JP2001048874A - New acid anhydride, polyamic acid, polyimide, liquid crystal oriented film and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an acid dianhydride suitable as a raw material for a polyimide liquid crystal oriented film having excellent adhesivity and orientation, a polyamic acid and a polyamide comprising the acid dianhydride as a raw material, a liquid crystal oriented film comprising the polyamic acid and the polyamide and a liquid crystal display element provided with the liquid crystal oriented film, having few burning phenomena. SOLUTION: This 2,3-dicarboxymethyl-2,3-disubstituted succinic dianhydride is shown by the formula (R is a 1-12C straight-chain or branched chain alkyl group, a cyclohexyl group, a 1-6C straight-chain or branched chain alkyl- substituted cyclohexyl group, a phenyl group or a 1-6C straight-chain or branched chain alkyl-substituted phenyl group, a 1-12C alkoxy group or a monofunctional organic group such as a hydroxyl group or a halogen atom, etc.). A polyamic acid is obtained by a ring opening polyaddition of a tetracarboxylic acid anhydride containing the acid dianhydride and a diamino compound. An oriented film is formed from the polyamic acid. A liquid crystal display element is obtained by using the oriented film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel acid dianhydride and to a polyamic acid and a polyimide using the same as a raw material. Further, the present invention relates to a liquid crystal alignment film using the same and a liquid crystal display device provided with the liquid crystal alignment film.

[0002]

2. Description of the Related Art Twisted nematic (hereinafter abbreviated as TN) having a structure in which nematic liquid crystal molecules are twisted at 90 degrees between two pairs of electrode substrates is used in a liquid crystal display element used for a timepiece or a calculator. ) Mode is mainly adopted. In addition, a super twisted nematic (hereinafter abbreviated as STN) mode in which the twist angle is increased to 180 to 300 degrees has been developed, and a liquid crystal display element having good display quality even on a large screen can be obtained. In recent years, since matrix display and color display have been performed in recent years, a multi-pixel MI and an active type twisted nematic mode which can perform ON-OFF of these pixel electrodes have been adopted.
M (metal-insulating layer-metal) devices and TFT (field effect thin film transistor) devices have been actively developed. In the liquid crystal alignment film used in these liquid crystal display elements, it is necessary to prevent the liquid crystal deterioration phenomenon due to the direct contact between the liquid crystal and the electrode formed on the glass substrate and to uniformly align the liquid crystal molecules. However, as a problem common to all of the above-mentioned modes, when the rubbing treatment is performed due to weak adhesion between the glass substrate and the alignment film, peeling of the alignment film,
Generation of film abrasion, generation of panel defects due to poor alignment,
Furthermore, when the same screen is displayed for a long time and then shifted to another screen, a phenomenon called burn-in occurs in which the previous image remains as an afterimage.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide an acid dianhydride suitable for a raw material for a polyimide liquid crystal alignment film having good adhesion and alignment. It is to be. Also provided are a polyamic acid and a polyimide using the acid dianhydride as a raw material. It is still another object of the present invention to provide a liquid crystal alignment film containing the polyamic acid and the polyimide and a liquid crystal display device provided with the liquid crystal alignment film and having a small image sticking phenomenon.

[0004]

Means for Solving the Problems As a result of intensive research and development, the present inventors succeeded in synthesizing a novel acid dianhydride, and obtained a polyamic acid by ring-opening polyaddition with various diamino compounds. And further a polyimide was obtained. The liquid crystal alignment film using this polyimide has good adhesion and alignment properties,
Further, they have found that there is no burn-in phenomenon and that they are excellent for liquid crystal display devices, and have completed the present invention.

The 2,3-dicarboxymethyl of the present invention
2,3-disubstituted succinic dianhydrides are represented by the following [1] to
This is shown in [5]. [1] General formula (1)

Embedded image Wherein R is a monovalent organic group.
-Dicarboxymethyl-2,3-disubstituted succinic dianhydride.

[2] In the general formula (1), R is a straight-chain or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a straight-chain or branched group having 1 to 6 carbon atoms. Cyclohexyl group, phenyl group, linear or branched alkyl group having 1 to 6 carbon atoms, phenyl group substituted with 1 to 6 carbon atoms, alkoxy group having 1 to 12 carbon atoms, hydroxyl group or 2. The compound according to item [1], which is a halogen atom.
3-dicarboxymethyl-2,3-disubstituted succinic dianhydride.

[3] In the general formula (1), R
Is a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group or a phenyl group, the 2,3-dicarboxymethyl-
2,3-disubstituted succinic dianhydride.

[4] The following equation (2)

Embedded image (Where n is an integer of 1 to 12),
3-dicarboxymethyl-2,3-dialkylsuccinic dianhydride.

[5] The following equation (3)

Embedded image 2,3-Dicarboxymethyl-2,3-dimethylsuccinic dianhydride represented by the formula:

The 2,3-dicarboxymethyl- of the present invention
The method for producing 2,3-disubstituted succinic dianhydride is described in the following items [6] to [7]. [6] General formula (4)

Embedded image Wherein R is a monovalent organic group, R ^C is a linear or branched alkyl group having 1 to 5 carbon atoms, and bromotrichloromethane. Is reacted in the presence of a radical initiator to obtain a compound of the general formula (5)

Embedded image (Here, the definition of each symbol is the same as described above.) A trichlorobutyric acid alkyl ester derivative represented by the following formula:

Embedded image (Here, the definitions of R and R ^C are the same as above.) 2,3-di (trichloroethyl) -2,3-disubstituted alkyl succinate; the obtained ester is generally hydrolyzed Equation (7)

Embedded image (Here, the definition of R is the same as described above.)
-Dicarboxymethyl-2,3-disubstituted succinic acid;
By performing a dehydration reaction of the di-substituted succinic acid, general formula (1)

Embedded image (Here, the definition of R is the same as described above.)
-A method for producing an acid dianhydride, which comprises producing dicarboxymethyl-2,3-disubstituted succinic dianhydride.

[7] R is a straight-chain or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, cyclohexyl substituted with a straight-chain or branched alkyl having 1 to 6 carbon atoms Group, phenyl group,
A phenyl group substituted with a linear or branched alkyl having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group or a halogen atom; Method for producing anhydride.

The polyamic acid of the present invention comprises the following [8] to
This is shown in [13]. [8] A tetracarboxylic anhydride containing a 2,3-dicarboxymethyl-2,3-disubstituted succinic dianhydride according to any one of the above items [1] to [5] and a diamino compound Polyamic acid obtained by ring-opening polyaddition of

[9] The following general formulas (8) and (9)

Embedded image

Embedded image Having a structural unit represented by the formula: at the molecular terminal, an amino group, an acid anhydride group, a carboxyl group hydrolyzed by the amino group, an acid anhydride group,

Embedded image Having a structural unit represented by the general formula (8) in an amount of 5 mol% or more, and N-methyl-
In 2-pyrrolidone, concentration 0.5 g / dl, temperature 30 ±
The logarithmic viscosity number measured at 0.01 ° C. is 0.1 to 5 dl /
g is a polyamic acid, where R is a monovalent organic group; G ⁴ is a tetravalent aromatic group having 6 to 30 carbon atoms, a tetravalent aromatic group having 4 to 30 carbon atoms. G ⁵ and G ⁶ are cycloaliphatic groups, or tetravalent linear aliphatic groups having 4 to 10 carbon atoms; G ⁵ and G ⁶ are valent aliphatic groups having 2 to 12 carbon atoms, Carbon number 4-3
A divalent cyclic aliphatic group having 6 carbon atoms, a divalent aromatic group having 6 to 36 carbon atoms, or a general formula (12)

Embedded image (Wherein R ⁹⁹ is an alkyl group having 1 to 6 carbon atoms,
R ¹⁰⁰ is independently an alkyl group having 1 to 3 carbon atoms of the same or different, or a phenyl group; b, c and d are each 0 or a positive integer, and 1 ≦ b + c + d ≦ 100. And R ⁴⁵ is 1 to 1 carbon atoms.
R ⁴⁶ is an alkyl, alkenyl, or alkoxyalkyl group having 1 to 10 carbon atoms;
Or a phenyl group; Z is an alkylene group having 2 to 10 carbon atoms or a phenyl group;
It is an integer of 3. ｝.

[10] In the general formula (8), R is a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a linear or branched group having 1 to 6 carbon atoms. A cyclohexyl group substituted with a linear alkyl, a phenyl group substituted with a linear or branched alkyl having 1 to 6 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group or The polyamic acid according to the item [9], which is a halogen atom.

[11] The above-mentioned [9], wherein R in the general formula (8) is a linear or branched alkyl group having 1 to 12 carbon atoms, cyclohexyl or phenyl.
Polyamic acid according to the item.

[12] The polyamic acid according to claim 9, wherein R in the general formula (8) is a linear or branched alkyl group having 1 to 6 carbon atoms.

[13] In the general formula (8), R is -CH
_3. The polyamic acid according to the item [9], which is ₃ .

The poimide of the present invention is represented by the following item [14]. [14] A polyimide obtained by dehydrating and cyclizing the polyamic acid according to any one of [8] to [13].

The alignment film for a liquid crystal display device of the present invention is represented by the following item [15]. [15] An alignment film for a polyimide-based liquid crystal display device obtained by dehydration-cyclization of the polyamic acid according to any one of [8] to [13].

The liquid crystal display device of the present invention comprises the following [16]
To [23]. [16] The alignment film according to the above [15] is formed on the opposing surfaces of a pair of electrode substrates having display pixel electrodes formed on one or both opposing surfaces, and a liquid crystal composition is provided between the opposing alignment films. A liquid crystal display device comprising:

[17] The liquid crystal composition has the general formula (1)
4) The liquid crystal display device according to the above item [16], which is a liquid crystal composition (a) containing a component A comprising at least one compound selected from the compound group represented by (15) and (16).

Embedded image

Embedded image

Embedded image Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, in which any non-adjacent methylene group may be substituted by -O- or -CH = CH-; , Any hydrogen atom in this group may be replaced by a fluorine atom; X ¹ is F, Cl, —CF ₃ , —OCF ₃ , —O
_{CF 2 H, -CF 2 H,} -CFH 2, be a -OCF ₂ CF ₂ H or -OCF ₂ CFHCF _3; L ¹ and L ² are each independently a hydrogen atom or a fluorine atom; Z ¹ and Z ² are each independently 1,2-ethylene, _{1,4-butylene, -COO -, - CF 2 O} -, - OCF 2 -, - CH =
Ring B is trans-1,4-
Cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene or 1,4-phenylene substituted by 1 to 4 fluorine atoms; ring C is trans-
1,4-cyclohexylene; 1,4-phenylene or 1,4-phenylene substituted with 1 to 4 fluorine atoms. ｝.

[18] The liquid crystal composition has the general formula (17)
The liquid crystal display device according to the above [16], which is a liquid crystal composition (b) containing a component B consisting of at least one compound selected from the group of compounds represented by (18) and (18).

Embedded image

Embedded image Wherein R ² and R ³ are each independently 1 to 10 carbon atoms
And any non-adjacent methylene group in this group may be substituted with -O- or -CH = CH-, and any hydrogen atom in this group is a fluorine atom. X ² may be -CN or -C
≡C—CN; ring D is trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane
Ring E is trans-1,4-cyclohexylene, 1,4-phenylene, substituted with 1-4 fluorine atoms, 1,5-diyl or pyrimidine-2,5-diyl;
4-phenylene, pyrimidine-2,5-diyl;
Ring F is trans-1,4-cyclohexylene or 1,
4-phenylene; Z ³ is 1,2-ethylene, -C
OO— or a single bond; L ³ , L ⁴ and L ⁵ are each independently a hydrogen atom or a fluorine atom, and e, f and g are each independently 0 or 1. ｝.

[19] The liquid crystal composition has the general formula (1)
The liquid crystal display device according to the above item [16], which is a liquid crystal composition (c) containing a component C comprising at least one compound selected from the compound group represented by 9), (20) and (21).

Embedded image

Embedded image

Embedded image Wherein R ⁴ and R ⁵ are each independently 1 to 10 carbon atoms
And any non-adjacent methylene group in this group may be substituted with -O- or -CH = CH-, and any hydrogen atom in this group is a fluorine atom. Ring G and Ring I may each be independently trans-1,4-cyclohexylene or 1,
L ⁶ and L ⁷ are each independently a hydrogen atom or a fluorine atom, but do not represent a hydrogen atom at the same time; Z ⁴ and Z ⁵ are each independently 1,2-ethylene; —COO— or a single bond. ｝.

[20] The liquid crystal composition contains the aforementioned component A and a component D consisting of at least one compound selected from the group of compounds represented by formulas (22), (23) and (24). The liquid crystal display device according to the item [16], which is a liquid crystal composition (a1).

Embedded image

Embedded image

Embedded image Wherein R ⁶ and R ⁷ are each independently 1 to 10 carbon atoms
An arbitrary methylene group which is not adjacent to each other may be substituted with -O- or -CH = CH-, and any hydrogen atom in the group may be substituted with a fluorine atom. Rings J, K and M are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene substituted with 1 to 4 fluorine atoms or 1,4-phenylene;
Z ⁶ and Z ⁷ are each independently 1,2-ethylene, -C
≡C—, —COO—, —CH ＝ CH— or a single bond. ｝.

[21] The liquid crystal display device according to the item [16], wherein the liquid crystal composition is a liquid crystal composition (b1) containing the component B and the component D.

[22] The liquid crystal display device according to the above item [16], wherein the liquid crystal composition is a liquid crystal composition (c1) containing the component C and the component D.

[23] The liquid crystal display device according to the above item [16], wherein the liquid crystal composition is a liquid crystal composition (d) containing the component A, the component B and the component D.

[0028]

DETAILED DESCRIPTION OF THE INVENTION The 2,3-dicarboxyme of the present invention
Tyl-2,3-disubstituted succinic dianhydride has the general formula
It is a compound represented by (1). Preferred compounds are
Wherein the monovalent organic group R in the formula (1)
Straight-chain or branched alkyl group having 12 groups,
Rohexyl group, straight-chain or 1 to 6 carbon atoms
Is a cyclohexyl group substituted with a branched alkyl,
Phenyl, straight or branched chain having 1 to 6 carbon atoms
Phenyl group substituted with a branched alkyl group, alkoxy
2,3-dicarbo which is a group, a hydroxyl group or a halogen atom
Xymethyl-2,3-disubstituted succinic dianhydride.
More preferred compounds include the monovalent compound represented by the formula (1)
The substituent R is a straight-chain or straight-chain having 1 to 12 carbon atoms.
Is a branched alkyl, cyclohexyl or phenyl
2,3-dicarboxymethyl-2,3-diposition
It is a substituted succinic dianhydride. Most preferred compound
Is 2,3-dicarboxymethyl- represented by the formula (2)
2,3-dialkyl succinic dianhydride. This compound
Specific examples of the alkyl group of the product include CH_Three−, C_TwoH
_Five−, C_ThreeH₇−, C_FourH₉−, C_FiveH₁₁−, C₆H₁₃−, C₇
H_Fifteen−, C₈H₁₇−, C₉H₁₉−, C_TenH_{twenty one}−, C₁₁H_{twenty three}
−, C₁₂H_{twenty five}A linear alkyl group represented by-; (CH
_Three)_TwoCH-, (CH_Three)_TwoCHCH_Two−, (CH_Three)_TwoCH
(CH_Two)_Two−, (CH_Three)_TwoCH (CH_Two)_Three−, (C
H_Three)_TwoCH (CH_Two)_Four−, (CH_Three)_TwoCH (CH_Two)
_Five−, (CH_Three)_TwoCH (CH_Two)₆−, (CH_Three)_TwoCH
(CH_Two)₇−, (CH_Three)_TwoCH (CH_Two)₈−, (C
H_Three)_TwoCH (CH _Two)₉A branched alkyl represented by-
And the like.

The 2,3-dicarboxymethyl of the present invention
Specific examples of preferred compounds of the 2,3-disubstituted succinic dianhydride will be listed below. 2,3-dimethyl-1,2,2
3,4-butanetetracarboxylic dianhydride, 3-diethyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-dipropyl-1,2,3,4-butanetetracarboxylic acid Dianhydride, 2,3-dibutyl-1,2,2
3,4-butanetetracarboxylic dianhydride, 2,3-dipentyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-dihexyl-1,2,3,4-butanetetra Carboxylic dianhydride, 2,3-diheptyl-1,1,
2,3,4-butanetetracarboxylic dianhydride, 2,3
-Dioctyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-dinonyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-didecyl-1,2
2,3,4-butanetetracarboxylic dianhydride, 2,3
-Diundecyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-didodecyl-1,2,3,4-
Butanetetracarboxylic dianhydride,

2,3-diphenyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (4-methylphenyl) -1,2,3,4-butanetetracarboxylic dianhydride Anhydride, 2,3-bis (4-ethylphenyl)-
1,2,3,4-butanetetracarboxylic dianhydride,
2,3-bis (4-propylphenyl) -1,2,3
4-butanetetracarboxylic dianhydride, 2,3-bis (4-butylphenyl) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (4-pentylphenyl)- 1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (4-hexylphenyl) -1,
2,3,4-butanetetracarboxylic dianhydride,

2,3-dicyclohexyl-1,2,3
4-butanetetracarboxylic dianhydride, 2,3-bis (4-methylcyclohexyl) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (4-ethylcyclohexyl)- 1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (4-propylcyclohexyl) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis ( 4-butylcyclohexyl)
-1,2,3,4-butanetetracarboxylic dianhydride,
2,3-bis (4-pentylcyclohexyl) -1,
2,3,4-butanetetracarboxylic dianhydride, 2,3
-Bis (4-hexylcyclohexyl) -1,2,3,
4-butanetetracarboxylic dianhydride,

2,3-bis (1-methylethyl) -1,
2,3,4-butanetetracarboxylic dianhydride, 2,3
-Bis (2-methylpropyl) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (3-methylbutyl) -1,2,3,4-butanetetracarboxylic dianhydride , 2,3-bis (4-methylpentyl) -1,
2,3,4-butanetetracarboxylic dianhydride, 2,3
-Bis (5-methylhexyl) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (6-methylheptyl) -1,2,3,4-butanetetracarboxylic dianhydride Anhydride, 2,3-bis (7-methyloctyl)-
1,2,3,4-butanetetracarboxylic dianhydride,
2,3-bis (8-methylnonyl) -1,2,3,4-
Butanetetracarboxylic dianhydride, 2,3-bis (9-
(Methyldecyl) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (10-methylundecyl) -1,2,3,4-butanetetracarboxylic dianhydride,

2,3-dimethoxy-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-diethoxy-
1,2,3,4-butanetetracarboxylic dianhydride,
2,3-dipropoxy-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-dibutoxy-1,2,2
3,4-butanetetracarboxylic dianhydride, 2,3-diphenoxy-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-diisobutoxy-1,2,3,4-
Butanetetracarboxylic dianhydride, 2,3-bis (4-
Methylphenoxy) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (4-ethylphenoxy) -1,2,3,4-butanetetracarboxylic dianhydride,

2,3-difluoro-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-dichloro-
1,2,3,4-butanetetracarboxylic dianhydride,
2,3-dibromo-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-diiodo-1,2,3,4-
Butanetetracarboxylic dianhydride, 3-bis (4-fluorophenyl) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (4-chlorophenyl)-
1,2,3,4-butanetetracarboxylic dianhydride,
2,3-bis (4-bromophenyl) -1,2,3,4
-Butanetetracarboxylic dianhydride, 2,3-bis (4
-Iodophenyl) -1,2,3,4-butanetetracarboxylic dianhydride,

2,3-dihydroxy-1,2,3,4-
Butanetetracarboxylic dianhydride, 2,3-bis (4-
(Hydroxyphenyl) -1,2,3,4-butanetetracarboxylic dianhydride.

Preferred compounds are as follows. 2,3-dimethyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-diethyl-1,2,2
3,4-butanetetracarboxylic dianhydride, 2,3-dipropyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-dibutyl-1,2,3,4-butanetetra Carboxylic dianhydride, 2,3-dipentyl-1,
2,3,4-butanetetracarboxylic dianhydride, 2,3
-Dihexyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-diheptyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-dioctyl-
1,2,3,4-butanetetracarboxylic dianhydride,
2,3-dinonyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-didecyl-1,2,3,4-
Butanetetracarboxylic dianhydride, 2,3-diundecyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-didodecyl-1,2,3,4-butanetetracarboxylic dianhydride object,

2,3-bis (1-methylethyl) -1,
2,3,4-butanetetracarboxylic dianhydride, 2,3
-Bis (2-methylpropyl) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (3-methylbutyl) -1,2,3,4-butanetetracarboxylic dianhydride , 2,3-bis (4-methylpentyl) -1,
2,3,4-butanetetracarboxylic dianhydride, 2,3
-Bis (5-methylhexyl) -1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (6-methylheptyl) -1,2,3,4-butanetetracarboxylic dianhydride Anhydride, 2,3-bis (7-methyloctyl)-
1,2,3,4-butanetetracarboxylic dianhydride,
2,3-bis (8-methylnonyl) -1,2,3,4-
Butanetetracarboxylic dianhydride, 2,3-bis (9-
Methyldecyl) -1,2,3,4-butanetetracarboxylic dianhydride and 2,3-bis (10-methylundecyl) -1,2,3,4-butanetetracarboxylic dianhydride.

Among these, more preferred are 2,3-dimethyl-1,2,3,4-butanetetracarboxylic dianhydride and 2,3-diethyl-1,2,3,3.
4-butanetetracarboxylic dianhydride, 2,3-dipropyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-dibutyl-1,2,3,4-butanetetracarboxylic acid Dianhydride, 2,3-dipentyl-1,2,2
3,4-butanetetracarboxylic dianhydride, 2,3-dihexyl-1,2,3,4-butanetetracarboxylic dianhydride, 2,3-bis (1-methylethyl) -1,2,2
3,4-butanetetracarboxylic dianhydride and 2,3-bis (2-methylpropyl) -1,2,3,4-butanetetracarboxylic dianhydride can be mentioned. The 2,3-dicarboxymethyl-2,3-disubstituted succinic dianhydride of the present invention contains a syn-anti isomer, but an anti-isomer is preferred.

The method for producing an acid anhydride of the present invention comprises reacting the alkyl ester of 2-substituted propenoic acid represented by the general formula (4) with bromotrichloromethane in the presence of a radical initiator. A trichlorobutyric acid alkyl ester derivative represented by the formula (5); this derivative is reacted with activated copper powder or light to obtain a 2,3-di (trichloroethyl)-compound represented by the general formula (6).
2,3-disubstituted alkyl succinic acid ester; obtained ester is hydrolyzed to 2,3-dicarboxymethyl-2,3-disubstituted succinic acid represented by the above general formula (7); By performing a dehydration reaction of succinic acid, 2,3-dicarboxymethyl- represented by the general formula (1) is obtained.
It is characterized by producing 2,3-disubstituted succinic dianhydride.

The 2-substituted propenoic acid alkyl ester represented by the general formula (4) used in this production method can be synthesized by a known method or purchased as a commercial product. Specific compounds include methyl methacrylate, methyl 2-ethylpropenoate, methyl 2-propylpropenoate,
Methyl butylpropenoate, methyl 2-pentylpropenoate, methyl 2-hexylpropenoate, methyl 2-heptylpropenoate, methyl 2-octylpropenoate, methyl 2-nonylpropenoate, methyl 2-decylpropenoate,
Methyl 2-undecylpropenoate, methyl 2-dodecylpropenoate,

Ethyl methacrylate, ethyl 2-ethylpropenoate, ethyl 2-propylpropenoate, ethyl 2-butylpropenoate, ethyl 2-pentylpropenoate, 2
-Ethyl hexylpropenoate, ethyl 2-heptylpropenoate, ethyl 2-octylpropenoate, ethyl 2-nonylpropenoate, ethyl 2-decylpropenoate, ethyl 2-undecylpropenoate, ethyl 2-dodecylpropenoate,

T-butyl methacrylate, t-butyl 2-ethylpropenoate, t-butyl 2-propylpropenoate, t-butyl 2-butylpropenoate, t-butyl 2-pentylpropenoate, 2-hexylpropenoic acid t-butyl, t-butyl 2-heptylpropenoate, t-butyl 2-octylpropenoate, t-butyl 2-nonylpropenoate, t-butyl 2-decylpropenoate, t-butyl 2-undecylpropenoate, T-butyl 2-dodecylpropenoate,

Methyl 2-phenylpropenoate, 2- (4
Methyl- (methylphenyl) propenoate, methyl 2- (4-ethylphenyl) propenoate, methyl 2- (4-propylphenyl) propenoate, methyl 2- (4-butylphenyl) propenoate, 2- (4-pentyl) Phenyl)
Methyl propenoate, methyl 2- (4-hexylphenyl) propenoate,

Ethyl 2-phenylpropenoate, 2- (4
-Methylphenyl) ethyl propenoate, ethyl 2- (4-ethylphenyl) propenoate, ethyl 2- (4-propylphenyl) propenoate, ethyl 2- (4-butylphenyl) propenoate, 2- (4-pentyl) Phenyl)
Ethyl propenoate, ethyl 2- (4-hexylphenyl) propenoate,

T-butyl 2-phenylpropenoate, 2-
T-butyl (4-methylphenyl) propenoate, 2-
T-butyl (4-ethylphenyl) propenoate, 2-
T-butyl (4-propylphenyl) propenoate, 2-
T-butyl (4-butylphenyl) propenoate, 2-
(4-pentylphenyl) t-butyl propenoate, 2-
T-butyl (4-hexylphenyl) propenoate,

Methyl 2-cyclohexylpropenoate, 2
Methyl- (4-methylcyclohexyl) propenoate, 2
Methyl- (4-ethylcyclohexyl) propenoate, 2
Methyl- (4-propylcyclohexyl) propenoate,
Methyl 2- (4-butylcyclohexyl) propenoate,
Methyl 2- (4-cyclohexylphenyl) propenoate, methyl 2- (4-cyclohexylphenyl) propenoate,

Ethyl 2-cyclohexylpropenoate, 2
Ethyl- (4-cyclohexylphenyl) propenoate,
Ethyl 2- (4-cyclohexylphenyl) propenoate, ethyl 2- (4-cyclohexylphenyl) propenoate, ethyl 2- (4-butylcyclohexyl) propenoate, ethyl 2- (4-pentylcyclohexyl) propenoate, (4-hexylcyclohexyl) ethyl propenoate,

T-butyl 2-cyclohexylpropenoate, t-butyl 2- (4-methylcyclohexyl) propenoate
Butyl, t-butyl 2- (4-ethylhexyl) propenoate, t-butyl 2- (4-propylcyclohexyl) propenoate, t-butyl 2- (4-butylcyclohexyl) propenoate, 2- (4-pentylcyclohexyl) )
T-butyl propenoate, t-butyl 2- (4-hexylcyclohexyl) propenoate,

Methyl 2- (2-methylpropyl) propenoate, methyl 2- (3-methylbutyl) propenoate, 2
Methyl- (4-methylpentyl) propenoate, 2- (5
Methyl-methylhexyl) propenoate, methyl 2- (5-methylheptyl) propenoate, methyl 2- (6-methyloctyl) propenoate, methyl 2- (7-methylnonyl) propenoate, 2- (8-methyldecyl) Methyl propenoate, methyl 2- (9-methylundecyl) propenoate,

Ethyl 2- (2-methylpropyl) propenoate, ethyl 2- (3-methylbutyl) propenoate, 2
Ethyl- (4-methylpentyl) propenoate, 2- (5
Ethyl-methylhexyl) propenoate, ethyl 2- (5-methylheptyl) propenoate, ethyl 2- (6-methyloctyl) propenoate, ethyl 2- (7-methylnonyl) propenoate, 2- (8-methyldecyl) Ethyl propenoate, ethyl 2- (9-methylundecyl) propenoate,

2- (2-methylpropyl) propenoic acid t
-Butyl, t-butyl 2- (3-methylbutyl) propenoate, t-butyl 2- (4-methylpentyl) propenoate, t-butyl 2- (5-methylhexyl) propenoate, 2- (5-methyl Tert-butyl heptyl) propenoate, t-butyl 2- (6-methyloctyl) propenoate, t-butyl 2- (7-methylnonyl) propenoate,
T-butyl 2- (8-methyldecyl) propenoate, 2-
(9-methylundecyl) t-butyl propenoate and the like can be mentioned.

The following are examples of the radical initiator used in the method for producing an acid dianhydride of the present invention. Azobisisobutyronitrile (AIBN), azobis-2,
4-dimethylvaleronitrile, benzoyl peroxide, tertiary butyl peroxide, tertiary butyl hydroperoxide, potassium peroxide, or hydrogen peroxide called a redox initiator (peroxide and reducing agent) and ferrous salt or peroxide Sulfate and ferrous salts, benzoyl peroxide and dimethylaniline, etc. are used.
BN is good.

In the method for producing an acid dianhydride of the present invention,
The reaction of the alkyl trichlorobutyrate derivative represented by the general formula (5) with light was carried out by heating to 60 ° C. and irradiating a pyrex transmitted light with a 100 w mercury lamp for 24 hours while stirring in a solvent under a nitrogen atmosphere. . In addition, the reaction with activated copper powder is performed by adding activated copper powder to a solvent,
This is carried out by reacting the derivative. In the method for producing an acid dianhydride of the present invention, the hydrolysis of the alkyl ester of 2,3-di (trichloroethyl) -2,3-disubstituted succinic acid represented by the general formula (6) is carried out by an acid such as concentrated sulfuric acid. At room temperature. In the method for producing an acid dianhydride of the present invention, 2,2 represented by the general formula (7)
The dehydration reaction of the 3-dicarboxymethyl-2,3-disubstituted succinic acid can be performed at room temperature using acetic anhydride or the like.

The polyamic acid of the present invention comprises the above [1] to
It is obtained by ring-opening polyaddition of a tetracarboxylic acid containing a 2,3-dicarboxymethyl-2,3-disubstituted succinic dianhydride according to any one of the items [5] and a diamino compound. That is, it is obtained by condensation of an acid dianhydride represented by the general formula (1) with a diamino compound or co-condensation of an acid dianhydride represented by the general formula (1) and another acid anhydride with a diamino compound. Can be. Preferred acid dianhydrides represented by the general formula (1) are the same as the acid dianhydrides of the present invention. These may be used alone or in combination of two or more.

The other acid anhydride used for the condensation is not particularly limited. For example, a tetracarboxylic anhydride having a skeleton represented by G ⁴ in the general formula (9) can be used. That is, G ⁴ is a tetravalent residue having 4 to 30 carbon atoms excluding the carboxyl group of the acid dianhydride of the present invention, and G ⁴ is 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms.
, More preferably 6 to 12 tetravalent aromatic groups, 4 to 30 carbon atoms, preferably 4 to 12, more preferably 4 to 6 tetravalent cyclic aliphatic groups, Or a tetravalent linear aliphatic group having 4 to 10, preferably 4 to 8, and more preferably 4 to 6 carbon atoms.

Specific examples of the tetracarboxylic anhydride having a skeleton represented by G ⁴ include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid Dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, bis (3,4 dicarboxyphenyl) Ether dianhydride, bis (3,4-dicarboxyphenyl)
Aromas such as sulfone dianhydride, 1,2,5,6 naphthalenetetracarboxylic dianhydride, 2,3,6,7 naphthalenetetracarboxylic dianhydride, bis (dicarboxyphenyl) methane dianhydride Aliphatic tetracarboxylic anhydride; cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, dicyclohexanetetracarboxylic dianhydride, dicyclopentanetetracarboxylic dianhydride Cyclic aliphatic tetracarboxylic anhydrides such as, bis (dicarboxycyclohexyl) ether dianhydride, bis (dicarboxycyclohexyl) sulfone dianhydride and bis (dicarboxycyclohexyl) methane dianhydride; 1,2,7, 8-
Octanetetracarboxylic dianhydride, 1,2,8,9-
Nonanetetracarboxylic dianhydride, 1,2,9,10-
Aliphatic tetracarboxylic anhydrides such as decanetetracarboxylic dianhydride;

Further, the following equation

Embedded image (Where a is an integer of 1 to 4).

Some of the above tetracarboxylic anhydrides contain isomers, but a mixture of these isomers may be used. Further, two or more compounds may be used in combination. Further, it is not necessary to limit the tetracarboxylic dianhydride according to the present invention to the above exemplified compounds.

Similarly, diamino compounds used for cocondensation are not particularly limited, but diamino compounds having a skeleton represented by G ⁵ and G ⁶ in the general formulas (8) and (9) can be used. G ⁵ and G ⁶ are divalent residues of an aliphatic compound having 2 to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, which are the same or different, and having 4 to 36 carbon atoms; Preferably a divalent residue of a cycloaliphatic compound having 4 to 12, more preferably 4 to 6, having 6 to 36, preferably 6 to 24, more preferably 6 to 12 carbon atoms It is a divalent residue of an aromatic compound or a polysiloxane group represented by the general formula (12).

Specific examples of the diamino compound having a divalent group represented by G ⁵ and G ⁶ include the following. Trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4-
Aliphatic diamines such as dimethylheptamethylenediamine and 2,11-dodecanediamine; 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, Alicyclic diamines such as 4,4'-diamino-3,3'-dimethyldicyclohexyl; bis (4
-Aminophenyl) ether, bis (4-aminophenyl) methane, bis (4-amino-3-methylphenyl)
Methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-aminophenyl) sulfone,
Bis (4-aminophenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, 2,
2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, 1,2-diaminobenzene, 1,3-
Diaminobenzene, 1,4-diaminobenzene, 1,4
-Diamino-2-butylbenzene, 1,4-diamino-
2-dodecyloxybenzene, benzidine, 2,2'-diaminobenzophenone, 4,4'diaminobenzophenone, 2,2-bis (4-aminophenyl) propane,
1,5-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4′-diamino-3-octyldiphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) -1,1,1,3,3 3-hexafluoropropane, 4,4′-bis (4-aminophenoxy) biphenyl, 1,2-bis (4-aminophenyl) ethane,
1,2-bis (4-amino-2-methylphenyl) ethane, 1,1-bis (4- (4-aminophenoxy) phenyl) cyclohexane, 1,1-bis (4- (4-aminophenoxy) phenyl) -4-propylcyclohexane 1,1-bis (4- (4-aminobenzyl) phenyl) cyclohexane, 1,3-bis (4- (4-aminobenzyl) phenyl) propane, 1,4-bis (4-aminophenoxy) benzene, bis-p-aminophenylaniline Aromatic diamines such as: Some of these compounds contain isomers, but a mixture of these isomers may be used.

Specific examples of the diamino compound having a polysiloxane group represented by the general formula (12) include:

[0062]

Embedded image (Where b, c, and d are integers of 1 or more).

These diamino compounds having divalent groups G ⁵ and G ⁶ may be used in combination of two or more compounds. Further, the diamino compound used in the present invention does not need to be limited to the above exemplified compounds.

The group represented by the general formula (10) which forms the molecular end of the polyamic acid according to the present invention is represented by the general formula (1)
It is a residue of a primary amine of an aminosilicon compound having a group represented by 0). Specific examples of the amino silicon compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 3-aminopropyltris ( 2-methoxyethoxy) silane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethylmethyldimethoxysilane, 2-aminoethylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4- Aminophenyltrimethoxysilane, 4-aminophenyltriethoxysilane, 4-
Aminophenylmethyldimethoxysilane, 4-aminophenylmethyldiethoxysilane, 4-aminophenyltris (2-methoxyethoxy) silane, 3- (4-aminophenyl) propyltrimethoxysilane, 3- (4-
(Aminophenyl) propyltriethoxysilane, 3-aminophenyltrimethoxysilane, 3-aminophenyltriethoxysilane, 3- (4-aminophenyl) propylmethyldimethoxysilane, 3- (4-aminophenyl) propylmethyldiethoxysilane , 3-aminophenylmethyldimethoxysilane, 3-aminophenylmethyldiethoxysilane, and the like.

The polyamic acid of the present invention can be prepared by converting the above-mentioned diamine and tetracarboxylic anhydride or the above-mentioned diamine, tetracarboxylic acid and the above diamino compound in the presence of a known solvent such as N-methyl-2-pyrrolidone. Can be obtained in a way. The amount of the acid dianhydride of the present invention represented by the general formula (1) in this reaction is at least 5 mol%, preferably at least 10 mol%, based on the total acid anhydride. The amount of the polysiloxane group-containing diamine represented by the general formula (12) is 50 mol% of the total diamine.
Or less, preferably 30 mol% or less, more preferably 10 mol% or less.
Mol% or less. Further, the content of the aminosilicon compound is preferably not more than 30 mol% of all the raw materials, more preferably 10 mol%.
Mol% or less. These raw materials may be subjected to random copolymerization, block copolymerization (co-condensation), or a mixture of polyamides co-condensed with different compositions.

The polyimide and the liquid crystal alignment film of the present invention
It can be formed by applying a polyamic acid synthesized by the above-described method on a substrate and performing a heat treatment. The alkoxysilane group represented by the general formula (10) at the terminal of the polyamic acid undergoes a condensation reaction between adjacent alkoxysilanes to form a three-dimensional polymer. Further, the polyimide and the liquid crystal alignment film of the present invention will be specifically described. Polyamide acid is N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DM
F), dissolved in a solvent such as dimethyl sulfoxide (DMSO), ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, etc. to prepare a 0.1 to 30% by weight solution, preferably a 1 to 10% by weight solution, and brush the solution. Method, dipping method, spin coating method, spray method,
Apply to the substrate by printing method, etc., and after drying, 50 ~ 15
After evaporating the solvent at 0 ° C, preferably 80-120 ° C,
A heat treatment is performed at 160 ° C. to 280 ° C., and a dehydration ring-closing reaction is performed to provide a polyimide-based film. In this case, this film does not necessarily have to have 100% imidation of the polyamic acid, and can be used depending on the application even with imidization of about 50 mol%. Before the application, the surface of the substrate is treated with a silane coupling agent, and a polyimide-based film is formed thereon, whereby the adhesion between the film and the substrate can be improved. The coated surface is rubbed in one direction with a cloth or the like to obtain a liquid crystal alignment film.

The liquid crystal display device of the present invention is manufactured by the following method. That is, an electrode (specifically, a transparent electrode of ITO (indium oxide-tin oxide) or tin oxide) is formed on a substrate such as glass, and the liquid crystal alignment film is formed on the electrode. Each of the plates is held at a fixed interval with the alignment film inside, and the periphery is sealed with an epoxy resin or the like to form a cell. Thereafter, the liquid crystal composition according to the present invention is injected into the cell, the injection port is sealed, and the cell is gradually cooled to produce a liquid crystal display device.
Alternatively, the liquid crystal composition according to the present invention is sprayed on the electrodes and the alignment films of the two plates on which the alignment films are formed and overlapped, and the liquid crystal composition is sealed so as not to leak to produce a liquid crystal display device. You may. Further, characters, graphics, color filters, and the like may be printed outside the cell as necessary, or a polarizing plate, a reflector, lighting, and the like may be arranged. Here, an undercoat film such as an insulating film for preventing alkali elution from the substrate, a color filter, and a color filter overcoat may be provided between the electrode and the substrate. An overcoat film such as a filter film may be provided. When the two plates are held at a fixed interval, a gap agent is usually sprayed to maintain a cell gap. As the gap agent, glass beads, silica, alumina, spherical particles of synthetic resin, and the like are used.

The liquid crystal composition used in the liquid crystal display device of the present invention is prepared by mixing compounds selected from the group of compounds represented by formulas (14) to (24) according to the purpose of the liquid crystal composition. I do. Further, a known compound may be mixed for the purpose of adjusting the threshold voltage, the liquid crystal phase temperature range, the refractive index anisotropy, the dielectric anisotropy and the viscosity.
Further, the atoms constituting these compounds may be substituted with their isotopes.

The following compounds can be mentioned as examples of the component A of the liquid crystal composition used in the liquid crystal display device of the present invention, that is, the compounds represented by the general formulas (14) to (16).

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image (In the formula, R ¹ and X ¹ have the same meaning as described above.)

The compound represented by the general formulas (14) to (16), that is, the component A is a compound having a positive dielectric anisotropy value, and has very excellent thermal stability and chemical stability. ,
In particular, it is a very useful compound when preparing a liquid crystal composition for a TFT that requires high reliability such as a high voltage holding ratio or a large specific resistance value.

The content of the component A of the liquid crystal composition used in the liquid crystal display device of the present invention is 0.1 to 99.9% by weight based on the total weight of the liquid crystal composition when preparing a liquid crystal composition for TFT. %, Preferably 10-97% by weight, more preferably 4%
0 to 95% by weight. Further, component D, that is, the compounds represented by the general formulas (22) to (24), may be further contained for the purpose of adjusting the viscosity. When preparing a liquid crystal composition for STN or TN, this component A can be contained, but the content is preferably 50% by weight or less based on the total amount of the composition.

Preferred examples of the component B of the liquid crystal composition used in the liquid crystal display device of the present invention, that is, the compounds represented by the general formulas (17) and (18) include the following compounds.

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image (In the formula, R ² , R ³ and X ² have the same meaning as described above.)

Component B, that is, the general formulas (17) and (1)
The compound represented by 8) has a large positive dielectric anisotropy value, and is particularly used for the purpose of reducing the threshold voltage of the liquid crystal composition. It is also used for the purpose of adjusting the value of the refractive index anisotropy and expanding the nematic range such as increasing the clearing point. Further, it is used for the purpose of improving the steepness of the voltage-transmittance characteristic of the liquid crystal composition for STN or TN.
This component B is a particularly useful compound when preparing a liquid crystal composition for STN and TN. When the component B increases in the liquid crystal composition, the threshold voltage of the liquid crystal composition decreases, but the viscosity increases. Therefore, as long as the viscosity of the liquid crystal composition satisfies the required value, it is more advantageous to use a large amount of the liquid crystal composition because it can be driven at a low voltage.

In preparing a liquid crystal composition for STN or TN, the content of the component B of the liquid crystal composition used in the liquid crystal display device of the present invention is 0.1 to 9 with respect to the total amount of the composition.
It is 9.9% by weight, preferably 10 to 97% by weight, more preferably 40 to 95% by weight. Component B in the liquid crystal composition
Increases, the threshold voltage of the liquid crystal composition decreases, but the viscosity increases. Therefore, as long as the viscosity of the liquid crystal composition satisfies the required value, it is advantageous to use a large amount of the liquid crystal composition because it can be driven at a low voltage.

Preferred examples of the component C of the liquid crystal composition used in the liquid crystal display device of the present invention, that is, the compounds represented by the general formulas (19) to (21) include the following compounds.

[0089]

Embedded image (In the formula, R ⁴ and R ⁵ have the same meaning as described above.)

Component C, that is, the general formulas (19) to (21)
Is a compound having a negative dielectric anisotropy value. Since the compound represented by the general formula (19) is a bicyclic compound, it is used mainly for the purpose of adjusting the threshold voltage, adjusting the viscosity or adjusting the refractive index anisotropy value. The compound represented by the general formula (20) is used for the purpose of expanding the nematic range such as increasing the clearing point or adjusting the value of the refractive index anisotropy. The compound represented by the general formula (21) is used for the purpose of increasing the nematic range, reducing the threshold voltage, and increasing the refractive index anisotropy value. It is mainly used for a liquid crystal composition having a negative dielectric anisotropy value.

The content of the component C of the liquid crystal composition used in the liquid crystal display device of the present invention is determined by using a TFT having a negative dielectric anisotropy value.
When preparing a composition for use, the total amount of the composition is 40%.
% By weight or more, more preferably 50 to 95% by weight. In some cases, the component C is mixed with a composition having a positive dielectric anisotropy value for the purpose of controlling the elastic constant and controlling the voltage-transmittance curve of the composition. In this case, the content is preferably 30% by weight or less. When the content of the component C increases, the threshold voltage of the composition decreases and the viscosity increases. Therefore, it is desirable to reduce the content as long as the required value of the threshold voltage is satisfied. However, since the absolute value of the dielectric anisotropy is 5 or less, if it is less than 40% by weight, voltage driving may not be performed in some cases.

Preferred examples of the component D of the liquid crystal composition used in the liquid crystal display device of the present invention, that is, the compounds represented by the general formulas (22) to (24) include the compounds represented by the following general formulas.

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image (In the formula, R ⁶ and R ⁷ have the same meaning as described above.)

Component D, that is, the general formulas (22) to (24)
The compound represented by has a small absolute value of dielectric anisotropy,
It is a nearly neutral compound. The compound represented by the general formula (22) is mainly used for adjusting the viscosity or adjusting the value of the refractive index anisotropy. Further, the general formulas (23) and (2)
The compound represented by 4) is used for the purpose of widening the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value.

In preparing a liquid crystal composition for a TFT, the content of the component D in the liquid crystal composition used in the liquid crystal display device of the present invention is preferably 40% by weight based on the total amount of the composition.
Or less, more preferably 35% by weight or less. Also, S
When preparing TN or a liquid crystal composition for TN, the content is preferably 70% by weight or less, more preferably 60% by weight or less. When the content of the component D increases, the threshold voltage of the liquid crystal composition increases, and the viscosity decreases. Therefore, it is desirable to use a large amount as long as the threshold voltage of the liquid crystal composition satisfies the required value.

In the liquid crystal display device of the present invention, OCB
(Optically Compensated Bi
Except for a special case such as a liquid crystal composition for a refrence mode, a helical structure of the liquid crystal composition is induced to adjust a required twist angle, and a reverse twist is obtained.
For the purpose of preventing wis), an optically active compound is usually added. For this purpose, any known optically active compound can be used. Preferred examples include the optically active compounds represented by the following formulas.

[0100]

Embedded image

The liquid crystal composition used in the liquid crystal display device of the present invention is usually added with these optically active compounds to adjust the twist pitch. The twist pitch is preferably adjusted in the range of 40 to 200 μm for a liquid crystal composition for TFT and TN. In the case of a liquid crystal composition for STN, it is preferable to adjust the composition to a range of 6 to 20 μm. In the case of a bistable TN (Bistable TN) mode, it is preferable to adjust the thickness to a range of 1.5 to 4 μm. Further, two or more optically active compounds may be added for the purpose of adjusting the temperature dependency of the pitch.

The liquid crystal composition used in the liquid crystal display device of the present invention can be prepared by a commonly used method such as a method in which various components are dissolved at a high temperature. Further, the liquid crystal display device of the present invention is improved and optimized by adding an appropriate additive to the liquid crystal composition according to the intended use. Such additives are well known to those skilled in the art and are described in detail in the literature and the like. In general, a necessary twist angle is adjusted by inducing a helical structure of the liquid crystal, and a chiral dopant for preventing reverse twist is added.

The range of the liquid crystal display device of the present invention includes a merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone and tetrazine compound in a liquid crystal composition used for the display device. Guest-host (GH) mode liquid crystal display device by including a dichroic dye such as NCAP; NCAP prepared by microencapsulation of a nematic liquid crystal; formed by forming a three-dimensional network polymer in the liquid crystal Polymer dispersed liquid crystal display (PDLCD) represented by polymer network liquid crystal display (PNLCD), including birefringence control (ECB) mode and dynamic scattering (DS) mode liquid crystal display It is.

The polyamic acid obtained by ring-opening polyaddition of the acid dianhydride of the present invention and various diamino compounds is subjected to a thermal treatment,
A polyimide or an alignment film for a polyimide-based liquid crystal display element having excellent alignment properties can be obtained by a dehydration cyclization reaction such as an acid treatment or a chemical treatment with pyridine or acetic anhydride.

The polyimide of the present invention can be used for various polyimide coating agents, polyimide resin molded products, films, fibers, etc., in addition to the alignment film for liquid crystal process elements.

[0106]

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

Example 1 Preparation of 2,3-dimethyl-1,2,3,4-tetracarboxylic dianhydride (a) t-butyl 2-bromo-4,4,4-trichloro-2-methylbutyrate Preparation of t-butyl methacrylate in a four-necked flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet.
42 g (1 mol) and 15 of bromotrichloromethane
84 g (8 mol) and 4.1 g (0.025 mol) of azobisisobutyronitrile (AIBN) were added, and 9
The reaction was performed at 0 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, unreacted bromotrichloromethane was removed by a rotary evaporator, and the residue was dissolved in toluene. After separation by silica gel column chromatography using this toluene solution, distillation under reduced pressure (bp 98-99 ° C / 2T)
orr. )) 2-Bromo-4,4,4-trichloro-2
142 g (yield 42%) of t-butyl-methylbutyrate was obtained.

(B) Preparation of di-tert-butyl 2,3-dimethyl-2,3-di (2,2,2-trichloroethyl) succinate A stirrer, thermometer, condenser and nitrogen gas inlet were attached. In a four-necked flask, 150 g (44 g) of t-butyl 2-bromo-4,4,4-trichloro-2-methylbutyrate was added.
1 mmol), 750 ml of methanol was poured, 37 g (582 mmol) of activated copper powder was added, and the mixture was stirred at 30 ° C. for 48 hours. After the reaction, the precipitate collected by filtration was subjected to Soxhlet extraction using toluene, while the filtrate was concentrated with a rotary evaporator,
The residue was dissolved in a mixed solvent of carbon tetrachloride / benzene = 3/1, subjected to silica gel chromatography using this solvent, and purified by recrystallization using hexane to give 2,3-dimethyl-2,3. -Di (2,2,2-trichloroethyl)
23 g (20% yield) of di-t-butyl succinate was obtained.

(C) Synthesis of 2,3-dimethyl-2,3-dicarboxyadipic acid In a three-necked flask equipped with a stirrer, a thermometer and a condenser, 2,3-dimethyl-2,3-di (2,3-dicarboxyadipic acid) was added. 2,2
-Trichloroethyl) di-t-butyl succinate 20.8
A mixed solvent of acetic acid / water = 3 liter / 4.8 liter was poured into g (40 mmol), 140 ml of concentrated sulfuric acid was added, and the mixture was reacted for 120 hours in a heated reflux state. After completion of the reaction, the solvent was distilled off, and extracted with ether.
5.86 g of dimethyl-2,3-dicarboxyadipic acid
(56% yield).

(D) 2,3-dimethyl-1,2,3
Synthesis of 4-tetracarboxylic dianhydride To a three-necked flask equipped with a stirrer, a thermometer and a condenser, 5.24 g (20 mmol) of 2,3-dimethyl-2,3-dicarboxyadipic acid was added, and acetic anhydride was added. 400 ml was poured and stirred at room temperature for 30 minutes. After completion of the stirring, the solvent was distilled off to dryness, followed by sublimation purification (180 ° C./2 Torr) to give 2,3-dimethyl-
4.42 g of 1,2,3,4-tetracarboxylic dianhydride
(98% yield).

Example 2 Dehydrated and purified N-methyl-2 was placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen purging apparatus.
25.5 g (0.26 mol) of pyrrolidone, then 4
2.00 g (10 mmol) of 4'-diaminodiphenyl ether was added and dissolved by stirring under a stream of dry nitrogen. While maintaining the temperature of the reaction system at 5 to 70 ° C, 2,3-dimethyl-
2.26 g of 1,2,3,4-tetracarboxylic dianhydride
(10 mmol), and the mixture was reacted for 5 to 30 hours. Then, a solvent of γ-butyl lactone: butyl cellosolve = 1: 1 was added to synthesize a polyamic acid having a polymer concentration of 6%.

Example 3 The polyamic acid solution selected in Example 2 was coated on one side with ITO.
A spin coating method (spinner method) was applied on a transparent glass substrate provided with electrodes under the following conditions, followed by drying and heating to obtain a polyimide film having a thickness of about 60 nm. (Rotation coating condition: 5000 rpm, 15 seconds, drying condition: 10 minutes after coating)
After drying at 0 ° C. for 10 minutes, 200 hours in an oven for 1 hour.
Heating is performed to 200 ° C. for 90 minutes. )

Example 4 The rubbing treatment was applied to each of the coating surfaces of the two substrates on which the polyimide-based films obtained in accordance with Example 3 were formed to form liquid crystal alignment films. No scraping or peeling of the film during rubbing was observed.

Example 5 A liquid crystal alignment film was formed in the same manner as in Example 3 on a glass substrate in which a transparent electrode having a width of 0.01 mm was laid down in a stripe shape with a width of 0.01 mm. No scraping or peeling of the film during rubbing was observed. Two substrates on which the liquid crystal alignment film is formed are prepared, and the alignment process in each liquid crystal alignment film, that is, the two substrates are set to have a cell gap of 9 microns so that the rubbing direction is perpendicular or antiparallel. The liquid crystal cell was assembled. In this cell, a liquid crystal for TFT {Liquid Crystal FB01 (Chisso Corporation) (equivalent mixture of the following compounds)}

Embedded image Was enclosed. After the encapsulation, an isotropic treatment was performed at 120 ° C. for 30 minutes, and the resultant was gradually cooled to room temperature to obtain a liquid crystal display device.
Observation of this liquid crystal display element with a polarizing microscope revealed no defects and the orientation was good. In the evaluation of the burn-in phenomenon, there was no delay between the electrodes at the time of ON-OFF, and the display quality was excellent.

The degree of the burn-in phenomenon was evaluated by the following method. In this liquid crystal element, since the transparent electrodes on the upper and lower substrates are orthogonal to each other when viewed from above, there are portions without electrodes above and below. After applying 5 V DC to the liquid crystal element for 3 hours, the electrodes are short-circuited. This element is driven by an alternating current of 4 V and 0.01 Hz while observing with a microscope. When image sticking occurs, the liquid crystal in the portion without electrodes cannot follow the voltage, so that the portion without electrodes above and below has a delay in the rise of the liquid crystal as compared with the electrode portions. In other words, it can be said that the longer the delay time of lighting is, the more the portion without electrodes on the upper and lower sides is burned in compared with the portion with electrodes.

[0116]

Industrial Applicability The novel acid dianhydride of the present invention provides a polyamic acid or polyimide having excellent performance for use in a liquid crystal alignment film. The liquid crystal alignment film of the present invention made of a polyamic acid or a polyimide does not peel off or scrape the alignment film when a rubbing treatment is performed. Furthermore, the present invention does not cause panel defects due to poor orientation, and does not cause a so-called burn-in phenomenon in which a previous image remains as an afterimage when the same screen is displayed for a long time and then moved to another screen. Provide an excellent liquid crystal display device. The acid dianhydride of the present invention is designed mainly for a raw material intermediate of a liquid crystal alignment film, but can also be used for other polymer compounds such as polyimide and its modification, and an epoxy crosslinking agent It can be expected to be used for other purposes such as, and to introduce new properties into polymer compounds.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2H090 HB08Y HB10Y HC06 HD14 KA04 MB01 4C037 KA02 KA04 KA05 KA06 KA10 4J043 PA04 PA08 PA09 PA19 PB19 PC015 PC035 PC115 QB15 QB26 QB31 RA35 SA05 SA06 SA42 SA01 TA02 TA02 SB TA43 TA46 TA47 TA67 TA70 TA71 TB01 TB02 UA022 UA032 UA041 UA042 UA052 UA062 UA082 UA121 UA122 UA131 UA132 UA141 UA151 UA261 UA262 UA632 UA662 UA672 UA761 UA762 UA771 UA772 UB011 UB012 UB021 UB061 UB121 UB122 UB131 UB151 UB152 UB281 UB301 UB302 UB352 UB401 UB402 VA011 VA012 VA021 VA022 VA031 VA041 VA051 VA062 VA091 VA092 VA101 VA102 WA09 WA16 XA16 YA06 ZB23

Claims (23)

[Claims] 1. A compound of the general formula (1) Wherein R is a monovalent organic group.
-Dicarboxymethyl-2,3-disubstituted succinic dianhydride. 2. In the general formula (1), R is a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a linear or branched group having 1 to 6 carbon atoms. A cyclohexyl group, a phenyl group, a linear or branched alkyl-substituted phenyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group or a halogen The 2,3-dicarboxymethyl-2,3-disubstituted succinic dianhydride according to claim 1, which is an atom. 3. The compound according to claim 1, wherein in the general formula (1), R is a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group or a phenyl group. -Dicarboxymethyl-2,3-disubstituted succinic dianhydride. 4. The following formula (2): (Where n is an integer of 1 to 12),
3-dicarboxymethyl-2,3-dialkylsuccinic dianhydride. 5. The following formula (3): 2,3-Dicarboxymethyl-2,3-dimethylsuccinic dianhydride represented by the formula: 6. A compound of the general formula (4) Wherein R is a monovalent organic group, R ^C is a linear or branched alkyl group having 1 to 5 carbon atoms, and bromotrichloromethane. Is reacted in the presence of a radical initiator to obtain a compound represented by the general formula (5): (Here, the definition of each symbol is the same as described above.) A trichlorobutyric acid alkyl ester derivative represented by the following formula: The derivative is reacted with activated copper powder or light to obtain a compound of the general formula (6) (Here, the definitions of R and R ^C are the same as above.) 2,3-di (trichloroethyl) -2,3-disubstituted alkyl succinate; the obtained ester is generally hydrolyzed Formula (7) (Here, the definition of R is the same as described above.)
-Dicarboxymethyl-2,3-disubstituted succinic acid;
By performing a dehydration reaction of the di-substituted succinic acid, a compound represented by the general formula (1): (Here, the definition of R is the same as described above.)
-A method for producing an acid dianhydride, which comprises producing dicarboxymethyl-2,3-disubstituted succinic dianhydride. 7. R is a straight-chain or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a cyclohexyl group substituted with a straight-chain or branched alkyl having 1 to 6 carbon atoms. 7. A phenyl group, a phenyl group substituted by linear or branched alkyl having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group or a halogen atom. A method for producing an acid dianhydride. 8. The method of claim 1, wherein the tetracarboxylic anhydride containing the 2,3-dicarboxymethyl-2,3-disubstituted succinic dianhydride according to any one of claims 1 to 5 and a diamino compound. Polyamic acid obtained by ring-opening polyaddition. 9. The following general formula (8) and general formula (9): Embedded image Having an amino group, an acid anhydride group or a carboxyl group hydrolyzed by the amino group or an acid anhydride group, or a general formula (10) Having a structural unit represented by the general formula (8) in an amount of 5 mol% or more, and N-methyl-
In 2-pyrrolidone, concentration 0.5 g / dl, temperature 30 ±
The logarithmic viscosity number measured at 0.01 ° C. is 0.1 to 5 dl /
g is a polyamic acid, where R is a monovalent organic group; G ⁴ is a tetravalent aromatic group having 6 to 30 carbon atoms, a tetravalent aromatic group having 4 to 30 carbon atoms. G ⁵ and G ⁶ are cycloaliphatic groups, or tetravalent linear aliphatic groups having 4 to 10 carbon atoms; G ⁵ and G ⁶ are valent aliphatic groups having 2 to 12 carbon atoms, Carbon number 4-3
A divalent cyclic aliphatic group having 6 carbon atoms, a divalent aromatic group having 6 to 36 carbon atoms, or a general formula (12) (Wherein R ⁹⁹ is an alkyl group having 1 to 6 carbon atoms,
R ¹⁰⁰ is independently an alkyl group having 1 to 3 carbon atoms of the same or different, or a phenyl group; b, c and d are each 0 or a positive integer, and 1 ≦ b + c + d ≦ 100. And R ⁴⁵ is 1 to 1 carbon atoms.
R ⁴⁶ is an alkyl, alkenyl, or alkoxyalkyl group having 1 to 10 carbon atoms;
Or a phenyl group; Z is an alkylene group having 2 to 10 carbon atoms or a phenyl group;
It is an integer of 3. ｝. 10. A linear or branched alkyl group having 1 to 12 carbon atoms, wherein R in the general formula (8) is:
Cyclohexyl group, cyclohexyl group substituted by straight or branched alkyl having 1 to 6 carbon atoms, phenyl group substituted by straight or branched alkyl having 1 to 6 carbon atoms, phenyl The polyamic acid according to claim 9, which is a group, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group or a halogen atom. 11. R in the general formula (8) is a linear or branched alkyl group having 1 to 12 carbon atoms,
The polyamic acid according to claim 9, which is cyclohexyl or phenyl. 12. The polyamic acid according to claim 9, wherein R in the general formula (8) is a linear or branched alkyl group having 1 to 6 carbon atoms. 13. The polyamic acid according to claim 9, wherein R in the general formula (8) is —CH ₃ . 14. A polyimide obtained by subjecting the polyamic acid according to claim 8 to dehydration cyclization. 15. An alignment film for a polyimide-based liquid crystal display device obtained by dehydrating and cyclizing the polyamic acid according to any one of claims 8 to 13. 16. A pair of electrode substrates having display pixel electrodes formed on one or both sides thereof facing each other.
6. A liquid crystal display device comprising the alignment film according to 5 and a liquid crystal composition between the opposed alignment films. 17. A liquid crystal composition represented by the following general formulas (14) and (1).
The liquid crystal display device according to claim 16, which is a liquid crystal composition (a) containing a component A comprising at least one compound selected from the group of compounds represented by 5) and (16). Embedded image Embedded image Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, in which any non-adjacent methylene group may be substituted by -O- or -CH = CH-; , Any hydrogen atom in this group may be replaced by a fluorine atom; X ¹ is F, Cl, —CF ₃ , —OCF ₃ , —O
_{CF 2 H, -CF 2 H,} -CFH 2, be a -OCF ₂ CF ₂ H or -OCF ₂ CFHCF _3; L ¹ and L ² are each independently a hydrogen atom or a fluorine atom; Z ¹ and Z ² are each independently 1,2-ethylene, _{1,4-butylene, -COO -, - CF 2 O} -, - OCF 2 -, - CH =
Ring B is trans-1,4-
Cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene or 1,4-phenylene substituted by 1 to 4 fluorine atoms; ring C is trans-
1,4-cyclohexylene; 1,4-phenylene or 1,4-phenylene substituted with 1 to 4 fluorine atoms. ｝. 18. The liquid crystal composition (b) containing a component B comprising at least one compound selected from the group of compounds represented by formulas (17) and (18). A liquid crystal display device according to item 16 Embedded image Wherein R ² and R ³ are each independently 1 to 10 carbon atoms
And any non-adjacent methylene group in this group may be substituted with -O- or -CH = CH-, and any hydrogen atom in this group is a fluorine atom. X ² may be -CN or -C
≡C—CN; ring D is trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane
Ring E is trans-1,4-cyclohexylene, 1,4-phenylene, substituted with 1-4 fluorine atoms, 1,5-diyl or pyrimidine-2,5-diyl;
4-phenylene, pyrimidine-2,5-diyl;
Ring F is trans-1,4-cyclohexylene or 1,
4-phenylene; Z ³ is 1,2-ethylene, -C
OO— or a single bond; L ³ , L ⁴ and L ⁵ are each independently a hydrogen atom or a fluorine atom, and e, f and g are each independently 0 or 1. ｝. 19. A liquid crystal composition represented by the following general formulas (19) and (2):
The liquid crystal display device according to claim 16, which is a liquid crystal composition (c) containing a component C comprising at least one compound selected from the group of compounds represented by (0) and (21). Embedded image Embedded image Wherein R ⁴ and R ⁵ are each independently 1 to 10 carbon atoms
And any non-adjacent methylene group in this group may be substituted with -O- or -CH = CH-, and any hydrogen atom in this group is a fluorine atom. Ring G and Ring I may each be independently trans-1,4-cyclohexylene or 1,
L ⁶ and L ⁷ are each independently a hydrogen atom or a fluorine atom, but do not represent a hydrogen atom at the same time; Z ⁴ and Z ⁵ are each independently 1,2-ethylene; —COO— or a single bond. ｝. 20. A liquid crystal composition comprising the above component A and a component D comprising at least one compound selected from the group consisting of compounds represented by formulas (22), (23) and (24). 2. The composition (a1), which is a composition (a1).
Liquid crystal display element according to 6 Embedded image Embedded image Wherein R ⁶ and R ⁷ are each independently 1 to 10 carbon atoms
An arbitrary methylene group which is not adjacent to each other may be substituted with -O- or -CH = CH-, and any hydrogen atom in the group may be substituted with a fluorine atom. Rings J, K and M are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene substituted with 1 to 4 fluorine atoms or 1,4-phenylene;
Z ⁶ and Z ⁷ are each independently 1,2-ethylene, -C
≡C—, —COO—, —CH ＝ CH— or a single bond. ｝. 21. The liquid crystal composition (b1) containing the component B and the component D.
3. The liquid crystal display device according to item 1. 22. The liquid crystal composition (c1) containing the component C and the component D.
3. The liquid crystal display device according to item 1. 23. A liquid crystal composition comprising the above components A and B
17. The liquid crystal display device according to claim 16, which is a liquid crystal composition (d) containing said component D.