KR20160095610A - Liquid crystal aligning agent, liquid crystal alignment film and manufacturing method therefor, liquid crystal device, polymer, diamine, and acid dianhydride - Google Patents

Abstract

Provide is a liquid crystal aligning agent capable of obtaining a liquid crystal device having fine afterimage and contrast features. A compound X having a partial structure expressed in formula 1 as mentioned below is contained into the liquid crystal aligning agent. (R^1 and R^2 are independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a monovalent organic group, and R^3 is a substituent; X^1 is an oxygen atom or -NR^4- (R^4 is a halogen atom or a monovalent organic group, and R^4 is preferably bonded to other groups to form a ring structure together with a nitrogen atom); R^3 is preferably bonded to other groups to form at least a part of the ring; n is an integer within a range of 0-3; and * is referred to as bonding loss.)

Description

TECHNICAL FIELD The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a method for producing a liquid crystal alignment film, a liquid crystal device, a polymer, a diamine and an acid anhydride,

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a process for producing a liquid crystal alignment film, a liquid crystal device, a polymer, a diamine and an acid dianhydride.

BACKGROUND ART Liquid crystal display devices are widely used in televisions, mobile devices, monitors, and the like. In the liquid crystal display element, a liquid crystal alignment film is used for alignment control of liquid crystal molecules in the liquid crystal cell. As a method of obtaining an organic film having a liquid crystal alignment regulating force, conventionally, a method of rubbing an organic film, a method of obliquely depositing silicon oxide, a method of forming a monomolecular film having a long chain alkyl group, a method of irradiating light to a photosensitive organic film (Photo alignment method) and the like are known.

The photo-alignment method has recently been undergoing various investigations because it can impart uniform liquid-crystal alignability to a photosensitive organic film while suppressing the generation of static electricity and dust, and can also precisely control the liquid crystal alignment direction ( For example, Patent Document 1). Patent Document 1 discloses that a liquid crystal alignment film is formed using a polyimide precursor having a cinnamoyl group in its main chain, a liquid crystal aligning agent containing polyimide or polyamide.

International Publication No. 2013/161984

In recent years, liquid crystal televisions, which are large in size and large in size, have become mainstreams, and the spread of small-sized display terminals such as smart phones and tablet PCs has been increasing, and the demand for fixed screens for liquid crystal panels is further increasing. Concretely, it is important to improve the display quality of the liquid crystal display element that the afterimage is difficult to occur (afterimage characteristic) and that the contrast is good (contrast characteristic), and further improvement of these properties is required.

An object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal device having good afterimage characteristics and contrast characteristics.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to achieve the above-mentioned problems of the prior art and as a result, they found that the above problems can be solved by producing a liquid crystal alignment film using a liquid crystal aligning agent containing a compound having a specific structure, And has reached the completion of the invention. Specifically, the following means are provided.

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

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group or a monovalent organic group; R ³ is a substituent;

X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ is bonded to another group to form a ring structure together with the nitrogen atom);

R ³ may be bonded to another group to form at least a part of a ring;

n is an integer of 0 to 3; when n is 2 or 3, plural R ³ may be the same or different;

&Quot; * " indicates a combined hand).

[2] A process for producing a liquid crystal alignment film, comprising the step of applying the liquid crystal aligning agent of [1] above to 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 aligning agent of [1] above.

[4] A liquid crystal device comprising the liquid crystal alignment film according to [3] above.

[5] A polymer having at least one polymer selected from the group consisting of a polyimide precursor, polyimide and polyamide, and having a partial structure represented by the formula (1).

[6] The diamine represented by the following formula (2-1):

(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, Or a group represented by the following formula (1-2);

R ⁵ is a divalent organic group when A ¹ is a group represented by the following formula (1-1) and is a single bond or a divalent organic group when A ¹ is a group represented by the following formula (1-2);

R ⁷ is a divalent organic group when A ² is a group represented by the following formula (1-1), A ² is a single bond or a divalent organic group when A ² is a group represented by the following formula (1-2), A ^{When the divalent group} is a single bond;

R ⁶ is a divalent organic group;

Provided that "* 1" in the following formulas (1-1) and (1-2) is bonded to R ⁶ );

(In the formulas (1-1) and (1-2), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group or a monovalent organic group; R ³ is a substituent;

X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ is bonded to another group to form a ring structure together with the nitrogen atom);

n is an integer of 0 to 3; when n is 2 or 3, plural R ³ may be the same or different;

Quot; * 1 " and " * "

[7] An acid anhydride represented by the following formula (3-1) or (3-2):

(In the formula (3-1), R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group or a monovalent organic group; i is 0 or 1;

R ⁵⁰ is a single bond or a divalent organic group when i = 0, and is a divalent organic group when i = 1;

X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ may be bonded to another group to form a ring structure together with the nitrogen atom);

However, in the case of i = 1, a plurality of X ¹ in the formula has at the defined independently);

(In the formula (3-2), R ⁵⁵ and R ⁵⁶ are each independently a trivalent organic group; R ⁵⁷ to R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, And k is 0 or 1;

X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ may be bonded to another group to form a ring structure together with the nitrogen atom);

However, in the case of k = 1, a plurality of X ¹ in the formula has at the defined independently).

According to the liquid crystal aligning agent containing the above compound (X), it is possible to obtain a liquid crystal device in which a residual image (in particular residual image due to an alternating voltage) is hardly generated and a contrast characteristic is excellent.

1 is a schematic configuration diagram of an FFS type liquid crystal display device.
2 is a schematic plan view of a top electrode used for manufacturing a liquid crystal display element by photo-alignment treatment. Fig. 2 (a) is a top view of the top electrode, and Fig. 2 (b) is a partial enlarged view of the top electrode.
Fig. 3 is a diagram showing four types of driving electrodes.

(Mode for carrying out the invention)

Hereinafter, each component contained in the liquid crystal aligning agent of the present invention and other components arbitrarily blended as required will be described. In the present specification, the term "organic group" means a group containing a hydrocarbon group, and may include a hetero atom in the structure.

≪ Compound (X) >

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

Examples of the monovalent organic group represented by 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, a fluoroalkyl group having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an epoxy group, an alkylsilyl group, and an alkoxysilyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Here, the alkyl group having 1 to 20 carbon atoms may be linear or branched. Specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, Decyl groups, and the like. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group;

Examples of the fluoroalkyl group having 1 to 20 carbon atoms include a perfluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group and the like;

Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group and the like;

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group and the like;

Examples of the aralkyl group having 6 to 20 carbon atoms include a benzyl group and the like;

Respectively.

R ¹ and R ² are preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

R ⁴ in -NR ⁴ - is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a protecting group. Examples of the protecting group include a carbamate-based protecting group, an amide-based protecting group, an imide-based protecting group, and a sulfonamide-based protecting group. Preferably, it is a carbamate-based protecting group, particularly preferably a t-butoxycarbonyl group. R ⁴ may bond to another group to form a ring structure together with the nitrogen atom. Examples of such a ring structure include a piperidine structure and a piperazine structure.

Examples of the substituent for R ³ include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, alkylsilyl groups, alkoxysilyl groups, . Examples of the ring formed by combining R ³ with another group include imide rings and acid anhydride groups. n is preferably 0 or 1, and more preferably 0. It also includes the case where " * " in the formula (1) is bonded to a hydrogen atom. In addition, "*" may be bonded to R ³ to form a ring structure such as an acid anhydride group.

The compound (X) may be a polymer component that can be a main component of the liquid crystal alignment film, or an additive component that is separately blended with the polymer component. When the compound (X) is a polymer, the compound (X) may have a partial structure represented by the formula (1) in the main chain of the polymer or may have the side chain. Here, the " main chain " of the polymer in the present invention refers to a portion of the " stem " composed of the longest chain of atoms in the polymer. It is also permissible for this part of the stem to include ring structures. Therefore, "having the partial structure represented by the above formula (1) in the main chain of the polymer" means that the partial structure constitutes a part of the main chain. However, it does not exclude that the partial structure represented by the above formula (1) is also present in a part other than the main chain, for example, a side chain (a part branched from the "stem" of the polymer).

Among them, the compound (X) is preferably a polymer having a partial structure represented by the above formula (1), and preferably has a partial structure represented by the above formula (1) in view of high anisotropy manifesting effect by the photoalignment method. It is particularly preferable that the polymer is in the main chain.

When the compound (X) is a polymer, the main skeleton is not particularly limited, and examples thereof include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylate, and the like. Among them, at least one (meth) acrylate selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyamide, polyorganosiloxane and poly (meth) acrylate is preferably used from the viewpoints of heat resistance, mechanical strength, And more preferably at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyamide, and more preferably at least one kind selected from the group consisting of polyamic acid, polyamic acid ester and polyimide More preferably at least one kind of polymer selected. The polymer used for the preparation of the liquid crystal aligning agent may be one kind or two or more kinds. (Meth) acrylate is meant to include acrylate and methacrylate.

[Polyamic acid]

The polyamic acid (hereinafter also referred to as "specific polyamic acid") as the compound (X) can be obtained, for example, by reacting a tetracarboxylic acid dianhydride with a diamine. Specifically, [1] a method of performing polymerization by using tetracarboxylic acid dianhydride having a partial structure represented by the above formula (1) (hereinafter also referred to as "specific tetracarboxylic acid dianhydride"), [2] (Hereinafter, also referred to as " specific diamine "), [3] a method of polymerizing the specific tetracarboxylic acid dianhydride and the specific diamine, and the like .

(Tetracarboxylic acid dianhydride)

The specific structure of the specific tetracarboxylic acid dianhydride is not particularly limited as long as it has the partial structure represented by the formula (1). Preferably, the partial structure represented by the formula (1) can be introduced into the main chain of the polymer. Specifically, the compound is selected from the group consisting of the compounds represented by the formulas (3-1) and (3-2) Is preferably used.

In the formula (3-1), examples of the divalent organic group represented by R ⁵⁰ include a divalent 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 divalent heterocyclic group, and the like. At least one hydrogen atom of the hydrocarbon group may be substituted with a substituent.

Here, the "hydrocarbon group" in the present specification is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these, "chain hydrocarbon group" means a straight chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and are composed of only a chain structure. However, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only a structure of an alicyclic hydrocarbon and not containing an aromatic ring structure as the ring structure. However, it is not always necessary to be constituted by only the structure of alicyclic hydrocarbons, and some of them include those having a chain structure. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it need not be constituted only of an aromatic ring structure, and a part thereof may contain a chain structure or a structure of an alicyclic hydrocarbon.

As specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R < ^{50 &} gt ;, the chain hydrocarbon group includes a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, An octanediyl group, a nonanediyl group, a decanediyl group and the like;

As the alicyclic hydrocarbon group, for example, a cyclohexylene group, -R ³⁰ -R ³¹ - (wherein R ³⁰ is a cyclohexylene group and R ³¹ is an alkanediyl group having 1 to 3 carbon atoms);

An aromatic hydrocarbon group, for example, phenylene group, biphenylene group, naphthylene group, -Ar ³ -R ³² - (However, Ar ³ is phenylene group, biphenylene group or naphthylene group, R ³² having a carbon number of 1 to An alkanediyl group or a cyclohexylene group;

Respectively.

Examples of the divalent heterocyclic group of R ⁵⁰ include a group in which two hydrogen atoms have been removed from a nitrogen-containing heterocycle such as piperidine, piperazine, piperidine and the like. Examples of the substituent which the divalent organic group of R ⁵⁰ may have include a halogen atom, an alkoxy group, a hydroxyl group, a carboxyl group and a cyano group. The description of R ¹ and R ^{2 in} the above formula (1) can be applied to R ⁵¹ to R ⁵⁴ . i is preferably 1.

In the formula (3-2), examples of the trivalent organic group represented by R ⁵⁵ and R ⁵⁶ include a benzene ring, a group obtained by removing three hydrogen atoms from a cyclohexane ring, and the like. For R ⁵⁷ to R ⁶⁰ , the description of R ¹ and R ^{2 in} the above formula (1) can be applied. k is preferably 1.

Specific examples of the specific tetracarboxylic acid dianhydride include compounds represented by the above-mentioned formulas (3-1-1) to (3-1-30) as compounds represented by the above formula (3-1) ;

Examples of the compound represented by the formula (3-2) include compounds represented by the following formulas (3-2-1) to (3-2-12), and the like. Specific tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

(In the formulas (3-1-29) and (3-1-30), R is a fluorine atom or a methyl group, and k1 is an integer of 0 to 2. A plurality of R in the formula may be the same or different.)

In the case of the method [1] and the method [3], the tetracarboxylic acid dianhydride used in the synthesis of a specific polyamic acid may be only the specific tetracarboxylic acid dianhydride. However, tetracarboxylic acid having no partial structure represented by the formula (1) Acid dianhydrides (hereinafter also referred to as "other tetracarboxylic dianhydrides") may be used in combination. In the method [2], other tetracarboxylic acid dianhydrides are used as tetracarboxylic acid dianhydrides in the synthesis of a specific polyamic acid. Examples of other tetracarboxylic acid dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like.

Specific examples of other tetracarboxylic acid dianhydrides include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic dianhydride, the following formulas (AN-2) and (AN-3)

(In the formula (AN-2), X ¹³ and X ¹⁴ are each independently a group in which one hydrogen atom has been removed from the methylene group or a nitrogen atom, and R ⁴¹ is an alkanediyl group having 1 to 10 carbon atoms. aN-3) of, and X ¹⁵ and X ¹⁶ are, each independently, a group removing one hydrogen atom from a methylene group or a nitrogen atom, B ¹ and B ² are each independently a phenyl group or a pyridinyl group, R ⁴² is an alkanediyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 3. When m is 2 or 3, a plurality of R ^{42 s} may be the same or different.)

And the like;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid 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 [ Furan-1, 3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione- 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2 : 3,5: 6-2 anhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydride, bicyclo [2.2.1] heptane- 2,3,5,6-tetracarboxylic acid. 2: 3,5: 6-2 anhydride, 4,9- dioxa-tricyclo [5.3.1.0 ^2,6] undeca -3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetra Carbonic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, the following formula (AN-4)

And the like;

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, the following formula (AN-1)

(Formula (AN-1) of, 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 represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms, "*" represents a bond with R ²² ), R ²² represents a single bond, A divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent group containing -O- between carbon-carbon bonds of the hydrocarbon group, or a divalent group having a nitrogen-containing heterocyclic group).

, Compounds represented by the following formulas (AN-5-1) to (AN-5-4)

And the like;

The tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used.

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ⁴¹ and R ⁴² in the formulas (AN-2) and (AN-3) include a methylene group, an ethylene group, a propylene group, a butane diyl group, A dodecyl group, a hexadiyyl group, a heptadialyl group, an octadiyl group, a nonanediyl group and a decanediyl group, and they may be linear or branched. B ¹ and B ² are preferably a 1,4-phenylene group or a 2,5-pyridinylene group.

Specific examples of the compound represented by the formula (AN-2) include a compound represented by the following formula (a-2), and specific examples of the compound represented by the formula (AN-3) And compounds represented by each of the following formulas (AN-3-1) to (AN-3-12).

(In the formulas (AN-3-1) to (AN-3-12), p is an integer of 2 to 6. The plurality of p in the formulas may be the same or different.)

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ²² in the formula (AN-1) include a methylene group, an ethylene group, a propylene group, a butane diyl group, a pentanediyl group, Alkanediyl groups such as heptanediyl, octanediyl, nonanediyl and decanediyl;

A divalent alicyclic hydrocarbon group such as a cyclohexylene group;

Bivalent aromatic hydrocarbon groups such as a phenylene group and a biphenylene group;

And the like. The number of oxygen atoms which may be introduced between the carbon-carbon bonds of the hydrocarbon group may be one or two or more. When R ²² is a divalent group having a nitrogen-containing heterocyclic ring, examples of the nitrogen-containing heterocyclic ring include pyrrole ring, imidazole ring, pyridine ring, pyrazine ring, pyridazin ring, piperidine ring, piperazine ring, Pyrrolidine ring and the like.

Specific examples of the compound represented by the formula (AN-1) include compounds represented by the following formulas (AN-1-1) to (AN-1-27) Compounds, and compounds represented by the following formula (a-3).

In the synthesis of a specific polyamic acid, the tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

Other tetracarboxylic acid dianhydrides preferably include at least one member selected from the group consisting of aliphatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrons from the viewpoint of electrical properties, The compound represented by the above formula (a-2), bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-2 anhydride, 1,2,3,4- Cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5- (2,5 -Dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [l, 2-c] furan-l, 3-dione, 5- (2,5-dioxotetrahydro Furan-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2- c] furan-1,3-dione, bicyclo [3.3.0] , 6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl, 1,3-propylene glycol And at least one compound selected from the group consisting of bis (anhydrotrimellitate) and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride. The amount of these preferable compounds to be used (in the case of using two or more kinds thereof, the total amount thereof) is preferably 10 mol% or more, more preferably 20 mol% or more based on the total amount of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid , And more preferably 50 mol% or more.

In the above method [1], the use ratio of the specific tetracarboxylic acid dianhydride is preferably at least 10 mol%, more preferably at least 10 mol%, based on the total amount of the tetracarboxylic acid dianhydride used for synthesis of the specific polyamic acid, , More preferably 20 mol% or more, and still more preferably 30 mol% or more.

The specific tetracarboxylic acid dianhydrides can be synthesized by appropriately combining the stereochemistry of organic chemistry. For example, by reacting a compound having "-C (R ¹ ) = C (R ² ) -CO-X ¹ -" with a phthalic acid derivative, a tetracarboxylic acid having a partial structure represented by the formula (1) And then conducting the acid anhydride treatment of the obtained tetracarboxylic acid. However, the method of synthesizing the specific tetracarboxylic acid dianhydride is not limited to the above.

(Diamine)

The specific structure of the specific diamine is not particularly limited as long as it has the partial structure represented by the formula (1). When the alignment regulating force is applied to the coating film by using the photo alignment method, the effect of reducing the AC afterimage (residual image caused by the accumulation of charges due to the application of the AC voltage) and improving the contrast in the resulting liquid crystal display element is high , It is preferable to use the compound represented by the formula (2-1).

In the formula (2-1), the description of R ⁵⁰ in the formula (3-1) can be applied to the divalent organic group of R ⁵ to R ⁷ . R ⁵ and R ⁷ are preferably a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, or -Ar ⁴ -COO- * ³ (Ar ⁴ represents a phenylene group, a biphenylene group, a naphthylene group, Cyclohexylene group, and " * ³ " represents a bonding bond with the benzene ring in the formula (1)). R ⁶ is preferably an alkanediyl group having 1 to 6 carbon atoms, a cyclohexylene group, a phenylene group, a biphenylene group or a naphthylene group. The description of the formula (1) can be applied to the description of R ¹ , R ² , R ³ and X ¹ in the formulas (1-1) and (1-2).

The specific diamine is preferably a compound having a partial structure represented by the following formula (4) in the molecule. By having the partial structure represented by the following formula (4), it is suitable in that the effect of reducing the occurrence of AC afterimage in the liquid crystal display element can be enhanced.

(In the formula (4), Ar ¹ and Ar ² are each independently a phenylene group or a cyclohexylene group, X ² is a single bond, -COO- or -CONR ²⁰ - (R ²⁰ is a hydrogen atom or a monovalent organic group unit Im) a. t is 1 or 2. when t = 2 il, Ar ^2, X ² has the above-defined independently of each other. "*" represents a bonding hand.)

Examples of the monovalent organic group represented by R ²⁰ in the formula (4) include an alkyl group having 1 to 6 carbon atoms, a protecting group, and the like. Specific examples of the protecting group include a t-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-. Specific examples of the partial structure represented by the formula (4) include, for example, 4,4'-biphenylene group, 4,4'-bicyclohexylene group, the following formulas (4-1) to ), And the like.

(In the formula, " * "

Specific examples of the specific diamine include compounds represented by each of the following formulas (b-1) to (b-53). The use of the compound represented by the formula (2-1) as the specific diamine is preferable in that a polymer having the partial structure represented by the formula (1) in the main chain can be obtained.

(In the formulas (b-34) to (b-39) and (b-46) to (b-50), R is a fluorine atom or a methyl group, and k1 is an integer of 0 to 2. In the formula R in the formula (b-46) to formula (b-50) may be the same or different from each other.

In the synthesis of a specific polyamic acid, specific diamines may be used singly or in combination of two or more. (B-1), (b-2), (b-7) -31) and the compound represented by the formula (b-50) correspond to the compound having the partial structure represented by the formula (4).

Specific diamines can be synthesized by appropriately combining the stereochemistry of organic chemistry. As an example thereof, a dinitro intermediate having a nitro group in place of the primary amino group of the compound represented by the formula (2-1) is synthesized, followed by amination of the resulting nitro group of the dinitro intermediate using a suitable reducing system . The method for synthesizing the dinitro intermediate can be appropriately selected depending on the desired compound. For example, a dehydration condensation reaction of a carboxylic acid having a group corresponding to the formula (1) and an alcohol, a dehydration condensation reaction of a carboxylic acid having a group corresponding to the formula (1) with an amine compound, or the like . The reduction reaction of the dinitro intermediate can be carried out in an organic solvent, for example, using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin or nickel. Examples of the organic solvent include ethyl acetate, toluene, tetrahydrofuran, alcohol, and the like. However, the order of synthesis of the specific diamine is not limited to the above method.

When a specific polyamic acid is synthesized by the above method [2] or [3], a specific diamine may be used alone, or a diamine (other diamine) having no partial structure represented by the formula (1) Maybe. In the method [1], the other diamine is used as the diamine.

Such other diamines include, for example, aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 2'-diamino-N-methyldiethylamine, a compound represented by the following formula (da-6), and the like;

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), a compound represented by the following formula (da-9) Compounds and the like;

As the aromatic diamine, there may be mentioned, for example, dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, pentadecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminobenzoyloxy) cholestane, diaminobenzoic acid cholestearyl, diaminobenzoic acid lanostanyl, Bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1- Heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4- ( (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4-

^Wherein X ^I and X ^II each independently represents a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^ⅱ is an alkanediyl group of a single bond or a carbon number of 1~3, a is 0 or 1, b is an integer of 0~2, c is an integer from 1 to 20, and d is 0 or 1. However, a And b are not 0 at the same time.)

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

Containing diamines such as compounds represented by the following formula:

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzo Bis (4-aminophenoxy) pentane, 1,7-bis (4-aminophenoxy) heptane, bis [2- ] Hexane diacid, N, N-bis (4-aminophenyl) 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, Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4 , 4 '- (p-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoalkane N, N'-bis (4-aminophenyl) benzene, N, N'-bis (Da-3) to (da-5), (di-3) to da-7) and (da-8);

As the diaminoorganosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like;

A compound represented by the following formula (da-11) and a diamine described in JP-A-2010-97188 can be used. As the diamine to be used for the synthesis of the polyamic acid, one of these compounds may be used alone or two or more of them may be appropriately selected and used.

(Of the formulas (da-9) to (da-11), u is an integer of 2 to 6)

In the case of synthesizing a specific polyamic acid by the above method [2], the use ratio of the specific diamine is preferably from 1 to 10, more preferably from 1 to 10, Is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more.

When the specific polyamic acid is synthesized by the above method [3], the total amount of the specific tetracarboxylic acid dianhydride and the specific diamine is preferably 10 mol% or more with respect to the total amount of the monomers used in the synthesis , More preferably 20 mol% or more, and still more preferably 30 mol% or more.

(Synthesis of polyamic acid)

The polyamic acid can be obtained by reacting a tetracarboxylic acid dianhydride and a diamine as described above together with a molecular weight modifier, if necessary. The ratio of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic acid dianhydride is 0.2 to 2 equivalents based on 1 equivalent of the amino group of the diamine. Examples of the molecular weight adjuster include maleic anhydride, phthalic anhydride, itaconic anhydride, the following formulas (F-1) to (F-4)

, Monoamine compounds such as aniline, cyclohexylamine and n-butylamine, monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate, and the like. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride and diamine to be used.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and the reaction time is preferably 0.1 to 24 hours. Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, Triamide, m-cresol, xylenol and halogenated phenol as a solvent, or a mixture of at least one selected from the group consisting of an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon and a hydrocarbon Is preferably used. The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50 wt% with respect to the total amount (a + b) of the reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided in the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution.

[Polyamic acid ester]

Examples of the polyamic acid ester as the compound (X) include: [I] a method of reacting a polyamic acid having a partial structure represented by the formula (1) with an esterifying agent; [II] a method of reacting a tetracarboxylic acid diester and a diamine [III] a method of reacting a diamine with a tetracarboxylic acid diester dihalide, and the like.

Examples of the esterifying agent used in the method [I] include a hydroxyl group-containing compound (methanol, ethanol, phenol, etc.), an acetal compound (N, N-dimethylformamide diethylacetal, etc.), a halide Methyl, etc.), and epoxy group-containing compounds. In the method [II], at least one of a tetracarboxylic acid diester having a partial structure represented by the above formula (1) and a specific diamine is used. In the method [III], at least one of a tetracarboxylic acid diester dihalogenide having a partial structure represented by the above formula (1) and a specific diamine is used.

The polyamic acid ester to be contained in the liquid crystal aligning agent may have only an amide ester structure, or may be a partial esterified product in which the amide structure and the amide ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be directly supplied to the preparation of the liquid crystal aligning agent, or the polyamic acid ester contained in the reaction solution may be isolated and then provided in the preparation of the liquid crystal aligning agent.

[Polyimide]

The polyimide as the compound (X) can be obtained, for example, by dehydrating and ring closure of a polyamic acid as the compound (X) synthesized as described above to imidize it. The polyimide may be a completely imidized product obtained by dehydrating and ring closure of the entire acid structure of the polyamic acid which is a precursor of the polyimide and may be a partially imidized product in which only a part of the acid structure is subjected to dehydration ring closure, good. The imide ratio of the polyimide used in the reaction is preferably 20% or more, and more preferably 30 to 99%. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating a polyamic acid, or a method of dissolving a polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and optionally heating . Of these, the latter method is preferable.

In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 占 폚, and the reaction time is preferably 1.0 to 120 hours.

In this way, a reaction solution containing polyimide is obtained. This reaction solution may be provided as it is in the preparation of the liquid crystal aligning agent as it is, or may be provided in the preparation of the liquid crystal aligning agent after the polyimide is isolated. In addition, the polyimide may be obtained by imidization of a polyamic acid ester.

The polyamic acid, the polyamic acid ester and the polyimide as the compound (X) obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s and a viscosity of 15 to 500 mPa · s s of solution viscosity. The solution viscosity (mPa 占 퐏) of the polymer is preferably 10% by weight or less, more preferably 10% by weight or less, based on the polymer Solution at 25 占 폚 using an E-type rotational viscometer (the same applies to the following polymers).

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of polyamic acid, polyamic acid ester and polyimide in the present invention is preferably 1,000 to 500,000, more preferably 2,000 ~ 300,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less. Within this molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

[Polyamide]

The polyamide as the compound (X) can be obtained by, for example, a method of reacting a dicarboxylic acid with a diamine. Here, it is preferable that the dicarboxylic acid is provided for the reaction with the diamine after acid chloridation using a suitable chlorinating agent such as thionyl chloride.

The dicarboxylic acid used for the synthesis of the polyamide is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid and fumaric acid;

Dicarboxylic acids having an alicyclic structure such as cyclobutanedicarboxylic acid and cyclohexanedicarboxylic acid;

Examples of the organic acid include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-carbonylbenzoic acid, Dicarboxylic acids having an aromatic ring such as phenylene diacrylic acid;

And the like. The dicarboxylic acid may be used singly or in combination of two or more kinds.

A polyamide having a partial structure represented by the above formula (1) can be obtained by using at least a part of a specific diamine as a diamine used for synthesizing a polyamide as the compound (X). In addition, other diamines may be used in combination at the time of synthesis. The diamines may be used singly or in combination of two or more.

The use ratio of the dicarboxylic acid and the diamine provided in the synthesis reaction of the polyamide is preferably such that the carboxyl group of the dicarboxylic acid is equivalent to 0.2 to 2 equivalents based on 1 equivalent of the amino group of the diamine. The reaction of the dicarboxylic acid (preferably dicarboxylic acid obtained by acid chloridation) with the diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature at this time is preferably 0 ° C to 200 ° C, and the reaction time is preferably 0.5 to 48 hours. As the organic solvent, for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like can be preferably used. The amount of the organic solvent to be used is preferably 400 to 900 parts by weight based on 100 parts by weight of the total amount of the dicarboxylic acid and the diamine. As the base used in the above reaction, for example, tertiary amines such as pyridine, triethylamine and N-ethyl-N, N-diisopropylamine can be preferably used. The base is preferably used in an amount of 2 to 4 mol based on 1 mol of the diamine.

As described above, a reaction solution obtained by dissolving polyamide is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided in the preparation of the liquid crystal aligning agent after the polyamide contained in the reaction solution is isolated.

The solution viscosity of the polyamide as the compound (X) preferably has a solution viscosity of 10 to 800 mPa · s and a solution viscosity of 15 to 500 mPa · s Do. The weight average molecular weight (Mw) of the polyamide in terms of polystyrene 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 "specific polyorganosiloxane") as the compound (X) can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. Examples thereof include [1] a hydrolyzable silane compound (s-1) having a partial structure represented by the above formula (1), or a hydrolyzable silane compound (s- (S-2) having an epoxy group or a mixture of the silane compound (s-2) and another silane compound is subjected to hydrolysis and condensation to form an epoxy group Containing polyorganosiloxane and then reacting the resultant epoxy group-containing polyorganosiloxane with a carbonic acid having a partial structure represented by the above formula (1) (hereinafter also referred to as "specific carbonic acid"), etc. .

Examples of the silane compound (s-1) include a silane compound having a partial structure represented by the above formula (1) in a molecular chain, and examples thereof include compounds represented by the following formula (s-1A).

(In the formula (s-1A), R ⁸ and R ⁹ are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and each of X ³ and X ⁴ is independently an alkyl group having 1 to 12 carbon atoms R ¹ and r 2 are each independently 1 or 2. A ¹ , A ² , R ⁵ , R ⁶ and R ⁷ have the same meanings as in the formula (2-1).)

Specific examples of the alkyl group and aryl group of R ⁸ and R ⁹ and the alkoxy group of X ³ and X ⁴ in the formula (s-1A) include those exemplified as R ¹ and R ² in the formula (1) , And the corresponding number of carbon atoms. The description of the formula (2-1) can be applied to each of the exemplified and preferable specific examples of A ¹ , A ² , R ⁵ , R ⁶ and R ⁷ in the formula (s-1A). The compound represented by the formula (s-1A) can be synthesized by appropriately combining the methods of organic chemistry.

In the above synthesis, the use ratio of the silane compound (s-1) is preferably 5 mol% or more, more preferably 10 to 100 mol%, based on the total amount of the monomers used in the synthesis, And more preferably 10 to 80 mol%.

Specific examples of the silane compound (s-2) include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like. As the silane compound (s-2), one kind or a mixture of two or more kinds of them can be used.

The other silane compounds are not particularly limited as long as they are hydrolyzable silane compounds. Examples thereof include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, Alkoxysilanes such as phenyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane;

3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Nitrogen-sulfur atom-containing alkoxysilanes such as propyltriethoxysilane, N- (3-cyclohexylamino) propyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane;

Acrylates such as 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 3- Unsaturated hydrocarbon-containing alkoxysilanes such as acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and p-styryltrimethoxysilane;

Trimethoxysilylpropylsuccinic anhydride, and the like. The other silane compounds may be used singly or in combination of two or more.

In the method [1], the silane compound (s-2) may be used as the other silane compound. In the method [2], the silane compound (s-1) may be used as the other silane compound.

The hydrolysis / condensation reaction of the silane compound is carried out by reacting one or more silane compounds as described above with water, preferably in the presence of a suitable catalyst and an organic solvent. In the hydrolysis-condensation reaction, the use ratio of water is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, per 1 mole of the silane compound (total amount). Examples of the catalyst used in the hydrolysis and condensation reaction include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. Of these, tertiary or quaternary organic bases are preferred. The amount of the organic base to be used differs depending on the kind of the organic base, the reaction conditions such as the temperature and the like, and should be appropriately set, but is preferably 0.01 to 3 times by mol, more preferably 0.05 to 1 It is a boat mall. Examples of the organic solvent used in the hydrolysis and condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols and the like, of which water-insoluble organic solvents are preferably used. The use ratio of the organic solvent is preferably 10 to 10,000 parts by weight based on 100 parts by weight of the total silane compound used in the reaction.

The hydrolysis / condensation reaction is preferably carried out by heating, for example, in a water bath. At this time, the heating temperature is preferably 130 ° C or less, and the heating time is preferably 0.5 to 12 hours. After completion of the reaction, the desired organic polyorganosiloxane can be obtained by drying the organic solvent layer collected from the reaction liquid, if necessary, with a desiccant and then removing the solvent. The method of synthesizing the polyorganosiloxane is not limited to the hydrolysis-condensation reaction as described above. For example, a method of reacting the hydrolyzable silane compound in the presence of oxalic acid and alcohol may be employed.

In the above method [2], the epoxy group-containing polyorganosiloxane obtained by the above reaction is subsequently reacted with a specific carbonic acid. As a result, the epoxy group of the epoxy group-containing polyorganosiloxane reacts with the carbonic acid, and a polyorganosiloxane having a partial structure represented by the formula (1) in the side chain can be obtained. Specific examples of the specific carbonic acid include, for example, compounds represented by the following formula (5).

(In the formula (5), A ¹ and A ² each have the same meaning as in the formula (2-1). However, "* 1" in the above formulas (1-1) represents a bonding hand bonded to R ^13. R ¹² is, a ¹ is a monovalent organic group in the case represented by the above formula (1-1), if a ¹ is a group represented by the above formula (1-2) is a hydrogen atom or a monovalent organic group. R ¹³ is a divalent organic group. R ¹⁴ is, a ² is a divalent organic group in the case group represented by the formula (1-1), a ² is the formula (1 S and r are each independently 0 or 1, provided that they have one carboxyl group in the formula (5)).

Examples of the monovalent organic group represented by R ¹² in the formula (5) include a monovalent hydrocarbon group of 1 to 20 carbon atoms, a part of the methylene group of the hydrocarbon group is -O-, -CO-, -COO- Or a monovalent group substituted with -NR ³³ - (R ³³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a monovalent heterocyclic group, and the like, which may have a substituent. Examples of the divalent organic groups represented by R ¹³ and R ¹⁴ may be the same as those described for R ⁵ to R ⁷ in the formula (2-1). For the explanation of R ¹ , R ² , R ³ and X ¹ of A ¹ and A ² , the description of the above formula (1) can be applied.

The specific carbonic acid preferably has a partial structure represented by the formula (1) and further a partial structure represented by the formula (4) in the molecule, from the viewpoint of enhancing the effect of reducing the AC residual image. In addition, as a preferable specific example of the partial structure represented by the formula (4), the description of the specific diamine can be applied. In the reaction of the epoxy group-containing polyorganosiloxane with the specific carbonic acid, the specific carbonic acid may be used singly or in combination of two or more kinds.

The content ratio of the partial structure represented by the formula (1) in one molecule of the specific polyorganosiloxane is preferably 3 to 3 for the silicon atom contained in the specific polyorganosiloxane from the viewpoint of improving the sensitivity to light To 100 mol%, more preferably 5 mol% to 95 mol%, and still more preferably 10 mol% to 90 mol%. Therefore, in the synthesis of a specific polyorganosiloxane, it is preferable to select the use ratio of the specific carbonic acid so that the content ratio of the partial structure represented by the formula (1) falls within the above range.

In addition, the specific carbonic acid can be synthesized by appropriately combining the stereochemistry of organic chemistry. As an example thereof, a compound represented by "R ¹² -A ¹ -H" and a compound represented by "HO-R ¹³ -A ² -R ¹⁴ -COOM (M is a protecting group of a carboxyl group) Preferably in an organic solvent, optionally in the presence of a catalyst, followed by deprotection. However, the synthesis procedure of the specific carbonic acid is not limited to the above method.

In the synthesis of a specific polyorganosiloxane, the carbonic acid used for the reaction with the epoxy group-containing polyorganosiloxane may be only a specific carbon acid, but other carbonic acid other than the specific carbonic acid may be used in combination. The other carbonic acid is not particularly limited as long as it is a carbonic acid having no partial structure represented by the formula (1). The other carbonic acid may be used singly or in combination of two or more kinds.

The use ratio of the carbonic acid to be reacted with the epoxy group-containing polyorganosiloxane is preferably 0.001 to 1.5 mol, more preferably 0.01 to 1.0 mol, per 1 mol of the total of the epoxy groups of the polyorganosiloxane. The use ratio of other carbonic acid is preferably 80 mol% or less, more preferably 50 mol% or less, based on the total amount of the carbonic acid to be reacted with the epoxy group-containing polyorganosiloxane from the viewpoint of sufficiently obtaining the effect of the present invention .

The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent. As the catalyst to be used, for example, known compounds such as so-called curing accelerators for promoting the reaction of organic bases and epoxy compounds can be used. The use ratio of the catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, based on 100 parts by weight of the epoxy group-containing polyorganosiloxane.

Examples of the organic solvent used in the reaction include hydrocarbons, ethers, esters, ketones, amides, and alcohols. Particularly preferred examples of the solvent include 2-butanone, 2-hexanone, methyl isobutyl ketone, and butyl acetate. The organic solvent is preferably used in such a ratio that the solid concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) becomes 0.1 wt% or more. The reaction temperature in the above reaction is preferably 0 to 200 캜, and the reaction time is preferably 0.1 to 50 hours.

The specific polyorganosiloxane obtained as described above preferably has a solution viscosity of 1 to 500 mPa · s and a solution viscosity of 3 to 200 mPa · s Do. The weight average molecular weight (Mw) of the specific polyorganosiloxane measured by GPC in terms of polystyrene is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 20,000.

[Poly (meth) acrylate]

The poly (meth) acrylate (hereinafter also referred to as "specific polymer (M)") as the compound (X) can be obtained by, for example, the following method [1] or [2];

[1] A method of polymerizing (meth) acrylic monomer (m-1) having a partial structure represented by the above formula (1) or a mixture of said (meth) acrylic monomer (m- A method of polymerization in the presence of an initiator,

(2) A method of polymerizing a mixture of the (meth) acrylic monomer (m-2) having an epoxy group or the mixture of the (meth) acrylic monomer (m-2) and other (meth) acrylic monomers in the presence of a polymerization initiator, A method of reacting the obtained polymer (hereinafter also referred to as "epoxy group-containing poly (meth) acrylate") with a specific carbon acid,

And the like.

Examples of the (meth) acrylic monomer (m-1) include a di (meth) acrylate compound having a molecular structure represented by the formula (1) And the like.

A ¹ , A ² , R ⁵ , R ⁶ and R ⁷ have the same meanings as in the above formula (2-1), and R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a methyl group. to be.)

The description of the formula (2-1) can be applied to each of the exemplified and preferable specific examples of A ¹ , A ² , R ⁵ , R ⁶ and R ⁷ in the formula (m-1A). The compound represented by the formula (m-1A) can be synthesized by appropriately combining the methods of organic chemistry.

The proportion of the (meth) acrylic monomer (m-1) used in the above synthesis is preferably 5 mol% or more, more preferably 10 to 100 mol%, based on the total amount of the monomers used in the synthesis , More preferably from 10 to 90 mol%.

Specific examples of the (meth) acrylic monomer (m-2) include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, 3,4-epoxybutyl (meth) acrylate, (Meth) acrylic acid (3-ethyloxetan-3-yl) methyl, and the like can be given as examples of the epoxy group- . The (meth) acrylic monomer (m-2) may be used alone or in combination of two or more.

Examples of other (meth) acrylic monomers include unsaturated carboxylic acids such as (meth) acrylic acid, (meth) acrylic acid? -Carboxypolycaprolactone, crotonic acid,? -Ethylacrylic acid, maleic acid, fumaric acid and vinylbenzoic acid;

(Meth) acrylate, methoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl Unsaturated carboxylic acids such as (meth) acrylic acid esters such as N, N-dimethylaminoethyl acrylate, methoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and 2-hydroxyethyl (meth) ester;

Unsaturated polycarboxylic acid anhydrides such as maleic anhydride;

And the like. As other (meth) acrylic monomers, one type may be used alone, or two or more types may be used in combination. In the method [1], the (meth) acrylic monomer (m-2) may be used as the other (meth) acrylic monomer, (m-1) may be used.

In the polymerization, other monomers other than the (meth) acrylic monomers may be used. Examples of other monomers include conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene;

Aromatic vinyl compounds such as styrene, methylstyrene and divinylbenzene;

And the like. The use ratio of other monomers is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total amount of monomers used in the synthesis of poly (meth) acrylate.

The polymerization reaction using the (meth) acrylic monomer is preferably carried out by radical polymerization. Examples of the polymerization initiator used in the polymerization reaction include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis Azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile) are preferable. The proportion of the polymerization initiator to be used is preferably 0.01 to 50 parts by weight based on 100 parts by weight of the total monomers used in the reaction. The polymerization reaction is preferably carried out in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds and the like, and diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate and the like are preferable. The amount (a) of the organic solvent used is preferably such that the total amount (b) of the monomers used in the reaction is from 0.1 to 50 wt% with respect to the total amount (a + b) of the reaction solution. The reaction temperature is preferably 30 ° C to 120 ° C, and the reaction time is preferably 1 to 36 hours.

In the method of [2] above, the epoxy group-containing poly (meth) acrylate obtained by the above reaction is subsequently reacted with a specific carboxylic acid. Thereby, the epoxy group of the epoxy group-containing poly (meth) acrylate reacts with the carbonic acid to obtain the poly (meth) acrylate having the partial structure represented by the formula (1) in the side chain.

As specific examples of the specific carbon acid, the description of the specific polyorganosiloxane can be applied. In the reaction, the specific carbonic acid may be used singly or other carbonic acid other than the specific carbonic 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 0.001 to 0.95 mol, more preferably 0.01 to 0.9 mol, per mol of the total epoxy group of the epoxy group-containing poly (meth) Is more preferable.

The reaction between the epoxy group-containing poly (meth) acrylate and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent. As the catalyst, a quaternary ammonium salt is particularly preferable. The amount of the catalyst to be used is preferably 100 parts by weight or less, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the epoxy group-containing poly (meth) acrylate. As the organic solvent to be used in the reaction, an example of an organic solvent that can be used at the time of polymerization of the (meth) acrylic monomer can be applied, and among them, an ester is preferable. The organic solvent is preferably used in such a ratio that the solid concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) becomes 0.1 wt% or more. The reaction temperature is preferably 0 to 200 캜, and the reaction time is preferably 0.1 to 50 hours.

Thus, a solution containing poly (meth) acrylate as compound (X) can be obtained. This reaction solution may be directly supplied to the preparation of a liquid crystal aligning agent or may be provided in preparation of a liquid crystal aligning agent after the poly (meth) acrylate contained in the reaction solution is isolated.

As to the poly (meth) acrylate, the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably such that the liquid crystal alignability of the liquid crystal alignment film to be formed is improved and the stability of the liquid crystal alignment property over time is ensured , It is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

<Other components>

The liquid crystal aligning agent of the present invention contains the compound (X) as described above, but may contain other components as necessary. For example, the liquid crystal aligning agent of the present invention may contain other polymers other than the compound (X) for the purpose of improving solution characteristics and electrical characteristics. Such another polymer is a polymer having no partial structure represented by the above formula (1), and its main skeleton is not particularly limited. Specific examples thereof include polyamidic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) ) Acrylate as a main skeleton. Among these, at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly (meth) acrylate and polyamide is preferable. When the other polymer is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 90 parts by weight or less, preferably 0.1 to 80 parts by weight, relative to 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent And more preferably 0.1 to 70 parts by weight.

As other components, additives commonly used for the preparation of a liquid crystal aligning agent can be used. Examples of the additives other than the above include a compound having at least one epoxy group in the molecule, a functional silane compound, a compound having a photopolymerizable group, a photosensitizer, a compound having at least one oxetanyl group in the molecule, Surfactants, dispersants, and the like. These compounding ratios can be appropriately selected depending on the compound.

<Solvent>

The liquid crystal aligning agent of the present invention is prepared as a liquid composition in which the above specific compound and other components to be used as required are dispersed or dissolved in an appropriate solvent.

Examples of the organic solvent to be used include organic solvents such as N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol- propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamylphosphate Propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used alone or in combination of two or more.

The liquid crystal aligning agent in the present invention may contain only one kind of polymer as a polymer component, or may contain two or more kinds of polymers. Preferable examples of the case of containing two or more kinds of polymers include, for example, the following [1] to [3] and the like.

[1] The positive resist composition according to any one of [1] to [4], wherein the positive resist composition contains at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, Sun.

[2] The sun having at least one specific polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide.

[3] The sun containing at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, wherein the specific polymer is a polyorganosiloxane and the other polymer is a polyorganosiloxane.

The compound (X) is at least one member selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and the compound represented by the formula (2-1), the compound represented by the formula (3-1) Is a polymer having a partial structure derived from at least one compound selected from the group consisting of a compound represented by the above formula (3-2) and a compound represented by the above formula (3-2). That is, a polymer having at least one kind selected from the group consisting of a partial structure represented by the following formula (6) and a partial structure represented by the following formula (7).

(In the formulas (6) and (7), R ⁶¹ represents a tetravalent organic group, R ⁶² represents a divalent organic group, and each of X ⁶¹ and X ⁶² independently represents a hydroxyl group or a monovalent organic group, R ⁶¹ and R ⁶² satisfy at least one of the following (i) and (ii): (i) R ⁶¹ is a group derived from a compound represented by the formula (3-1) or the formula (3-2) (Ii) R ⁶² is a residue obtained by removing two primary amino groups from the compound represented by the above formula (2-1).

The monovalent organic group of X ⁶¹ and X ⁶² is preferably a monovalent hydrocarbon group or a group having a cinnamic acid structure.

The reason why the effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element is obtained when using the liquid crystal aligning agent containing the compound (X) is not clear, but one hypothesis is that, for example, , The "-CR ¹ ═CR ² -CO-" moiety in the formula (1) is isomerized into a cis structure in the molecular chain of the compound (X) in which the major axis direction of the molecular chain is parallel to the polarization direction, (Cyclization) reaction proceeded to cleave the molecular chain (see Scheme A below). As a result, it was presumed that anisotropy was developed in a direction perpendicular to the polarization direction, and a sufficient liquid crystal aligning ability was imparted to the coating film, resulting in improvement of afterimage characteristics and contrast characteristics of the liquid crystal display element.

The solid concentration of the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., Is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent in the present invention is applied to the surface of the substrate as described later, and preferably heated to form a coating film which is a liquid crystal alignment film or a liquid crystal alignment film. At this time, when the solid concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large and it becomes difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent tends to be increased and the coatability tends to be lowered. The temperature for preparing the liquid crystal aligning agent is preferably 10 to 50 캜, more preferably 20 to 30 캜.

<Liquid Crystal Alignment Film and Liquid Crystal Device>

By using the above-described liquid crystal aligning agent, a liquid crystal alignment film can be produced. Further, the liquid crystal device of the present invention comprises a liquid crystal alignment film formed using the liquid crystal aligning agent. The operation mode of the liquid crystal in the liquid crystal device is not particularly limited. For example, TN mode, STN mode, VA mode (including VA-MVA type and VA-PVA type), IPS mode, FFS mode, And the like.

The liquid crystal device of the present invention can be produced, for example, by a process including the following steps (1-1) to (1-3). In the step (1-1), the substrate to be used differs depending on the desired operation mode. Processes (1-2) and (1-3) are common to the respective operation modes.

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

First, a liquid crystal aligning agent of the present invention is coated on a substrate, and then a coated film is formed on the substrate by heating the coated surface.

(1-1A) For example, in the case of producing a liquid crystal display device of TN type, STN type or VA type, first, two substrates on which a patterned transparent conductive film is formed are paired, The liquid crystal aligning agent of the present invention is preferably applied by offset printing, spin coating, roll coatering, or inkjet printing. Examples of the substrate include glass such as float glass and soda glass;

A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film to be formed on one surface of the substrate, an ITO film made of NESA film (a registered trademark of PPG Corporation of the US) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) .

Preheating (prebaking) is preferably performed for the purpose of preventing the liquid flow of the applied liquid crystal aligning agent after application of the liquid crystal aligning agent. The prebaking temperature is preferably 30 to 200 占 폚, and the prebaking time is preferably 0.25 to 10 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the acid structure present in the polymer. The baking temperature (post baking temperature) at this time is preferably 80 to 300 占 폚, and the post baking time is preferably 5 to 200 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 mu m.

(1-1B) In the case of producing an IPS or FFS type liquid crystal display element, the electrode formation surface of the substrate on which the electrode made of the transparent conductive film or the metal film patterned in the comb shape is formed, The liquid crystal aligning agent of the present invention is applied to one side of the counter substrate, and then each coated side is heated to form a coated film. The preferable thicknesses of the substrate and the transparent conductive film used, the coating method, the heating conditions after coating, the method of patterning the transparent conductive film or the metal film, the pretreatment of the substrate, and the coating film to be formed are the same as in the above (1-1A) Do. As the metal film, for example, a film made of a metal such as chromium can be used.

In both cases (1-1A) and (1-1B), a liquid crystal alignment film is formed by applying a liquid crystal aligning agent on a substrate and then removing the organic solvent. At this time, by further heating after forming the coating film, dehydration ring closure reaction of polyamic acid, polyamic acid ester and polyimide mixed with the liquid crystal aligning agent of the present invention may be advanced to form a more imaged coating film.

[Process (1-2): Orientation-imparting treatment]

In the case of producing a liquid crystal display element of TN type, STN type, IPS type or FFS type, a treatment for imparting liquid crystal alignment ability to the coating film formed in the above step (1-1) is performed. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Examples of the orientation-imparting treatment include a rubbing treatment for rubbing the coating film in a predetermined direction with a roll formed of fibers such as nylon, rayon, and cotton, and a photo-alignment treatment for irradiating the coating film with polarized or unpolarized radiation have. It is preferable to use the photo alignment method from the viewpoint that uniformity of liquid crystal alignability can be given to the coating film while suppressing the photoreactivity of the compound (X), generation of static electricity and dust, and precise control of the liquid crystal alignment direction Do.

The light irradiation in the photo alignment treatment is carried out in the following manner: [1] a method of irradiating a coating film after the post-baking step, [2] a method of irradiating the coating film after the pre-baking step and before the post-baking step, [3] And a method of irradiating the coating film during heating of the coating film in at least one of the post-baking process. Among them, the method of [1] or [2] is preferable in that the afterimage characteristic and the contrast characteristic of the liquid crystal display element are effectively improved. As the radiation to be irradiated on the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. The radiation may be polarized light or unpolarized light. As the light source to be used, 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 and an excimer laser can be used. The irradiation dose of the radiation is preferably 100 to 50,000 J / m 2, and more preferably 300 to 20,000 J / m 2. The light irradiation to the coating film may be carried out while heating the coating film to enhance the reactivity. The temperature at the time of heating is usually 30 to 250 占 폚, preferably 40 to 200 占 폚, more preferably 50 to 150 占 폚.

In addition, it is also possible to apply a treatment for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film to the rubbed liquid crystal alignment film, or a process for forming a resist film on a part of the surface of the liquid crystal alignment film, After the rubbing treatment is performed in a direction different from the rubbing treatment, a treatment for removing the resist film may be performed so that the liquid crystal alignment film has a liquid crystal aligning ability different for each region. In this case, it is possible to improve the visual field characteristic of the obtained liquid crystal display element. A liquid crystal alignment film suitable for VA type liquid crystal display elements can be suitably used for liquid crystal display devices of the PSA (Polymer Sustained Alignment) type. After the light irradiation on the coating film on the substrate, the surface of the substrate may be cleaned using, for example, water, an organic solvent or a mixture thereof. Examples of the organic solvent include alcohols such as methanol and ethanol, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, diacetone alcohol, Methyl propoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, and the like. By this cleaning, it becomes possible to remove the low molecular weight component generated by the light irradiation. After the cleaning, a heating treatment may be carried out if necessary in order to remove the used solvent. Further, after the light irradiation to the coating film on the substrate, a treatment for further heating the coating film to remove the low molecular weight component may be performed. The heating temperature at this time is preferably within a range of 150 to 300 캜, and more preferably within a range of 200 to 290 캜. The heating time is preferably 5 to 60 minutes, more preferably 5 to 15 minutes.

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

(1-3A) A liquid crystal cell is prepared by preparing two substrates on which a liquid crystal alignment film is formed as described above, and arranging liquid crystals between two substrates opposed to each other. In order to manufacture a liquid crystal cell, for example, two substrates are disposed opposite each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other, the peripheral portions of the two substrates are bonded together using a sealant, A liquid crystal is injected and filled in the cell gap defined by the surface of the substrate and the sealant, and then the injection port is sealed; a method in which a sealant is applied on one of the substrates and liquid crystal is dropped to a predetermined number of places on the liquid crystal alignment film surface A method of bonding the other substrate to the liquid crystal alignment film so as to face each other and spreading the liquid crystal on the entire surface of the substrate, followed by curing the sealant.

As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Of these, nematic liquid crystals are preferable, and examples thereof include a cypher base liquid crystal, an agar watch liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane liquid crystal, , Terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, quaternary type liquid crystals and the like. These liquid crystals include, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate;

Chiral agents such as those sold under the trade names "C-15" and "CB-15" (Merck);

p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate and the like may be added and used.

The liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state is sandwiched by a cellulose acetate protective film or a polarizing plate made of H film itself .

The liquid crystal display element of the present invention can be effectively applied to various applications and can be applied to various applications such as a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, And can be used for various display devices such as smart phones, various monitors, liquid crystal televisions, and information displays, and light control films. The liquid crystal device formed using the liquid crystal aligning agent of the present invention may also be applied to a retardation film.

(Example)

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

In the following examples, the weight average molecular weight (Mw) of the polymer was measured by the following method. Hereinafter, the compound represented by formula A may be simply referred to as &quot; compound A &quot;.

[Weight average molecular weight (Mw) of polymer]: Polystyrene reduced value measured by GPC under the following conditions.

Column: TSKgelGRCXLII, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

<Synthesis of Compound>

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

Compound (b-1) was synthesized according to Reaction Scheme 1 below.

5.0 g of 4-nitrosalicylaldehyde was dissolved in 200 ml of N, N-dimethylformamide, and the solution was cooled to 0 占 폚. 8.15 g of imidazole and 9.02 g of t-butyldimethylchlorosilane were added thereto, followed by stirring at room temperature for 16 hours. Then, pure water was added, and extraction was performed with ethyl acetate. This organic layer was concentrated to obtain 8.0 g of intermediate (b-1-1) and a purity of 99%.

8.0 g of the obtained intermediate (b-1-1) and 5.92 g of malonic acid were dissolved in 50 ml of pyridine, to which 5.6 ml of piperidine was added, followed by stirring at 80 占 폚 for 5 hours. After the reaction solution was allowed to cool to room temperature, 50 ml of ethyl acetate was added, and then 50 ml of hydrochloric acid was added to separate the mixture. After separating again with pure water, this was concentrated to obtain 8.0 g of the intermediate (b-1-2) and a purity of 99%.

8.0 g of the resulting intermediate (b-1-2) was added to 30 ml of thionyl chloride, and a catalytic amount of N, N-dimethylformamide was added, followed by stirring at 80 DEG C for 1 hour. The reaction solution was concentrated, and the residue was dissolved in 80 ml of tetrahydrofuran (this solution was referred to as reaction solution (A)). Separately, 4.8 g of 4-amino-4'-nitrobiphenyl and 4.6 g of triethylamine were added to 40 ml of tetrahydrofuran, which was cooled to 0 ° C and stirred for 5 minutes. Subsequently, the reaction solution (A) was slowly added dropwise to this solution. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours to complete the reaction. 300 ml of ethyl acetate and 100 ml of tetrahydrofuran were placed and the resulting solution was partitioned between hydrochloric acid, an aqueous solution of sodium carbonate and pure water and then concentrated to obtain 10.5 g of intermediate (b-1-3) at a purity of 99%.

10 ml of the resulting intermediate (b-1-3) was dissolved in 80 ml of tetrahydrofuran, to which was added 30 ml of tetrabutylammonium fluoride as a 1 mol / L tetrahydrofuran solution, and the mixture was stirred at room temperature for 2 hours . Thereafter, 100 ml of ethyl acetate was added, and the resulting solution was separated from pure water. This solution was concentrated to obtain 8.0 g of intermediate (b-1-4) at a purity of 99%.

8.0 g of the obtained intermediate (b-1-4) and 7.9 g of zinc powder were added to 100 ml of tetrahydrofuran, and further 5.9 g of acetic acid was added. Thereafter, the mixture was stirred at 60 占 폚 for 5 hours. The reaction solution was allowed to cool to room temperature, and 150 ml of ethyl acetate was added. The mixture was separated from pure water and concentrated to obtain 6.2 g of a compound (b-1) at a purity of 99%.

Example 1-2: Synthesis of compound (b-2)

Compound (b-2) was obtained in the same manner as in Example 1-1 except that malonic acid was changed to methylmalonic acid in the second step of Reaction Scheme 1 of Example 1-1.

[Example 1-3: Synthesis of compound (b-4)

Synthesis was conducted in the same manner as in Example 1-1 except that 4-amino-4'-nitrobiphenyl was changed to 4-nitroaniline in the third step of Reaction Scheme 1 of Example 1-1 to give compound (b- 4).

Example 1-4: Synthesis of compound (b-9)

In the third step of Reaction Scheme 1 of Example 1-1, 4-amino-4'-nitrobiphenyl was changed to 1,4-cyclohexanediamine, and the equivalent number of 1,4-cyclohexanediamine was added Compound (b-9) was obtained in the same manner as in Example 1-1 except that the amount of 4-amino-4'-nitrobiphenyl in Example 1-1 was changed to half.

[Example 1-5: Synthesis of compound (b-12)] [

In the second step of Reaction Scheme 1 of Example 1-1, malonic acid was changed to methylmalonic acid and 4-amino-4'-nitrobiphenyl was reacted with 4-hydroxy-4 ' -Nitrobiphenyl, the compound (b-12) was obtained.

&Lt; Synthesis of Polymer &

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

100 molar parts of 4,4'-oxydiphthalic anhydride as a tetracarboxylic acid dianhydride and 100 mol parts of the compound (b-1) as a diamine were dissolved in N-methyl-2-pyrrolidone (NMP) The reaction was carried out for 6 hours to obtain a solution containing 20 wt% of polyamic acid. The weight average molecular weight (Mw) of the resulting polyamic acid (polymer (A-1)) was 45,000.

[Examples 2-2 to 2-8 and Synthesis Examples 1-1 and 1-2]

(Polymers (A-2) to (A-8) and Polymer (A-2)) were obtained in the same manner as in Example 2-1, except that tetracarboxylic acid dianhydride and diamine used were changed as shown in Table 1 below. (B-1) and (B-2)) were synthesized.

In Table 1, the numerical values in parentheses of the tetracarboxylic dianhydrides and diamines indicate the ratio (molar amount) of each compound to the total of 100 moles of the tetracarboxylic acid dianhydrides used in the synthesis of the polymer. The abbreviations in Table 1 are as follows.

&Lt; Tetracarboxylic acid dianhydride &gt;

a-1: 4,4'-Oxydiphthalic anhydride

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

a-3: 1,3-propylene glycol bis (anhydrotrimellitate) (compound represented by the above formula (a-3)

a-4: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

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

a-6: Pyromellitic acid dianhydride

a-7: 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride

<Diamine>

b-1: The compound represented by the above formula (b-1)

b-2: Compound represented by the above formula (b-2)

b-4: The compound represented by the above formula (b-4)

b-9: Compound represented by the above formula (b-9)

b-12: Compound represented by the above formula (b-12)

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

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

c-3: p-phenylenediamine

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

[Example 3-1]

1. Preparation of liquid crystal aligning agent

NMP and butyl cellosolve (BC) were added to a solution containing the polymer (A-1) obtained in the above Example 2-1 as a polymer component and sufficiently stirred to obtain a polymer having 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 diameter of 0.45 mu m to prepare a liquid crystal aligning agent.

2. Fabrication of FFS type liquid crystal display device

An FFS type liquid crystal display element 10 shown in Fig. 1 was produced. First, a glass substrate 11a having a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a comb electrode having a comb electrode pattern 13 formed in this order on one side are formed in this order. And a pair of opposing glass substrates 11b on which electrodes are not formed are formed on one surface of the glass substrate 11a and on the surface of the glass substrate 11a having the transparent electrode and the opposite glass substrate 11b, Was applied using a spinner to form a coating film.

A schematic plan view of the top electrode 13 used is shown in Fig. 2 (a) is a top view of the top electrode 13, and Fig. 2 (b) is an enlarged view of a portion C1 surrounded by a broken line in Fig. 2 (a). In this embodiment, the line width d1 of the electrode is 4 mu m and the distance d2 between the electrodes is 6 mu m. As the top electrode 13, drive electrodes of four lines of electrode A, electrode B, electrode C and electrode D were used (Fig. 3). Further, the bottom electrode 15 functions as a common electrode acting on all the four driving electrodes, and each of the areas of the four driving electrodes becomes a pixel area.

After formation of the coating film by the spinner, the coating film was prebaked on a hot plate at 80 DEG C for 1 minute. Then, polarizing ultraviolet rays of 5,000 J / m &lt; 2 &gt; were irradiated to each surface of the coating film using an Hg-Xe lamp and a Glane Taylor prism to obtain a pair of substrates having a liquid crystal alignment film. At this time, the irradiation direction of the polarized ultraviolet ray is set from the normal direction of the substrate, and the direction of the line segment in which the polarizing plane of the polarized ultraviolet ray is projected on the substrate is set to be the direction of both arrows in Fig. 2 (b) Treatment. After light irradiation, the interior of the chamber was heated (post-baking) at 230 DEG C for 1 hour in an oven substituted with nitrogen to form a coating film having an average film thickness of 0.1 mu m.

Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 was applied to the periphery of the surface having one liquid crystal alignment film in the above-mentioned substrate by screen printing, and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, The polarizing surfaces of the ultraviolet rays were bonded so as to be parallel to the direction of projection onto the substrate, followed by compression bonding, and the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a liquid crystal &quot; MLC-7028 &quot; manufactured by Merck Ltd. was filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Thereafter, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated to 150 캜 and then slowly cooled to room temperature. Next, a polarizing plate was bonded to both outer sides of the substrate to produce an FFS type liquid crystal display element. One of the polarizing plates is adhered so that the polarizing direction of the polarizing plate is parallel to the projection direction of the polarizing plane of the polarized ultraviolet ray of the liquid crystal alignment film to the substrate surface and the other polarizing direction is perpendicular to the polarizing direction of the polarizing plate did.

Further, three or more liquid crystal display elements having different ultraviolet ray doses were prepared by changing the above-described series of operations in the range of 100 to 10,000 J / m 2 before the post-baking.

3. Evaluation of Liquid Crystal Display

The following evaluation (1) was carried out using the liquid crystal display element prepared in the above 2.. A liquid crystal display element (a liquid crystal cell not bonded to a polarizing plate) was produced by performing the same operation as the above-mentioned 2. except that the polarizing plate was not bonded, and the following evaluation (2) was performed. In addition, as to the evaluation results, the best results were selected from among three or more liquid crystal display elements having different ultraviolet ray irradiation amounts, and the results were provided for evaluation of liquid crystal display elements.

(1) Evaluation of AC afterimage characteristic

The FFS type liquid crystal display device manufactured in the above 2. was placed under an environment of 25 캜 and 1 atm. The bottom electrode was used as all the common electrodes of the four driving electrodes, and the potential of the bottom electrode was set to 0V potential (grand potential). The electrode B and the electrode D were short-circuited with the common electrode and 0 V was applied, and a composite voltage of 5 V AC voltage was applied to the electrode A and the electrode C for 100 hours. After 100 hours elapsed, a voltage of 1.5 V AC was applied to all of the electrodes A to D immediately. From the start of application of a voltage of AC 1.5 V to all of the electrodes A to D, the driving stress application areas (the pixel areas of the electrodes A and C) and the driving stress non-coverage areas (the pixel areas of the electrodes B and D ) Was measured by the naked eye to determine the afterimage time Ts. Also, the shorter the time, the less the afterimage is generated. The case where the afterimage erase time Ts was less than 30 seconds was evaluated as &quot; good (O) &quot;, the case where it was less than 120 seconds and less than 120 seconds as & As a result, the liquid crystal display element of this example was evaluated as "afterimage characteristic".

(2) Evaluation of contrast after driving stress

The minimum relative transmittance (%) expressed by the following formula (1) was measured using a device in which the liquid crystal display device prepared in the above 2. was driven with an AC voltage of 10 V for 30 hours and then a polarizer and an analyzer were arranged between the light source and the light amount detector. ) Were measured.

Minimum relative transmittance (%) = (B-B ⁰ ) / (B ¹⁰⁰ -B ⁰ ) × 100 (One)

(B ⁰ is the transmittance of light under cross-nicol in the blank, B ¹⁰⁰ is the transmittance of light under para-nicol in the blank, and β is the transmittance of light between the polarizer and the analyzer And the minimum light transmission amount.)

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element, and the lower the black level in the dark state, the better the contrast. (?), And those having a minimum relative transmittance of less than 0.5% were regarded as "good (O)", those having a relative relative transmittance of less than 0.5% As a result, the contrast evaluation of this liquid crystal display element was judged as &quot; good &quot;.

[Examples 3-2 to 3-7 and Comparative Example 1]

A liquid crystal aligning agent was prepared at the same solvent ratio and solid concentration as in Example 3-1 except that the kind of polymer used was changed as shown in Table 2 below. Using each liquid crystal aligning agent, a liquid crystal display element was produced 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 Table 2, the numerical values in parentheses of the polymer column indicate the compounding ratio (parts by weight) of each polymer to the total 100 parts by weight of the polymer components used for preparing the liquid crystal aligning agent.

[Example 3-8]

A liquid crystal aligning agent was prepared at the same solvent ratio and solid concentration as in Example 3-1 except that the kind of polymer used was changed to polymer (A-8). A liquid crystal display device was manufactured in the same manner as in Example 3-1 except that the liquid crystal aligning agent prepared in this example was used and that the photo alignment treatment by polarized ultraviolet light was performed after post baking, Various evaluations were performed using the obtained liquid crystal display element. The results are shown in Table 2 below.

In the liquid crystal display device manufactured using the liquid crystal aligning agent containing the compound (X), the evaluation of the AC afterimage characteristic and the contrast characteristic was either "good" or "acceptable" (Examples 3-1 to 4 3-8). It has also been found that the use of a diamine having a polycyclic structure such as a biphenyl structure or the use of a diamine having a structure in which a plurality of partial structures represented by the formula (1) are connected, enhances the effect of improving the afterglow characteristics of the AC (see Examples 3-1 to 3-5, and Examples 3-7). On the other hand, in the liquid crystal aligning agent of the comparative example not containing the compound (X), the AC afterimage characteristic and the contrast characteristic were inferior to those of the examples.

[Example 3-9]

(A-3): Polymer (A-8) = 50: 50 (weight ratio) was used as the polymer (A-3) and the polymer ), A liquid crystal aligning agent was prepared at the same solvent ratio and solid concentration as in Example 3-1. Instead of performing the polarizing ultraviolet irradiation and post baking in this order after using the liquid crystal aligning agent prepared in this embodiment and after prebaking, post baking was first performed at 230 캜 for 30 minutes after prebaking, and then polarizing ultraviolet light And then rinsed with ethyl lactate for 3 minutes at 25 ° C, rinsed with isopropanol for 1 minute, and dried in an oven at 80 ° C where the inside of the chamber was replaced with nitrogen, for 10 minutes. To prepare liquid crystal display elements, and various evaluations were carried out in the same manner as in Example 3-1. As a result, in this embodiment, both the AC residual image characteristic and the contrast characteristic were evaluated as &quot; good &quot;.

[Example 3-10]

(A-7): polymer (B-2) = 20: 80 (weight ratio) was used as the polymer (A-7) and the polymer ), A liquid crystal aligning agent was prepared at the same solvent ratio and solid concentration as in Example 3-1. Instead of performing the polarizing ultraviolet irradiation and post baking in this order after using the liquid crystal aligning agent prepared in this embodiment and after prebaking, post baking was first performed at 230 캜 for 30 minutes after prebaking, and then polarizing ultraviolet light A liquid crystal display device was produced in the same manner as in Example 3-1 except that the chamber was further heated in an oven at 230 캜 in which the inside of the chamber was replaced by nitrogen for 10 minutes. Various evaluations were conducted in the same manner. As a result, in this embodiment, both the AC residual image characteristic and the contrast characteristic were evaluated as &quot; good &quot;.

10: Liquid crystal display element
11a and 11b: glass substrate
12: liquid crystal alignment film
13: Top electrode
14: Insulating layer
15: bottom electrode
16: liquid crystal layer

Claims (10)

A liquid crystal aligning agent containing a compound (X) having a partial structure represented by the following formula (1)

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group or a monovalent organic group; R ³ is a substituent;
X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ is bonded to another group to form a ring structure together with the nitrogen atom);
R ³ may be bonded to another group to form at least a part of a ring;
n is an integer of 0 to 3; when n is 2 or 3, plural R ³ may be the same or different;
&Quot; * &quot; indicates a combined hand). The method according to claim 1,
Wherein the compound (X) is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyamide, polyorganosiloxane and poly (meth) acrylate. The method according to claim 1,
The compound (X) is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and is a compound represented by the following formula (2-1), a compound represented by the following formula And a partial structure derived from at least one compound selected from the group consisting of a compound represented by the following formula (3-2): Liquid crystal aligning agent:

(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, Or a group represented by the following formula (1-2);
R ⁵ is a divalent organic group when A ¹ is a group represented by the following formula (1-1) and is a single bond or a divalent organic group when A ¹ is a group represented by the following formula (1-2);
R ⁷ is a divalent organic group when A ² is a group represented by the following formula (1-1), A ² is a single bond or a divalent organic group when A ² is a group represented by the following formula (1-2), A ^{When the divalent group} is a single bond;
R ⁶ is a divalent organic group;
Provided that "* 1" in the following formulas (1-1) and (1-2) is bonded to R ⁶ );

(In the formulas (1-1) and (1-2), R ¹ , R ² , R ³ , X ¹ and n have the same meanings as in the formula (1);
&Quot; * 1 &quot; and &quot; * &quot; represent combined hands);

(In the formula (3-1), R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group or a monovalent organic group; i is 0 or 1;
R ⁵⁰ is a single bond or a divalent organic group when i = 0, and is a divalent organic group when i = 1;
X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ may be bonded to another group to form a ring structure together with the nitrogen atom);
However, in the case of i = 1, a plurality of X ¹ in the formula has at the defined independently);

(In the formula (3-2), R ⁵⁵ and R ⁵⁶ are each independently a trivalent organic group; R ⁵⁷ to R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, And k is 0 or 1;
X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ may be bonded to another group to form a ring structure together with the nitrogen atom);
However, in the case of k = 1, a plurality of X ¹ in the formula has at the defined independently). The method of claim 3,
The compound represented by the formula (2-1) is a liquid crystal aligning agent having a partial structure represented by the following formula (4) in the molecule:

(In the formula (4), Ar ¹ and Ar ² are each independently a phenylene group or a cyclohexylene group, X ² is a single bond, -COO- or -CONR ²⁰ - (R ²⁰ is a hydrogen atom or a monovalent organic group Device);
t is 1 or 2; When t = 2, Ar ² and X ² each independently have the above definition;
&Quot; * &quot; indicates a combined hand). A method for producing a liquid crystal alignment film, comprising the steps of: applying a liquid crystal aligning agent according to any one of claims 1 to 4 on a substrate to form a coated film; and irradiating the coated film with light. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 4. A liquid crystal device comprising the liquid crystal alignment film according to claim 6. A polymer having at least one kind of polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyamide, and having a partial structure represented by the following formula (1):

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group or a monovalent organic group; R ³ is a substituent;
X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ is bonded to another group to form a ring structure together with the nitrogen atom);
R ³ may be bonded to another group to form at least a part of a ring;
n is an integer of 0 to 3; when n is 2 or 3, plural R ³ may be the same or different;
&Quot; * &quot; indicates a combined hand). The diamine represented by the following formula (2-1):

(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, Or a group represented by the following formula (1-2);
R ⁵ is a divalent organic group when A ¹ is a group represented by the following formula (1-1) and is a single bond or a divalent organic group when A ¹ is a group represented by the following formula (1-2);
R ⁷ is a divalent organic group when A ² is a group represented by the following formula (1-1), A ² is a single bond or a divalent organic group when A ² is a group represented by the following formula (1-2), A ^{When the divalent group} is a single bond;
R ⁶ is a divalent organic group;
Provided that "* 1" in the following formulas (1-1) and (1-2) is bonded to R ⁶ );

(In the formulas (1-1) and (1-2), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group or a monovalent organic group; R ³ is a substituent;
X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ is bonded to another group to form a ring structure together with the nitrogen atom);
n is an integer of 0 to 3; when n is 2 or 3, plural R ³ may be the same or different;
Quot; * 1 &quot; and &quot; * &quot; An acid anhydride represented by the following formula (3-1) or (3-2):

(In the formula (3-1), R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group or a monovalent organic group; i is 0 or 1;
R ⁵⁰ is a single bond or a divalent organic group when i = 0, and is a divalent organic group when i = 1;
X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ may be bonded to another group to form a ring structure together with the nitrogen atom);
However, in the case of i = 1, a plurality of X ¹ in the formula has at the defined independently);

(In the formula (3-2), R ⁵⁵ and R ⁵⁶ are each independently a trivalent organic group; R ⁵⁷ to R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, And k is 0 or 1;
X ¹ is an oxygen atom or -NR ⁴ - (wherein R ⁴ is a hydrogen atom or a monovalent organic group, and R ⁴ may be bonded to another group to form a ring structure together with the nitrogen atom);
However, in the case of k = 1, a plurality of X ¹ in the formula has at the defined independently).

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