TW201343720A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element using same, and compound - Google Patents

Abstract

A liquid crystal aligning agent which contains a compound represented by formula [1] and at least one kind of polymer that is selected from among polyimide precursors and polyimides. (In formula [1], R1 represents a hydrogen atom or a methyl group; R2 represents a benzene ring; R3 represents a hydrogen atom or a benzene ring; and X represents a single bond or an oxygen atom.)

Description

Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element and compound using the same

The present invention relates to a liquid crystal alignment treatment agent used for forming a liquid crystal alignment film, and a liquid crystal display element using the same.

Now, as a liquid crystal alignment film of a liquid crystal display element, a liquid crystal alignment treatment agent which is prepared by coating a solution of a polyimine precursor such as polyacrylamide or a solution of soluble polyimine as a main component, and firing is mainly used. Polyimine-based liquid crystal alignment film. The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.

The characteristics required for the liquid crystal alignment film include control of liquid crystal alignment, excellent voltage holding ratio, rapid relaxation of charges accumulated by a DC voltage, and a small amount of ions in a liquid crystal cell. In recent years, with the increase in size of liquid crystal display elements, liquid crystal display elements which can be used for a long period of time have been demanded. In order to be used for a long period of time, it is required that the characteristics do not change even if light from the backlight unit or sunlight containing ultraviolet rays is irradiated for a long period of time. Therefore, there is a demand for a liquid crystal alignment treatment agent which does not have a large change in display characteristics with backlight light or ultraviolet light irradiation.

In addition to these characteristics, in the manufacturing process of a liquid crystal display element in recent years, a process of irradiating ultraviolet rays to align liquid crystals is also employed (for example, refer to Non-Patent Document 1). In addition, in the liquid crystal display device manufacturing process in recent years, a process of irradiating ultraviolet rays is also employed in a liquid crystal dropping method (ODF) or a PSA (Polimer Sustained Alignment) process, and the like is required. A material having ultraviolet resistance (for example, see Non-Patent Document 2).

As a method of improving the light resistance of the liquid crystal display element, for example, in Patent Documents 1 and 2, a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber is added to the liquid crystal alignment agent to increase the lifetime of the liquid crystal. try. Further, in Patent Document 3, an attempt is made to further add an antioxidant to a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber to increase the life of the liquid crystal. Further, Patent Document 4 reports that a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, or a dialkyldithiocarbamic acid metal salt is added to an alignment agent to cause an internal offset voltage. Become 100mV or less. Further, Patent Documents 5 and 6 report a method of producing a liquid crystal panel excellent in light resistance by adding a benzotriazole-based compound or a hindered amine compound to an alignment agent.

However, these compounds have an effect of suppressing a decrease in voltage holding ratio (hereinafter also referred to as VHR) due to UV irradiation, but there is a problem that the initial VHR is lowered by the addition. When the firing temperature is high, these compounds may sublime or thermally decompose, and thus there is also a problem that the effect is reduced.

In order to solve such problems, a diamine having a triazine skeleton has been proposed (Patent Document 7).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 56-116012

[Patent Document 2] Japanese Laid-Open Patent Publication No. SHO 57-84429

[Patent Document 3] Japanese Laid-Open Patent Publication No. SHO 57-108828

[Patent Document 4] Japanese Patent Laid-Open No. Hei 10-148835

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-215592

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2004-53685

[Patent Document 7] Japanese Laid-Open Patent Publication No. 2011-128597

[Non-patent literature]

[Non-Patent Document 1] Liquid Crystal Handbook, Maruzen Co., Ltd., LCD Handbook Compilation Committee, p. 233

[Non-Patent Document 2] Liquid Crystal, Vol. 14, No. 3, 2010, 175 (27)

However, when the diamine of Patent Document 7 is used, although the VHR after UV irradiation is high, the reactivity of the diamine having a triazine skeleton and the acid dianhydride is poor, and the amount of introduction cannot be increased. When a large amount of introduction is carried out, although the VHR reduction is suppressed, there is a problem that a high molecular weight body cannot be obtained and the frictional resistance is deteriorated.

In view of the above circumstances, an object of the present invention is to provide a liquid crystal alignment treatment agent, a liquid crystal alignment film, a liquid crystal display element, and a novel compound which can form a liquid crystal alignment film having excellent friction resistance, high light resistance, and high voltage holding ratio.

As a result of intensive studies to achieve the above object, the present inventors have found that a liquid crystal alignment treatment agent containing a novel compound (hereinafter, also referred to as a specific additive) containing a triazine skeleton and a polymerizable skeleton can achieve the above. Purpose, the present invention has been completed. That is, the case is the one having the following gist.

A liquid crystal alignment treatment agent comprising a compound represented by the following formula [1] and at least one polymer selected from the group consisting of a polyimide and a polyimide. (In the formula [1], R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a benzene ring, R ₃ represents a hydrogen atom or a benzene ring, and X represents a single bond or an oxygen atom).

2. The liquid crystal alignment treatment agent according to 1, wherein the compound represented by the formula [1] is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer.

3. The liquid crystal alignment treatment agent according to 1 or 2, wherein the polymer has a double bond in its structure.

4. The liquid crystal alignment treatment agent according to any one of 1 to 3, wherein the polymer is obtained by reacting a diamine component containing a diamine compound selected from the following formula with a tetracarboxylic dianhydride component. At least one selected from the group consisting of a polyimide precursor and a polyimine obtained by imidating the oxime thereof, (wherein n is an integer of 1 to 20, and R ₄ is a hydrogen atom or a methyl group).

A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of 1 to 4.

A liquid crystal display element comprising a liquid crystal alignment film such as 5.

A compound characterized by the following formula [1], (In the formula [1], R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a benzene ring, R ₃ represents a hydrogen atom or a benzene ring, and X represents a single bond or an oxygen atom).

8. The compound according to 7, which is represented by any one of the following formulae.

According to the present invention, it is possible to provide a liquid crystal alignment treatment agent which can obtain a liquid crystal alignment film which is excellent in friction resistance, has high light resistance, and has a high voltage holding ratio (VHR). Further, the specific additive contained in the liquid crystal alignment treatment agent provided by the present invention is a novel compound.

The invention is described in detail below.

The liquid crystal alignment treatment agent of the present invention contains at least one polymer selected from the group consisting of a polyimine imide and a polyimine.

<specific additives>

The specific additive contained in the liquid crystal alignment treatment agent of the present invention means a compound represented by the following formula [1].

(In the formula [1], R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a benzene ring, R ₃ represents a hydrogen atom or a benzene ring, and X represents a single bond or an oxygen atom).

The benzene ring of R ₂ or R ₃ , that is, the phenyl group of R ₂ or the phenyl group of R ₃ has an effect of suppressing sublimation and decomposition of a specific additive when the coating film is fired. Further, the acrylic group or the methacrylic group is formed by inhibiting the reaction of a specific additive or the reaction of a polymer such as a polyimide or a polyimide with a polymer such as a polyimide or a polyimide. The basis of the decomposition effect.

The amount of the specific additive to be added to the liquid crystal alignment agent is preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of at least one polymer selected from the group consisting of a polyimide and a polyimide. It is preferably 1 to 5 parts by weight. Here, the usual additives are adversely affected by the liquid crystal alignment property when added to the liquid crystal alignment agent, and the specific additives of the present invention are not added to the liquid crystal alignment agent as shown in the later-described examples. This will deteriorate the alignment of the liquid crystal.

The method of adding the liquid crystal alignment treatment agent to the liquid crystal alignment treatment agent is not particularly limited, but a specific additive may be directly added to the liquid crystal alignment treatment agent to be stirred and dissolved, or a specific additive may be previously dissolved in the organic solvent to be about 0.5 wt% to 10 wt%. And adding this solution to the liquid crystal alignment treatment agent.

<Synthesis of specific additives>

The synthesis method of the specific additive can be synthesized by a combination of organic synthetic chemical methods, and is not particularly limited. For example, it can be synthesized by the following method.

The specific additive represented by the formula [1] and having the bonding group X as a single bond is as shown in the following synthetic scheme (A), and the compound (i) can be made with 2-hydroxyethyl methacrylate or acrylic acid 2 Synthesis of hydroxyethyl ester by reaction.

The compound represented by the formula (i) in the synthesis scheme (A) can be synthesized by reacting cyanuric chloride with a Grignard reagent represented by the formula (ii) as shown in the following synthesis scheme (B). .

Further, a specific additive represented by the formula [1] and having a bonding group X as an oxygen atom can be obtained by using 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate as shown in the following synthetic scheme (C). After reacting with cyanuric chloride, compound (iii) is synthesized, and compound (iv) is reacted to synthesize.

The raw materials used in the synthesis scheme of the above-mentioned synthetic schemes (A) to (C) may be used as needed, or may be separately synthesized and used.

<Polyimide precursors and polyimines>

The polyimine precursor contained in the liquid crystal alignment treatment agent of the present invention means polyamic acid (also referred to as polyamic acid) and polyphthalate. The polyimine precursor is obtained by reacting a diamine component with a tetracarboxylic dianhydride component. Specifically, polylysine is obtained by reacting a diamine component with tetracarboxylic dianhydride. Polyammonium esters are obtained by reacting a diamine component with a tetracarboxylic acid diester dichloride in the presence of a base or by reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or a base. Got it. The polyimine contained in the liquid crystal alignment agent of the present invention is obtained by dehydration of the polyamine or ring closure of the polyglycolate. The polyamic acid, polyphthalate, and polyimine are used as a polymer for obtaining a liquid crystal alignment film.

<Diamine component>

The diamine component to be used is not particularly limited. Specific examples thereof are as follows.

Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, and 4,4'. -Diamino-3,3'-dimethyldicyclohexylamine, isophorone diamine, and the like.

Examples of the aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5- Diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5- Diamine benzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino- 2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-Diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostilbene, 4,4'-diaminostilbene, 4,4' -diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3 , 3'-diaminodiphenylanthracene, 4,4'-diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-amine Benzophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic acid, 4,4'-bis(4-amine Phenoxy group) bibenzyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2- [4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-amino) Phenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, 1,1-bis(4-aminophenyl)cyclohexane, α,α'-double (4-Aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis(3-aminophenyl)hexafluoropropane , 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diamino Naphthalene, 1,5-diamino Naphthalene, 1,5-diamino hydrazine, 1,3-diamino hydrazine, 1,6-diamino hydrazine, 1,8-diamino hydrazine, 2,7-diamino hydrazine, 1, 3-bis(4-aminophenyl)tetramethyldioxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4-aminophenyl)ethane, 1 , 3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6- Bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis ( 4-aminophenyl)decane, 1,10-bis(4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4- Aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis (4) -aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis ( 4-aminophenoxy)decane, bis(4-aminophenyl)propane-1,3-diacid, bis(4-aminophenyl)butane-1,4-diacid, di( 4-aminophenyl)pentane-1,5-diacid, bis(4-aminophenyl)hexane-1,6-dioic acid, bis(4-aminophenyl)heptane-1, 7-diacid, bis(4-aminophenyl)octane-1,8-diacid, di(4) -aminophenyl)decane-1,9-diacid, bis(4-aminophenyl)decane-1,10-diacid, 1,3-bis[4-(4-aminophenoxy) Phenoxypropane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4-aminophenoxy)benzene Oxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-aminophenoxy)phenoxy Heptane, 1,8-bis[4-(4-aminophenoxy)phenoxy]octane, 1,9-bis[4-(4-aminophenoxy)phenoxy]indole Alkane, 1,10-bis[4-(4-aminophenoxy)phenoxy]decane, and the like.

Examples of the aromatic-aliphatic diamine include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3-(3 -aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3- (4-Aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylaminobutyl)aniline, 3-(5-Aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl) Aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-(6-amine Naphthyl)ethylamine and the like.

Examples of the heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7- Diaminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-amine Phenyl)-1,3,4-oxadiazole and the like.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1 ,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1 , 3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylglycol Alkane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-Diaminododecane, 1,18-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, and the like.

<Diamine compound having a double bond in a side chain>

When a double bond is introduced into the polymer contained in the liquid crystal alignment agent of the present invention, the effect of suppressing sublimation and decomposition of the specific additive is further enhanced by reacting the specific additive with the double bond site in the polymer at the time of firing. The crosslinking resistance of the liquid crystal alignment film is also improved by the crosslinking reaction between the polymers, which is preferable.

The method of introducing a double bond into the polymer contained in the liquid crystal alignment agent of the present invention may be a diamine compound or a tetracarboxylic dianhydride obtained by introducing a double bond. Among them, in terms of the ease of synthesis, it is preferred to use a diamine compound in which a double bond is introduced into a side chain as a diamine component. Specific examples of such a diamine compound include the following diamine compounds.

(wherein n is an integer of 1 to 20, and R ₃ is a hydrogen atom or a methyl group.)

The preferred content of such a diamine compound is preferably all diamine components. 1 to 60% by weight, more preferably 5 to 50% by weight, still more preferably 10 to 40% by weight.

Further, the diamine component may be used in combination with a diamine compound having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a hetero ring, and a macrocyclic substituent constituted by the above-mentioned side chain. Specifically, a diamine represented by the following formula [DA-1] to formula [DA-26] can be exemplified.

(In the formula [DA-1] to the formula [DA-5], R ₆ is an alkyl group having 1 to 22 carbon atoms or an alkyl group containing fluorine).

(In the formula [DA-6] to the formula [DA-9], S ₅ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or - NH-, R ₆ represents an alkyl group having 1 to 22 carbon atoms or an alkyl group containing fluorine).

(In the formula [DA-10] and the formula [DA-11], S ₆ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, or -CH ₂ OCO-, and R ₇ is carbon Alkyl groups of 1 to 22, alkoxy groups, alkyl groups containing fluorine or alkoxy groups containing fluorine).

(Formula [DA-12] to Formula [DA-14], S ₇ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O- , -OCH ₂ -, or -CH ₂ -, R ₈ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formula [DA-15] and the formula [DA-16], S ₈ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O-, or -NH-, R ₉ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, Ethyloxy, or hydroxy).

(In the formula [DA-17]~[DA-20], R ₁₀ is an alkyl group having a carbon number of 3 to 12, and the cis-trans isomerism of the 1,4-cyclohexylene group is a transantibody).

Further, as the diamine component, the following diamine may be used in combination.

(In the formula [DA-30], m is an integer from 0 to 3; in the formula [DA-33], n is an integer from 1 to 5).

By introducing [DA-27], the voltage protection of the liquid crystal display element can be further improved. The holding ratio (also referred to as VHR), [DA-28]~[DA-33] is preferable in that it reduces the cumulative charge of the liquid crystal display element.

In addition, examples of the diamine component include diamine siloxanes represented by the following formula [DA-34].

(in the formula [DA34], m is an integer of 1 to 10).

The diamine component may be used alone or in combination of two or more kinds depending on the characteristics of the liquid crystal alignment property, the voltage retention property, and the cumulative charge when the liquid crystal alignment film is used.

<tetracarboxylic dianhydride component>

The tetracarboxylic dianhydride which reacts with the diamine component in order to obtain the polyphthalic acid contained in the liquid crystal alignment treatment agent of the present invention is not particularly limited. Specific examples thereof are listed below.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4. - cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2, 4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Succinic dianhydride, 1,2,3,4-butane tetracarboxylate Acid dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2, 3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctadecta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, tricyclo[ 4.2.1.02,5]decane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride, hexacyclo[6.6.0.12,7.03,6.19,14.010,13]hexadecane -4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetra Hydronaphthalene-1,2-dicarboxylic anhydride and the like.

Further, in addition to the tetracarboxylic dianhydride having the above alicyclic structure or aliphatic structure, if an aromatic tetracarboxylic dianhydride is used, liquid crystal alignment property is improved and the cumulative charge of the liquid crystal cell is lowered, so that Preferably. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetra Carboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like.

The tetracarboxylic dianhydride may be used alone or in combination of two or more kinds depending on the characteristics of the liquid crystal alignment property, the voltage holding property, and the accumulated electric charge when the liquid crystal alignment film is used.

The dicarboxylic acid dialkyl ester which is reacted with the diamine component in order to obtain the polyphthalate ester contained in the liquid crystal alignment agent of the present invention is not particularly limited. Specific examples thereof are as follows.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester and 1,2-dimethyl-1,2,3,4-ring. Butane tetracarboxylic acid Dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3, Dialkyl 4-cyclobutanetetracarboxylate, dialkyl 1,2,3,4-cyclopentanetetracarboxylate, dialkyl 2,3,4,5-tetrahydrofurantetracarboxylate, 1 , 2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4 - Dialkyl tetrahydro-1-naphthalene succinate, dialkyl 1,2,3,4-butane tetracarboxylate, bicyclo[3,3,0]octane-2,4,6,8 - dialkyl tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentyl acetate, cis-3 , 7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.02,5]decane-3,4,7 , 8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclo[6.6.0.12,7.03,6.19,14.010,13]hexadecane-4,5,11,12-tetracarboxylic acid -4,5:11,12-dialkyl ester, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarbon Alkyl esters and the like.

Examples of the dialkyl aromatic tetracarboxylic acid include dialkyl pyromellitate, dialkyl 3,3',4,4'-biphenyltetracarboxylate, 2,2',3,3. '-Biphenyltetracarboxylic acid dialkyl ester, 2,3,3',4-biphenyltetracarboxylic acid dialkyl ester, 3,3',4,4'-benzophenone tetracarboxylic acid Dialkyl ester, 2,3,3',4-benzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-di Carboxyphenyl) decyl dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, and the like.

<Synthesis of polyaminic acid>

When the polyamic acid contained in the liquid crystal alignment agent of the present invention is obtained by the reaction of a tetracarboxylic dianhydride and a diamine component, a known synthetic hand can be used. law. In general, a method of reacting a tetracarboxylic dianhydride with a diamine component in an organic solvent. The reaction between the tetracarboxylic dianhydride and the diamine component is relatively easy to carry out in an organic solvent, and is advantageous from the viewpoint of not producing a by-product.

The organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine is not particularly limited as long as the polyamic acid formed is dissolved. Specific examples thereof are as follows.

Examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-methyl. Caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentane Alkene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cyproterone, ethyl cyproterone, methyl celluloid Subacetate, ethyl cyproterone acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol Monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethyl Glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol monoacetate monopropyl ether, acetic acid 3-methyl-3-methoxybutyl , tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, isobutylene, amyl acetate, butyl butyrate, butyl ether, two Isobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, N-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate , propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4- Methyl-2-pentanone, 3-methoxy-N,N-dimethylpropane decylamine, 3-ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N, N-dimethylpropane decylamine and the like. These may be used singly or in combination. Further, even if the solvent of the poly-proline is not dissolved, it can be used by mixing with the above solvent within the range in which the produced polyamic acid is not precipitated.

Further, since the water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polylysine, it is preferred that the organic solvent be desalted as much as possible.

When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, a solution obtained by dispersing or dissolving the diamine component in an organic solvent may be mentioned, and the tetracarboxylic dianhydride may be directly dispersed or dissolved in an organic solvent. a method of adding; instead, a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride in an organic solvent; and a method of alternately adding a tetracarboxylic dianhydride and a diamine component, etc., may be used. Any of these methods. Further, when the tetracarboxylic dianhydride or the diamine component is composed of a plurality of compounds, it may be reacted in a state of being mixed beforehand, or may be reacted individually, or may be subjected to a mixed reaction of individual reacted low molecular weight bodies. Become a high molecular weight body.

At this time, the polymerization temperature can be selected from any temperature of -20 ° C to 150 ° C. Degree, but preferably in the range of -5 ° C to 100 ° C. Further, although the reaction can be carried out at any concentration, it is difficult to obtain a polymer having a high molecular weight when the concentration is too low, and when the concentration is too high, the viscosity of the reaction liquid becomes too high, and it is difficult to uniformly stir, so tetracarboxylic dianhydride and two The total concentration in the reaction solution of the amine component is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization reaction of polyamic acid, the total number of moles of tetracarboxylic dianhydride and the total number of moles of the diamine component are preferably from 0.8 to 1.2. As with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyamine.

The polyimine contained in the liquid crystal alignment treatment agent of the present invention is a polymer obtained by dehydrating and ring-closing the polyamic acid, and is used as a polymer for obtaining a liquid crystal alignment film. Further, the polyimine contained in the liquid crystal alignment agent of the present invention is a solvent-soluble polyimine which is soluble in a solvent contained in the liquid crystal alignment treatment agent.

In the polyimine contained in the liquid crystal alignment treatment agent of the present invention, the dehydration ring closure ratio (the imidization ratio) of the proline group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the use or purpose.

<Synthesis of Polyimine>

The method for imidizing polyphosphonium amide is exemplified by hydrazine imidization by heating a poly phthalic acid solution directly and adding a catalyst to a polyaminic acid solution.

The temperature at which the polyaminic acid is thermally imidized in solution is 100 ° C It is preferably carried out at 400 ° C, preferably at 120 ° C to 250 ° C, preferably while removing water formed by the imidization reaction to the outside of the system.

The imidization of the polyaminic acid catalyst can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution, and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, per mole of the amidate group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity for the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, in particular, when acetic anhydride is used, purification after completion of the reaction is easy, which is preferable. The imidization rate of the imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

<Synthesis of polyamidomate>

As a method for synthesizing a polyphthalate, a reaction of a tetracarboxylic acid diester dichloride with a diamine or a reaction of a tetracarboxylic acid diester with a diamine in the presence of a suitable condensing agent or a base can be obtained. One of the polyimine precursors is a polyamidomate. Alternatively, it may be obtained by polymerizing polylysine in advance and esterifying a carboxylic acid in proline by a polymer reaction.

Specifically, the tetracarboxylic acid diester dichloride and the diamine can be reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It is preferably synthesized by 1 to 4 hours.

As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used. In order to carry out the reaction gently, pyridine is preferred. The amount of the base to be added is preferably 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal amount and easy availability of a high molecular weight body.

When the condensation polymerization is carried out in the presence of a condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide can be used. Hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N, N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-Dihydro-2-thioketo-3-benzoxazolyl)phosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,3,5-triazine-2 -yl) 4-methoxymorpholinium chloride n-hydrate and the like.

Further, in the method using the above condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount with respect to the above condensing agent.

The solvent used in the above reaction can be carried out in the solvent used for the polymerization of the polyamic acid described above, and the solubility of the monomer and the polymer is preferably N-methyl-2-pyrrolidone. Γ-butyrolactone may be used alone or in combination of two or more. The concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the polymer is less likely to occur and that a high molecular weight body is easily obtained. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred to dehydrate the solvent used for the synthesis of the polyphthalate as much as possible to prevent the incorporation of outside air in a nitrogen atmosphere.

<Recycling of Polymers>

When recovering the produced polyamic acid, polyphthalate, or polyimine from the reaction solution of poly-proline, polyphthalate, or polyimine, the reaction solution is poured into a poor solvent to precipitate. can. Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, butyl cyanidin, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer precipitated by being thrown into a poor solvent can be recovered by filtration, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, if the polymer recovered by precipitation is redissolved in an organic solvent, the operation of repeating the reprecipitation recovery is repeated 2 to 10 times to reduce impurities in the polymer. In the case of the poor solvent at this time, for example, an alcohol, a ketone, a hydrocarbon, or the like is used. When three or more kinds of poor solvents selected from the above are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the polyimine precursor or the polyimine contained in the liquid crystal alignment treatment agent of the present invention is considered in view of the coating film strength obtained therefrom and the workability at the time of formation of the coating film, and the uniformity of the coating film. The weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, and at least one polymer selected from the above polyimine precursor and polyimine and a specific additive are dissolved in an organic solvent. Solution in the middle. The solid content concentration in the liquid crystal alignment agent of the present invention can be appropriately changed depending on the thickness of the liquid crystal alignment film to be formed, but it is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass. When the solid content concentration is less than 0.5% by mass, it is difficult to form a uniform and defect-free coating film, and when it is more than 10% by mass, the storage stability of the solution may be poor. The solid component as used herein refers to a component obtained by removing a solvent from a liquid crystal alignment treatment agent, and means at least one polymer selected from the above polyimine precursor and polyimine, a specific additive, and the above. Various additives.

The method for producing the liquid crystal alignment agent of the present invention is not particularly limited. It is usually produced by mixing a solution of the above polyamic acid, a solution of the above soluble polyimine or a solution of soluble polyimine with a solution of polyamic acid. In the case of poly-proline, the reaction solution of poly-lysine obtained by polycondensation can be used as it is; after the poly-proline is obtained, it can be redissolved in an organic solvent as a poly-proline solution. use. The polyaminic acid solution can also be diluted to the desired concentration for use.

On the other hand, in the case of a soluble polyimine, a reaction solution of a soluble polyimine obtained by ruthenium imidization may be used as it is, or a polyimine powder may be obtained at one time and then dissolved in an organic solvent. The solvent is used as a polyimine solution. The polyimine solution can also be diluted to the desired concentration for use.

The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it dissolves the above polymer and the organic solvent of the compound represented by the formula [1]. Specific examples thereof are as follows.

Examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urinary , pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 3-methoxy-N,N-dimethylpropane decylamine, 3-ethoxy-N,N-dimethyl Propane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, 1,3-dimethyl-tetrahydroimidazolidone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl Ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl carbonate, propyl carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2- Pentanone and the like. These may be used alone or in combination.

The liquid crystal alignment agent of the present invention may contain components other than the above. As an example thereof, a solvent or a compound which improves film thickness uniformity or surface smoothness when a liquid crystal alignment treatment agent is applied, a compound which improves adhesion between a liquid crystal alignment film and a substrate, and the like are used.

Specific examples of the solvent (lean solvent) for increasing the uniformity of the film thickness or the surface smoothness include the following.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cyproterone, ethyl cyproterone, butyl cyanisol, methyl cyproterone acetate, ethyl cyproterone acetate Ester, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol II Methyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol single Acetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, B Isobutyl ether, isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, N-Pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate , 3-methoxypropionic acid methyl ester, 3-ethoxypropionic acid methyl ethyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3 -propyl methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol Alcohol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2 - acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. having a low surface The solvent of the tension, etc.

These poor solvents may be used alone or in combination of plural kinds. When the solvent is used as described above, it is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass based on the total of the solvent contained in the liquid crystal alignment treatment agent.

Examples of the compound for improving the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant.

More specifically, Eftop EF301, EF303, EF352 (made by TOHKEM Products), Megaface F171, F173, R-30 (made by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (made by Sumitomo 3M); AsahiGuard AG710 ;Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The ratio of use of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer contained in the liquid crystal alignment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a compound containing a functional decane or a compound containing an epoxy group as shown below.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N -(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-indoleurea Propyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxydecyl propyl triethylene glycol triamine, N-trimethoxydecyl propyl tris-ethyltriamine, 10-trimethoxydecyl-1, 4, 7 - triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9 -triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethyl Oxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl)-3-amine Propyltrimethoxydecane, N-bis(oxyethyl)-3- Aminopropyl triethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol condensate Glycerol ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N' ,-tetraepoxypropyl-m-xylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N',- Tetraepoxypropyl-4,4'-diaminodiphenylmethane, and the like.

<Liquid alignment film>

The liquid crystal alignment treatment agent of the present invention is preferably applied to a substrate before being applied to a substrate, and then applied to a substrate, dried as needed, and then fired to form a coating film, by rubbing the surface of the coating film or The alignment treatment such as light irradiation is used as the liquid crystal alignment film of the present invention.

In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used, and a liquid crystal-driven method can be used from the viewpoint of simplifying the process. A substrate such as an ITO (Indium Tin Oxide) electrode is preferred. Further, in the reflective liquid crystal display device, if only one side substrate is used, an opaque substrate such as a germanium wafer or the like may be used. In this case, a material such as aluminum that reflects light may be used.

Examples of the coating method of the liquid crystal alignment agent include a spin coating method, a printing method, an inkjet method, and the like. In terms of productivity, an industrial flexographic printing method is widely used, and the liquid crystal alignment treatment agent of the present invention is widely used. Also suitable for use.

The drying step after the application of the liquid crystal alignment agent is not necessarily required, but the time from the application to the completion of the firing is not uniform with each substrate, or is not immediately after the coating. Preferably, the drying step is included Step. This drying is not particularly limited as long as the solvent is evaporated so that the shape of the coating film is not deformed by the transfer of the substrate or the like. For a specific example, it may be dried on a hot plate at 50 to 150 ° C, preferably 80 to 120 ° C for 0.5 to 30 minutes, preferably 1 to 5 minutes.

The baking of the substrate coated with the liquid crystal alignment agent can be carried out at any temperature of from 100 to 350 ° C, preferably from 150 ° C to 300 ° C, more preferably from 180 ° C to 250 ° C. The polyamine acid contained in the liquid crystal alignment treatment agent is changed by the calcination to change the conversion rate of the phthalic acid to ruthenium, but the polyamine acid is not necessarily 100% ruthenium. However, it is preferably fired at a temperature higher than the heat treatment temperature of the sealant hardening or the like necessary for the production process of the liquid crystal cell by 10 ° C or higher.

When the thickness of the coating film after firing is too thick, the power consumption of the liquid crystal display element is unfavorable, and the reliability of the liquid crystal display element may be lowered, so that it is preferably 10 to 200 nm, more preferably 50 to 100 nm.

As the rubbing treatment of the coating film surface formed on the substrate as described above, an existing friction device can be used. The material of the rubbing cloth at this time may, for example, be cotton, crepe, nylon or the like. Since the liquid crystal alignment film formed by using the liquid crystal alignment treatment agent of the present invention has good friction resistance, it is less likely to cause scratches or peeling of the film during the rubbing treatment.

<Liquid crystal display element>

In the liquid crystal display device of the present invention, a liquid crystal alignment cell is produced by a known method from the liquid crystal alignment treatment agent of the present invention, and a liquid crystal cell is produced by a known method.

In the case of manufacturing a liquid crystal cell, generally, a pair of substrates on which a liquid crystal alignment film is formed is preferably sandwiched between 1 and 30 μm, more preferably 2 to 10 μm, and the rubbing direction is set. Any angle from 0 to 270°, which is fixed by a sealant and injected into the liquid crystal to seal. The method of encapsulating the liquid crystal is not particularly limited, and for example, a vacuum method in which a liquid crystal cell to be produced is decompressed and then injected into a liquid crystal, a dropping method in which a liquid crystal is dropped, and a sealing method may be used.

In the liquid crystal display device obtained in this manner, the liquid crystal alignment property is good, and the liquid crystal alignment film has good friction resistance, so that it is less likely to cause display defects due to scratches or film peeling of the liquid crystal alignment film which occur during the rubbing treatment. Further, since the liquid crystal alignment film has high resistance to light, the electrical characteristics of the ultraviolet ray irradiation by the backlight irradiation, the sunlight exposure, or the manufacturing step are reduced, and the voltage holding ratio is high, so that it can be used as a highly reliable liquid crystal display device.

[Examples]

The examples are shown below to explain the present invention in further detail, but the invention is not limited thereto.

<Synthesis Example of Specific Additives>

A synthesis example of the specific additive of the present invention is shown. Each measurement method and analysis device used is as follows.

<Measurement of NMR>

The compound was dissolved in dihydrochloroform and measured using ¹ H NMR (manufactured by Varian Co., Ltd.) at 400 MHz.

(Synthesis Example 1) Synthesis of specific additive (M1)

To a 500 mL four-necked flask, 15.0 g of cyanuric chloride, 12.7 g of 2-hydroxyethyl methacrylate, and 150 g of tetrahydrofuran were added, and the mixture was cooled in an ice bath. 3.9 g of sodium hydride was added at a temperature of 0 ° C, and stirred at room temperature for 3 hours. Further, an aqueous solution of 12.5 g of 4-phenylphenol, 2.9 g of sodium hydroxide, 23 g of tetrahydrofuran, and 30 g of water was added. Thereafter, a 15 wt% aqueous solution of ammonium chloride was added, followed by extraction with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, and after filtration, solvent distillation was carried out using a rotary evaporator. The residue was purified by recrystallization to give a white solid (21.7 g). The results of NMR measurement of this white solid are shown below. From this result, it was confirmed that the obtained white solid is an intermediate compound represented by the following formula (L1).

^{1 H-NMR (400MHz, CDCl} 3): δ 7.67-7.55 (m, 4H), 7.47-7.33 (m, 3H), 7.27-7.21 (m, 2H), 6.14-6.09 (m, 1H), 5.62- 5.57 (m, 1H), 4.68-4.62 (m, 2H), 4.48-4.44 (m, 2H), 1.96-1.90 (m, 3H)

21.4 g of an intermediate compound (L1) and 170 g of acetone were added to a 500 mL four-necked flask, and an aqueous solution of 9.3 g of 4-phenylphenol, 2.2 g of sodium hydroxide, 43 g of acetone, and 43 g of water was added dropwise under reflux. Thereafter, a 15 wt% aqueous solution of ammonium chloride is added, and the resulting crystals are filtered and refined by recrystallization. To a white solid 25.2 g. The results of NMR measurement of this white solid are shown below. From this result, it was confirmed that the obtained white solid is a compound represented by the following formula (M1).

^{1 H-NMR (400MHz, CDCl} 3): δ 7.62-7.52 (m, 8H), 7.46-7.39 (m, 4H), 7.39-7.33 (m, 2H), 7.26-7.21 (m, 4H), 6.13- 6.10(m,1H),5.62-5.56(m,1H),4.65-4.58(m,2H),4.48-4.42(m,2H),1.95-1.92(m,3H)

(Synthesis Example 2) Synthesis of specific additive (M2)

To a 500 mL four-necked flask, 15.0 g of cyanuric chloride, 12.7 g of 2-hydroxyethyl methacrylate, and 150 g of tetrahydrofuran were added, and the mixture was cooled in an ice bath. 3.9 g of sodium hydride was added at a temperature of 0 ° C, and stirred at room temperature for 3 hours. Further, an aqueous solution of 14.9 g of phenol, 6.3 g of sodium hydroxide, and 60 g of water was added, and the mixture was heated to a temperature of 50 ° C and stirred for 2 hours. Thereafter, the mixture was cooled to room temperature, and a 15 wt% aqueous ammonium chloride solution was added thereto, followed by extraction with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, and after filtration, solvent distillation was carried out using a rotary evaporator. The residue was purified by silica gel column chromatography to give a white solid 20.5g. The results of NMR measurement of this white solid are shown below. From this result, it was confirmed that the obtained white solid is a compound represented by the following formula (M2).

^{1 H-NMR (400MHz, CDCl} 3): δ 7.43-7.34 (m, 4H), 7.28-7.22 (m, 2H), 7.19-7.12 (m, 4H), 6.14-6.08 (m, 1H), 5.60- 5.55 (m, 1H), 4.58-4.52 (m, 2H), 4.42-4.37 (m, 2H), 1.94-1.90 (m, 3H)

(Synthesis Example 3) Synthesis of specific additive (M3)

To a 1 L four-necked flask, 38.5 g of cyanuric chloride and 385 g of tetrahydrofuran were added, and the mixture was cooled in an ice bath. At a temperature of 0 °C, 240 mL of a 2 mol/L phenylmagnesium chloride tetrahydrofuran solution was added and stirred at room temperature for 15 hours. To the reaction liquid, 300 mL of 1 N hydrochloric acid was added, and the mixture was extracted with ethyl acetate. A saturated aqueous solution of sodium hydrogencarbonate was added to the organic layer, and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer, and after filtration, solvent distillation was carried out using a rotary evaporator. The residue was purified by silica gel column chromatography to give 42.8 g of the intermediate compound (L2).

10.0 g of the intermediate compound (L2) was placed in a 300 mL four-necked flask, and 100 g of tetrahydrofuran was added to dissolve. The solution was cooled to a temperature of 0 ° C, and 1.8 g of sodium hydride was added thereto, and a solution of 5.3 g of 2-hydroxyethyl methacrylate and 80 g of tetrahydrofuran was added thereto, followed by stirring for 30 minutes. A 15 wt% aqueous solution of ammonium chloride was added to the reaction mixture, followed by extraction with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, and after filtration, solvent distillation was carried out using a rotary evaporator. The residue was purified by silica gel column chromatography to yield 9.7 g of white solid. The results of NMR measurement of this white solid are shown below. From this result, it was confirmed that the obtained white solid is a compound represented by the following formula (M3).

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.66-8.61 (m, 4H), 7.64 - 7.50 (m, 6H), 6.15-6.12 (m, 1H), 5.57-5.53 (m, 1H), 4.94 4.89 (m, 2H), 4.66-4.61 (m, 2H), 1.94-1.90 (m, 3H)

<Synthesis of Polymer (Polyuric Acid, Polyimine)>

A synthesis example of a polymer and a polymer solution is shown. The measurement methods and the analysis apparatuses used for the explanation and use are as follows.

A brief description of the use

<tetracarboxylic dianhydride>

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

PMDA: pyromellitic dianhydride

TCA: 2,3,5-tricarboxycyclopentyl acetic acid-1,4:2,3-dianhydride

<Diamine>

p-PDA: p-phenylenediamine

DDM: 4,4'-diaminodiphenylmethane

2,4-DAA: 2,4-diamino-N,N-diallylamine

4-ABA: 4-aminobenzylamine

C12DAB: 4-dodecyloxy-1,3-diaminobenzene

DTT: 2,4-diamino-6-phenyl-1,3,5-triazine

DABEMA: 3,5-diamino benzoic acid ethyl methacrylate

<organic solvent>

NMP: N-methyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BS: butyl cycas

<Measurement of molecular weight>

The molecular weight of the polymer (polyglycolic acid, polyimine) is determined by a GPC (normal temperature gel permeation chromatography) apparatus as a conversion of polyethylene glycol and polyethylene oxide. The values are calculated as a number average molecular weight and a weight average molecular weight.

GPC device: (share) made by Shodex (GPC-101)

Pipe column: made by Shodex (series of KD803, KD805)

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (lithium bromide-hydrate (LiBr.H ₂ O) 30 mmol/L, phosphoric acid, anhydrous crystal (o-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) 10 mL/L as additive)

Flow rate: 1.0 mL/min

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, 4000, 1000) manufactured by Polymer Laboratories.

<Measurement of sulfhydrylation rate>

The imidization ratio of the polyimine was determined by dissolving the polyimine in d6-DMSO (dimethyl sulfonium-d6) using a 400 MHz ¹ H NMR (manufactured by Varian Co., Ltd.) from the proton peak. The ratio of the integral values is used to calculate the ratio of the proline groups remaining in the imidization.

(Synthesis Example 4) Polymer solution P-1

To a 500 ml four-necked flask, 39.6 g of DDM, 222 g of NMP, and 222 g of γ-BL were added and dissolved, and 19.6 g of CBDA and 19.2 g of PMDA were added. The solution of poly-proline was prepared by reacting at room temperature for 5 hours under a nitrogen atmosphere. The polyamine has a number average molecular weight of 10,900 and a weight average molecular weight of 27,300. 450 g of γ-BL and 150 g of BS were added to 400 g of the obtained polyamic acid solution, and the mixture was stirred at room temperature for 2 hours to obtain a polymer solution P-1.

(Synthesis Example 5) Polymer solution P-2

To a 1 L separable flask, 40.6 g of 2,4-DAA, 18.4 g of 4-ABA, 43.9 g of C12DAB, and 813 g of NMP were added and dissolved, and 67.7 g of CBDA and 32.7 g of PMDA were added. The solution of polylysine was prepared by reacting at room temperature for 22 hours under a nitrogen atmosphere.

To 192 g of the obtained polyaminic acid solution, 345 g of NMP was added to dilute, and 28.4 g of acetic anhydride and 12.1 g of pyridine were added, and reacted at 50 ° C for 3 hours to imidize. The reaction solution was cooled to room temperature, and then poured into 2000 ml of methanol to recover a precipitated solid. Further, the solid was washed with methanol several times, and then dried under reduced pressure at 100 ° C to obtain a white powder (polyimine). The polyimine had a number average molecular weight of 12,500 and a weight average molecular weight of 34,100. Further, the hydrazine imidation ratio was 90%.

Further, 6 g of the obtained white powder was stirred in a mixed solution of 74 g of γ-BL and 20 g of BS at 50 ° C for 24 hours to obtain a polymer solution P-2 having a polymer concentration of 6 wt%.

(Synthesis Example 6) Polymer solution P-3

To a 500 ml four-necked flask, 17.3 g of p-PDA, 10.6 g of DABEMA, and 410 g of NMP were added and dissolved, and 44.4 g of TCA was added. The solution of polylysine was prepared by reacting at room temperature for 24 hours under a nitrogen atmosphere. The polyamine has a number average molecular weight of 11,500 and a weight average molecular weight of 32,200. 400 g of NMP and 200 g of BS were added to 400 g of the obtained polyamic acid solution, and the mixture was stirred at room temperature for 2 hours to obtain a polymer solution P-3.

"Assessment of Specific Additives" <Evaluation of Mohr Absorption Coefficient>

The molar absorption coefficient of the specific additives (M1) to (M3) synthesized was measured using UV3100PC manufactured by SHIMADZU.

(Example 1)

4.14 mg of (M1) produced in Synthesis Example 1 was dissolved in chloroform for spectroscopic analysis manufactured by Wako Pure Chemical Industries, Ltd., and diluted in a measuring flask to prepare a solution of 0.0000152 mmol/cm ³ . The modulation of the solution is measured molar absorption coefficient, 400nm to 0cm ² / mmol, 375nm to 0cm ² / mmol, 350nm to 0cm ² / mmol, 325nm to 0cm ² / mmol, 300nm to 145cm ² / mmol, 275nm to 16130cm ² /mmol, 250nm is 38006cm ² /mmol, 225nm is 11814cm ² /mmol, and 200nm is 119349cm ² /mmol. From this data, it is known that the specific additive (M1) hardly absorbs ultraviolet rays having a longer wavelength than 325 nm.

(Example 2)

4.65 mg of (M2) produced in Synthesis Example 2 was dissolved in chloroform for spectroscopic analysis by Wako Pure Chemical Industries, Ltd., and diluted with a measuring flask to prepare a solution of 0.0000152 mmol/cm ³ . The modulation of the solution is measured molar absorption coefficient, 400nm to 0cm ² / mmol, 375nm to 0cm ² / mmol, 350nm to 0cm ² / mmol, 325nm to 0cm ² / mmol, 300nm to 0cm ² / mmol, 275nm to 0cm ² /mmol, 250 nm is 1760 cm ² /mmol, 225 nm is 10376 cm ² /mmol, and 200 nm is 57202 cm ² /mmol. From this data, it is known that the specific additive (M2) hardly absorbs ultraviolet rays having a longer wavelength than 275 nm.

(Example 3)

4.95 mg of (M3) produced in Synthesis Example 3 was dissolved in chloroform for spectroscopic analysis manufactured by Wako Pure Chemical Industries, Ltd., and diluted in a measuring flask to prepare a solution of 0.0000273 mmol/cm ³ . The modulation of the solution is measured molar absorption coefficient, 400nm to 0cm ² / mmol, 375nm to 0cm ² / mmol, 350nm to 0cm ² / mmol, 325nm to 238cm ² / mmol, 300nm of 7220cm ² / mmol, 275nm to 29850cm ² /mmol, 250 nm is 23890 cm ² /mmol, 225 nm is 12425 cm ² /mmol, and 200 nm is 65761 cm ² /mmol. From this data, it is known that the specific additive (M3) hardly absorbs ultraviolet rays having a wavelength longer than 350 nm.

<Evaluation of Liquid Crystal Alignment Treatment Agent> (Example 4)

(M1) produced in Synthesis Example 1 in an amount of 2 parts by weight based on 100 parts by weight of the polymer of the polymer solution P-1, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment treatment agent . Using this liquid crystal alignment treatment agent, a liquid crystal cell was produced by the following method to obtain a liquid crystal cell showing good liquid crystal alignment. Further, the liquid crystal alignment property was visually observed. When the initial VHR of the liquid crystal cell and the VHR after the UV irradiation were measured, it was found that the initial VHR was higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound (specific additive) represented by the formula [1] was not added, and After UV irradiation, the VHR is high and the light resistance is high. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

<Manufacture of liquid crystal cell>

The liquid crystal alignment treatment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C for 70 seconds, and then fired on a hot plate at 250 ° C for 10 minutes to form a coating film having a thickness of 100 nm. For the coating surface, the friction device with a roll diameter of 120 mm is used, and the number of rolls is used. The substrate was attached with a liquid crystal alignment film at a temperature of 1000 rpm, a roll speed of 50 mm/sec, and a pressing depth of 0.3 mm. Two substrates with a liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on one of the liquid crystal alignment film surfaces, and then a sealant was printed thereon, and the other substrate was faced with a liquid crystal alignment film surface, rubbing direction. After bonding in a straight manner, the sealant is hardened to produce an empty unit cell. The liquid crystal MLC-2003 (C080) (manufactured by Merck) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain a twisted nematic liquid crystal cell.

<Measurement of initial voltage holding ratio (VHR)>

The twisted nematic liquid crystal cell produced by the above method was applied with a voltage of 4 V for 60 μs at a temperature of 23 ° C, and a voltage of 16.67 msec was measured, and the initial voltage holding ratio was used to calculate how much the voltage can be maintained. Further, the voltage holding ratio was measured by using a VHR-1 voltage holding ratio measuring device manufactured by Dongyang Technica Co., Ltd.

<UV irradiation>

The twisted nematic liquid crystal cell produced by the method described in the above-mentioned "manufacture of liquid crystal cell" was irradiated with light by Sen Lights Corporation (Sen Lights Corporation) and a table UV curing device HCT3B28HEX-1. 83sec. At this time, when the illuminance was measured using a UV-35 sensor using an illuminometer (UV Light MEASUREMODEL UV-M02 manufactured by CRC), the illuminance was 60.0 mW/cm ² .

<Measurement of voltage retention rate (VHR) after UV irradiation>

The twisted nematic liquid crystal cell treated by the above-mentioned <UV irradiation> method was applied with a voltage of 4 V for 60 μs at a temperature of 23 ° C, and a voltage of 16.67 msec was measured, and the voltage retention rate after UV irradiation was used to calculate how much the voltage can be maintained. . Further, the voltage holding ratio was measured by using a VHR-1 voltage holding ratio measuring device manufactured by Dongyang Technica Co., Ltd.

[Evaluation of friction resistance]

The surface of the substrate to which the liquid crystal alignment film was attached was obtained in the above-mentioned <Production of Liquid Crystal Cell>, and the surface of the liquid crystal alignment film was visually observed by a conjugated-focus laser microscope and evaluated on the following basis. The results are shown in Table 1.

○: No grinding or friction scars were observed by both the visual and the laser microscope.

△: Grinding dross or friction scars were not observed visually, but grinding slag or friction scars were observed by a laser microscope.

×: The film was peeled off, or a rubbing flaw was observed both in the laser microscope and in the visual observation.

(Example 5)

In the polymer solution P-1, (M1) produced in Synthesis Example 1 was added in an amount of 5 parts by weight based on 100 parts by weight of the polymer of the polymer solution P-1, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. Measuring this liquid crystal In the initial stage of VHR and VHR after UV irradiation, it is found that the initial VHR is high and the VHR after UV irradiation is high as compared with the liquid crystal alignment treatment agent (Comparative Example 1) in which the ultraviolet absorber of the compound represented by the formula [1] is not added. Light tolerance is high. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Example 6)

In the polymer solution P-1, 10 parts by weight of the polymer of the polymer solution P-1 was added in an amount of 10 parts by weight to the (M1) produced in Synthesis Example 1, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. When the initial VHR of the liquid crystal cell and the VHR after the UV irradiation were measured, it was found that the initial VHR was high and the VHR after the UV irradiation was higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] was not added. High, high light tolerance. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Example 7)

In the polymer solution P-1, (M2) produced in Synthesis Example 2 was added in an amount of 2 parts by weight based on 100 parts by weight of the polymer of the polymer solution P-1, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. Measuring this liquid crystal In the initial stage of the VHR and the VHR after the UV irradiation, it is found that the initial VHR is high and the VHR after UV irradiation is high, and the light resistance is higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] is not added. high. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Example 8)

In the polymer solution P-1, (M2) produced in Synthesis Example 2 was added in an amount of 5 parts by weight based on 100 parts by weight of the polymer of the polymer solution P-1, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. When the initial VHR of the liquid crystal cell and the VHR after the UV irradiation were measured, it was found that the initial VHR was high and the VHR after the UV irradiation was higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] was not added. High, high light tolerance. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Example 9)

In the polymer solution P-1, 10 parts by weight of the polymer of the polymer solution P-1 was added in an amount of 10 parts by weight (M2) produced in Synthesis Example 2, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. Measuring this liquid crystal In the initial stage of the VHR and the VHR after the UV irradiation, it is found that the initial VHR is high and the VHR after UV irradiation is high, and the light resistance is higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] is not added. high. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Embodiment 10)

In the polymer solution P-1, (M3) produced in Synthesis Example 3 was added in an amount of 2 parts by weight based on 100 parts by weight of the polymer of the polymer solution P-1, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. When the initial VHR of the liquid crystal cell and the VHR after the UV irradiation were measured, it was found that the initial VHR was high and the VHR after the UV irradiation was higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] was not added. High, high light tolerance. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Example 11)

In the polymer solution P-1, 5 parts by weight of the polymer of the polymer solution P-1 was added in an amount of 5 parts by weight (M3) produced in Synthesis Example 3, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. Measuring this liquid crystal In the initial stage of the VHR and the VHR after the UV irradiation, it is found that the initial VHR is high and the VHR after UV irradiation is high, and the light resistance is higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] is not added. high. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Embodiment 12)

In the polymer solution P-1, 10 parts by weight of the polymer of the polymer solution P-1 was added in an amount of 10 parts by weight (M3) produced in Synthesis Example 3, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. When the initial VHR of the liquid crystal cell and the VHR after the UV irradiation were measured, it was found that the initial VHR was high and the VHR after the UV irradiation was higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] was not added. High, high light tolerance. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Example 13)

In the polymer solution P-2, (M1) produced in Synthesis Example 1 was added in an amount of 2 parts by weight based on 100 parts by weight of the polymer of the polymer solution P-2, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment treatment. Agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. Measuring this liquid crystal In the initial stage of the VHR and the VHR after the UV irradiation, it is found that the initial VHR is high and the VHR after UV irradiation is high, and the light resistance is higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] is not added. high. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Example 14)

In the polymer solution P-2, (M2) produced in Synthesis Example 2 was added in an amount of 2 parts by weight based on 100 parts by weight of the polymer of the polymer solution P-2, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. When the initial VHR of the liquid crystal cell and the VHR after the UV irradiation were measured, it was found that the initial VHR was high and the VHR after the UV irradiation was higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] was not added. High, high light tolerance. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Example 15)

In the polymer solution P-2, (M3) produced in Synthesis Example 3 was added in an amount of 2 parts by weight based on 100 parts by weight of the polymer of the polymer solution P-2, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. Measuring this liquid crystal In the initial stage of the VHR and the VHR after the UV irradiation, it is found that the initial VHR is high and the VHR after UV irradiation is high, and the light resistance is higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] is not added. high. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Embodiment 16)

In the polymer solution P-3, 100 parts by weight of the polymer of the polymer solution P-3 was added in an amount of 1 part by weight to the (M1) produced in Synthesis Example 1, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. When the initial VHR of the liquid crystal cell and the VHR after the UV irradiation were measured, it was found that the initial VHR was high and the VHR after the UV irradiation was higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] was not added. High, high light tolerance. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Example 17)

In the polymer solution P-3, 100 parts by weight of the polymer of the polymer solution P-3 was added in an amount of 1 part by weight to the (M2) produced in Synthesis Example 3, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. Measuring this liquid crystal In the initial stage of the VHR and the VHR after the UV irradiation, it is found that the initial VHR is high and the VHR after UV irradiation is high, and the light resistance is higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] is not added. high. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Embodiment 18)

In the polymer solution P-3, 100 parts by weight of the polymer of the polymer solution P-3 was added in an amount of 1 part by weight to the (M3) produced in Synthesis Example 3, and stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, a liquid crystal cell was formed in the same manner as in Example 4 to obtain a liquid crystal cell showing good liquid crystal alignment. When the initial VHR of the liquid crystal cell and the VHR after the UV irradiation were measured, it was found that the initial VHR was high and the VHR after the UV irradiation was higher than that of the liquid crystal alignment treatment agent (Comparative Example 1) in which the compound represented by the formula [1] was not added. High, high light tolerance. Further, after observing the substrate with the liquid crystal alignment film after the rubbing, no grinding residue or friction scratches were observed. The results are shown in Table 1.

(Comparative Example 1)

The polymer solution P-1 was used instead of the liquid crystal alignment treatment agent, and the friction resistance, VHR, and VHR after UV irradiation were evaluated in the same manner as in Example 4. The results are shown in Table 1. When the substrate to which the liquid crystal alignment film was attached after rubbing was observed, the scratch/grinding residue was observed. Further, the VHR after the UV irradiation is lower than the system in which the compound represented by the formula [1] is added.

(Comparative Example 2)

To the polymer solution P-1, 5 parts by weight of the compound benzoguanamine having a triazine skeleton with respect to 100 parts by weight of the polymer of the polymer solution P-1 was added, and the mixture was stirred at room temperature for 1 hour to obtain a liquid crystal alignment. Treatment agent. Using this liquid crystal alignment treatment agent, the friction resistance, VHR, and VHR after UV irradiation were evaluated in the same manner as in Example 4. The results are shown in Table 1. Although the improvement effect was seen in comparison with the comparative example 1, the rubbing residue was observed more than the liquid crystal alignment treatment agent containing the compound represented by the formula [1] of the present invention, and the VHR after UV irradiation was low and the UV resistance was low.

(Comparative Example 3)

In the polymer solution P-1, a benzotriazole-based ultraviolet absorber JF-83 manufactured by Seongbuk Chemical Industry Co., Ltd. was added so that the amount of the ultraviolet absorber added to the polymer of the polymer solution P-1 was 100 parts by weight. 5 parts by weight and stirred at room temperature for 1 hour to obtain a liquid crystal alignment treatment agent. Using this liquid crystal alignment treatment agent, the friction resistance, VHR, and VHR after UV irradiation were evaluated in the same manner as in Example 4. The results are shown in Table 1. Friction dross was observed, and the VHR after initial VHR and UV irradiation was low.

[Industrial availability]

The liquid crystal alignment treatment agent of the present invention has good friction resistance and light resistance, and therefore has a TN (Twisted Nematic) element, a STN (Super-twisted nematic display) element, and a TFT (Thin) for performing rubbing treatment. Film Transistor) Liquid crystal element, liquid crystal element of horizontal electric field type (IPS (In-Plane Switching), FFS (Fringe Field Switching), etc.). Further, since the light resistance is good, there is also a liquid crystal alignment film for forming a vertical alignment type liquid crystal display element which is not subjected to rubbing treatment or a liquid crystal display element which uses light alignment.

Claims (8)

A liquid crystal alignment treatment agent comprising: a compound represented by the following formula [1]; and at least one polymer selected from the group consisting of a polyimide and a polyimide. (In the formula [1], R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a benzene ring, R ₃ represents a hydrogen atom or a benzene ring, and X represents a single bond or an oxygen atom). The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the compound represented by the formula [1] is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer. The liquid crystal alignment treatment agent of claim 1, wherein the polymer has an unsaturated double bond in its structure. The liquid crystal alignment treatment agent according to claim 1, wherein the polymer is a polycondensation obtained by reacting a diamine component having a diamine compound selected from the following formula with a tetracarboxylic dianhydride component. At least one selected from the group consisting of an imine precursor and a polyimine obtained by imidating the oxime thereof, (wherein n is an integer of 1 to 20, and R ₄ is a hydrogen atom or a methyl group). A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 4. A liquid crystal display element comprising the liquid crystal alignment film of item 5 of the patent application. A compound characterized by the following formula [1], (In the formula [1], R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a benzene ring, R ₃ represents a hydrogen atom or a benzene ring, and X represents a single bond or an oxygen atom). A compound of claim 7 which is expressed by any one of the following formulae