JPH09120070A - Method for dividing orientation of liquid crystal oriented film and liquid crystal display device using liquid crystal oriented film obtained by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress decrease in the pretilt angle of a liquid crystal display element or deterioration in orientation of a liquid crystal by using a specified solvent to remove a resist pattern. SOLUTION: A radiation-sensitive resin compsn. is applied on a liquid crystal oriented film and irradiated with radiation to form a resist pattern so as to partially protect the liquid crystal oriented film. The liquid crystal oriented film in exposed area is oriented in the different direction from the protected part. Then, the resist pattern is removed by using at least one kind of solvent selected from among 4-10C alkylketones, solvents expressed by R<1> -(O-R<2> )n -O-R<3> (R<1> is hydrogen atom or a 1-4C alkyl group, R<2> is a 2-3C alkylene group, R<3> is hydrogen atom or a 1-4C alkyl group, and n is 1 or 2) or solvents expressed by the formula. In the formula, R<4> -R<8> are each independently hydrogen atom, a 1-4C alkoxy group, etc., and R<9> is a 1-5C alkyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alignment division method for a liquid crystal alignment film and a liquid crystal device using the obtained liquid crystal alignment film. More specifically, the present invention relates to an alignment division method of a liquid crystal alignment film which has a small decrease in pretilt angle of a liquid crystal display device and is excellent in liquid crystal alignment characteristics, and a liquid crystal display device using the obtained liquid crystal alignment film.

[0002]

2. Description of the Related Art Conventionally, a nematic liquid crystal having a positive dielectric anisotropy is sandwiched by a substrate with a transparent electrode having a liquid crystal alignment film made of polyimide or the like, and the long axis of liquid crystal molecules is 90 to 270 between the substrates. There is known a liquid crystal display element (TN type or STN type liquid crystal display element) having a TN type or STN type liquid crystal cell that is twisted continuously. However, since this TN type or STN type liquid crystal display element uses the rising and falling edges of liquid crystal molecules having a refractive index anisotropy to turn the display on and off, the display is particularly performed in the halftone display. Has a problem of a narrow viewing angle. In order to solve this, the radiation-sensitive resin composition is applied onto the liquid crystal alignment film that has been subjected to an alignment treatment in advance, and a resist pattern is partially formed to protect the liquid crystal alignment film, and then the alignment direction and A method has been reported in which the orientation is divided in different directions to widen the viewing angle of display (SID ').
92 Digest, p.792, Japan Displ
ay'92 Digest, p.591). However, after removing the radiation-sensitive resin composition, the pretilt angle of the liquid crystal display element is lowered, and there is a problem in that alignment failure occurs in the liquid crystal display element.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to reduce the pretilt angle of the liquid crystal display device and the alignment characteristics of the liquid crystal so that the alignment characteristics of the liquid crystal alignment film are less likely to occur. To provide.

Another object of the present invention is to provide a liquid crystal display device having a liquid crystal display device having a liquid crystal alignment film that is alignment-divided by the above-mentioned alignment division method. Still other objects and advantages of the present invention will be apparent from the following description.

[0005]

According to the present invention, the above objects and advantages of the present invention can be achieved by the following method for alignment division of a liquid crystal alignment film. (1) A radiation-sensitive resin composition is applied onto an oriented liquid crystal alignment film on a substrate, irradiated with radiation through a predetermined pattern, and developed to form a resist pattern to partially form the liquid crystal alignment film. A method for alignment division of a liquid crystal alignment film, which comprises protecting and exposing the exposed liquid crystal alignment film in a direction different from the above alignment, and then removing the resist pattern. Ketones, general formula (A)

R ^1- (O-R ² ) _n -O-R ³

(Where R ¹ is a hydrogen atom or 1 carbon atom)
To R 4 are alkyl groups, R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acetyl group or a propionyl group, and n
Is 1 or 2. ) And a general formula (B)

[0008]

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(Here, R ^{4 to} R ⁸ are independently of each other a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms.
3 represents an alkyl group, and R ⁹ represents an alkyl group having 1 to 5 carbon atoms. ) A method for alignment division of a liquid crystal alignment film, which is carried out with at least one solvent selected from the group consisting of solvents represented by

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As a liquid crystal alignment film used in the present invention, a polyamic acid obtained by a reaction of a tetracarboxylic dianhydride and a diamine compound and / or a polyimide which is an imidized polymer thereof is preferably used. .

Examples of the tetracarboxylic dianhydride at this time include butanetetracarboxylic dianhydride, 1,2,
3,4-cyclobutanetetracarboxylic dianhydride, 1,3
-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,
4-cyclobutanetetracarboxylic dianhydride, 1,2,
3,4-cyclopentanetetracarboxylic dianhydride, 2,
3,5-tricarboxycyclopentyl acetic acid dianhydride,
Tetracyclo [6.2.1.1.0 ^2,7 ] dodeca-4,5,9,
10-Tetracarboxylic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5
-Tetrahydrofuran tetracarboxylic 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-5-methyl-5 (tetrahydro-2,
5-dioxo-3-furanyl) -naphtho [1,2-c]
-Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-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, 1,3,3a, 4,5,9b-hexahydro-9-methyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,
3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo [2.2.2] -oct-7
Aliphatic and alicyclic tetracarboxylic dianhydrides such as -ene-2,3,5,6-tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone Tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,
8-naphthalenetetracarboxylic dianhydride, 2,3,6,
7-naphthalene tetracarboxylic dianhydride 3,3 ′,
4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic acid Dianhydride, 1,2,3,4-
Furantetracarboxylic dianhydride, 4,4'-bis (3,
4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis (3,
4-Dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride , Bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-
Aromatic such as bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride A tetracarboxylic dianhydride can be mentioned.

Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride Anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, tetracyclo [6.2. 1.1.0 ^2,7 ] dodeca-4,5,9,10-tetracarboxylic dianhydride, 5-
(2,5-Dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic 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-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,
2-c] -furan-1,3-dione, 1,3,3a, 4,5,
9b-hexahydro-7-methyl-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, 1,3,3a, 4,5,9b-hexahydro-9-methyl-5 (tetrahydro-2,5-
Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, pyromellitic dianhydride, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyl sulfone tetracarboxylic acid dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene dihydrate Phthalic acid dianhydride 3,3 ', 4,4'-
Biphenyltetracarboxylic dianhydride and the like are preferable.
These can be used alone or in combination of two or more.

As the diamine compound, for example, p
-Phenylenediamine, m-phenylenediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,
4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 3,4 '
-Diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,
4'-diaminobenzophenone, 2,2-bis [4-
(4-Aminophenoxy) phenyl] propane, 2,2
-Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4- Bis (4-
Aminophenoxy) benzene, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-
(M-phenylenediisopropylidene) bisaniline,
1,3-bis (4-aminophenoxy) benzene, 1,3
-Bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9,9-bis (4-aminophenyl) fluorene,
4,4'-methylene-bis (2-chloroaniline), 2,
2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,
5'-dimethoxybiphenyl, 3,3'-dimethoxy-
Aromatic diamines such as 4,4′-diaminobiphenyl;
Aromatic diamine having a hetero atom such as diaminotetraphenylthiophene; 1,1-metaxylylenediamine, 1,2-ethylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene Diamine, octamethylenediamine, nonamethylenediamine,
1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine,
Hexahydro-4,7-methanoindanylene dimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine) and other aliphatic or alicyclic diamines ;

H ₂ N- (CH ₂ ) _p- (Si (R) ₂ -O) _q -Si (R) _2- (CH ₂ ) _p -NH ₂

(In the formula, R represents an alkyl group such as a methyl group, an ethyl group, a propyl group, a cycloalkyl group such as a cyclohexyl group, or a hydrocarbon group having 1 to 12 carbon atoms such as an aryl group such as a phenyl group. , P is 1 to 3 and q is an integer of 1 to 20) and the like; and the following formulas (1) to (7)

[0016]

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[0017]

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[0018]

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[0019]

[Chemical 6]

[0020]

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[0021]

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[0022]

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A diamine containing a steroid skeleton represented by

Of these, p-phenylenediamine,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4
-Aminophenyl) fluorene, 2,2-bis [4-
(4-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane and a diamine containing a steroid skeleton represented by the above formulas (1) to (7) are preferable. These can be used alone or in combination of two or more. These diamines may be used as they are, or may be used after being reduced again.

The polyamic acid used in the present invention is obtained by reacting a tetracarboxylic dianhydride and a diamine compound. Such a reaction is usually performed in an organic solvent at 0 to 150.
C., preferably at a temperature of 0-100.degree.

The above-mentioned organic solvent used in the reaction includes
There is no particular limitation as long as it can dissolve the tetracarboxylic acid dianhydride, the diamine compound and the polyamic acid produced by the reaction. For example, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N,
Aprotic polar solvents such as N-dimethylacetamide, dimethylsulfoxide, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. These can be used alone or in combination of two or more.

The above organic solvents include alcohols, ketones, esters which are poor solvents for polyamic acid,
Ethers, halogenated hydrocarbons, hydrocarbons and the like can be used in combination as long as the generated polyamic acid does not precipitate. Specific examples of such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol,
Triethylene glycol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether,
Ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol-n-hexyl ether, 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 Monobutyl ether,
Diethylene glycol monomethyl ether acetate,
Diethylene glycol monoethyl ether acetate,
Ethylene glycol methyl ether acetate, ethylene glycol-n-propyl ether acetate, ethylene glycol-i-propyl ether acetate, ethylene glycol-n-butyl ether acetate, ethylene glycol-n-hexyl ether acetate,
4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate,
Methyl 3-ethoxypropionate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-
Dichlorobutane, trichloroethane, chlorobenzene,
Examples thereof include o-dichlorobenzene, hexane, heptane, octane, benzene, toluene and xylene.

The amount of the organic solvent used is usually preferably such that the total amount of the tetracarboxylic dianhydride and all the amine compounds is 0.1 to 30% by weight based on the total amount of the reaction solution.

The ratio of the tetracarboxylic dianhydride and the diamine compound used is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 with respect to 1 equivalent of the amino group in the diamine compound.
The ratio of about 2 equivalents is preferable, and more preferably 0.3.
It is a ratio of about 1.4 equivalents.

The polyimide used in the present invention is obtained by heating the above-mentioned polyamic acid or by imidizing it in the presence of a dehydrating agent and an imidizing catalyst. The reaction temperature for imidization by heating is usually 6
It is 0 to 200 ° C, preferably 100 to 170 ° C. If the reaction temperature is less than 60 ° C, the reaction progresses slowly,
If the temperature exceeds ℃, the molecular weight of the soluble polyimide may be significantly reduced. In addition, the reaction in the case of imidization in the presence of a dehydrating agent and an imidization catalyst can be carried out in the above-mentioned organic solvent. The reaction temperature is generally 0 to 180 ° C, preferably 60 to 150 ° C. As the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. Further, as the imidization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used.
It is not limited to these. The amount of dehydrating agent used is
From 1.6 to 1 mol of repeating unit of polyamic acid
It is preferably 20 mol. Further, the amount of the imidization catalyst used is preferably 0.5 to 10 mol with respect to 1 mol of the dehydrating agent used. In the imidization reaction, the imidization ratio of the polyamic acid can be adjusted by adjusting the reaction temperature.

Intrinsic viscosity [ηinh = ln ηr of the polyamic acid and / or polyimide thus obtained
el / C, C = 0.5 g / dl, 30 ° C., N-methyl-
In 2-pyrrolidone, the following measurement is performed under the same conditions]
0.05-10 dl / g, preferably 0.05-5 dl / g
g.

By the above synthesis reaction, a polymer solution obtained by dissolving polyamic acid and / or polyimide can be obtained. Then, the polymer solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid and / or a polyimide. Further, the polyamic acid and / or polyimide can be purified by repeating the step of dissolving the polyamic acid and / or polyimide again in the organic solvent and then precipitating with the poor solvent once or several times.

The radiation-sensitive resin composition used in the present invention is
It contains (a) an alkali-soluble resin and (b) a compound that produces an acid upon irradiation with radiation (hereinafter referred to as "radiation-sensitive acid-producing compound").

Examples of the alkali-soluble resin (a) include acidic groups such as phenolic hydroxyl group, carboxylic acid group, sulfonic acid group, imide group, sulfonamide group, N-sulfonamide group, N-sulfone urethane group and active methylene group. A resin having an organic group containing a hydrogen atom may be mentioned. Suitable alkali-soluble resins include phenol formaldehyde resin, xylenol-formaldehyde resin, o-
Cresol-formaldehyde resin, m-cresol-
Examples thereof include novolak phenol resins such as formaldehyde resin, p-cresol-formaldehyde resin, and co-condensates thereof; and (co) polymers of unsaturated carboxylic acids such as acrylic acid and methacrylic acid.

Examples of the radiation-sensitive acid-forming compound include 1,2-benzoquinonediazide sulfonic acid ester, 1,2
2-naphthoquinonediazide sulfonic acid ester, 1,2
Examples thereof include benzoquinone diazide sulfonic acid amide and 1,2-naphthoquinone diazide sulfonic acid amide. Specifically, J. Kosar's “Light-
Sensitive Systems "339-352
(1965), John Wiley & Sons (New York) and WS De Forest, "Photoresist" 50 (1975), McG.
The 1,2-quinonediazide compounds described in raw-Hill, Inc. (New York) can be mentioned.

Specifically, 1,2-dihydroxydiphenylmethane, 2,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane and the like
2-naphthoquinonediazide-4 or 5-sulfonic acid ester; 1- (4-hydroxyphenyl) -1- (4 '
1,2-naphthoquinonediazide-4 or 5-sulfonic acid ester of -hydroxyphenyl) ethane; 2- (4
-Hydroxyphenyl) -2- (4'-hydroxyphenyl) propane 1,2-naphthoquinonediazide-4 or 5-sulfonic acid ester; 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone 1,2, naphthoquinonediazide-4 or 5 of 2,3,4,4'-tetrahydroxybenzophenone or 2,3,4,2 ', 4'-pentahydroxybenzophenone
-Sulfonic acid ester; 2,2 ', 2 "-trihydroxytriphenylmethane, 2,2', 4" -trihydroxytriphenylmethane, 2,4 ', 4 "-trihydroxytriphenylmethane, 1,2-naphthoquinonediazide-4 or 5-sulfonic acid ester of trihydroxytriphenylmethane such as 4,4 ′, 4 ″ -trihydroxyphenylmethane;

2,2 ', 2 "-trihydroxytriphenylethane, 2,2', 4" -trihydroxytriphenylethane, 2,4 ', 4 "-trihydroxytriphenylethane, 4, A trihydroxyphenylethane such as 4 ′, 4 ″ -trihydroxytriphenylethane,
2-naphthoquinonediazide-4 or 5-sulfonic acid ester; (2- (1,1-dimethyl-1- (p-hydroxyphenyl) methyl) phenyl) -bis (p-hydroxyphenyl) methane 1,2-naphtho Quinonediazide-4 or 5-sulfonic acid ester; 1- (4- (p-
Preferred is the 1,2-naphthoquinonediazide-4 or 5-sulphonic acid ester of hydroxyphenylmethyl) phenyl) -2,2-bis (p-hydroxyphenyl) ethane.

The amount of the radiation-sensitive acid-forming compound added is preferably 5 to 100 parts by weight of the alkali-soluble resin.
100 parts by weight, particularly preferably 10 to 50 parts by weight. When the amount is less than 5 parts by weight, the amount of acid generated by absorbing radiation is small, and it is difficult to make a difference in the solubility of the radiation-sensitive resin composition in an alkaline aqueous solution before and after irradiation with radiation, and patterning is difficult. Becomes
On the other hand, if it exceeds 100 parts by weight, most of the added radiation-sensitive acid-forming compound remains in its original form in a short-time irradiation, so that the insolubilizing effect in the alkaline aqueous solution is too high and the radiation-sensitive resin composition is too high. It may be difficult to develop the product.

The radiation-sensitive resin composition used in the present invention can be easily prepared by uniformly mixing the above-mentioned components. When mixing, it is dissolved in a suitable solvent and used in the form of a solution. As the solvent to be used, a solvent that can uniformly dissolve the alkali-soluble resin and the radiation-sensitive acid-forming compound and does not react with each component is used.

Examples of such a solvent include methanol,
Alcohols such as ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol monomethyl ether and diethylene glycol mono Diethylene glycols such as ethyl ether and diethylene glycol dimethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone,
Ketones such as 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate,
Esters such as ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate and butyl acetate can be used.

Further, N-methylformamide, N, N
-Dimethylformamide, N-methylformanilide,
N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1
It is also possible to add a high-boiling solvent such as -octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate.

Among these solvents, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ethers such as ethyl cellosolve acetate are used because of their solubility, reactivity with each component, and ease of forming a coating film. Acetates; Esters such as ethyl 2-hydroxypropionate; Diethylene glycols such as diethylene glycol monomethyl ether; Cyclohexanone, 4-hydroxy-4-methyl-
Ketones such as 2-pentanone are preferred.

In preparing the solution, for example, a solution of the alkali-soluble resin, a solution of the radiation-sensitive acid-forming compound and a solution of other compounding agents are separately prepared, and these solutions are mixed at a predetermined ratio immediately before use. Can be mixed with. The composition solution prepared as described above,
It is preferably used after being filtered with a Millipore filter having a pore size of 0.2 μm.

The developer of the radiation-sensitive resin composition in the present invention includes, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia; ethylamine, n-propyl. Primary amines such as amines; secondary amines such as diethylamine and di-n-propylamine; aliphatic tertiary amines such as trimethylamine, dimethylethylamine, triethylamine, methyldiethylamine, tri-n-propylamine; methyl Tertiary alcohol amines such as diethanolamine, dimethylethanolamine, ethyldiethanolamine, diethylethanolamine and triethanolamine; aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; pyrrole and piperidine Pyrrolidine, N- methylpiperidine, N- methylpyrrolidine, 1,8-diazabicyclo -
Cyclic tertiary amine such as [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonane;
Examples thereof include quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline. Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the developing solution as long as the developing characteristics are not deteriorated.

In the present invention, the solvent used for removing the radiation-sensitive resin composition is an alkyl ketone having 4 to 10 carbon atoms, a general formula (A), and a general formula (1) shown below.

R ^1- (OR ² ) _n -OR ³

(Here, R ¹ is a hydrogen atom or a carbon number 1
To R 4 are alkyl groups, R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acetyl group or a propionyl group, and n
Is 1 or 2. ), And a general formula (B)

[0048]

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(Here, R ^{4 to} R ⁸ are independently of each other a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
3 represents an alkyl group, and R ⁹ represents an alkyl group having 1 to 5 carbon atoms. ) At least one solvent selected from the group consisting of solvents represented by

Examples of the alkyl ketones having 4 to 10 carbon atoms include methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2
-Pentanone, 3-pentanone, 2-hexanone, 3-
Hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone,
5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-decanone and the like can be mentioned.

The alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ³ in the above general formula (A) may be linear or branched, and examples thereof include a methyl group and an ethyl group. , N-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group and ter
A t-butyl group may be mentioned. The alkylene group having 2 or 3 carbon atoms represented by R ² is, for example, 1,
A 2-ethylene group, a 1,3-propylene group and a 1,2-propylene group can be mentioned.

Specific examples of the solvent represented by the general formula (A) include alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol;

Ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol Mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono n-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono-n-butyl ether, dipropylene Alkylene glycol alkyl ethers such as glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;

Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate,
Ethylene glycol propyl ether acetate, ethylene glycol-n-butyl ether acetate, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol propyl ether propionate, ethylene glycol n-butyl ether propionate, propylene glycol Methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol-n-butyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol -N- And alkylene glycol alkyl ether esters, such as chill ether propionate can be mentioned.

The alkyl group and alkoxyl group represented by R ^{4 to} R ⁹ in the above general formula (B) may be linear or branched. Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^{4 to} R ⁸ include a methyl group, an ethyl group,
Examples thereof include an n-propyl group and an iso-propyl group, and as the alkyl group having 1 to 5 carbon atoms represented by R ⁹ ,
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, te
Examples thereof include rt-butyl group, n-amyl group, iso-amyl group, sec-amyl group and tert-amyl group.

Examples of the alkoxyl group having 1 to 4 carbon atoms represented by R ^{4 to} R ⁸ include methoxyl group, ethoxyl group, propoxyl group and butoxyl group. Specific examples of the solvent represented by the above general formula (B) include, for example, methyl acetate, ethyl acetate, propyl acetate, -n-butyl acetate, acetic acid-iso-butyl, acetic acid-n.
-Amyl, acetic acid-iso-amyl, methyl propionate,
Ethyl propionate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, propoxyacetic acid Butyl, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2-ethoxypropione. Acid methyl, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-propoxypropionate, 2-propoxyp Ethyl pionate, propyl 2-propoxypropionate, butyl 2-propoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxypropionate Methyl acid, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxypropionic acid Butyl, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionate Ethyl phosphate, 3-butoxy-propionic acid propyl, alkoxy carboxylic acid esters such as 3-butoxy-propionic acid butyl.

Among these, particularly, 2-heptanone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene. Glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, acetic acid-n-butyl, acetic acid-iso-butyl, methyl 2-methoxypropionate, ethyl 2-ethoxypropionate and the like are preferable.

The liquid crystal display device obtained by using the method of alignment division of the liquid crystal alignment film of the present invention can be manufactured, for example, by the following method.

First, a liquid crystal aligning agent is applied to the transparent conductive film side of the substrate provided with the transparent conductive film by, for example, a printing method,
The coating film is formed by heating at a temperature of 80 to 200 ° C, preferably 120 to 200 ° C. This coating is usually 0.0
It is from 01 to 1 μm, preferably from 0.005 to 0.5 μm.

The coating film formed as described above is subjected to a rubbing treatment with a roll wound with a cloth made of synthetic fiber such as nylon. Next, the radiation-sensitive resin composition is applied onto the liquid crystal alignment film by a spin coating method or a printing method, and then 50 to 1 is applied.
The coating film is formed by heating at a temperature of 80 ° C, preferably 50 to 120 ° C. This coating is usually 0.1-10μ
m, preferably 0.3-5 μm.

Next, the obtained radiation-sensitive resin composition on the liquid crystal alignment film is irradiated with, for example, ultraviolet rays through a mask having a predetermined pattern, and then developed with a developing solution to remove unnecessary portions. Then, a resist pattern is formed to partially protect the liquid crystal alignment film.

The developing time is usually 10 to 240 seconds,
Further, the developing method may be any of a puddle method and a dipping method. After the development, washing with running water is carried out for 30 to 180 seconds, followed by air drying with compressed air or compressed nitrogen.

Next, a rubbing process is performed in the opposite direction to the above on the substrate on which the resist pattern is partially formed to protect the liquid crystal alignment film. Next, the obtained substrate is washed with the above specific solvent to remove only the resist pattern.

The two substrates thus formed with the liquid crystal alignment film are made to face each other so that the rubbing directions of the facing portions of the liquid crystal alignment film are orthogonal or antiparallel, and the peripheral portion between the substrates is sealed. Seal with an agent, fill the liquid crystal, seal the filling hole to make a liquid crystal display element, and stick the polarizing plates on both sides so that the polarization direction matches or is orthogonal to the rubbing direction of the liquid crystal alignment film of the substrate, respectively. To be a liquid crystal display element.

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

Examples of the above-mentioned liquid crystals include nematic liquid crystals and smectic liquid crystals.
Among them, those which form a nematic liquid crystal are preferable, for example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals. liquid crystal,
Bicyclooctane liquid crystal, Cuban liquid crystal, etc. are used. In addition to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate and cholesteryl carbonate, and trade names C-15 and CB.
It is also possible to add and use a chiral agent such as that sold as -15 (Merck Ltd.).
Furthermore, p-decyloxybenzylidene-p-amino-2
Ferroelectric liquid crystals such as methylbutyl cinnamate can also be used.

As a polarizing plate used outside the liquid crystal display element, a polarizing film in which polyvinyl alcohol is stretched and oriented while a polarizing film called an H film absorbing iodine is sandwiched between cellulose acetate protective films, or Examples thereof include a polarizing plate made of the H film itself.

[0068]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The pretilt angle of the liquid crystal display element and the orientation of the liquid crystal display element were evaluated for each of the liquid crystal display elements produced in the following examples and comparative examples. The evaluation method is as follows.

[Pretilt Angle of Liquid Crystal Display Element] The pretilt angle of the liquid crystal display element is [TJ Schffer et al., J. A.
ppl. Phys., 19, 2013 (1980)],
It was performed by a crystal rotation method using He-Ne laser light.

[Orientation of Liquid Crystal Display Element] The orientation of the liquid crystal display element was evaluated by observing the presence or absence of an abnormal domain in the liquid crystal display element when a voltage was turned on and off with a polarizing microscope and recognizing the abnormal domain. If not, it was judged as good.

Synthesis Example 1 44.83 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 20.55 g of p-phenylenediamine
And 5.21 g of a diamine having a steroid skeleton represented by the above formula (1) was added to N-methyl-2-pyrrolidone 67
It was dissolved in 2 g and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Then, wash with methanol and depressurize at 40 ℃.
After drying for 15 hours, 65.2 g of polyamic acid Ia having an intrinsic viscosity of 1.24 dl / g was obtained.

Synthesis Example 2 30 g of the polyamic acid Ia obtained in Synthesis Example 1 was added to 570
It was dissolved in g of γ-butyrolactone, 21.6 g of pyridine and 16.74 g of acetic anhydride were added, and an imidization reaction was performed at 110 ° C. for 3 hours. Then, the reaction product solution was precipitated in the same manner as in Synthesis Example 1 to obtain 25.8 g of polyimide IIa having an intrinsic viscosity of 1.26 dl / g.

Synthesis Example 3 Polyamic acid Ib was obtained in the same manner as in Synthesis Example 1, except that 37.67 g of 4,4′-diaminodiphenylmethane was used as the diamine, and the polyamic acid Ib was used for synthesis. In the same manner as in Example 2, 25.2 g of polyimide IIb having an intrinsic viscosity of 1.06 dl / g was obtained.

Synthetic Example 4 Intrinsic viscosity 1.16 dl / g in the same manner as in Synthetic Example 1, except that 39.22 g of cyclobutanetetracarboxylic dianhydride was used as the tetracarboxylic dianhydride.
60.5 g of polyamic acid Ic was obtained.

Synthesis Example 5 m-cresol 17.0 g, 3,5-xylenol 52.
2g, 37% by weight formaldehyde aqueous solution 130.3g
And 0.73 g of oxalic acid dihydrate were subjected to polycondensation in a separable flask at 100 ° C. for 35 minutes while stirring, and then 108.0 g of m-cresol and 13.1 g of 3,5-xylenol were added, The reaction was continued for another 2 hours.
After the reaction, the pressure in the reaction vessel was reduced to 30 to 40 mmHg, and water, oxalic acid, unreacted formaldehyde, m
-Cresol, 3,5-xylenol etc. were removed.
Then, the reaction product was dissolved in ethyl cellosolve acetate so that the solid content concentration became 20% by weight, and then twice the amount of methanol and an equal amount of water were added to this solution and the mixture was left to stir with stirring. After the solution was separated into two layers, the lower layer was taken out, concentrated, dehydrated and dried to recover an alkali-soluble resin consisting of novolac phenol resin. Then, a solution was prepared using diethylene glycol so that the solid content concentration became 25% by weight.

Synthesis Example 6 After replacing the inside of the flask with nitrogen, 459 g of a diethylene glycol dimethyl ether solution in which 9 g of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 6 g of butadiene, 30 g of styrene, 42 g of methacrylic acid and 42 g of dicyclopentanyl methacrylate were charged, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization. After the polymerization, the reaction product solution was dropped into a large amount of water to solidify the reaction product. After washing this coagulated product with water, it is redissolved in 200 g of tetrahydrofuran,
It was solidified again with a large amount of water. This redissolving-coagulation operation was performed three times in total, and the obtained coagulated product was vacuum dried at 60 ° C. for 48 hours to obtain an alkali-soluble resin composed of a copolymer of a compound containing an unsaturated carboxylic acid. Then, a solution was prepared using diethylene glycol so that the solid content concentration became 25% by weight.

Preparation Example 1 After adding 13.64 g of diethylene glycol dimethyl ether to 100 g of the alkali-soluble resin solution obtained in Synthesis Example 5, 4,4 '-[1- [4- (1- (4
-Hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester (average esterification rate: 66.7 mol%) (7.5 g) was dissolved and the pore size was adjusted to 0. A radiation-sensitive resin composition solution a was prepared by filtering with a 22 μm Millipore filter.

Preparation Example 2 Radiation-sensitive resin composition was prepared in the same manner as in Preparation Example 1 except that the alkali-soluble resin solution obtained in Synthesis Example 6 was used instead of the alkali-soluble resin solution obtained in Synthesis Example 5. Product solution b was prepared.

Example 1 5 g of the polyamic acid Ia obtained in Synthesis Example 1 was dissolved in N-methyl-2-pyrrolidone to give a solid content of 4% by weight.
And a liquid crystal aligning agent was prepared by filtering this solution with a filter having a pore size of 1 μm. This liquid crystal aligning agent was applied to a transparent electrode surface on a glass substrate with a transparent electrode made of an ITO film using a printer for applying a liquid crystal aligning film, and dried at 180 ° C. for 1 hour to give a dry film thickness of 0.05 μm. Was formed. The number of rotations of the roll is 500 r by a rubbing machine having a roll in which a nylon cloth is wrapped around this coating film.
The rubbing treatment was performed at pm at a stage moving speed of 1 cm / sec.

Next, the radiation-sensitive resin composition solution a obtained in Preparation Example 1 was applied onto the above liquid crystal alignment film by spin coating and dried at 100 ° C. for 30 minutes to form a 1 μm coating film. Let On the coating film of the obtained radiation sensitive resin composition, through a mask having a pattern of 100 μm × 100 μm,
After irradiation with light having a wavelength of 365 nm at an intensity of 200 mJ / cm ² , development was performed for 60 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. After that, the surface of the coating film was washed with running water for 120 seconds and air-dried with compressed nitrogen to form a substrate in which the liquid crystal alignment film was partially protected by a resist pattern. Then, using the above substrate, rubbing treatment was performed in the opposite direction to that described above, and the obtained substrate was washed with diethylene glycol dimethyl ether for 240 seconds. Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 17 μm is screen-printed and applied to each outer edge of the pair of rubbed substrates having the liquid crystal alignment film, and then the pair of substrates face each other. As described above, the rubbing direction was perpendicular to the rubbing direction, and the adhesive was cured by pressing. Then, a nematic type liquid crystal (Merck & Co., Z
After filling LI-4792), the liquid crystal injection port is sealed with an epoxy adhesive, polarizing plates are provided on both sides of the substrate, and the polarization direction of the polarizing plate matches the rubbing direction of the liquid crystal alignment film of each substrate. When the liquid crystal display element was produced by laminating the liquid crystal as described above, the alignment of the liquid crystal was good. In addition, the pretilt angle of the liquid crystal display element was a high value of 4.2 °, and no display defect was observed even when a voltage was applied. Table 1 shows the results.

Examples 2 to 18 Liquid crystals were prepared in the same manner as in Example 1 except that the liquid crystal alignment film, the radiation-sensitive resin composition solution, the developing solution and the removing solution were combined as shown in Table 1. A display element was manufactured. The orientation and pretilt angle of the liquid crystal display device were evaluated, and the results are shown in Table 1 (Examples 2 to 10) and Table 2 (Examples 11 to 18).

Comparative Example 1 A liquid crystal display device was prepared in the same manner as in Example 1 except that ethyl cellosolve acetate was used as the removing liquid, and the same evaluation was carried out. Table 2 shows the results. With this removing liquid, the pretilt angle was reduced, and a display defect occurred when a voltage was applied.

Comparative Example 2 A liquid crystal display device was prepared in the same manner as in Example 1 except that acetone was used as the removing liquid, and the same evaluation was performed. Table 2 shows the results. With this remover,
The pretilt angle was reduced, and a display defect occurred when a voltage was applied.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

According to the liquid crystal alignment film alignment division method of the present invention, it is possible to obtain a liquid crystal display device having excellent liquid crystal alignment characteristics, in which a decrease in the pretilt angle of the liquid crystal display element and deterioration of the liquid crystal alignment characteristics hardly occur. To be In addition, the liquid crystal display device manufactured by using the liquid crystal alignment film alignment division method of the present invention can be used not only in TN type and STN type liquid crystal display devices but also in SH type (Super Homeotropi) by selecting the liquid crystal to be used.
c), it can be preferably used also in ferroelectric and antiferroelectric liquid crystal display devices. Furthermore, the liquid crystal display element produced by using the method for dividing the alignment of the liquid crystal alignment film of the present invention has excellent liquid crystal orientation and reliability, and can be effectively used in various devices. For example, desktop calculators, wrist watches, clocks, and coefficients. It is used for display devices such as display boards, word processors, personal computers, and liquid crystal televisions.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuo Matsuki 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd.

Claims (2)

[Claims] 1. A liquid crystal alignment film is formed by applying a radiation-sensitive resin composition on an oriented liquid crystal alignment film on a substrate, irradiating radiation through a predetermined pattern, and developing to form a resist pattern. Of the liquid crystal alignment film, in which the exposed portion of the liquid crystal alignment film is aligned in a direction different from the above alignment direction, and then the resist pattern is removed. ~ 1
Alkyl ketones of 0, general formula (A) R ^1- (O-R ² ) _n- O-R ³ (wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² is Represents an alkylene group having 2 or 3 carbon atoms, R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acetyl group or a propionyl group, and n represents 1 or 2
It is. ) And a solvent represented by the general formula (B): (Here, R ^{4 to} R ⁸ each independently represent a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and R ⁹ represents an alkyl group having 1 to 5 carbon atoms. .)
The method for aligning and splitting a liquid crystal alignment film is performed by using at least one solvent selected from the group consisting of solvents represented by 2. A liquid crystal display device comprising a liquid crystal alignment film that is alignment-divided by the method of claim 1.