamidate, and polyimide And has a partial structure derived from a specific acid dianhydride that is at least one selected from the group consisting of a compound represented by the following formula (5-2), (In formula (5-2), R ¹⁸ is a divalent organic group, R ¹⁹ is an aromatic ring group, an alicyclic group, or a heterocyclic group; R ¹ , R ^2, and X ¹ and the formula (1) are Same meaning). The liquid crystal alignment agent according to item 1 of the patent application range, wherein the polymer (A) contains a partial structure formed by a reaction of a polyorganosiloxane having an epoxy group with a carboxylic acid, and The acid includes a compound represented by the following formula (3), (In formula (3), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula (1- A group represented by 1) or a group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ¹¹ is a monovalent organic group In the case where A ¹ is a group represented by the following formula (1-2), R ¹¹ is a hydrogen atom or a monovalent organic group; R ¹² is a divalent organic group; and A ² is the following formula (1 In the case of a group represented by -1), R ¹³ is a divalent organic group, and when A ² is a group represented by the following formula (1-2), R ¹³ is a single bond or a divalent organic group S and r are each independently 0 or 1; wherein, there is one carboxyl group in formula (3); "* 1" in the following formula (1-1) and formula (1-2) is bonded to R ¹² ) (In the formula (1-1) and formula (1-2), R ¹ , R ² , R ³ , X ¹ and n have the same meaning as the formula (1); “* 1” represents a bonding bond). The liquid crystal alignment agent according to item 5 of the scope of patent application, wherein the compound represented by the formula (3) has a partial structure represented by the following formula (4) in a molecule, (In formula (4), Ar ¹ and Ar ² are each independently substituted or unsubstituted phenylene or substituted or unsubstituted cyclohexyl, and X ² is a single bond, -COO-, or- CONR ^20- (R ²⁰ is a hydrogen atom or a monovalent organic group); wherein, Ar ¹ may also constitute a benzene ring in the formula (1); t is 1 or 2; when t = 2, Ar ² and X ² Have the definitions independently; "*" indicates a bond). The liquid crystal alignment agent according to any one of claims 1 to 6, wherein R ² is an alkyl group having 1 to 10 carbon atoms. A method for manufacturing a liquid crystal alignment film, comprising: applying a liquid crystal alignment agent according to any one of claims 1 to 7 on a substrate to form a coating film; and applying the coating film; The film is subjected to a step of light irradiation. A liquid crystal alignment film is formed by using the liquid crystal alignment agent according to any one of claims 1 to 7 of the scope of patent application. A liquid crystal display element includes the liquid crystal alignment film according to item 9 of the scope of patent application. A polymer selected from the group consisting of polyamidic acid, polyamidoimide, polyamidate, and polyorganosiloxane, and having a formula (1) Partial structure, (In formula (1), R ¹ is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms, R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and R ³ is a monovalent organic group; wherein, At least one of R ¹ and R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms; X ¹ is an oxygen atom; R ³ may also be bonded to other groups to form at least a part of a ring; n is 0 to 4 Integer; when n is 2 or more, multiple R ³ may be the same or different; "*" represents a bonding bond). A diamine compound represented by the following formula (2-1) or formula (2-2): H ₂ NR ⁵ -A ¹ -R ⁶ -A ² -R ⁷ -NH ₂ (2-1) (In formula (2-1), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula ( A group represented by 1-1) or a group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ⁵ is divalent An organic group, when A ¹ is a group represented by the following formula (1-2), R ⁵ is a single bond or a divalent organic group; and A ² is a group represented by the following formula (1-1) In the case of a group, R ⁷ is a divalent organic group, and when A ² is a group or a single bond represented by the following formula (1-2), R ⁷ is a single bond or a divalent organic group; R ⁶ is a divalent organic group; wherein "* 1" in the following formulae (1-1) and (1-2) is bonded to R ⁶ ) R ⁸ -A ¹ -R ⁹ -A ² -R ¹⁰ (2-2) (In the formula (2-2), A ¹ and A ² have the same meaning as the formula (2-1); and A ¹ is a group represented by the following formula (1-1) case, R ⁸ is a monovalent organic group, a ¹ is in the (1-2) in the case of a group represented by, R ⁸ is a hydrogen atom or a monovalent organic group of the following formula; wherein R ⁸ is in Case atom, A ¹ has diaminophenyl, R ⁸ is in the case of a monovalent organic group, R ⁸ having diaminophenyl; to A ² is represented by the following formula (1-1) In the case of a group, R ¹⁰ is a monovalent organic group, and when A ² is a group or a single bond represented by the following formula (1-2), R ¹⁰ is a hydrogen atom or a monovalent organic group; R ⁹ is a divalent organic group; "* 1" in the following formulae (1-1) and (1-2) is bonded to R ⁹ ) (In formulas (1-1) and (1-2), R ¹ is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms, R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and R is ³ is a substituent; wherein at least one of R ¹ and R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms; X ¹ is an oxygen atom; n is an integer of 0 to 4; and when n is 2 or more In the following, multiple R ³ may be the same or different; "* 1" represents a bonding bond). An acid dianhydride represented by the following formula (5-2), (In formula (5-2), R ¹⁸ is a divalent organic group, R ¹⁹ is an aromatic ring group, an alicyclic group, or a heterocyclic group; R ¹ is a hydrogen atom, a fluorine atom, or an alkane having 1 to 10 carbon atoms. And R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms, wherein at least one of R ¹ and R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms; X ¹ is an oxygen atom). A carboxylic acid represented by the following formula (3), (In formula (3), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula (1- A group represented by 1) or a group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ¹¹ is a monovalent organic group In the case where A ¹ is a group represented by the following formula (1-2), R ¹¹ is a hydrogen atom or a monovalent organic group; R ¹² is a divalent organic group; and A ² is the following formula (1 In the case of a group represented by -1), R ¹³ is a divalent organic group, and when A ² is a group represented by the following formula (1-2), R ¹³ is a single bond or a divalent organic group S and r are each independently 0 or 1; wherein, there is one carboxyl group in formula (3); "* 1" in the following formula (1-1) and formula (1-2) is bonded to R ¹² ) (In formulas (1-1) and (1-2), R ¹ is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms, R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and R is ³ is a substituent; wherein at least one of R ¹ and R ² is a fluorine atom or an alkyl group having 1 to 10 carbon atoms; X ¹ is an oxygen atom; n is an integer of 0 to 4; and when n is 2 or more In the following, multiple R ³ may be the same or different; "* 1" represents a bonding bond).