TW201418326A - Liquid crystal alignment agent, liquid crystal alignment film, phase difference film of liquid crystal display device and liquid crystal cell of liquid crystal display device - Google Patents

Abstract

A liquid crystal alignment agent is provided. The liquid crystal alignment agent provides a liquid crystal alignment film having an improved liquid crystal alignment property, improved electrical characteristics and an improved heat-resisting property, and meanwhile, the liquid crystal alignment agent has a good coating (printing) property. The liquid crystal alignment agent is characterized in that the liquid crystal alignment agent includes at least one polymer selected from a group consisting of polyorganosiloxane, polyamide, poly(thio)ester and (meth)acrylic acid copolymer, wherein the polymer includes a bivalent group represented by formula (1) below. (In the formula (1), Q is a tetravalent organic group, Y1 and Y2 are bivalent organic groups respectively, and ''*'' represents a bond linking to a polymer chain.)

Description

Liquid crystal alignment agent, liquid crystal alignment film, retardation film of liquid crystal display element, and liquid crystal Display unit liquid crystal cell

The present invention relates to a liquid crystal alignment agent.

The present invention provides a liquid crystal alignment agent having a property of a liquid crystal alignment agent that exceeds a partially sulfimine-containing polymer containing polyamic acid.

The liquid crystal display element is provided with a liquid crystal alignment film having a function of aligning liquid crystal molecules in a fixed direction. The liquid crystal alignment film is usually formed by a step of coating (printing) a liquid crystal alignment agent containing a polymer on a substrate. As the polymer contained in the liquid crystal alignment agent, a polyamidic acid, a ruthenium iodide polymer of polyglycine, a polyamine, a polyester, a polyorganosiloxane, etc. are known (Patent Document 1 to Patent) Document 3).

Among these polymers, a liquid crystal alignment agent containing a polyamic acid as a polymer is excellent in coatability (printability), but there is room for improvement in electrical properties and heat resistance of the obtained liquid crystal alignment film. Liquid crystal alignment agent containing a ruthenium imidized polymer of poly-proline provides liquid crystal alignment, A liquid crystal alignment film excellent in electrical characteristics, etc., but the coating property of the liquid crystal alignment agent itself is not sufficient. Polyimine, a polyester, or a polyorganosiloxane is excellent in solubility in a general-purpose organic solvent, and therefore the liquid crystal alignment agent containing these polymers is excellent in coating property, but the liquid crystal alignment film formed has insufficient liquid crystal alignment property. .

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 3764250

[Patent Document 2] Japanese Patent No. 3912859

[Patent Document 3] Japanese Patent No. 3775514

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-97188

[Non-patent literature]

[Non-Patent Document 1] "Ultraviolet (UV) Curable Liquid Crystal and Its Application", Liquid Crystal, Vol. 3, No. 1 (1999), pages 34 to 42

[Non-Patent Document 2] T.J. Scheffer et al., J. Appl. Phys, Vol. 48, p. 1783 (1977)

[Non-Patent Document 3] F. Nakano et al., Journal of Applied Physics (JPN. J. Appl. Phys), Vol. 19, p. 2013 (1980)

The present invention has been made to solve the above-mentioned state of the art, and an object thereof is to provide a liquid crystal alignment agent which can provide a liquid crystal alignment film having improved liquid crystal alignment, electrical properties, heat resistance and the like, and Excellent in coatability (printability).

According to the present invention, the objects and advantages of the present invention are achieved by the following liquid crystal alignment agent Achieved that the liquid crystal alignment agent is characterized by comprising at least one polymer selected from the group consisting of polyorganosiloxane, polyamine, poly(thio)ester, and (meth)acrylic copolymer, wherein The polymer has a divalent group represented by the following formula (1).

(In the formula (1), Q is a tetravalent organic group, Y ¹ and Y ² are each a divalent organic group, and "*" represents a bond bonded to a polymer chain, respectively)

In the present specification, a polymer which satisfies the conditions described below is also referred to as a "specific polymer".

The present invention provides a liquid crystal alignment film which is formed of the liquid crystal alignment agent.

The present invention provides a retardation film of a liquid crystal display element, comprising: a liquid crystal alignment film formed of the liquid crystal alignment agent.

The present invention provides a liquid crystal cell of a liquid crystal display element, comprising: a liquid crystal alignment film formed of the liquid crystal alignment agent.

According to the present invention, there is provided a liquid crystal alignment agent which is excellent in coatability (printability) and which can provide liquid crystal alignment excellent in liquid crystal alignment, electrical properties, heat resistance and the like. membrane. In other words, the polymer contained in the liquid crystal alignment agent of the present invention has a highly soluble polymer skeleton which contributes to the coating property of the liquid crystal alignment agent, and contributes to liquid crystal alignment and electrical properties of the obtained liquid crystal alignment film. Both of them have a heat-resistant quinone ring structure, and therefore the balance between the two is excellent.

A‧‧‧glass substrate

b‧‧‧Liquid alignment film

C‧‧‧ top electrode

D‧‧‧ nitride film

E‧‧‧ bottom electrode

f‧‧‧Direction of polarized surface of polarized ultraviolet light

1 is a schematic cross-sectional view for explaining a structure of an electrode pair of an FFS type liquid crystal display element manufactured in Example FFS-1.

2(a) and 2(b) are plan schematic views for explaining the comb structure of the top electrode of the FFS type liquid crystal display element manufactured in the example FFS-1.

The liquid crystal alignment agent of the present invention contains a specific polymer.

<specific polymer>

The specific polymer in the present invention is at least one polymer selected from the group consisting of polyorganosiloxane, polyamine, poly(thio)ester, and (meth)acrylic copolymer, and has The divalent group represented by the formula (1).

In the divalent group represented by the formula (1), two bond bonds "attached to the polymer chain" appended with "*" indicate that the divalent group is present in the main chain of the polymer, or It exists as a part of a crosslink bond which bonds a polymer chain to each other two-dimensionally or three-dimensionally. That is, the divalent group is not a group existing as a side chain of a polymer or a part thereof, or a side chain of a crosslinked structure or a part thereof. However, the specific polymer may be present in the main chain or crosslinked structure of the polymer as long as the divalent group represented by the formula (1) is present, and it is not prohibited to have the same structure as the side chain of the polymer or A portion, or a side chain of a crosslinked structure or a portion thereof.

The content ratio of the divalent group represented by the above formula (1) in the specific polymer is preferably 1.0 × 10 ^-4 mol / g or more, more preferably 3.0 × 10 ^-4 mol / g to 2.0 × 10 ^-3 mol. /g.

The specific polymer may be, for example, a polymer obtained by reacting a diamine with a compound represented by the following formula (C) (hereinafter referred to as "compound (C)"); a poly(thio)ester obtained by reacting at least one of a group consisting of a diol compound, a dithiol compound, and a diepoxy compound with a compound (C); and represented by the following formula (E) a poly(thio)ester obtained by reacting a compound (hereinafter referred to as "compound (E)") with a dicarboxylic acid; and containing (meth)acrylic acid and a compound represented by the following formula (A) (hereinafter, a (meth)acrylic copolymer obtained by addition polymerization of a mixture of polymerizable unsaturated compounds referred to as "compound (A)"); containing a compound represented by the following formula (S) (hereinafter referred to as The polyorganosiloxane obtained by hydrolysis and condensation of the decane compound of the "compound (S)").

(In the formula (C), the meanings of Q, Y ¹ and Y ^{2 are the} same as Q, Y ¹ and Y ² in the formula (1), respectively, and n3 and n4 are independently 1 or 2)

[Chemical 3]

(In the formula (E), Q, Y ¹ and Y ² are the meanings of the formula (1) Q, Y ¹ and Y ² the same, Z ¹ and Z ² are each independently a hydroxyl group, a thiol group or a cycloalkyl Oxyl)

(In the formula (A), the meanings of Q, Y ¹ and Y ^{2 are the} same as Q, Y ¹ and Y ² in the formula (1), respectively, and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group)

[Chemical 5]

(In the formula (S), the meanings of Q, Y ¹ and Y ^{2 are the} same as Q, Y ¹ and Y ² in the above formula (1), and R ¹ and R ² are each independently a carbon number of 1 to 12. An alkyl group or an aryl group having 6 to 12 carbon atoms, and X ¹ and X ² are each independently an alkoxy group having 1 to 12 carbon atoms or a halogen atom, and n1 and n2 are each independently an integer of 1 to 3)

As is clear from the chemical formula, the divalent group represented by the formula (1) is derived from the compound (C), the compound (E), the compound (A) or the compound (S). As described later, these compounds can be obtained by a reaction of a tetracarboxylic dianhydride represented by the following formula (T-1) with a primary amine compound, and therefore the following formula (T) in the formula (1) The unit represented (hence, the unit represented by the following formula (T) in the compound (C), the compound (E), the compound (A) or the compound (S)) is a source free from the following formula (T-1) The tetravalent group of the tetracarboxylic dianhydride represented.

(In the formula (T), the meaning of Q is the same as Q in the formula (1), and "*" represents a knot, respectively. Key combination)

(In the formula (T-1), the meaning of Q is the same as Q in the above formula (1))

The tetravalent group derived from the tetracarboxylic dianhydride represented by the formula (T-1) is a tetravalent group obtained by removing two oxygen atoms constituting the ring from the tetracarboxylic dianhydride. .

As the tetracarboxylic dianhydride represented by the above formula (T-1), it can be used without any particular limitation as four for producing a polyaminic acid or a quinone imidized polymer contained in the liquid crystal alignment agent. A tetracarboxylic dianhydride known as a carboxylic acid dianhydride. For example, the tetracarboxylic dianhydride described in Patent Document 4 (Japanese Laid-Open Patent Publication No. 2010-97188) is exemplified. A particularly preferred tetracarboxylic dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4 ,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3, 3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3 -dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5 -dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, bicyclo[3.3.0]octane- At least one of the group consisting of 2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride.

The primary amine compound to be reacted with the tetracarboxylic dianhydride as described above is described in the description of the compound (C), the compound (E), the compound (A) or the compound (S).

[Synthesis of Compound (C)]

The compound (C) can be obtained, for example, by a reaction of a tetracarboxylic dianhydride represented by the above formula (T-1) with an amino acid. The amino acid is a compound having one primary amino group and one or two carboxyl groups in the molecule. In this case, in the formula (C) ¹ the Y group (and therefore in the formula (1) group Y ¹⁾ is removed from an amino group and a carboxyl group in the amino acids obtained by a divalent or trivalent group .

Examples of the amino acid having one carboxyl group include glycine, alanine, leucine, isoleucine, phenylalanine, proline, and 4-aminobutyric acid; Examples of the amino acid having two carboxyl groups include aspartic acid, glutamic acid, 2-aminoadipate, carbocysteine, 2,3-dicarboxyaniline, and 3,4-di Carboxyaniline, 3-amino-1,2-dicarboxynaphthalene, 4-amino-1,2-dicarboxynaphthalene, 5-amino-1,2-dicarboxynaphthalene, 6-amino-1,2-dicarboxynaphthalene , 7-Amino-1,2-dicarboxynaphthalene, 8-amino-1,2-dicarboxynaphthalene, 1-amino-2,3-dicarboxynaphthalene, 4-amino-2,3-dicarboxynaphthalene, 5 -Amino-2,3-dicarboxynaphthalene, 6-amino-2,3-dicarboxynaphthalene, 7-amino-2,3-dicarboxynaphthalene, 8-amino-2,3-dicarboxynaphthalene, etc., can be used One or more selected from these amino acids.

The reaction of the tetracarboxylic dianhydride represented by the above formula (T-1) with an amino acid can be carried out by heating a mixture of these compounds, preferably in a suitable solvent.

The ratio of the two compounds in the reaction is preferably from 1.0 mol to 4.0 mol, and more preferably from 1.5 mol to 3.0 mol, as a ratio of use of one mole of amino acid to tetracarboxylic dianhydride. The ear is further preferably set to 1.8 mol to 2.5 mol.

As the solvent used in the reaction, an organic solvent is preferred, and for example, an aprotic property can be used. Polar solvents, phenols and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like.

Specific examples of the organic solvent include, as the aprotic polar solvent, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamidine. Amine, dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, etc.; Examples of the phenol derivative include m-cresol, xylenol, and halogenated phenol. Examples of the alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, and propylene glycol. 4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc., and examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, and propylene carbonate. Diethyl acid or the like; as the ether, for example, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-positive Dibutyl ether, Diol 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, tetrahydrofuran, etc.; examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, and trichloroethane. An alkane, a chlorobenzene, an o-dichlorobenzene or the like; examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, and It is preferred to use one or more selected from the group consisting of these organic solvents, such as isoamyl ether.

The use ratio of the solvent is preferably 50 parts by weight to 5,000 parts by weight, more preferably 100 parts by weight to 3,000 parts by weight based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the amino acid. The weight part is more preferably 100 parts by weight to 2,000 parts by weight.

The reaction between the tetracarboxylic dianhydride and the amino acid is preferably from 50 ° C to 300 ° C, more preferably from 80 ° C to 200 ° C, preferably from 0.1 to 10 hours, more preferably from 0.1 to 20 hours. If necessary, the reaction may be carried out while gradually increasing the reaction temperature within the range of the temperature and the reaction time.

[Synthesis of Compound (E)]

The compound in which Z ¹ and Z ² in the compound (E) are a hydroxyl group or a thiol group may correspond to the kind of Z ¹ and Z ² , for example, by the tetracarboxylic dianhydride represented by the formula (T-1). Obtained by the reaction of an amino alcohol, an aminophenol or an amino mercaptan. In this case, (Y ¹ group is thus the formula (1)) of the formula (E) removing the group Y ¹ is an amino group and a hydroxyl group or a thiol group from the amino alcohol or aminothiol in the The divalent base obtained.

Examples of the amino alcohol include 2-aminoethanol, 3-aminopropanol, 4-aminobenzyl alcohol, and 2-(4-aminophenyl)ethanol; and examples of the aminophenol include 4 An aminophenol or the like; examples of the aminothiol include 3-thiol aniline, 4-thiol aniline, and 1-thiol-3-aminopropane.

The reaction of the tetracarboxylic dianhydride with an amino alcohol, an aminophenol or an amino mercaptan can be carried out by heating a mixture of these compounds, preferably in a suitable solvent.

The ratio of use of the two compounds in the reaction is preferably from 1.0 mol to 4.0 mol, as a ratio of use of 1 mol of amino alcohol, aminophenol or amino mercaptan to tetracarboxylic dianhydride. It is preferably set to 1.5 mol to 3.0 mol, and particularly preferably set to 1.8 mol to 2.5 mol.

As the solvent to be used in the reaction, the same solvent as the solvent exemplified above as the solvent which can be used in the synthesis of the compound (C) can be used. Ratio of use as solvent, relative to four The total amount of the carboxylic acid dianhydride and the amino alcohol, the aminophenol or the amino mercaptan is preferably 50 parts by weight to 5,000 parts by weight, more preferably 100 parts by weight to 3,000 parts by weight, still more preferably 100 parts by weight. Parts to 2,000 parts by weight.

The reaction is preferably carried out at a temperature of from 50 ° C to 300 ° C, more preferably from 80 ° C to 200 ° C, preferably from 0.1 to 10 hours, more preferably from 0.1 to 20 hours. If necessary, the reaction may be carried out while gradually increasing the reaction temperature within the range of the temperature and the reaction time.

Thus, a diol compound in which the group Z ¹ and the group Z ² are each a hydroxyl group in the formula (E) or a dithiol compound in which the group Z ¹ and the group Z ² are each a thiol group can be obtained.

The compound in which Z ¹ and Z ² in the compound (E) are each an epoxy group can be obtained, for example, by a reaction of a diol compound or a dithiol compound obtained in the above manner with a compound having an epoxy group and a halogen atom. . In this case, in the formula (E) the Y ¹ group (and therefore in the formula (1) group Y ¹⁾ is a diol compound obtained in the manner described dithiol compound or divalent The group Y ¹ and a divalent group obtained by binding a divalent group obtained by removing an epoxy group and a halogen atom from a compound having an epoxy group and a halogen atom by an ether bond.

Here, the epoxy group may be any of an oxirane group and an oxetanyl group. Examples of the compound having an oxirane group and a halogen atom include epichlorohydrin, 2-(chloromethyl)-1,2-epoxypropane, and 2-(chloromethyl)-1,2- Epoxybutane, 2-(bromomethyl)-1,2-epoxypropane, 2-(bromomethyl)-1,2-epoxybutane, etc.; as having an oxetanyl group Examples of the halogen atom compound include 3-(chloromethyl)oxetane, 3-(chloromethyl)-3-methyloxetane, and 3-(bromomethyl)oxyheterocycle. Butane, 3-(bromomethyl)-3-methyloxetane, etc.; as a compound having a (meth)acryl fluorenyl group and a halogen atom, for example, (meth) propylene As the ruthenium chloride or the like, one or more selected from the group consisting of these compounds can be used.

The reaction can be carried out by heating a mixture of a diol compound or a dithiol compound obtained in the above manner, preferably a compound having an epoxy group and a halogen atom, preferably in the presence of a suitable catalyst, and preferably in a suitable solvent. Come on.

With respect to the use ratio of the diol compound or the dithiol compound to the compound having an epoxy group and a halogen atom, it is preferable to use 0.5 mol to 10 mol of the latter with respect to 1 mol of the former, and it is more preferable to use 1.0 mol of the latter. ~3.0 moles, particularly preferably the latter 1.8 moles to 2.5 moles.

Examples of the catalyst which can be used in the reaction include a quaternary amine salt and the like. Specific examples thereof include tetrabutylammonium chloride and tetrabutylammonium bromide. The use ratio of the catalyst is preferably 20 parts by weight or less, and more preferably 0.001 parts by weight to 10 parts by weight, based on 100 parts by weight of the diol compound or the dithiol compound.

The solvent used herein is preferably an organic solvent, and the same solvent as the solvent exemplified above as the solvent used in the synthesis of the compound (C) can be used.

The solvent is preferably used in an amount of 10 parts by weight to 3,000 parts by weight, more preferably 50 parts by weight, based on 100 parts by weight of the total of the diol compound, the dithiol compound, and the compound having an epoxy group and a halogen atom. 2,000 parts by weight, and more preferably 50 parts by weight to 1,000 parts by weight.

The reaction is preferably carried out at a temperature of from -78 ° C to 60 ° C, more preferably from -78 ° C to 40 ° C, preferably from 0.5 to 30 hours, more preferably from 2 to 15 hours. If necessary, the reaction may be carried out while gradually increasing the reaction temperature within the range of the temperature and the reaction time.

[Synthesis of Compound (A)]

The compound (A) can be obtained, for example, by a reaction of a diol compound in which the group Z ¹ and the group Z ² are each a hydroxyl group in the formula (E) with (meth)acrylic acid. In this case, the same formula (A) in the Y ¹ group (and therefore in the formula (1) group Y ¹⁾ with the compound (E) used as starting materials in the group Y ^1. Here, (meth)acrylic acid is preferably subjected to hydrazine chlorination by a known method and then supplied to the reaction.

Regarding the use ratio of the compound (E) as the diol compound and preferably the fluorinated (meth)acrylic acid, it is preferred to set the use ratio of the (meth)acrylic acid relative to the compound (E) 1 mol to 0.5 mol. The ear is ~10 moles, more preferably 1.0 moles to 3.0 moles, and particularly preferably 1.8 moles to 2.5 moles.

The reaction can be carried out by dissolving the compound (E) as a diol compound in a suitable solvent in advance, preferably in a state in which the fluorinated (meth)acrylic acid is dissolved in a suitable solvent as needed. Make a drop.

As the solvent usable herein, the same solvent as the solvent exemplified above as the solvent usable in the synthesis of the compound (C) can be used. The ratio of the total weight of the compound (E) and the (meth)acrylic acid as the diol compound in the reaction solution is preferably 0.5% by weight to 50% by weight, more preferably The ratio of the total weight of the compound (E) and (meth)acrylic acid as the diol compound in the reaction solution becomes a ratio of 1% by weight to 30% by weight.

The reaction is preferably carried out at a temperature of from -100 ° C to 100 ° C, more preferably from -20 ° C to 40 ° C. Here, when (meth)acrylic acid is directly reacted, it is preferred to set the reaction temperature to a temperature of room temperature (25 ° C) or more; in the case where the reaction is carried out by subjecting (meth)acrylic acid to ruthenium chlorination Preferably, the reaction temperature is set to a temperature lower than room temperature. The reaction time is preferably from 0.1 to 40 hours, more preferably from 0.5 to 20 hours. In the case where the reaction is carried out by dropwise addition of (meth) chlorinated (meth)acrylic acid, the reaction time is measured from the end of the dropwise addition.

[Synthesis of Compound (S)]

The compound (S) can be obtained, for example, by dehydrating a diol compound in which the group Z ¹ and the group Z ² are each a hydroxyl group in the formula (E) to form a double bond at the terminal, and then by a hydrogenation reaction. An alkoxydecane compound is added to the double bond. In this case, the same as in the formula (S) ¹ the Y group (and therefore in the formula (1) group Y ¹⁾ with the compound (E) used as starting materials in the group Y ^1.

The dehydration reaction of the diol compound can be carried out by contacting the diol compound with sulfuric acid, preferably in a suitable organic solvent.

Examples of the organic solvent which can be used herein include acetic acid, acetic anhydride, tetrahydrofuran, acetonitrile, chloroform, dichloromethane, diethyl ether, benzene, toluene, xylene, acetone, methyl ethyl ketone, and dimethyl group. Guanidine, dimethyl hydrazine, hexane, 1,4-dioxane, and the like. The use ratio of the organic solvent is preferably from 50 parts by weight to 2,000 parts by weight, more preferably from 100 parts by weight to 1,000 parts by weight, per 100 parts by weight of the compound (E) as the diol compound.

The proportion of sulfuric acid used is preferably 0.0001 part by weight to 100 parts by weight, more preferably 0.001 part by weight to 10 parts by weight, per 100 parts by weight of the compound (E) as the diol compound. Preferably, sulfuric acid is slowly added to the reaction system.

The dehydration reaction of the diol compound is preferably carried out at a temperature of from 0 ° C to 300 ° C, more preferably from 25 ° C to 150 ° C, preferably from 0.1 to 40 hours, more preferably from 0.5 to 20 hours. In the case where the reaction is carried out by dropwise addition of sulfuric acid, the reaction time is measured from the end of the dropwise addition.

The reaction of adding an alkoxydecane compound to the dehydrated product obtained in the manner described can be carried out in accordance with a known hydrogenation reaction of hydrazine.

The alkoxydecane compound used herein is a compound having at least one H-Si bond and at least one alkoxy-Si bond, and specific examples thereof include, for example, dimethylmethoxydecane and dimethyl. Ethoxy decane, methyl dimethoxy decane, diethyl methoxy decane, diphenyl methoxy hydrazine One type or more selected from these compounds can be used as the organic hydrocarbon hydroalkane or the like.

The ratio of use of the alkoxydecane compound is preferably from 0.5 mol to 5.0 mol, more preferably from 1.0 mol to 3.0 mol, as a ratio of the alkoxydecane compound to the dehydrated product of 1 mol. It is particularly preferably set to 1.8 mol to 2.5 mol.

The rhodium hydrogenation reaction is preferably carried out in the presence of a suitable catalyst, and preferably in a suitable organic solvent.

Examples of the catalyst which can be used herein include chloroplatinic acid, wilkinson complex (RhCl(P(C ₆ H ₅ ) ₃ ) ₃ ), karstedt catalyst (ethylene chloride of chloroplatinic acid). One type or more selected from these catalysts can be used, for example, a sulfonium oxide complex, a Speier catalyst (alcohol solution of chloroplatinic acid), or the like. The catalyst is preferably used in a ratio of from 0.01 micromolar to 200 micromolar (μmol), more preferably from 0.05 micromolar to 50 micromolar, relative to 1 mole of the alkoxydecane compound.

Examples of the organic solvent that can be used herein include a hydrocarbon, a halogenated hydrocarbon, an ether, an ester, and the like. Among these organic solvents, hydrocarbons are preferably used, and at least one selected from the group consisting of toluene, heptane, hexane, benzene, and xylene is particularly preferably used. The use ratio of the organic solvent is preferably from 10 parts by weight to 2,000 parts by weight, and more preferably from 50 parts by weight to 1,000 parts by weight, based on 100 parts by weight of the dehydrated product.

The hydrogenation reaction is preferably carried out at a temperature of from 30 ° C to 200 ° C, more preferably from 50 ° C to 120 ° C, preferably from 0.1 to 60 hours, more preferably from 0.5 to 40 hours.

[Manufacture of specific polymers]

Next, a method of producing a specific polymer in the present invention will be described. A liquid crystal alignment film containing a specific polymer produced by the method described below and which is produced by the method described below as a liquid crystal alignment film formed by rubbing a coating film can be suitably applied to a twisted nematic ( Twisted Nematic, TN), Super Twisted Nematic (STN) Liquid crystal display elements such as In-Plane Switching (IPS) type and Fringe Field Switching (FFS) type. However, when a monomer having a pretilt-developing group is used as at least a part of the monomer, the liquid crystal alignment agent containing the specific polymer is suitably used as a liquid crystal alignment film which is formed by rubbing the coating film. A liquid crystal display element of a vertical alignment type (VA) type; when a monomer having a photo-alignment group is used as at least a part of a monomer, a liquid crystal alignment film formed by light-treating a coating film can be suitably used. Any type of liquid crystal display element.

The pretilt angle-developing group and the photo-alignment group will be described later.

(1) Production of polyamine

The polyamine which is an example of the specific polymer in the present invention can be obtained by reacting a diamine with the compound (C) obtained in the above manner. Here, the compound (C) is preferably subjected to hydrazine chlorination by a known method and then supplied to the reaction.

Examples of the diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl, and 4,4'. -diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4 -aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, ethyl 2-(2,4-diaminophenoxy)methacrylate, twelve Alkoxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, octadecyloxy-2,5- Diaminobenzene, cholestaneyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diamino Benzene, cholesteneoxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, 1,1-double ( 4-((Aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclo One type or more selected from these diamines can be used as hexane or the like.

Compound (C) may be used alone, or compound (C) may be used in combination with other polycarboxylates. acid. As the other polycarboxylic acid used herein, a dicarboxylic acid is preferable, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, and isophthalic acid. For the terephthalic acid, 5-nonyloxyisophthalic acid or the like, one or more selected from the group consisting of these dicarboxylic acids can be used.

When the compound (C) and the other polycarboxylic acid are used in combination, the use ratio of the compound (C) is preferably 5 mol% or more, and more preferably 10 mol, based on the total of the compound (C) and the other polycarboxylic acid. %the above.

The ratio of use of the diamine to the total amount of the carboxyl group of the compound (C) and other polyvalent carboxylic acids is preferably from 0.7 mol to 1.2 mol, more preferably 0.9. Moer ~ 1.1 Mo Er.

The reaction can be carried out by dissolving the diamine in a suitable solvent in advance, and mixing the compound (C) or the compound (C) with other polycarboxylic acids (hereinafter, in the item, they are also collectively referred to as " The polycarboxylic acid ") is preferably chlorinated with hydrazine, and if necessary, added dropwise in a state of being dissolved in a suitable solvent (for example, tetrahydrofuran).

As the solvent usable herein, the same solvent as the solvent exemplified above as the solvent usable in the synthesis of the compound (C) can be used. The ratio of use of the solvent is preferably such that the ratio of the total weight of the polycarboxylic acid and the diamine to the reaction solution becomes 3 wt% to 50 wt%.

The reaction is preferably carried out at a temperature of from -100 ° C to 200 ° C, more preferably from -20 ° C to 150 ° C. When the polycarboxylic acid is directly reacted, it is preferred to set the reaction temperature to a temperature of room temperature (25 ° C) or higher. When the polycarboxylic acid is chlorinated and then reacted, it is preferred to carry out the reaction. The temperature is set to a temperature lower than room temperature. The reaction time is preferably from 0.1 to 40 hours, more preferably from 0.5 to 20 hour. In the case where the reaction is carried out by dropwise addition of a polycarboxylic acid (preferably fluorinated), the reaction time is measured from the end of the dropwise addition.

The Mw of the polyamine which is a specific polymer in the present invention (the polystyrene-equivalent weight average molecular weight measured by Gel Permeation Chromatography (GPC). The same applies hereinafter) preferably 1,000 to 500,000. More preferably, it is 5,000 to 300,000.

(2) Production of poly(thio)ester

The poly(thio)ester which is an example of the specific polymer in the present invention can be obtained by at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxy compound. a method of reacting with the compound (C); or a method of reacting the compound (E) with a dicarboxylic acid.

Examples of the diol compound include 3,6-dihydroxycholesterane, 3,5-dihydroxybenzoic acid-3-cholesteryl ester, 3,5-dihydroxybenzoic acid, and ethylene glycol. , 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,4-cyclohexanediol, phenyl-1,2-ethanediol, dimethyl-2,3 -butanediol, α,α'-p-xylylene glycol, α,α'-m-xylylene glycol, hydroquinone, methyl hydroquinone, tert-butyl pair Hydroquinone, chlorohydroquinone, 2-methoxy hydroquinone, phenyl hydroquinone, 2,3-dimethyl hydroquinone, 2,3,5,6-tetramethyl Hydroquinone, 2,3,5,6-tetrachlorohydroquinone, resorcinol, 2-methylresorcinol, 4-hexyl resorcinol, 5-phenyl resorcinol 1,4-dihydroxynaphthalene or the like; as the dithiol compound, for example, benzene-1,4-dithiol, 2-methylpropane-1,1-dithiol, butane-1 , 1-dithiol, 2-methylbutane-1,1-dithiol, 3-methylbutane-1,1-dithiol, pentane-1,1-dithiol, 2- Methylpentane-1,1-dithiol, 3-methylpentane-1,1-dithiol, hexane-1,1-dithiol, 2-methylhexane-1,1- Dithiol, 3-methylhexyl -1,1-dithiol or the like; examples of the diepoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl Ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin One or more selected from the group consisting of diglycidyl ether and 2,2-dibromoneopentyl glycol diglycidyl ether can be used.

When the poly(thio)ester is synthesized by reacting at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound with the compound (C), the compound (C) may be used alone. Compound (C) and other polycarboxylic acids may also be used in combination. As the other polycarboxylic acid to be used herein, the same as the polyvalent carboxylic acid exemplified above as the polyvalent carboxylic acid which can be used together with the compound (C) in the synthesis of polyamine can be used. When the compound (C) and the other polycarboxylic acid are used in combination, the use ratio of the compound (C) is preferably 5 mol% or more, and more preferably 10 mol, based on the total of the compound (C) and the other polycarboxylic acid. %the above.

A synthesis reaction of a poly(thio)ester which is at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound and a compound (C) is used in addition to a diol compound selected from At least one of the group consisting of a dithiol compound and a diepoxy compound may be carried out in substantially the same manner as the synthesis of the polyamine, in place of the diamine.

As the compound (E) used in the synthesis of the poly(thio)ester by a method of reacting the compound (E) with a dicarboxylic acid, it is preferred that both Z ¹ and Z ² in the formula (E) are epoxy groups. Diepoxide compound. The compound (E) which is a diepoxy compound may be used singly, and the compound (E) and other diepoxide compounds may be used in combination. As the other diepoxy compound used herein, the same as the diepoxy compound exemplified above as the diepoxy compound which can be used in the method for synthesizing the former of the poly(thio)ester can be used. When the compound (E) and another diepoxy compound are used in combination, the use ratio of the compound (E) is preferably 5 mol% or more, and more preferably 10, based on the total of the compound (E) and other diepoxide compounds. More than Mole.

The compound (E) and other diepoxides as the diepoxide compound are preferably respectively Dioxirane based compound.

As the dicarboxylic acid in the present reaction, the same dicarboxylic acid as the dicarboxylic acid exemplified as the polyvalent carboxylic acid which can be used together with the compound (C) in the synthesis of the polydecylamine can be used.

The synthesis reaction of the poly(thio)ester by reacting the compound (E) with a dicarboxylic acid may be carried out in addition to the compound (E) (or a mixture of the compound (E) and another diepoxide) instead of the diamine. The synthesis of the polyamine is carried out in substantially the same manner.

The Mw of the poly(thio)ester which is a specific polymer in the present invention is preferably from 1,000 to 500,000, more preferably from 5,000 to 300,000.

(3) Manufacture of (meth)acrylic acid copolymer

The (meth)acrylic copolymer which is an example of the specific polymer in the present invention can be obtained by subjecting a mixture of a polymerizable unsaturated compound containing (meth)acrylic acid and the compound (A) to addition polymerization.

In this case, as the unsaturated compound, only (meth)acrylic acid and the compound (A) may be used, and other polymerizable unsaturated compounds may be used in addition to the (meth)acrylic acid and the compound (A). Examples of the other polymerizable unsaturated compound which can be used herein include a conjugated diene, an aromatic vinyl compound, a (meth) acrylate, an α, β-unsaturated nitrile compound, and a cis-butylene. Amine compounds and the like. Specific examples of the compound include, as the conjugated diene, 1,3-butadiene, 2-methyl-1,3-butadiene, and 2,3-dimethyl-1. 3-butadiene, 2-chloro-1,3-butadiene, etc.; examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, and vinyl. Toluene, chlorostyrene, divinylbenzene, etc.; as the (meth) acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 4-(4-n-propylcyclohexyl) phenyl (meth) acrylate, from the following formula (MA-2)

The compound to be represented, etc., and examples of the α,β-unsaturated nitrile compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethyl acrylonitrile, dicyanethylene, and the like; Examples of the maleimide compound include N-cyclohexylmethyleneimine, N-phenylmethyleneimine, and the like, and one selected from the compounds may be used. the above.

In the (meth)acrylic copolymer, the content of the repeating unit derived from (meth)acrylic acid is preferably 0.1% by weight to 80% by weight, more preferably 5% by weight to 60% by weight; and the content of the repeating unit derived from the compound (A) The ratio is preferably from 0.1% by weight to 15% by weight, more preferably from 0.5% by weight to 10% by weight.

The (meth)acrylic copolymer can be synthesized by using, for example, a known solution polymerization, using a polymerizable unsaturated compound as described above. The solution polymerization can be carried out in an organic solvent in the presence of a suitable polymerization initiator, preferably further in the presence of a suitable chain transfer agent.

As the organic solvent, for example, an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol alkyl ether, a propylene glycol monoalkyl ether, a propylene glycol alkyl ether acetate, a propylene glycol alkane can be used. Alkyl ether propionate, aromatic hydrocarbon, ketone, ester, and the like. The use ratio of the organic solvent is preferably from 120 parts by weight to 600 parts by weight, and more preferably from 150 parts by weight to 400 parts by weight, based on 100 parts by weight of the total of the polymerizable unsaturated compound.

Examples of the polymerization initiator include cumene hydroperoxide, benzammonium peroxide, t-butyl hydroperoxide, acetam peroxide, dicumyl hydroperoxide, 1,1,3. , 3-tetramethylbutyl hydroperoxide, azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethyl One or more selected from these polymerization initiators can be used as the valeronitrile or the like. The use ratio of the polymerization initiator is preferably 2 parts by weight to 10 parts by weight, more preferably 3 parts by weight to 8 parts by weight, based on 100 parts by weight of the total of the polymerizable unsaturated compound.

Examples of the chain transfer agent include a xanthogen compound, a thiuram compound, a phenol derivative, an allyl compound, a halogenated hydrocarbon compound, a vinyl ether compound, triphenylethane, and pentaphenylethane. Acrolein, methacrolein, thioglycolic acid, thiomalic acid, thioglycollate 2-ethylhexyl ester, α-methylstyrene dimer, etc., which may be selected from these chain transfer agents One or more of them. The proportion of the chain transfer agent used is preferably 3 parts by weight or less, more preferably 0.1 parts by weight to 1.5 parts by weight, based on 100 parts by weight of the total of the polymerizable unsaturated compound.

The solution polymerization for synthesizing the (meth)acrylic copolymer is preferably from 50 ° C to 100 ° C, more preferably from 60 ° C to 90 ° C, preferably from 30 minutes to 500 minutes, more preferably from 60 minutes to 300 minutes. The reaction time is carried out.

The Mw of the (meth)acrylic copolymer as the specific polymer in the present invention is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

(4) Manufacture of polyorganosiloxane

The polyorganosiloxane which is an example of the specific polymer in the present invention can be obtained by hydrolyzing and condensing a decane compound containing the compound (S) in the presence of a suitable organic solvent and a catalyst.

As the decane compound, the compound (S) may be used alone, or the compound (S) and other decane compounds may be used in combination. As other decane compounds which can be used herein, for example, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3-(methyl) propylene oxime Propyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane,allyltrimethoxydecane,ene Propyltriethoxydecane, octadecyltrimethoxydecane, octadecyltriethoxydecane,phenyltrimethoxydecane,phenyltriethoxydecane, 3-mercaptopropyltrimethoxy Decane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, 3- Glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyl A Diethoxy decane, 3-glycidoxypropyl dimethyl methoxy decane, 3-glycidoxy propyl dimethyl ethoxy An alkane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, or the like, which may be selected from these decane compounds. One or more.

When the compound (S) and another decane compound are used in combination, the use ratio of the compound (S) is preferably 5 mol% or more, and more preferably 10 mol% or more based on the total of the compound (S) and the other decane compound. .

The organic solvent to be used in the synthesis of the polyorganosiloxane may, for example, be a hydrocarbon, a ketone, an ester, an ether or an alcohol, and one or more selected from these organic solvents may be used. As a specific example of these organic solvents, the above can be used as a solvent which can be used in the synthesis of the compound (C). The same organic solvent as the organic solvent exemplified for the hydrocarbon, ketone, ester, ether or alcohol. As the organic solvent, a water-insoluble organic solvent is preferably used. The use ratio of the organic solvent is preferably from 10 parts by weight to 10,000 parts by weight, more preferably from 50 parts by weight to 1,000 parts by weight, based on 100 parts by weight of all the decane compounds.

As the catalyst, for example, an acid, a base, an organic base, a titanium compound, a zirconium compound or the like can be used. Among these catalysts, a base is preferably used.

Examples of the base include an organic base, a basic alkali metal compound, and the like. Specific examples of the base include, as an organic base, a primary organic amine to a secondary organic amine such as ethylamine, diethylamine, oxazine, acridine, pyrrolidine or pyrrole; triethylamine and tri-n-propylamine; A tertiary organic amine such as tri-n-butylamine, pyridine, 4-dimethylaminopyridine or diazabicycloundecene; or a fourth-order organic amine such as tetramethylammonium hydroxide. Among these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine or tetramethylammonium hydroxide is preferably used. Examples of the basic alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.

The catalyst may preferably be used in a ratio of from 0.01 mol to 5 mol, more preferably from 0.05 mol to 3 mol, based on 1 mol of the total amount of the decane compound used as the raw material.

The proportion of water used in the synthesis of the polyorganosiloxane is preferably from 0.5 mol to 100 mol, more preferably from 1 mol to 30 mol, based on 1 mol of the total amount of the decane compound used as the raw material.

The synthesis reaction of the polyorganosiloxane is preferably carried out at a temperature of from 0 ° C to 200 ° C, more preferably from 10 ° C to 150 ° C, preferably from 0.1 to 40 hours, more preferably from 0.5 to 20 hours.

The Mw of the polyorganosiloxane which is a specific polymer in the present invention is preferably 1,000~ 500,000, more preferably 5,000 to 300,000.

[When a specific polymer has a pretilt appearance group or a photo-alignment group]

The specific polymers in the present invention can be synthesized in the manner described.

Next, a case where the specific polymer in the present invention has a pretilt appearance group or a photo-alignment group will be described.

The pretilt angle-developing group is a group having a property of imparting a pretilt angle by aligning liquid crystal molecules, and examples thereof include a linear alkyl group having 4 to 30 carbon atoms (however, it is contained in the following chemical formula (A-1). In the case of the above, a linear fluoroalkyl group having a carbon number of 4 to 30, a group having a steroid structure, a group represented by the following formula (A-1), and the like.

(In the formula (A-1), a is 0 or 1, and b is an integer of 0 to 2. However, when a and b are not different, c is an integer of 1 to 20, and "*" is a binding bond)

Specific examples of the group C _c H _2c+1 - in the formula (A-1) include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-glycol. Base, n-octyl, n-decyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, N-octadecyl, n-nonadecyl, n-icosyl and the like.

Specific examples of the group represented by the formula (A-1) include the following formula (A-1-1-1), formula (A-1-1-2), and formula (A-). The base or the like represented by each formula of 1-2).

[化10]

(In the formula, "n-" denotes a linear shape, respectively, and "*" denotes a binding bond, respectively)

The photo-alignment group is a group having a property of generating at least one of isomerization and dimerization by irradiation of light. Examples of such a photo-alignment group include a group having an azobenzene structure, a group having a cinnamic acid structure, a group having a chalcone structure, a group having a benzophenone structure, and a coumarin structure. Base. Among these, a group having a cinnamic acid structure is preferably used from the viewpoint of high liquid crystal alignment, synthesis of a monomer, and easy introduction into a polymer. The cinnamic acid structure may be either cis or trans.

When the liquid crystal alignment agent of the present invention is used to form a liquid crystal alignment film formed by rubbing a coating film, the total of the monomer having a pretilt appearance group and the monomer having a photoalignment group as described above The ratio of the molar number to the molar number of all the monomers, preferably a monomer having a pretilt appearance group as described above and having light at a ratio of 15 mol% or less The monomer having an alignment group, more preferably a monomer having a pretilt appearance group and a monomer having a photo-alignment group as described above in a ratio of 10 mol% or less, and particularly preferably not using the above. A monomer having a pretilt-developing group and a monomer having a photo-alignment group.

When the liquid crystal alignment agent of the present invention is used to form a liquid crystal alignment film formed by performing rubbing treatment on a coating film (for example, applied to a VA type liquid crystal display element or the like), it is preferably 2 mol% or more based on all monomers. The ratio of the monomer having a pretilt appearance group as described above is used, and it is more preferable to use a monomer having a pretilt angle-developing group as described above at a ratio of 3 mol% to 30 mol%, and further The monomer having a pretilt-developing group as described above is preferably used in a ratio of 5 mol% to 20 mol%.

When the liquid crystal alignment agent of the present invention is used to form a liquid crystal alignment film formed by light irradiation of a coating film, it is preferable to use photoalignment as described above at a ratio of 2 mol% or more with respect to all monomers. The monomer of the group, more preferably, the monomer having a photo-alignment group as described above is used in a ratio of 5 mol% or more, and more preferably the photo-alignment as described above is used at a ratio of 10 mol% or more. A monomer based on a base.

The specific polymer in the present invention may have both a pretilt appearance group and a photoalignment group.

<Other ingredients>

The liquid crystal alignment agent of the present invention contains a specific polymer as described above as an essential component. The liquid crystal alignment agent of the present invention may contain other components arbitrarily used in addition to the specific polymer.

Examples of other components which can be used herein include a polymer other than a specific polymer, a compound having at least one epoxy group in the molecule (hereinafter also referred to as "epoxy compound"), a functional decane compound, and the like. .

[Polymers other than specific polymers]

Polymers other than the specific polymers can be used to improve solution properties and electrical properties. The other polymer is a polymer having no divalent group represented by the formula (1), and may be, for example, a polymer selected from the group consisting of ruthenium iodide polymerization of polyglycine and polyglycolic acid. , polyglycolate, polyester, polyamine, polyoxyalkylene, cellulose derivatives, polyacetal, polystyrene and its derivatives, poly(styrene-phenylbutylene) One or more of the group consisting of an amine), a derivative thereof, and a poly(meth) acrylate, and having no divalent group represented by the above formula (1).

The total amount of the polymer (referred to as the total of the specific polymer and the polymer other than the specific polymer. The same applies hereinafter), and the use ratio of the polymer other than the specific polymer is preferably 50% by weight or less, and more preferably 20% by weight. Hereinafter, it is more preferably 10% by weight or less. It is particularly preferred that the polymer other than the specific polymer is not contained.

[epoxy compound]

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N For the N-diglycidyl-cyclohexylamine or the like, one or more selected from the group consisting of these epoxy compounds can be used.

The ratio of use of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 parts by weight to 30 parts by weight, based on 100 parts by total of the total of the polymer.

[functional decane compound]

Examples of the functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethyl. Oxyl Decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxy decane, 3-ureidopropyltriethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxy Baseline, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4,7-triazine Heteroane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-trimethoxy矽alkyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, 9-trimethoxydecyl-3,6-diaza Methyl sulfonate, methyl 9-triethoxydecyl-3,6-diazepine, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amino Propyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, glycidoxymethyltrimethoxydecane, Glycidol Methyltriethoxydecane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3 - glycidyloxypropyl triethoxy decane or the like, one or more selected from the group consisting of these functional decane compounds can be used.

The use ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 0.02 parts by weight to 0.2 parts by weight, based on 100 parts by weight of the total of the polymer.

<Preparation of liquid crystal alignment agent>

The liquid crystal alignment agent of the present invention is composed of a composition in which a specific polymer and optionally other components which are optionally used are dissolved in a solution in the form of a solution.

The organic solvent used in the liquid crystal alignment agent of the present invention may, for example, be N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, N,N-dimethylformamide , N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, B Ethyl oxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, Ethylene glycol-isopropyl 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, isoamyl propionate, isobutyric acid The amyl ester, the diisoamyl ether, the ethylene carbonate, the propylene carbonate, and the like may be one or more selected from the organic solvents, depending on the type of the specific polymer to be used.

The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, and the like, but is appropriately selected. A range of from 1% by weight to 10% by weight is preferred. By setting the solid content concentration in this range, a liquid crystal alignment film having a suitable film thickness can be formed with good coatability, which is preferable.

The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 10 ° C to 50 ° C, more preferably 20 ° C to 30 ° C.

<Formation of liquid crystal alignment film>

By using the liquid crystal alignment agent of the present invention, for example, a liquid crystal alignment film can be formed by a step of forming a coating film (coating film forming step) at least by applying the liquid crystal alignment agent of the present invention onto a substrate.

A liquid crystal alignment agent containing a specific polymer obtained by using a monomer having a pretilt angle-developing group in a ratio of preferably 2 mol% or more with respect to all monomers, a coating film formed by the coating film forming step It is used as a liquid crystal display element or a retardation film of a VA type as a liquid crystal alignment film, but may be used after performing the following liquid crystal alignment imparting step on the formed coating film as needed. In other cases, the coating film formed by the coating film forming step can be applied to any type of liquid crystal display element or retardation film after the liquid crystal alignment imparting step described below.

(1) Coating film forming step

When the liquid crystal alignment agent of the present invention is applied to a liquid crystal display element of a liquid crystal cell having a vertical electric field type such as a TN type, an STN type, or a VA type, two sheets are provided with patterned transparent conductive The substrate of the film was applied as a pair, and the liquid crystal alignment agent of the present invention was applied to the surface of each of the transparent conductive films of the two substrates to form a coating film. When the liquid crystal alignment agent of the present invention is applied to a liquid crystal display element having a liquid crystal cell of a transverse electric field type such as an IPS type or an FFS type, a pair of transparent conductive films or metal films are patterned into a comb shape on one surface. The substrate of the electrode and the counter substrate not provided with the electrode are paired, and the liquid crystal alignment agent of the present invention is applied to each of the surface on which the comb-shaped electrode is formed and the surface of the counter substrate to form a coating film. Further, when the liquid crystal alignment agent of the present invention is applied to a retardation film, the liquid crystal alignment agent of the present invention is applied onto one substrate (substrate having no electrode) to form a coating film.

In the above, when the liquid crystal alignment agent of the present invention is applied to a liquid crystal display element, as the substrate, for example, glass such as float glass or soda glass may be used; and polyethylene terephthalate may be contained. A transparent substrate of plastic such as polybutylene terephthalate, polyether oxime or polycarbonate. As the transparent conductive film, for example, an Indium Tin Oxide (ITO) film containing In ₂ O ₃ —SnO ₂ , a NESA (registered trademark) film containing SnO ₂ , or the like can be used. As the metal film, for example, a film containing a metal such as chromium can be used. For the patterning of the transparent conductive film and the metal film, for example, a method of forming a pattern by a photo-etching method, a sputtering method, or the like after forming a transparent conductive film having no pattern can be used; A method of using a mask having a desired pattern when using a conductive film.

On the other hand, when the liquid crystal alignment agent of the present invention is applied to a retardation film, as the substrate, Triacetyl Cellulose (TAC), polyethylene terephthalate, and polybutylene can be suitably exemplified. A transparent substrate of synthetic resin such as butyl phthalate, polyether oxime, polyamidamine, polyimide, polymethyl methacrylate or polycarbonate. Among these, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element.

In most cases, the retardation film is used in combination with a polarizing film. At this time, in order to be able to play The expected optical characteristics must be precisely controlled to a specific direction with respect to the angle of the polarizing axis of the polarizing film to fit the retardation film. Therefore, if a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle is formed on the TAC film, the step of laminating the retardation film while controlling the angle of the retardation film on the polarizing film can be omitted. It can help to improve the productivity of the liquid crystal display element. The formation of the liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle can be carried out by a photoalignment method using a liquid crystal alignment agent containing a (B) polymer containing a liquid crystal alignment group having a photoalignment ability.

Therefore, by using the TAC film as the substrate for forming the retardation film, in addition to the above advantages, it contributes to downsizing and weight reduction of the liquid crystal display element, and can also be applied to a flexible display.

When the liquid crystal alignment agent is applied to the substrate, in order to improve the adhesion between the substrate and the electrode and the coating film, the substrate and the electrode may be subjected to pretreatment by applying a functional decane compound, titanate or the like before heating. .

The application of the liquid crystal alignment agent to the substrate can be preferably carried out by an appropriate coating method such as an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. After coating, the coated surface is preheated (prebaked), followed by calcination (post-baking), whereby a coating film can be formed. The prebaking conditions are, for example, a heating temperature of 40 ° C to 120 ° C, a heating time of 0.1 minutes to 5 minutes, and a post-baking condition of, for example, a heating temperature of 120 ° C to 300 ° C, preferably 150 ° C to 250 ° C, for example, 5 Heating time of minutes to 200 minutes, preferably 10 minutes to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(2) Liquid crystal alignment imparting step

[rubbing processing step]

When the specific polymer contained in the liquid crystal alignment agent of the present invention is the following polymer, The ratio of the number of moles of the total of the monomer having the pretilt angle-developing group and the monomer having the photo-alignment group to the number of moles of all the monomers is preferably 2 mol% or less. The polymer obtained by the film can be subjected to a rubbing treatment by the (1) coating film forming step to impart a liquid crystal alignment ability to the coating film as a liquid crystal alignment film.

The rubbing treatment is performed by rubbing a coating film formed by the (1) coating film forming step in a fixed direction by, for example, a roll on which a cloth containing long fibers such as nylon, rayon, or cotton is wound. Friction treatment. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.

The liquid crystal alignment film to which the liquid crystal alignment property is imparted by the rubbing treatment can be preferably applied to a TN type, STN type, IPS type or FFS type liquid crystal display element or retardation film.

[Light irradiation processing step]

When the specific polymer contained in the liquid crystal alignment agent of the present invention is a polymer obtained by using a monomer having a photo-alignment group in a ratio of 2 mol% or more with respect to all monomers, 1) The coating film formed by the coating film forming step can impart a liquid crystal alignment ability to the coating film by irradiating the polarized light thereto as a liquid crystal alignment film.

As the light to be irradiated here, for example, ultraviolet rays, visible rays, or the like containing light having a wavelength of 150 nm to 800 nm can be used. Ultraviolet light containing light having a wavelength of 200 nm to 400 nm is preferred. As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an Hg-Xe lamp, an excimer laser or the like can be used. The ultraviolet light in the preferred wavelength region can be obtained by a method in which the light source is used in combination with, for example, a filter, a diffraction grating, or the like.

When the light is polarized (linearly polarized or partially polarized) used for light irradiation, it may be irradiated from a direction perpendicular to the surface of the coating film, or may be irradiated from an oblique direction in order to impart a pretilt angle. On the other hand, in the case of illuminating non-polarized light, the illumination is preferably from relative to the coating The film surface is tilted in the direction.

The amount of light to be irradiated is preferably 1 J/m ² or more and less than 10,000 J/m ² , and more preferably 10 J/m ² to 3,000 J/m ² .

The liquid crystal alignment film to which the liquid crystal alignment property is imparted by the light irradiation treatment can be applied to any type of liquid crystal display element in accordance with the structure of the polymer contained in the liquid crystal alignment agent.

<Liquid crystal display element and retardation film>

A liquid crystal display element and a retardation film can be manufactured using the substrate having the liquid crystal alignment film formed in the above manner.

[Manufacture of liquid crystal display elements]

A liquid crystal display element can be manufactured in the following manner by using a substrate in which the liquid crystal alignment film is formed in the above manner.

First, a liquid crystal cell having a structure in which liquid crystal is sandwiched between gaps (cell gaps) in which a pair of substrates on which a liquid crystal alignment film is formed is disposed is sandwiched.

In the case of constituting the liquid crystal cell, the following method or the like can be used to bond the two substrates so that the liquid crystal alignment film faces face each other by the sealant disposed on the peripheral portion of the two substrates on which the liquid crystal alignment film is formed, and the film is aligned toward the liquid crystal alignment film. And a method of injecting a liquid crystal into the cell gap divided by the sealant and then sealing the injection hole; and arranging, for example, an ultraviolet curable sealant at a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed Further, after the liquid crystal is placed on a predetermined portion of the liquid crystal alignment film surface, the other substrate is bonded to the liquid crystal alignment film so as to be opposed to each other, and the liquid crystal is diffused to the entire surface of the liquid crystal alignment film, and then A method in which the entire surface of the substrate is irradiated with ultraviolet rays to harden the sealant.

In any of the above cases, when the rubbing treatment is performed when the liquid crystal alignment film is formed, it is preferable that the rubbing directions of the liquid crystal alignment films of the two substrates are orthogonal or antiparallel; When the polarized light is irradiated when the liquid crystal alignment film is formed, it is preferable that the direction in which the polarizing surface of the irradiation light is projected on the two substrate faces is orthogonal or antiparallel.

Further, the liquid crystal display element can be manufactured by bonding a polarizing plate to the outer surface of the liquid crystal cell in a predetermined direction.

As the sealant, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used.

As the liquid crystal, a nematic liquid crystal or a smectic liquid crystal can be used. Among these liquid crystals, nematic liquid crystals are preferred. Specific examples thereof include a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, and a terphenyl. A liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, etc. For example, the following compounds may be added to these liquid crystals: cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate; as the trade names "C-15" and "CB-15" ( A chiral agent sold by Merck (manufactured by Merck); a ferroelectric liquid crystal such as p-oxybenzylidene-p-amino-2-methylbutylcinnamate or the like.

The polarizing plate to be bonded to the outer surface of the liquid crystal cell is, for example, a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film, or a polarizing plate including the H film itself. The H film is a polarizing film in which iodine is absorbed while extending the polyvinyl alcohol.

The liquid crystal display element obtained in the above manner can be effectively applied to various devices such as a clock, a portable game machine, a word processor, a note personal computer, and a car navigation system. System), camcorder, personal digital assistant (PDA), digital camera, mobile phone, various monitors, LCD TVs and other display devices.

[Relativity film]

The retardation film can be produced by preparing one substrate on which the liquid crystal alignment film is formed as described above, forming a coating film of a polymerizable liquid crystal on the substrate, and then curing the coating film of the polymerizable liquid crystal to form a liquid crystal. Floor.

The polymerizable liquid crystal is a liquid crystal compound or a liquid crystal composition which is polymerized by at least one of heating and light irradiation.

Examples of such a polymerizable liquid crystal include those described in Non-Patent Document 1 ("UV-curable liquid crystal and its application", liquid crystal, Vol. 3, No. 1 (1999), pages 34 to 42). Column type liquid crystal compound. It may also be a cholesteric liquid crystal; a disc-shaped liquid crystal; a twisted nematic alignment type liquid crystal to which a chiral agent is added. The polymerizable liquid crystal may also be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may be a composition containing a known polymerization initiator, a suitable solvent, or the like.

When the polymerizable liquid crystal as described above is applied onto the formed liquid crystal alignment film, for example, a suitable coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, or an inkjet method can be employed.

Then, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more kinds of treatments selected from the group consisting of heating and light irradiation, whereby the coating film is cured to form a liquid crystal layer. In terms of obtaining a good alignment, it is preferred to carry out these treatments in an overlapping manner.

The heating temperature of the coating film is appropriately selected depending on the kind of the polymerizable liquid crystal to be used. For example, when RMS03-013C manufactured by Merck & Co., Ltd. is used, it is preferred to carry out heating at a temperature ranging from 40 °C to 80 °C. The heating time is preferably from 0.5 minutes to 5 minutes.

As the irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be preferably used. The amount of light to be irradiated is preferably 50 mJ/cm ² to 10,000 mJ/cm ² , and more preferably 100 mJ/cm ² to 5,000 mJ/cm ² .

The thickness of the formed liquid crystal layer is appropriately set in accordance with desired optical characteristics. For example, when a 1/2 wavelength plate under visible light having a wavelength of 540 nm is produced, the phase difference of the retardation film formed is changed to a thickness of 240 nm to 300 nm, and if it is a quarter wave plate, the phase difference is changed to 120 nm. ~150nm thickness. The thickness of the liquid crystal layer in which the target phase difference can be obtained varies depending on the optical characteristics of the polymerizable liquid crystal to be used. For example, when RMS03-013C manufactured by Merck is used, the thickness for fabricating the quarter-wavelength plate is in the range of 0.6 μm to 1.5 μm.

The retardation film obtained in the above manner can be suitably used as a retardation film of a liquid crystal display element.

The driving method of the liquid crystal display element using the retardation film produced by using the liquid crystal alignment agent of the present invention is not limited, and may be, for example, TN mode, STN mode, IPS mode, FFS mode, or VA mode (including VA-multi-quadrant vertical alignment) Various known methods such as a (Multi-Domain Vertical Alignment, MVA) method, a VA-Patterned Vertical Alignment (PVA) method, and the like.

The liquid crystal display device generally has a structure in which a polarizing film is attached to both surfaces of a liquid crystal cell in which liquid crystal is sandwiched between a pair of substrates on which an electrode pair and a liquid crystal alignment film are formed. The retardation film is used by attaching a surface on the substrate side to the outer surface of the polarizing film on the viewer side of the liquid crystal display element. Therefore, it is most preferable that the substrate of the retardation film is made of TAC, and the substrate of the retardation film also functions as a protective film of the polarizing film.

A liquid crystal display element having a retardation film produced by using the liquid crystal alignment agent of the present invention as described above has an advantage that the liquid crystal alignment property is excellent and stable for a long period of time.

[Examples]

In the following synthesis examples, the compounds are repeatedly synthesized in the same manner as described in the respective synthesis examples, thereby ensuring a necessary amount of the compound in the subsequent synthesis examples.

<Synthesis of a monomer having a divalent group represented by the formula (1)>

[Synthesis of Compound (C)]

Synthesis Example C-1

Compound (C-1) was synthesized according to the following Scheme 1.

In a 2 L three-necked flask equipped with a reflux tube, 218.12 g of pyromellitic dianhydride, 266.2 g of L-aspartic acid, and 1,000 mL of pyridine were mixed, and the mixture was stirred at 45 ° C for 2 hours, and then reacted under reflux for 4 hours. After the reaction, the solvent was removed by distillation under reduced pressure, whereby 448 g of Compound (C-1) was obtained.

Synthesis Example C-2

Compound (C-2) was synthesized according to the following Scheme 2.

218.12 g of pyromellitic dianhydride, 206.24 g of 4-aminobutyric acid and 1,000 mL of dimethylformamide were mixed in a 2 L three-necked flask equipped with a reflux tube, and stirred at 45 ° C for 2 hours, followed by reflux. 4 hours reaction. After the reaction, distilled water was added to carry out crystallization, and then the solid was collected by filtration and recovered. The recovered solid was recrystallized with ethanol, whereby 322 g of the compound (C-2) was obtained.

[Synthesis of Compound (E)]

Synthesis Example E-1

Compound (E-1) was synthesized according to the following Scheme 3.

2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride 250.2 g and 3-aminopropanol 150.22 g were mixed in a 2 L three-necked flask equipped with a reflux tube. Pyridine 1,000 mL was stirred at 45 ° C for 2 hours, followed by reflux for 4 hours. After the reaction, distilled water was added to carry out crystallization, and then the solid was collected by filtration and recovered. The solid recovered was washed with ethanol, and then dried under reduced pressure at 60 ° C to obtain 306 g of compound (E-1).

Synthesis Example E-2

Compound (E-2) was synthesized according to the following Scheme 4.

200 g of epichlorohydrin, 500 mL of 2N (equivalent) sodium hydroxide aqueous solution and 2.71 g of tetrabutylammonium bromide were placed in a 2 L three-necked flask equipped with a dropping funnel. A solution obtained by dissolving 306 g of the compound (E-1) obtained in the same manner as in the above-mentioned Synthesis Example E-1 in 200 mL of tetrahydrofuran was slowly added dropwise from the dropping funnel. During the dropwise addition, the flask was cooled with an ice bath and maintained at an internal temperature of not more than 40 °C. After completion of the dropwise addition, the reaction was carried out at 80 ° C for 8 hours with stirring. After the reaction, 2,000 mL of ethyl acetate was added to the reaction mixture. 500 mL of distilled water was added thereto to carry out liquid separation washing to carry out a liquid separation cleaning operation of the waste water layer. This liquid separation cleaning operation was repeated, and a total of four liquid separation cleaning operations were performed. Thereafter, the organic layer was concentrated by distillation under reduced pressure to give a crude product as a solid. This crude product was recrystallized from a mixed solvent of ethyl acetate as a good solvent and hexane as a poor solvent to obtain 210 g of the compound (E-2).

[Synthesis of Compound (A)]

Synthesis Example A-1

Compound (A-1) was synthesized according to the following Scheme 5.

Into a 2 L three-necked flask equipped with a dropping funnel, 364 g of a compound (E-1), 303 g of triethylamine and 800 mL of tetrahydrofuran which were synthesized in the same manner as in the above-mentioned Synthesis Example E-1 were added. A solution obtained by dissolving 210 g of acrylonitrile chloride in 200 mL of tetrahydrofuran was slowly added dropwise from the dropping funnel. During the dropwise addition, the flask was cooled with an ice bath and the internal temperature did not exceed 40 ° C. The way to keep. After the completion of the dropwise addition, the reaction was carried out for 6 hours at room temperature. After the reaction, 2,000 mL of ethyl acetate was added to the reaction mixture. Further, 500 mL of distilled water was added thereto to carry out liquid separation washing to carry out a liquid separation cleaning operation of the waste water layer. This liquid separation cleaning operation was repeated, and a total of four liquid separation cleaning operations were performed. Thereafter, the solvent was removed by distillation under reduced pressure to obtain a crude product as a solid. This crude product was recrystallized from ethanol, whereby 338 g of Compound (A-1) was obtained.

[Synthesis of Compound (S)]

Synthesis Example S-1

Compound (S-1) was synthesized according to the following Scheme 6.

[Chemistry 16]

364 g of the compound (E-1) and 800 mL of acetic acid synthesized in the same manner as in the above-mentioned Synthesis Example E-1 were placed in a 2 L three-necked flask equipped with a dropping funnel. 200 mL of sulfuric acid was slowly added thereto from the dropping funnel. During the dropwise addition, the flask was cooled with an ice bath and maintained at an internal temperature of not more than 10 °C. After the completion of the dropwise addition, the reaction was carried out for 6 hours at room temperature. After the reaction, 2,000 mL of ethyl acetate was added to the reaction mixture. Further, 500 mL of distilled water was added thereto. Perform liquid separation cleaning to perform a liquid separation cleaning operation of the waste water layer. This liquid separation cleaning operation was repeated, and a total of four liquid separation cleaning operations were performed. Thereafter, the solvent was removed by distillation under reduced pressure to obtain a crude product in the form of a liquid. This crude product was dissolved in ethyl acetate, and then purified by a cerium oxide column to remove the solvent, thereby obtaining 308 g of the compound (S-1a). Then, 40 μL of a compound (S-1a) 262.7 g, toluene 400 mL, and a concentration of 0.2 mol/L of chloroplatinic acid hexahydrate in an isopropanol solution was added to a 1000 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube. After bubbling under a nitrogen gas stream for about 10 minutes to carry out nitrogen substitution in the system, 145 g of dimethyl monomethoxydecane was added, followed by a reaction under nitrogen for 10 hours under reflux. After the reaction mixture was passed through a short column of silica gel, it was purified by a column of cerium oxide, and the solvent was removed to obtain 85 g of the compound (S-1).

<Synthesis of Polymer>

[Synthesis of polyoxyalkylene]

Synthesis Example P-1 to Synthesis Example P-3

The oxime compound was added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube in the molar ratio shown in Table 1, and then methyl isobutyl ketone was added in such a manner that the total concentration of the decane compound became 20% by weight. To dissolve. Further, with respect to the total number of moles of the decane compound, only triethylamine corresponding to 10 mol% was added thereto, and the mixture was mixed at room temperature. The amount of deionized water corresponding to 0.2 times by weight of methyl isobutyl ketone was added dropwise from the dropping funnel, and then the reaction was carried out at 80 ° C for 6 hours.

After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% ammonium nitrate aqueous solution until the washed wastewater became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polypyroxyne (P-1). ) ~ polyoxyalkylene (P-3).

[Synthesis of Polyamine]

Synthesis Example P-4

With a molar ratio of 1,4-diaminobenzene 30 mol%, 3,5-diaminobenzoic acid 60 mol%, and 2,4-diamino-n-octadecyloxybenzene 10 mol%, a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, and adding 1,4-diaminobenzene, 3,5-diaminobenzoic acid, and 2,4-diamino-n-octadecyloxybenzene, and then The tetrahydrofuran was added so as to be dissolved so that the total concentration of the diamine compound became 20% by weight. To the total number of moles of the diamine compound, only triethylamine equivalent to 300 mol% was added thereto, and the mixture was mixed at room temperature. Further, a polymerization reaction is carried out by slowly dropping a solution in which a total amount of moles relative to the diamine compound is 100 mol% with respect to the diamine compound by slowly dropping a solution from the dropping funnel. -2) (The compound obtained in the synthesis example C-2) was a solution obtained by dissolving ruthenium chloride in a concentration of 20% by weight in tetrahydrofuran. After the end of the reaction, the reaction mixture was poured into extremely excess methanol to precipitate a reaction product. The recovered precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain a polydecylamine (P-4).

[Synthesis of Polyester and Polythioester]

Synthesis Example P-5 to Synthesis Example P-11

With the molar ratio described in Table 2, a mixer, a thermometer, a dropping funnel, and a reflux are provided. A diol compound, a diepoxide compound, or a dithiol compound (compound (A)) was added to the reaction vessel of the cooling tube, and then tetrahydrofuran was added so as to have a total concentration of these compounds of 20% by weight. Further, to the total number of moles of the compound, only triethylamine corresponding to 300 mol% was added thereto, and the mixture was mixed at room temperature. The polymerization was carried out by slowly dropping a solution from the dropping funnel to the chlorination of the molar ratio of the diergic compound described in Table 2 using sulfinium chloride. A solution in which a concentration of 20% by weight is dissolved in tetrahydrofuran. After the end of the reaction, the reaction mixture was poured into extremely excess methanol to precipitate a reaction product. After the recovered precipitate was washed with methanol, it was dried at 40 ° C for 15 hours under reduced pressure, thereby obtaining polyester (P-5) to polyester (P-9) and polyester (P-11). And polythioester (P-10).

The abbreviations of the compound names in Table 2 are as follows.

HY-1: hydroquinone

HY-2: 3,5-dihydroxybenzoic acid

HY-3: 3,6-dihydroxy-cholestane

HY-4: 3,5-dihydroxybenzoic acid-3-cholesteryl ester

SH-1: Benzene-1,4-dithiol

CA-1: 1,4-dicarboxybenzene

CA-2: 1,3-dicarboxybenzene

CA-3: 1,3-dicarboxy-5-n-octadecyloxybenzene

[Synthesis of methacrylic acid copolymer]

Synthesis Example P-12 and Synthesis Example P-13

The polymerizable unsaturated compound was added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube in the molar ratio described in Table 3, and the total concentration of the polymerizable unsaturated compound was changed to 50% by weight. Diethylene glycol ethyl methyl ether was added for dissolution. 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, and only 3 mol% of the polymerization initiator was added to the total number of moles of the polymerizable unsaturated compound. The α-methylstyrene dimer as a chain transfer agent is 0.5 times by weight based on the weight of the polymerization initiator. Then, after bubbling under a nitrogen gas stream for 10 minutes to carry out nitrogen substitution in the system, the polymerization reaction was carried out at 70 ° C for 5 hours in a nitrogen atmosphere. After the end of the reaction, the reaction mixture was poured into extremely excess methanol to precipitate a reaction product. After the recovered precipitate was washed with methanol, it was dried at 40 ° C for 15 hours under reduced pressure, thereby obtaining a (meth)acrylic copolymer (P-12) and a (meth)acrylic copolymer (P- 13).

The abbreviations of the compound names in Table 3 are as follows.

MA-1: 4-(4-n-propylcyclohexyl)phenyl methacrylate

MA-2: a compound represented by the formula MA-2

[Synthesis of polyglycine]

Synthesis Example P-14

13.179 g of pyromellitic dianhydride and 11.835 g of 1,2,3,4-cyclobutyric dianhydride as tetracarboxylic dianhydride, and 4,4'-diaminodiphenylmethane 23.478 as diamine g and 3,6-bis(4-aminobenzylideneoxy)cholestane 1.554 g were dissolved in 200 g of N-methyl-2-pyrrolidone, and reacted at room temperature for 6 hours. Then, the reaction mixture was poured into extremely excess methanol to precipitate a reaction product. The recovered precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 48.5 g of polyamine acid (P-14).

[Synthesis of ruthenium iodide polymer]

In the following synthesis examples, the oxime imidization ratio of the ruthenium iodide polymer was measured in the following manner.

The obtained ruthenium iodide polymer was dissolved in deuterated dimethyl hydrazine, and tetramethyl decane was used as a reference material, and ¹ H-NMR was measured at room temperature. From the obtained ¹ H-NMR spectrum, the ruthenium iodide ratio was determined by the following formula (1).

醯 imidization rate (%) = (1-A ¹ /A ² ×α)×100(1)

(In the mathematical formula (1), A ¹ is a peak area of a proton derived from an NH group appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is another proton to a polymer Proportion of the number of protons of the NH group in the precursor (polyproline)

Synthesis Example P-15

3.53 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 24.72 g of 1,2,3,4-cyclobutyric acid dianhydride and 2,4,6,8-tetra Carboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride 3.94 g, and 1,4-diaminobenzene as diamine 16.70 g and by the following formula

1.108 g of the compound represented was dissolved in 200 g of N-methyl-2-pyrrolidone, and reacted at room temperature for 6 hours to obtain a polyamidonic acid solution.

Then, 250 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and After adding 37.39 g of pyridine and 80.43 g of acetic anhydride, a dehydration ring-closure reaction was carried out at 90 ° C for 6 hours. Then, the reaction mixture was poured into extremely excess methanol to precipitate a reaction product. The recovered precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 47.1 g of a quinone imidized polymer (P-15) having a ruthenium iodide ratio of 94%.

Synthesis Example P-16

25.895 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 12.079 g of 3-(3,5-diaminobenzylideneoxy)cholane as a diamine 4.97 g of 1,4-diaminobenzene and 7.030 g of 2,5-diaminobenzoic acid were dissolved in 200 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours to obtain polylysine. Solution.

Then, 250 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 18.27 g of pyridine and 23.59 g of acetic anhydride were added, followed by a dehydration ring-closure reaction at 110 ° C for 6 hours. The obtained reaction mixture was poured into extremely excess methanol to precipitate a reaction product. The recovered precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 49.1 g of a ruthenium iodide polymer (P-16) having a oxime imidation ratio of 96%.

<Preparation and evaluation of liquid crystal alignment agent>

[Application example for TN type liquid crystal display element]

Example TN-1

(1) Preparation of liquid crystal alignment agent

The polyoxyalkylene (P-1) obtained in the synthesis example P-1 as a polymer was dissolved in a mixed solvent containing N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) ( In NMP: BC = 50: 50 (mass ratio), a solution having a solid concentration of 6.5% by weight was prepared. After the solution was sufficiently stirred, it was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

(2) Evaluation of printability

The liquid crystal alignment agent prepared in the "(1) Preparation of liquid crystal alignment agent" was applied to a glass substrate with a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). On the transparent electrode surface, the substrate was heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated on a hot plate at 200 ° C for 10 minutes (post-baking) to form an average film thickness of 600 Å. Coating film. The coating film was observed with a microscope having a magnification of 20 times, and the presence or absence of uneven printing and pinholes was examined. As a result, uneven printing and pinholes were not observed, and the printability was "good".

(3) Manufacture of TN type liquid crystal cell

The liquid crystal alignment agent prepared in the "(1) Preparation of liquid crystal alignment agent" was applied to a glass substrate with a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). On the transparent electrode surface, the substrate was heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated on a hot plate at 200 ° C for 10 minutes (post-baking) to form an average film thickness of 600 Å. Coating film. The coating film was subjected to a rubbing treatment using a friction machine having a roll wound with a rayon cloth at a roll rotation speed of 500 rpm, a table moving speed of 3 cm/sec, and a hair press-in length of 0.4 mm to impart liquid crystal alignment ability. Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a clean oven at 100 ° C for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film.

The operation was repeated to obtain a pair (2 pieces) of a substrate having a liquid crystal alignment film.

Next, an epoxy resin binder having an alumina ball having a diameter of 5.5 μm is applied to the outer edge of the surface of the one of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film surface is opposed. The method is such that the pair of substrates are overlapped and then crimped, and the binder is hardened. Then, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a TN liquid crystal cell.

By repeating the above method, a total of three TN-type liquid crystal cells were produced, and one of them was evaluated for liquid crystal alignment, evaluation of pretilt stability, and evaluation of heat resistance.

(4) Evaluation of TN type liquid crystal cell

i) Evaluation of liquid crystal alignment

For the liquid crystal cell fabricated in the manner described above, the microscopic observation with a magnification of 100 times is turned on under crossed nicols. When the voltage of 5 V was disconnected, there was no abnormal region, and the case where no abnormal region was observed was evaluated as "good" liquid crystal alignment, and observation was performed with a microscope having a magnification of 50 times, and the case where no abnormal region was observed was evaluated as "may". In the case where the abnormal region was observed even at a magnification of 50 times, the liquid crystal alignment "bad" was evaluated, and as a result, the liquid crystal alignment property of the liquid crystal cell was "good".

Ii) Evaluation of pretilt stability

With respect to the liquid crystal cell manufactured in the above manner, the angle of inclination from the liquid crystal molecule from the substrate surface was measured by a crystal rotation method using a He-Ne laser, and this value was set as an initial pretilt angle (θ _IN ). The crystal rotation method is based on Non-Patent Document 2 (TJ Scheffer et al., Journal of Applied Physics, Vol. 48, p. 1783 (1977)), and Non-Patent Document 3 (F. Nakano et al., "Applied Physics of Japan" The method described in Journal, Vol. 19, p. 2013 (1980)).

An AC voltage of 5 V was applied to the liquid crystal cell after measuring the pretilt angle (θ _IN ) as described above for 100 hours. Thereafter, the pretilt angle is measured again by the same method as described above, and this value is set as the pretilt angle (θ _AF ) after the voltage application.

These measured values were substituted into the following formula (2), and the amount of change in the pretilt angle (Δθ (°)) before and after the voltage application was obtained.

△θ=| θ _AF -θ _IN | (2)

When the value Δθ is less than 0.05°, the pretilt stability is evaluated as “good”, and when the value Δθ is 0.05° or more and less than 0.2°, the evaluation is “OK”, and when the value Δθ is 0.2° or more, the evaluation is performed. As a result of "poor", the amount of change Δθ of the pretilt angle in the liquid crystal cell was 1%, and the pretilt stability was "good".

Iii) Evaluation of heat resistance

After applying a voltage of 5 V to the liquid crystal cell manufactured in the manner described above with an application time of 60 microseconds and a span of 167 milliseconds, "VHR-1 manufactured by Toyo Corporation" was used. The voltage holding ratio (initial voltage holding ratio (VHR _BF )) after 167 milliseconds after the release of the measurement was measured, and it was 99.4%.

The liquid crystal display element after the VHR _BF measurement was statically placed in an oven at 100 ° C, and thermal stress was applied for 1,000 hours. Thereafter, the liquid crystal display element was allowed to stand at room temperature, and after standing to cool to room temperature, the voltage holding ratio (VHR _AF ) after the application of thermal stress was measured under the same conditions as the measurement of the initial voltage holding ratio.

Then, the rate of change (ΔVHR (%)) of the voltage holding ratio before and after the application of the thermal stress is obtained by the following formula (3).

△VHR(%)=((VHR _BF -VHR _AF )÷VHR _BF )×100(3)

When the rate of change was less than 4%, the heat resistance was "good", and when the rate of change was 4% or more and less than 5%, the heat resistance was "may", and the rate of change was 5% or more. The case was evaluated as "poor" in heat resistance, and as a result, the heat resistance of the liquid crystal cell was "good".

Example TN-2 to Example TN-8 and Comparative Example TN-1 to Comparative Example TN-4

In the above-described Example TN-1, liquid crystal alignment was prepared in the same manner as in Example TN-1 except that the kind of the polymer used for the preparation of the liquid crystal alignment agent was as described in Table 4. And evaluate it.

The evaluation results are shown in Table 4.

In addition, in Comparative Example TN-2 and Comparative Example TN-3, since printing unevenness was observed in the evaluation of printability, the printability was made "poor".

[Application example for VA type liquid crystal display element]

Example VA-1

(1) Preparation of liquid crystal alignment agent

The polyester (P-8) obtained in the synthesis example P-8 as a polymer was dissolved in a mixed solvent containing N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (NMP: In BC = 50:50 (mass ratio), a solution having a solid concentration of 6.5% by weight was prepared. After the solution was sufficiently stirred, it was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

(2) Evaluation of printability

Using the liquid crystal alignment agent prepared in the manner described above, the printability was investigated in the same manner as in "(2) Evaluation of printability" in the Example TN-1, and as a result, uneven printing and pinholes were obtained. Neither was observed, and the printability was "good."

(3) Manufacture of VA type liquid crystal cell

The liquid crystal alignment agent prepared in the manner described above was applied on a transparent electrode surface of a glass substrate (thickness: 1 mm) having a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). Heating on a hot plate at 80 ° C for 1 minute (prebaking), and further heating (post-baking) on a hot plate at 200 ° C for 60 minutes to form a coating film having an average film thickness of 800 Å (liquid crystal alignment film) . This operation was repeated to obtain a pair (two sheets) of a glass substrate having a liquid crystal alignment film on a transparent conductive film.

Next, an epoxy resin binder having an alumina ball having a diameter of 5.5 μm is applied to the outer edge of the surface of the one of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film surface is opposed. The method is such that the pair of substrates are overlapped and then crimped, and the binder is hardened. Then, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a VA liquid crystal cell.

(4) Evaluation of VA type liquid crystal cell

With respect to the liquid crystal cell fabricated in the above manner, the liquid crystal alignment property and heat resistance were evaluated in the same manner as in Example TN-1, and as a result, the liquid crystal alignment property was "good", the initial voltage holding ratio was 99.0%, and heat resistance (thermal stress) The rate of change in voltage holding ratio before and after application is "OK".

Example VA-2 and Comparative Example VA-1

In the above-mentioned Example VA-1, liquid crystal alignment was prepared in the same manner as in Example VA-1 except that the kind of the polymer used for the preparation of the liquid crystal alignment agent was as described in Table 5. And evaluate it.

The evaluation results are shown in Table 5.

In addition, in Comparative Example VA-1, since printing unevenness was observed in the evaluation of printability, the printability was made "poor".

[Application example for FFS type liquid crystal display element]

Example FFS-1

(1) Preparation of liquid crystal alignment agent

The acrylic copolymer (P-13) obtained in the synthesis example P-13 as a polymer was dissolved in a mixed solvent (NMP) containing N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC). : BC = 50: 50 (mass ratio)), a solution having a solid concentration of 3.0% by weight was prepared. After the solution was sufficiently stirred, it was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

(2) Evaluation of coating properties

The liquid crystal alignment agent prepared in the manner described above was coated on a glass substrate using a spinner, prebaked on a hot plate at 80 ° C for 1 minute, and then subjected to an oven at 200 ° C in which the inside of the tank was purged with nitrogen. Heating was performed for an hour (post-baking), thereby forming a coating film having an average film thickness of 1,000 Å. The coating film was observed with a microscope having a magnification of 20 times, and the film thickness unevenness and pinholes were examined. As a result, uneven film thickness and pinholes were not observed, and the film coating property was "good".

(3) Manufacture of FFS type liquid crystal display elements

A glass substrate a having two systems having electrode pairs on one surface and a counter glass substrate a not provided with electrodes are used as a pair, and the electrode pairs are sequentially laminated with a bottom electrode having no pattern A bottom electrode e and a tantalum nitride film d, and a top electrode c patterned into a comb shape.

Hereinafter, each of the electrode pairs of the two systems will be referred to as "electrode A" and "electrode B", respectively. A schematic cross-sectional view of a pair of these electrode pairs and a plan view of the top electrode c are shown in Fig. 1 and Figs. 2(a) and 2(b), respectively. Fig. 2(b) is an enlarged view of a portion surrounded by a broken line of Fig. 2(a).

Using a rotator, the liquid crystal alignment agent prepared in the manner described above was applied to the surface of the glass substrate a having the electrode pair and the surface facing the glass substrate a, respectively, and prebaked on a hot plate at 80 ° C for 1 minute. The film was heated at 200 ° C for 1 hour in an oven substituted with nitrogen in the tank (post-baking) to form a coating film having an average film thickness of 1,000 Å. Then, using a Hg-Xe lamp and a Glan-Taylor prism, each of the surfaces of the coating films was irradiated with a polarized ultraviolet ray of 300 J/m ² including an open line of 313 nm from the normal direction of the glass substrate a. A pair of glass substrates a having a liquid crystal alignment film b.

On the outer periphery of the surface of the one glass substrate a in the glass substrate a having the liquid crystal alignment film b, an epoxy resin binder having an alumina ball having a diameter of 5.5 μm is applied by screen printing, and then The facing direction of the liquid crystal alignment film b of the glass substrate a is superposed so that the polarizing surface of the polarized ultraviolet light is superimposed so as to be parallel to the direction projected on the glass substrate a, and then bonded at 150 ° C for 1 hour. The agent is thermally hardened. Then, the liquid crystal "MLC-6221" manufactured by Merck was filled in the gap between the liquid crystal injection port and the glass substrate a, and then the liquid crystal injection port was sealed with an epoxy resin binder. Thereafter, in order to remove the flow alignment at the time of injecting the liquid crystal, it was heated to 150 ° C and then slowly cooled to room temperature.

Then, a polarizing plate was bonded to both outer surfaces of the glass substrate a, whereby an FFS type liquid crystal display element was produced. In this case, one of the polarizing plates is attached such that the direction in which the polarizing direction and the polarizing surface of the polarized ultraviolet light of the liquid crystal alignment film b are parallel to the projection direction of the surface of the glass substrate a. The other one is attached so that the polarization direction thereof is orthogonal to the polarization direction of the conventional polarizing plate.

By repeating the above method, a total of three FFS-type liquid crystal cells were produced, and one of them was evaluated for liquid crystal alignment, evaluation of heat resistance, and evaluation of afterimage characteristics.

(4) Evaluation of FFS type liquid crystal display elements

i) Evaluation of liquid crystal alignment

In the liquid crystal display device manufactured as described above, the presence or absence of an abnormal region in the change in brightness and darkness when the voltage of 5 V was turned on and off (applied or released) was observed with a microscope having a magnification of 50 times. The case where the abnormal region was not observed was evaluated as "good" in the liquid crystal alignment property, and the case where the abnormal region was observed was evaluated as the liquid crystal alignment "bad", and as a result, the liquid crystal alignment property of the liquid crystal display element was "good".

Ii) Evaluation of heat resistance

The heat resistance was evaluated in the same manner as in Example TN-1 for the liquid crystal display element manufactured in the above manner, and as a result, the initial voltage holding ratio was 99.2%, and the heat resistance (the rate of change of the voltage holding ratio before and after the application of the thermal stress) was " good".

Iii) Evaluation of afterimage characteristics

The liquid crystal display element manufactured in the above manner was placed in an environment of 25 ° C and 1 atm. without applying a voltage to the electrode B, a combined voltage of an alternating current voltage of 3.5 V and a direct current voltage of 5 V was applied to the electrode A for 2 hours. Shortly thereafter, a voltage of 4 V was applied to both the electrode A and the electrode B. In addition, the time from the time when the voltage of the alternating current of 4 V was applied to the both electrodes was started, and the time until the difference in the light transmittance of the electrode A and the electrode B was not visually recognized (after-image erasure time) was measured, and the time was investigated. Which stage of the following five stages.

A: less than 20 seconds

B: 20 seconds or more, less than 60 seconds

C: 60 seconds or more, less than 100 seconds

D: 100 seconds or more, less than 150 seconds

E: 150 seconds or more

The shorter the time, the more difficult it is to generate an afterimage.

The afterimage evaluation time of the liquid crystal display element of the present embodiment was evaluated to be at the shortest "A" level.

[Application example for retardation film]

Example PD-1

(1) Fabrication of retardation film

The liquid crystal alignment agent prepared in the above Example FFS-1 was coated on one side of a TAC film as a substrate using a bar coater, and baked in an oven at 120 ° C for 2 minutes to form a film thickness of 100 nm. Coating film. Then, using a Hg-Xe lamp and a Glan-Taylor prism, a surface of the coating film was irradiated with a polarized ultraviolet ray of 100 J/m ² including an open line of 313 nm from the normal direction of the substrate to form a liquid crystal alignment film.

On the liquid crystal alignment film formed as described above, a polymerized liquid crystal (manufactured by Merck & Co., trade name "RMS03-013C") was filtered by a bar coater using a filter having a pore size of 0.2 μm. Thereafter, baking was performed for 1 minute in an oven set at 50 ° C to form a film of a polymerizable liquid crystal. Then, the film surface of the polymerizable liquid crystal was irradiated with 10,000 J/m ² of non-polarized light containing a bright line of 365 nm using an Hg-Xe lamp to cure the polymerizable liquid crystal, thereby producing a retardation film.

(2) Evaluation of retardation film

i) Liquid crystal alignment

With respect to the retardation film produced in the above manner, the liquid crystal alignment property was observed by a visual observation and a polarizing microscope under orthogonal polarization. Good visual alignment and unobserved in polarized light microscopy When the film is in an abnormal region, the liquid crystal alignment property is excellent; when the alignment property is good under visual observation, when the abnormal region is observed in the polarizing microscope, the liquid crystal alignment property is set to be good; when the liquid crystal alignment property is observed under visual observation. In the case of an abnormality, the liquid crystal alignment property was set to be poor, and as a result, the liquid crystal alignment property of the retardation film was evaluated as "excellent".

Ii) Adhesion

For the retardation film manufactured in the manner described above, a 10×10 lattice pattern was formed using an equally spaced spacer having a guide and cutting the slit at a 1 mm interval with a cutter knife. Then, after the cellophane tape is adhered to the lattice pattern, the cellophane tape is peeled off. The notch portion of the lattice pattern after peeling the cellophane tape was visually observed. At this time, when the peeling of the pattern was not confirmed at all along the slit line or at the intersection of the lattice pattern, the adhesion was evaluated as "excellent"; when the number of the lattices which were peeled off was less than 15, the adhesion was made The evaluation was "good"; when the number of the lattices which were peeled off was 15 or more, the adhesion was evaluated as "poor", and as a result, the adhesion of the retardation film was "excellent".

A‧‧‧glass substrate

b‧‧‧Liquid alignment film

C‧‧‧ top electrode

D‧‧‧ nitride film

E‧‧‧ bottom electrode

Claims (11)

A liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polyorganosiloxanes, polyamines, poly(thio)esters, and (meth)acrylic copolymers, wherein The polymer has a divalent group represented by the following formula (1), In the formula (1), Q is a tetravalent organic group, Y ¹ and Y ² are each a divalent organic group, and * represents a bonding bond bonded to a polymer chain, respectively. The liquid crystal alignment agent according to claim 1, wherein the polymer is a polyorganosiloxane obtained by hydrolyzing and condensing a decane compound containing a compound represented by the following formula (S). In the formula (S), Q, Y ¹ and Y ² are the meanings of the formula (1) Q, Y ¹ and Y ² the same, R ¹ and R ² each independently having 1 to 12 carbon atoms The alkyl group or the aryl group having a carbon number of 6 to 12, X ¹ and X ² are each independently an alkoxy group having 1 to 12 carbon atoms or a halogen atom, and n1 and n2 are each independently an integer of 1 to 3. The liquid crystal alignment agent according to claim 1, wherein the polymer is a polyamine obtained by reacting a diamine with a compound represented by the following formula (C). In the formula (C), the meanings of Q, Y ¹ and Y ^{2 are the} same as Q, Y ¹ and Y ² in the formula (1), respectively, and n3 and n4 are each independently 1 or 2. The liquid crystal alignment agent according to claim 1, wherein the polymer is at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound, and the following a poly(thio)ester obtained by reacting a compound represented by the formula (C), [Chem. 18] In the formula (C), the meanings of Q, Y ¹ and Y ^{2 are the} same as Q, Y ¹ and Y ² in the formula (1), respectively, and n3 and n4 are each independently 1 or 2. The liquid crystal alignment agent according to claim 1, wherein the polymer is a poly(thio)ester obtained by reacting a compound represented by the following formula (E) with a dicarboxylic acid, In the formula (E), Q, Y ¹ and Y ² are the meanings of the formula (1) Q, Y ¹ and Y ² the same, Z ¹ and Z ² are each independently a hydroxyl group, a thiol group, or Epoxy group. The liquid crystal alignment agent according to claim 1, wherein the polymer is a mixture of a polymerizable unsaturated compound containing (meth)acrylic acid and a compound represented by the following formula (A). (meth)acrylic copolymer obtained by polymerization, [Chemical 4] In the formula (A),, Y ¹ and Y are the same Q, Y ¹ and Y ² are the meanings of (1) of the formula Q ^2, R ³ and R ⁴ are each independently a hydrogen atom or a methyl group. The liquid crystal alignment agent according to any one of claims 1 to 6, which is used for forming a liquid crystal alignment film in a retardation film of a liquid crystal display element. The liquid crystal alignment agent according to any one of claims 1 to 6, which is used for forming a liquid crystal alignment film in a liquid crystal cell of a liquid crystal display element. A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 8. A retardation film of a liquid crystal display element, comprising: a liquid crystal alignment film formed of the liquid crystal alignment agent according to claim 7 of the patent application. A liquid crystal cell of a liquid crystal display element, comprising: a liquid crystal alignment film formed of the liquid crystal alignment agent according to claim 8 of the patent application.