KR20120079810A - Liquid crystal alignment agents for photo-alignment, liquid crystal photo-alignment layers, and liquid crystal displays using the same - Google Patents

Abstract

PURPOSE: A liquid crystal alignment film is provided to have high voltage maintaining ratio, to have low ion amount, to have low residual current, and to have excellent sensitivity of chemical changes due to light irradiation, and excellent orientation of liquid crystal molecules. CONSTITUTION: A liquid crystal alignment film comprises polyamic acid or derivatives thereof obtained by reaction of tetracarboxylic dianhydride, and diamines. The tetracarboxylic dianhydride is in chemical formula 1, and the diamine comprises at least one selected from a group consisting of diamine in chemical formula N-1, and diamine in chemical formula N-2. The liquid crystal alignment agent additionally comprises at least one selected from an alkenyl-substituted nadimide compound, an epoxy compound, and a silane coupling agent.

Description

A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element using the same for forming a liquid crystal aligning film for photo-alignment, and TECHNICAL FIELDS AND LIQUID CRYSTAL DISPLAYS USING THE SAME, LIQUID CRYSTAL ALIGNMENT AGENTS FOR PHOTO-ALIGNMENT

This invention relates to the liquid crystal aligning agent for photoalignments using the photo-alignment method, the photo-alignment film using the same, and a liquid crystal display element.

Various display devices such as PC monitors, liquid crystal TVs, viewfinders for video cameras, projection displays, and optoelectronic-related devices such as optical printer heads, optical Fourier conversion elements, and light valves, etc. As for the liquid crystal display elements distributed in the market, display elements using nematic liquid crystals are mainstream. As the display method of the nematic liquid crystal display device, TN (Twisted Nematic) mode and STN (Super Twisted Nematic) mode are well known. In recent years, in order to improve the narrow viewing angle which is one of the problems of these modes, the TN type liquid crystal display element using an optical compensation film, the MVA (Multi-domain Vertical Alignment) mode which combined the technique of a vertical alignment and a projection structure, or a transverse (Iii) In-plane switching (IPS) mode of an electric field system has been proposed and put into practical use.

In order to give these liquid crystal display elements uniform display characteristics, it is necessary to uniformly control the molecular arrangement of the liquid crystal. Specifically, the liquid crystal molecules on the substrate are orientated uniformly in one direction, and the liquid crystal molecules are given a constant inclination angle (pretilt angle) from the substrate surface. It is a liquid crystal aligning film which plays such a role. A liquid crystal aligning film is one of the important elements which are related to the display quality of a liquid crystal display element, and the role of a liquid crystal aligning film becomes important year by year with the high quality of a display element.

A liquid crystal aligning film is formed using a liquid crystal aligning agent. The liquid crystal aligning agent currently mainly used is the solution (varnish) which melt | dissolved polyamic acid or soluble polyimide in the organic solvent. After apply | coating this solution to a board | substrate, it forms into a film by means, such as a heating, and forms a polyimide-type liquid crystal aligning film. A rubbing method is currently used industrially as a method of imparting the property of orienting liquid crystal molecules to the film (orientation treatment). The rubbing method is a process of rubbing the surface of a liquid crystal aligning film to one direction using the cloth | flour which flocked fibers, such as nylon, rayon, and polyester, and, thereby, the fixed orientation of a liquid crystal molecule can be obtained. However, the rubbing method has problems such as display defects caused by adhesion of debris or fiber debris generated during the process, or display defects caused by destruction of TFT (Thin-Film-Transistor) elements due to the generation of static electricity. have.

In order to solve the said problem, the photo-alignment method which irradiates light to the formed film | membrane and performs an orientation process is proposed, and many orientation mechanisms, such as a photolysis method, a photoisomerization method, a photodimerization method, and an optical crosslinking method, are introduced so far. (For example, see following nonpatent literature 1 and following patent documents 1-5.). Since the photo-alignment method has a higher uniformity in orientation than the rubbing method and a non-contact alignment method, the film is not damaged and the cause of display defects in liquid crystal display elements such as oscillation and static electricity can be reduced. And the like.

Although the examination of the material used for the liquid crystal aligning film by a photo-alignment system (it may abbreviate as "photoalignment film" after this) is made | formed a lot, the polyimide which used tetracarboxylic dianhydride, especially cyclobutanetetracarboxylic dianhydride as a raw material It has been reported that the photo-alignment film which uses is able to orientate liquid crystal molecules uniformly and stably (for example, refer patent document 1 below). This is a method of giving the function which orientates a liquid crystal to a fixed direction by irradiating a film formed on a board | substrate with ultraviolet-ray etc. and making a chemical change generate | occur | produce a polyimide. However, compared with the alignment film by the rubbing method, the photoalignment film by such a method had the problem that electrical characteristics fell, such as the amount of impurity ions increasing and voltage retention ratio falling. In order to solve this problem, various studies have been made on the molecular structure constituting the polyimide (see Patent Documents 2 and 3, for example).

On the other hand, in the photo-alignment method, the anchoring energy is smaller than the rubbing method, and the orientation of the liquid crystal molecules is inferior. Therefore, the problem of causing a decrease in the response speed or burning of the liquid crystal display device has been pointed out. . In order to overcome such a problem, the present inventors apply the method of apply | coating the liquid crystal aligning agent which consists of a polyamic acid to a board | substrate, for example by the method of following patent document 4, and then irradiating and then baking the method. Found. According to this method, the photoalignment film which has big anchoring energy was obtained. However, the photoalignment film using the polyamic acid manufactured from the diamine which has an azo group as a raw material has the problem that the light transmittance is low and the brightness of a liquid crystal display element falls.

Japanese Patent Application Publication No. 9-297313 Japanese Patent Application Publication No. 2004-206091 International Publication 2005/83504 Brochure Japanese Patent Application Publication No. 2005-275364 Japanese Patent Application Publication No. 2006-171304

Liquid Crystal, Vol. 3, No. 4, page 262, 1999

The problem of this invention is that the sensitivity of the chemical change by light irradiation is good, maintaining the electrical characteristics common to liquid crystal aligning films, such as a high voltage retention ratio, a small amount of ions, and a small residual charge, and a liquid crystal molecule It is excellent in the orientation of and provides the liquid crystal aligning agent for forming the photo-alignment film with high light transmittance. The subject of this invention also provides the photoalignment film using this liquid crystal aligning agent, and provides the liquid crystal display element using this photoalignment film.

The inventors of the present invention provide a polyamic acid obtained by reacting a mixture of a tetracarboxylic dianhydride containing a cyclobutanetetracarboxylic dianhydride or a cyclobutanetetracarboxylic dianhydride with a specific diamine having at least two nitrogen atoms in addition to the nitrogen atom of an amino group in a molecule or The photoalignment film formed by the liquid crystal aligning agent containing the derivative has the favorable sensitivity of the chemical change by light irradiation, was excellent in the orientation of liquid crystal molecules, and also found the high light transmittance, and completed this invention.

This invention consists of the following structures.

[1] The liquid crystal aligning agent for forming the liquid crystal aligning film for photoalignment containing the polyamic acid obtained by making tetracarboxylic dianhydride and diamine react, or its derivative (s),

The tetracarboxylic dianhydride contains tetracarboxylic dianhydride represented by the following formula (I);

The said diamine contains the liquid crystal aligning agent containing at least 1 chosen from the group of the diamine represented by following formula (N-1) and formula (N-2).

In Formula (I), R ^A -R ^D are independently hydrogen or alkyl having 1 to 4 carbon atoms.

In formula (N-1), R ^E is independently a monovalent organic group;

R ^F is independently hydrogen, a monovalent organic group or halogen; And,

Z is a divalent group containing alkylene having 1 to 5 carbon atoms.

In formula (N-2), R ^G is independently a monovalent organic group or halogen;

R ^H is independently a monovalent organic group;

m is independently an integer of 0-3; And,

n is an integer of 0-4.

[2] Diamines or diamines represented by formula (N-1) wherein R ^E is independently alkyl having 1 to 3 carbons, and R ^F is independently hydrogen, alkyl having 1 to 3 carbons, fluorine, chlorine, or bromine; The liquid crystal aligning agent as described in said [1] containing the polyamic acid obtained by making the diamine mixture containing these react with tetracarboxylic dianhydride, or its derivative (s).

[3] Polyamic acids or derivatives thereof obtained by reacting a diamine represented by formula (N-1) having an amino group in each para position with a phenyl at both ends of a molecule or a diamine mixture containing this diamine with tetracarboxylic dianhydride The liquid crystal aligning agent as described in said [1] or said [2] containing containing.

[4] A polyamic acid obtained by reacting at least one selected from the group of diamines represented by the following formulas (N-1-1)? (N-1-20) or a diamine mixture containing this diamine with tetracarboxylic dianhydride Or liquid crystal aligning agent in any one of said [1]-[3] containing the derivative.

[5] Formulas wherein R ^G is independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, carbamoyl, fluorine, chlorine or bromine, and R ^H is independently alkyl having 1 to 3 carbon atoms (N- The liquid crystal aligning agent in any one of said [1]-[4] containing the polyamic acid obtained by making diamine represented by 2) or the diamine mixture containing this diamine react with tetracarboxylic dianhydride, or its derivative (s).

[6] A polyamic acid or derivative thereof obtained by reacting a diamine represented by formula (N-2) having an amino group in each para position with a phenyl at both ends of a molecule or a diamine mixture containing this diamine with tetracarboxylic dianhydride The liquid crystal aligning agent in any one of said [1]-[5] containing containing.

[7] A polyamic acid obtained by reacting at least one selected from the group of diamines represented by the following formulas (N-2-1) to (N-2-15) or a diamine mixture containing this diamine with tetracarboxylic dianhydride: Or liquid crystal aligning agent in any one of said [1]-[6] containing the derivative.

[8] A polya obtained by reacting at least one of the diamines represented by the formulas (N-2-1) and (N-2-2) described in [7] or a diamine mixture containing this diamine with tetracarboxylic dianhydride The liquid crystal aligning agent in any one of said [1]-[6] containing a mixed acid or its derivative (s).

[9] A polyamic acid or derivative thereof obtained by reacting a diamine mixture further containing at least one selected from the group of diamines represented by the following formulas (III) to (IX) and (XV) with tetracarboxylic dianhydride: The liquid crystal aligning agent in any one of said [1]-[8].

In formula (III), A ¹ is-(CH ₂ ) _m- , m is an integer of 1-6;

In formulas (V), (VII) and (IX), X is a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -NH-, -N (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- (CH ₂ ) _m -S-, m is an integer of 1-6;

In formula (VII), L ¹ and L ² are -H, but X is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) when ₂ -may be bonded to each other to form a single bond;

In the formulas (VIII) and (IX), Y is a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or 1? Alkylene of 3;

In formula (XV), R ³³ and R ³⁴ are independently alkyl or phenyl having 1 to 3 carbon atoms; G is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10; And,

In each of the above formulas, -H of the cyclohexane ring or the benzene ring is substituted with -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , benzyl, or hydroxybenzyl. You may be.

[10] The liquid crystal according to any one of the above [1] to [9], containing a polyamic acid or derivative thereof obtained by reacting a diamine mixture further comprising a diamine having a side chain structure with a tetracarboxylic dianhydride. Aligning agent.

[11] The liquid crystal aligning agent for photoalignment according to the above [10], wherein the diamine having a side chain structure is at least one selected from the group of diamines represented by the following formulas (X) to (XIV).

In formula (X),

Z ¹ is a single bond, -O-, -CO-, -COO-, -OCO- , -CONH-, -CH 2 O-, -OCH 2 -, -CF 2 O-, -OCF 2 -, or -(CH ₂ ) _m- , m is an integer of 1 to 6, and any -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH- or -C≡C- Become;

R ³ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by the following formula (Xa). Arbitrary -CH ₂ -in alkyl of 1 to 30 may be substituted with -O-, -CH = CH- or -C≡C-;

In formula (X-a),

A ² and A ³ are independently a single bond, -O-, -COO-, -OCO-, -CONH-, -CH = CH-, or alkylene having 1 to 12 carbon atoms, and a and b are independently It is an integer of 0-4;

Ring B and Ring C are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5 -Diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;

R ⁴ and R ⁵ are independently -F or CH ₃ , f and g are independently an integer of 0-2;

R <^6> is -F, -OH, -CN, C1-C30 alkyl, C1-C30 alkoxy, or C2-C30 alkoxyalkyl, In these alkyl, alkoxy, alkoxyalkyl, arbitrary -H May be substituted with -F, and arbitrary -CH ₂ -may be substituted with -CF ₂ -or a divalent group represented by the following formula (s);

In formula (s), R ³⁵ and R ³⁶ are independently alkyl having 1 to 3 carbon atoms, m is an integer of 1 to 6;

c, d, and e are the integers of 0-3 independently, and c + d + e≥1.

In formulas (XI) and (XII),

R ⁷ is independently —H or —CH ₃ ;

R ⁸ is —H, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;

A ⁴ is independently a single bond, -CO- or -CH _2- ;

In formula (XII),

R ⁹ and R ¹⁰ are independently alkyl or phenyl having 1 to 20 carbon atoms.

In formulas (XIII) and (XIV), A ⁵ is independently —O— or alkylene having 1 to 6 carbon atoms;

In formula (XIII), R ¹¹ is -H or alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl may be substituted with -O-, -CH = CH- or -C≡C-. Become;

A ⁶ is a single bond or alkylene having 1 to 3 carbon atoms;

Ring T is 1,4-phenylene or 1,4-cyclohexylene;

h is 0 or 1;

In formula (XIV), R ¹² is alkyl having 6 to 22 carbon atoms; And,

R ¹³ is alkyl having 1 to 22 carbons.

[12] The above-mentioned [1] to [11], further using at least one selected from the group of compounds represented by the following formulas (An-1) to (An-6) as tetracarboxylic dianhydride to be reacted with diamine: ] Liquid crystal aligning agent in any one.

In formulas (An-1), (An-4) and (An-5), X ¹ is independently a single bond or -CH _2- ;

In formula (An-2), G ¹ is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2- ;

In formula (An-2)? (An-4), Y ¹ is independently one selected from the group of the following trivalent groups;

In formula (An-3)? (An-5), ring E represents a group of a C3-C10 monocyclic hydrocarbon or a group of a C6-C20 condensed polycyclic hydrocarbon, and any hydrogen of this group is methyl May be substituted with ethyl or phenyl; The bond connected to the ring is linked to any carbon constituting the ring, and two bonds may be linked to the same carbon;

In formula (An-6), X ¹¹ is alkylene having 2 to 6 carbon atoms;

Me represents methyl and Ph represents phenyl.

[13] A tetracarboxylic dianhydride to be reacted with diamine, at least one selected from the group of aromatic tetracarboxylic dianhydrides represented by the following formulas (1), (2), (5) to (7) and (17): The liquid crystal aligning agent in any one of said [1]-[11] to be used.

[14] An alicyclic compound represented by the following formulas (23), (25), (36)-(39), (44), (49) and (68), which is a tetracarboxylic dianhydride reacted with diamine. The liquid crystal aligning agent in any one of said [1]-[11] which further uses at least 1 chosen from the group of tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride.

[15] A tetracarboxylic dianhydride to be reacted with a diamine, comprising at least one selected from the group of aromatic tetracarboxylic dianhydrides as described in the above [13], and alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides as described in the above [14]. The liquid crystal aligning agent in any one of said [1]-[11] which further uses at least 1 selected from the group.

[16] A liquid crystal aligning agent obtained by mixing at least two of the liquid crystal aligning agents according to any one of [1] to [15].

[17] The liquid crystal aligning agent according to any one of [1] to [16], further comprising at least one selected from an alkenyl substituted naimide compound, an epoxy compound, and a silane coupling agent.

[18] The alkenyl-substituted nadimide compound is selected from the group consisting of bis [4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl] methane, N, N'-m-xylene -Bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), and N, N'-hexamethylenebis (allylbicyclo [2.2.1] hepto-5-ene- The liquid crystal aligning agent as described in said [17] which is at least 1 chosen from the group which consists of 2, 3- dicarboxyimide).

[19] The liquid crystal according to the above [17], wherein the alkenyl substituted nadimide compound is bis [4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl] methane. Aligning agent.

[20] The liquid crystal aligning agent according to any one of [17] to [19], in which an alkenyl-substituted nadimide compound is contained in an amount of 0.01 to 50% by weight based on the total amount of the polyamic acid or its derivative.

[21] The epoxy compound is N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N , N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- Bis [4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, N-phenylmaleimide The liquid crystal aligning agent as described in said [17] which is at least 1 selected from the group which consists of a-glycidyl methacrylate copolymer and 2- (3, 4- epoxycyclohexyl) ethyl trimethoxysilane.

[22] The epoxy compound is N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And liquid crystal aligning agent as described in said [17].

[23] The liquid crystal aligning agent according to the above [17], [21] or [22], wherein an epoxy compound is contained in an amount of 1 to 40% by weight based on the total amount of the polyamic acid or the derivative thereof.

[24] The silane coupling agent is vinyl trimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propylmethyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-metha Krilloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N ' -Bis [3- (trimethoxysilyl) propyl] ethylene at least one selected from the group consisting of [17] ] Liquid crystal aligning agent.

[25] The liquid crystal aligning agent according to the above [17], wherein the silane coupling agent is 3-aminopropyltriethoxysilane.

[26] The liquid crystal aligning agent according to the above [17], [24] or [25], wherein the silane coupling agent is contained in an amount of 0.1 to 10% by weight based on the total amount of the polyamic acid or its derivative.

[27] a step of applying the liquid crystal aligning agent according to any one of the above [1] to [26] to a substrate, a step of heating and drying the substrate coated with the alignment agent, and a step of irradiating polarized ultraviolet rays to the film. The liquid crystal aligning film for photoalignments formed through.

[28] A step of applying the liquid crystal aligning agent according to any one of the above [1] to [26] to a substrate, heating and drying the substrate coated with the alignment agent, and irradiating polarized ultraviolet rays to the dried film. The liquid crystal aligning film for photoalignments formed through a process and then, heating and baking the said film.

[29] a step of applying the liquid crystal aligning agent according to any one of the above [1] to [26] to a substrate, a step of heating and drying the substrate coated with the alignment agent, a step of heating and baking the dried film; Next, the liquid crystal aligning film for photoalignments formed through the process of irradiating a polarized ultraviolet-ray to the said film.

[30] A liquid crystal display device having the liquid crystal alignment film for photo alignment according to any one of the above [27] in the magnetic domain.

Advantageous Effects of Invention The present invention has electrical characteristics such as high voltage retention ratio, small ion amount, small residual charge, etc., good sensitivity of chemical change by light irradiation, excellent alignment of liquid crystal molecules, and high light transmittance. This high photoalignment film can be obtained. And the liquid crystal display element excellent in the display characteristic which has this photo-alignment film can be obtained.

The liquid crystal aligning agent of this invention contains the polyamic acid or its derivative which is a reaction product of tetracarboxylic dianhydride and diamine. The derivative of the polyamic acid is a component that is dissolved in the solvent when it is made into a liquid crystal aligning agent which will be described later, and contains a liquid crystal aligning film having polyimide as a main component. It is a component that can be formed. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, polyamic acid amides, and the like. More specifically, 1) polyimide in which the entire amino group and the carboxyl group of the polyamic acid are subjected to dehydration ring closure reaction; 3) polyhydric acid partially dehydration ring-closure reaction, 3) polyamic acid ester in which the carboxyl group of polyamic acid is converted to ester, and 4) a part of acid dianhydride contained in tetracarboxylic dianhydride compound with organic dicarboxylic acid. The polyamic acid-polyamide copolymer and 5) the polyamideimide which carried out the dehydration ring-closure reaction of part or all of the said polyamic acid-polyamide copolymer is mentioned. The polyamic acid or its derivatives may be one kind of compound or two or more kinds.

The said tetracarboxylic dianhydride contains the tetracarboxylic dianhydride represented by following formula (I).

After apply | coating the liquid crystal aligning agent of this invention to a board | substrate, and drying by preheating, when irradiating the linearly polarized light of an ultraviolet-ray through a polarizing plate, the said Formula (I) of the polymer main chain generally parallel to a polarization direction The cyclobutane ring of the structural unit derived from tetracarboxylic dianhydride represented by) causes a photolysis reaction. By selectively decomposing the main chain of the polymer, which is generally parallel to the polarization direction, the main chain of the polymer forming the film is dominant in a component that is generally orthogonal to the polarization direction of the irradiated ultraviolet rays. Therefore, after the substrate is heated to dehydrate and ring the polyamic acid to form a polyimide film, the liquid crystal molecules of the liquid crystal composition injected into the cells assembled using the substrate have a long axis perpendicular to the polarization direction of the irradiated ultraviolet rays. Align and align side by side. The step of irradiating the linearly polarized light of the ultraviolet ray to the film may be performed before the heating step for polyimidization, or may be performed after heating to polyimide.

R ^{A to} R ^D in Formula (I) are independently hydrogen or alkyl having 1 to 4 carbons. Specifically, alkyl having 1 to 4 carbon atoms is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl. R ^{A to} R ^D are preferably hydrogen or methyl, and more preferably hydrogen.

The tetracarboxylic dianhydride represented by formula (I) may be used individually by 1 compound, and may be used in mixture of 2 or more. You may use the tetracarboxylic dianhydride represented by Formula (I) in mixture with another tetracarboxylic dianhydride. The tetracarboxylic dianhydride represented by Formula (I) in the mixture of tetracarboxylic dianhydride at this time is used by the ratio of 10 weight% or more, It is preferable that it is 50 weight% or more, It is more preferable if it is 80 weight% or more.

The aforementioned diamine includes at least one selected from the group of diamines represented by the following formulas (N-1) and (N-2).

In formula (N-1), R ^E is a monovalent organic group independently. In monovalent organic group, alkyl is preferable and C1-C3 alkyl is preferable. Specifically, alkyl having 1 to 3 carbons is methyl, ethyl, n-propyl, and isopropyl, and methyl is more preferable. R ^F is independently hydrogen, a monovalent organic group, or halogen. In monovalent organic group, alkyl is preferable and C1-C3 alkyl is preferable. Specifically, alkyl having 1 to 3 carbons is methyl, ethyl, n-propyl, and isopropyl, and methyl is more preferable. Halogen is preferably fluorine, chlorine and bromine. And among these, hydrogen is more preferable. Although Z is a divalent group containing C1-C5 alkylene, it is preferable that it is C1-C5 alkylene. Although the position of the amino group in phenyl at both ends of the molecule may be any position, the para position and the meta position are preferable, and the para position is more preferable.

In formula (N-2), R ^G is independently a monovalent organic group or a halogen. Of the monovalent organic groups, alkyl, alkoxy and carbamoyl are preferred. Among the alkyl having 1 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms is more preferable. Specifically, alkyl having 1 to 4 carbon atoms is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl, and methyl is more preferable. Among the alkoxy having 1 to 10 carbon atoms, the alkoxy having 1 to 4 carbon atoms is more preferable. Specifically, alkoxy having 1 to 4 carbon atoms is methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, and tert-butyloxy, and methoxy is more preferable. Halogen is preferably fluorine, chlorine and bromine. R ^H is independently a monovalent organic group. In monovalent organic group, alkyl is preferable and C1-C3 alkyl is preferable. Specifically, alkyl having 1 to 3 carbons is methyl, ethyl, n-propyl, and isopropyl, and methyl is more preferable. m is an integer of 0-3 independently. When m is chosen from the integer of 1-3, it is preferable that it is 1-2, and it is more preferable that it is 1. It is preferable that m is 0 or 1. When m is 2 or 3, R ^G may be the same and may differ. n is an integer of 0-4. When n is selected from the integers of 1-4, it is preferable that it is 1-2, and it is more preferable that it is 1. It is preferable that n is 0 or 1, and it is more preferable that it is zero. Although the position of the amino group in phenyl at both ends of the molecule may be any position, the para position and the meta position are preferable, and the para position is more preferable.

Specific examples of the diamine represented by the formula (N-1) are compounds represented by the following formulas (N-1-1) to (N-1-20).

Specific examples of the diamine represented by the formula (N-2) are compounds represented by the following formulas (N-2-1) to (N-2-15).

In the said specific example, the diamine represented by Formula (N-1-2), (N-2-1), and (N-2-2) is preferable.

The diamine represented by a formula (N-1) and the diamine represented by a formula (N-2) may be used individually by 1 compound, and may mix and use two or more. The diamine represented by the formula (N-1) and the diamine represented by the formula (N-2) may be used in combination with other diamines. In this case, the diamine represented by the formula (N-1) and the diamine represented by the formula (N-2) in the mixture of diamines are used in a proportion of 10% by weight or more, preferably 50% by weight or more, and more preferably 80% by weight or more. desirable.

Other diamines which can be used in combination with the diamine represented by the formula (N-1) and the diamine represented by the formula (N-2) include, for example, diamines having no side chain structure and diamines having side chain structure. Such another diamine may be one compound or two or more compounds.

The liquid crystal aligning agent of this invention is used suitably for the liquid crystal display element of the system which orientates liquid crystal molecules parallel with respect to a board | substrate, and operates in an electric field like IPS mode, for example. In such a case, since the liquid crystal molecules do not need to have a pretilt angle with respect to the substrate surface, diamines having no side chain structure are preferably used as other diamines.

The diamine which does not have a side chain structure is at least 1 chosen from the group of the diamine represented by following formula (III)-(IX) and (XV).

In the formula (III), A ¹ is - (CH _{2) m} - and, m is an integer of 16?. In formulas (V), (VII) and (IX), X is a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -NH-, -N (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- (CH ₂ ) _m -S-, m is an integer of 1-6. In formula (VII), L ¹ and L ² are -H, but X is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) When _2- , may be bonded to each other to form a single bond. In the formulas (VIII) and (IX), Y is a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or 1? Alkylene of 3. In formula (XV), R ³³ and R ³⁴ are independently alkyl or phenyl having 1 to 3 carbon atoms, G is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms, m is 1 Is an integer of? 10. In each of the above formulas, -H of the cyclohexane ring or the benzene ring is -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , benzyl, or hydroxybenzyl. It may be substituted.

As diamine represented by Formula (III), the diamine represented by following formula (III-1) (III-3)-is mentioned, for example.

As diamine represented by Formula (IV), the diamine represented by following formula (IV-1) and (IV-2) is mentioned, for example.

As the diamine represented by the formula (V), there are diamines represented by the following formulas (V-1) to (V-3), for example.

As a diamine represented by Formula (VI), the diamine represented by following formula (VI-1) (VI-17) is mentioned, for example.

As diamine represented by Formula (VII), the diamine represented by following formula (VII-1) (VII-36)-is mentioned, for example.

As diamine represented by Formula (VIII), the diamine represented by following formula (VIII-1) (VIII-6)-is mentioned, for example.

As diamine represented by Formula (IX), the diamine represented by following formula (IX-1) (IX-16)-is mentioned, for example.

As a diamine represented by a formula (XV), there exists a compound represented by a following formula (XV-1), for example.

The liquid crystal aligning agent of this invention can be used also for liquid crystal display elements, such as TN mode, for which liquid crystal molecules need to have a pretilt angle with respect to a board | substrate surface. In this case, you may mix and use the diamine which has a side chain structure in the diamine represented by Formula (N-1), and the diamine represented by Formula (N-2). In addition, when it is going to adjust the pretilt angle suitably, the diamine represented by Formula (N-1) and the diamine represented by Formula (N-2) does not have the above-mentioned side chain structure, and the diamine which has side chain structure. It is also possible to use a mixture of both sides.

The diamine having a side chain structure is at least one selected from the group of diamines represented by the following formulas (X) to (XIV).

In formula (X),

Z ¹ is a single bond, -O-, -CO-, -COO-, -OCO- , -CONH-, -CH 2 O-, -OCH 2 -, -CF 2 O-, -OCF 2 -, or -(CH ₂ ) _m- , m is an integer of 1 to 6, and any -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH- or -C≡C- Become;

R ³ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by the following formula (Xa). Arbitrary -CH ₂ -in alkyl of 1 to 30 may be substituted with -O-, -CH = CH- or -C≡C-;

In formula (X-a),

A ² and A ³ are independently a single bond, -O-, -COO-, -OCO-, -CONH-, -CH = CH-, or alkylene having 1 to 12 carbon atoms, and a and b are independently It is an integer of 0-4;

Ring B and Ring C are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5 -Diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;

R ⁴ and R ⁵ are independently -F or CH ₃ , f and g are independently an integer of 0-2;

R <^6> is -F, -OH, -CN, C1-C30 alkyl, C1-C30 alkoxy, or C2-C30 alkoxyalkyl, In these alkyl, alkoxy, alkoxyalkyl, arbitrary -H May be substituted with -F, and arbitrary -CH ₂ -may be substituted with -CF ₂ -or a divalent group represented by the following formula (s);

In formula (s), R ³⁵ and R ³⁶ are independently alkyl having 1 to 3 carbon atoms, m is an integer of 1 to 6;

c, d, and e are the integers of 0-3 independently, and c + d + e≥1.

In formulas (XI) and (XII),

R ⁷ is independently —H or —CH ₃ ;

R ⁸ is —H, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;

A ⁴ is independently a single bond, -CO- or -CH _2- ;

In formula (XII),

R ⁹ and R ¹⁰ are independently alkyl or phenyl having 1 to 20 carbon atoms.

In formulas (XIII) and (XIV), A ⁵ is independently —O— or alkylene having 1 to 6 carbon atoms;

In formula (XIII), R ¹¹ is -H or alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl may be substituted with -O-, -CH = CH- or -C≡C-. Become;

A ⁶ is a single bond or alkylene having 1 to 3 carbon atoms;

Ring T is 1,4-phenylene or 1,4-cyclohexylene;

h is 0 or 1;

In formula (XIV), R ¹² is alkyl having 6 to 22 carbon atoms; And,

R ¹³ is alkyl having 1 to 22 carbons.

Examples of the diamine represented by the formula (X) include diamines represented by the following formulas (X-1) to (X-37) and (X-38) to (X-43).

In formula (X-1)? (X-11), R ²³ is preferably alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and preferably alkyl having 5 to 25 carbon atoms or alkoxy having 5 to 25 carbon atoms. More preferred. Moreover, it is preferable that R <^24> is C1-C30 alkyl or C1-C30 alkoxy, and it is more preferable that it is C3-C25 alkyl or C3-C25 alkoxy.

In formula (X-12)-(X-17), it is preferable that R <^25> is C4-C30 alkyl, and it is more preferable that it is C6-C25 alkyl. In formulas (X-16) and (X-17), R ²⁶ is preferably an alkyl having 6 to 30 carbon atoms, and more preferably an alkyl having 8 to 25 carbon atoms.

In formula (X-18)? (X-37), R ²⁷ is preferably an alkyl having 1 to 30 carbon atoms or an alkoxy having 1 to 30 carbon atoms, and preferably an alkyl having 3 to 25 carbon atoms or an alkoxy having 3 to 25 carbon atoms. More preferred. Further, R ²⁸ is a -H, -F, C 1? 30 alkyl, C1? 30 _{alkoxy, -CN, -OCH 2 F, -OCHF} 2 or -OCF ₃ is preferable, and a carbon number of 3? 25 It is more preferable that they are alkyl or alkoxy of 3-25 carbon atoms.

The diamine represented by the formula (X) is preferably a diamine represented by formulas (X-1) to (X-11), and is represented by formulas (X-2) and (X-4) to (X-6). Diamine is more preferred.

In the diamine represented by the formula (XI), in formula (XI), one of the two "NH ₂ -Ph-A ⁴ -O-" is bonded to the 3 position of the steroid skeleton, the other is bonded to the 6 position It is preferable that it is done. Moreover, it is preferable that two amino groups are respectively couple | bonded with phenyl, and are couple | bonded with the meta position or the para position with respect to the bonding position of A <^4> .

As diamine represented by Formula (XI), the diamine represented by following formula (XI-1) (XI-4)-is mentioned, for example.

In the diamine represented by the formula (XII), in formula (XII), the two "NH _2- (R ^10- ) Ph-A ⁴ -O-" are each bonded to phenyl, but the steroid skeleton is bonded It is preferable to be bonded to the carbon of meta position or para position with respect to the carbon which exists. In addition, although two amino groups are each couple | bonded with phenyl, it is preferable that they are couple | bonded with the meta position or para position with respect to A <^4> .

As diamine represented by Formula (XII), the diamine represented by following formula (XII-1) (XII-8)-is mentioned, for example.

In the diamine represented by the formula (XIII), in the formula (XIII), the two amino groups are each bonded to phenyl, but are preferably bonded to the meta position or the para position with respect to A ⁵ .

As diamine represented by Formula (XIII), the diamine represented by following formula (XIII-1) (XIII-8)-is mentioned, for example.

In Formulas (XIII-1) to (XIII-3), R ²⁹ is preferably -H, alkyl having 1 to 30 carbon atoms, or alkoxy having 1 to 30 carbon atoms, and alkyl having 3 to 30 carbon atoms or 3 to 30 carbon atoms. It is more preferable that it is alkoxy of. In formulas (XIII-4) to (XIII-8), R ³⁰ is preferably -H, alkyl having 1 to 30 carbon atoms, or alkoxy having 1 to 30 carbon atoms, and alkyl having 3 to 30 carbon atoms or 3 to 30 carbon atoms. It is more preferable that it is alkoxy of -30.

In the diamine represented by the formula (XIV), in the formula (XIV), the two amino groups are each bonded to phenyl, but are preferably bonded to the meta position or the para position with respect to A ⁵ .

As diamine represented by a formula (XIV), the diamine represented by following formula (XIV-1) (XIV-3)-is mentioned, for example.

In Formula (XIV-1)? (XIV-3), R ³¹ is preferably alkyl having 6 to 22 carbon atoms, and more preferably alkyl having 6 to 20 carbon atoms. R ³² is preferably -H or alkyl having 1 to 22 carbon atoms, and more preferably alkyl having 1 to 10 carbon atoms.

The diamine which has a side chain structure is chosen from the compound represented by Formula (X-2), (X-4)-(X-6), (XIII-2), (XIII-4), and (XIII-6). At least one is preferable.

As another diamine in this invention, diamines other than the diamine represented by Formula (III)-(IX), (XV) and (X)-(XIV) mentioned above can also be used. Such other diamines include, for example, naphthalene-based diamines having a naphthalene structure, fluorene-based diamines having a fluorene structure, and diamines having a side chain structure other than formulas (VIII) to (XII).

As another diamine, there exists a compound represented, for example by following formula (1 ')-(8').

In Formulas (1 ') to (8'), R ³⁵ and R ³⁶ each independently represent an alkyl group having 3 to 30 carbon atoms.

Said other diamine can be used in the range in which the effect of this invention is not impaired in the diamine which comprises the polyamic acid of the liquid crystal aligning agent of this invention.

As for the said other diamine, in each diamine, one part of diamine may be substituted by monoamine in the range whose ratio of the monoamine with respect to diamine is 40 mol% or less. Such substitution can cause termination of the polymerization reaction when producing a polyamic acid, and can suppress the further progress of the polymerization reaction. Therefore, by such substitution, the molecular weight of the polymer (polyamic acid or derivative thereof) obtained can be easily controlled, and for example, the coating property of the liquid crystal aligning agent can be improved without impairing the effect of the present invention. . As long as the effect of this invention is not impaired, the diamine substituted by monoamine may be 1 type, or 2 or more types. As said monoamine, it is aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, for example. , n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n- Octadecylamine, and n-eicosylamine.

The other tetracarboxylic dianhydride used in admixture with the tetracarboxylic dianhydride represented by formula (I) in the present invention is at least selected from the group of compounds represented by the following formulas (An-1) to (An-6): One.

In formulas (An-1), (An-4) and (An-5), X ¹ is independently a single bond or -CH _2- ;

In formula (An-2), G ¹ is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2- ;

In formula (An-2)? (An-4), Y ¹ is independently one selected from the group of the following trivalent groups;

In formula (An-3)? (An-5), ring E represents a group of a C3-C10 monocyclic hydrocarbon or a group of a C6-C20 condensed polycyclic hydrocarbon, and any hydrogen of this group is methyl May be substituted with ethyl or phenyl;

The bond connected to the ring is linked to any carbon constituting the ring, and two bonds may be linked to the same carbon;

In formula (An-6), X ¹¹ is alkylene having 2 to 6 carbon atoms;

Me represents methyl and Ph represents phenyl.

The other tetracarboxylic dianhydride may be one compound or two or more compounds.

The said tetracarboxylic dianhydride is divided roughly into aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and silsesquioxane type tetracarboxylic dianhydride.

Aromatic tetracarboxylic dianhydride is a compound in which at least one of two acid anhydrides is an acid anhydride by two carboxy bonds to an aromatic compound. As said aromatic tetracarboxylic dianhydride, there exists a compound represented by following formula (1)-(18), for example.

It is preferable that the said aromatic tetracarboxylic dianhydride is a compound represented by Formula (1), (2), (5)-(7), and (17), It is more preferable that it is a compound represented by Formula (1). .

The alicyclic tetracarboxylic dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride with two carboxy bonds to the alicyclic compound. As said alicyclic tetracarboxylic dianhydride, For example, following formula (24)-(34), (36)-(40), (42)-(44) and (49)-(58), and (62) (64) is a compound.

It is preferable that an alicyclic tetracarboxylic dianhydride is a compound represented by Formula (25), (36)-(39), (44), (49), and (68), and said Formula (37) and (49) It is more preferable that it is a compound represented by).

Aliphatic tetracarboxylic dianhydride is a compound which has two acid anhydrides by two carboxy bonds to an aliphatic compound. As said aliphatic tetracarboxylic dianhydride, there exist a compound represented by following formula (23), (45)-(48), (66), (67), and (68), for example.

It is preferable that aliphatic tetracarboxylic dianhydride is a compound represented by Formula (23) and (68).

Tetracarboxylic dianhydride may substitute a part of dicarboxylic acid anhydride. Such substitution can cause the termination of the polymerization reaction when producing the polyamic acid, and can suppress the further progress of the polymerization reaction. Therefore, by such substitution, the molecular weight of the obtained polymer (polyamic acid or its derivative) can be easily controlled, and for example, the coating property of the liquid crystal aligning agent can be improved without impairing the effect of the present invention. . The ratio of the dicarboxylic acid dianhydride to the tetracarboxylic dianhydride may be in a range that does not impair the effects of the present invention, but is preferably 10 mol% or less of the total amount of tetracarboxylic dianhydride as a reference. The tetracarboxylic dianhydride substituted by the dicarboxylic acid anhydride may be one kind or two or more kinds, as long as the effect of the present invention is not impaired. Examples of the dicarboxylic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and Cyclohexanedicarboxylic acid anhydride.

In tetracarboxylic dianhydride, a part of tetracarboxylic dianhydride may be substituted by dicarboxylic acid in the range whose ratio of dicarboxylic acid with respect to tetracarboxylic dianhydride is 10 mol% or less. The tetracarboxylic dianhydride substituted with dicarboxylic acid may be one kind or two or more kinds, as long as the effect of the present invention is not impaired.

The polyamic acid or its derivative of this invention may further contain the monoisocyanate compound in the monomer. By including a mono isocyanate compound in a monomer, the terminal of the obtained polyamic acid or its derivative is modified, and molecular weight is adjusted. By using this terminal-modified polyamic acid or its derivative, the coating characteristic of a liquid crystal aligning agent can be improved, for example, without the effect of this invention being impaired. It is preferable that content of the monoisocyanate compound in a monomer is 1-10 mol% with respect to the total amount of the diamine and tetracarboxylic dianhydride in a monomer from the above-mentioned viewpoint. Examples of the mono isocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid or derivative thereof of the present invention can be produced in the same manner as a known polyamic acid or derivative thereof used for forming a film of polyimide. It is preferable to make the total amount of tetracarboxylic dianhydride into the mole (molar ratio about 0.9-1.1) approximately equal to the total mole number of diamine.

It is preferable that it is 10,000-500,000, and, as for the molecular weight of the polyamic acid or its derivative (s) of polystyrene in terms of weight average molecular weight (Mw), it is more preferable that it is 20,000-200,000. The molecular weight of the said polyamic acid or its derivative can be calculated | required by the measurement by the gel permeation chromatography (GPC) method.

The polyamic acid or its derivative of the present invention can be confirmed by analyzing the solid content obtained by precipitation with a large amount of poor solvent by IR and NMR. Moreover, the monomer used can be confirmed by analyzing the extract by the organic solvent of the decomposition product of the said polyamic acid or its derivative (s) by strong alkaline aqueous solution, such as KOH and NaOH, by GC, HPLC, or GC-MS.

The liquid crystal aligning agent of this invention may further contain other components other than the said polyamic acid or its derivative (s). The other component may be one kind or two or more kinds.

For example, the liquid crystal aligning agent of this invention may contain the alkenyl substituted nadimide compound further from a viewpoint of stabilizing the electrical characteristic of a liquid crystal display element for a long time. The alkenyl substituted naimide compound may be one kind of compound or two or more kinds of compounds. It is preferable that it is 0.01-1.00 by weight ratio with respect to the polyamic acid or its derivative in a liquid crystal aligning agent, as for content of an alkenyl substituted nadimide compound from 0.01 to 0.70, It is more preferable that it is 0.01-0.50 Most preferred.

It is preferable that an alkenyl substituted nadimide compound is a compound melt | dissolved in the solvent which melt | dissolves the polyamic acid or its derivative (s) used by this invention. Examples of such alkenyl-substituted namidide compounds include compounds represented by the following formula (Ina).

In formula (Ina), L ¹ and L ² are each independently hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl or benzyl, and n is 1 or 2

When n = 1, W is alkyl having 1 to 12 carbons, alkenyl having 2 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, -Z ^1- (O) _q- ( Z ² O) represented by _r -Z ³ -H (Z ¹ , Z ² and Z ³ are independently alkylene having 2 to 6 carbon atoms, q is 0 or 1, and r is an integer of 1 to 30) -(Z ⁴ ) _s -BZ ⁵ -H (Z ⁴ and Z ⁵ are independently alkylene having 1 to 4 carbon atoms or cycloalkylene having 5 to 8 carbon atoms, B is phenylene, and s Is a group represented by 0 or 1), -BTBH (B is phenylene, and T is -CH _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S- or SO _2- ), or a group in which 1 to 3 hydrogens of these groups are substituted with hydroxyl groups.

At this time, preferable W is C1-C8 alkyl, C3-C4 alkenyl, cyclohexyl, phenyl, benzyl, C4-C10 poly (ethyleneoxy) ethyl, phenyloxyphenyl, phenylmethylphenyl, phenyliso Propylidenephenyl and groups in which one or two hydrogens of these groups are substituted with hydroxyl groups.

Formula when n = 2 In one (Ina), W is C2? 20 alkylene, C5? 8 cycloalkylene, C 6? ^{Allyl-alkylene, -Z 1 -O- (Z 2 O} ) of 12 _{a group represented by r} -Z ^3- (the meaning of Z ^1- Z ³ and r is as described above), -Z ⁴ -BZ ^5- (the meaning of Z ⁴ , Z ⁵ and B is as described above) Group represented, -B- (OB) _s -T- (BO) _s -B- (B represents phenylene, T is C1-C3 alkylene, -O- or SO _2- , s is The group represented by 0 or 1) or 1-3 hydrogen of these groups is the group substituted by the hydroxyl group.

In this case, preferred W is C2-C12 alkylene, cyclohexylene, phenylene, tolylene, xylene, -C ₃ H ₆ -O (-Z ² -O) _r -OC ₃ H _6- (Z ² Is an alkylene having 2 to 6 carbon atoms, r is a group represented by 1 or 2), -BTB- (B represents phenylene, and T represents -CH _2- , -O- or SO _2-. ), A group represented by -BOBC ₃ H ₆ -BOB- (B is phenylene), and a group in which one or two hydrogens of these groups are substituted with a hydroxyl group.

Such an alkenyl substituted naimide compound is, for example, by maintaining an alkenyl substituted nadic acid anhydride derivative and a diamine at a temperature of 80 to 220 캜 for 0.5 to 20 hours, as described in Japanese Patent No. 2729565. The compound obtained by synthesis | combination and the commercially available compound can be used. As a specific example of an alkenyl substituted nadimide compound, the compound shown below is mentioned.

N-methyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-methyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-di Carboxylimide, N-Methyl-Metalyl Bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-methyl-Metalylmethylbicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2-ethylhexyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-allyl-allylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide, N-allyl-allylmethylbicyclo [2.2.1] hepto-5-en-2,3-dicarboxyimide, N-allyl-metallylbicyclo [2.2.1] hepto -5-ene-2,3-dicarboxyimide, N-isopropenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-isopropenyl-allyl (methyl ) Bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-isopropenyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide, N-cyclohexyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-phenyl-allylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide,

N-phenyl-allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-benzyl-allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide, N-benzyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-benzyl-metallylbicyclo [2.2.1] hepto-5-ene- 2,3-dicarboxyimide, N- (2-hydroxyethyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2-hydroxyethyl)- Allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2-hydroxyethyl) -metallylbicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide,

N- (2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2,2-dimethyl-3-hydroxy Oxypropyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyl Mead, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-hydroxycyclohexyl) -allyl (Methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4-hydroxyphenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide, N- (4-hydroxyphenyl) -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N -(4-hydroxyphenyl) -metallmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxyethoxy) ethyl} -allyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2- (2-hydroxyethoxy) ethyl} -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxy Hydroxyethoxy) ethyl} -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxyethoxy) ethyl} -metallylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hepto -5-ene-2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allyl (methyl) bicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -metallylbicyclo [2.2.1] hepto-5-ene-2,3- Dicarboxyimide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {4- ( 4-hydroxyphenylisopropylidene) phenyl} -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, and oligomers thereof,

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Trimethylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-hexamethylenebis (allylbicyclo [2.2.1] hepto-5- N-2,3-dicarboxyimide), N, N'-hexamethylenebis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dode Camethylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dodecamethylenebis (allylmethylbicyclo [2.2.1] hepto-5- N-2,3-dicarboxyimide), N, N'-cyclohexylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclo Hexylenebis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

1,2-bis {3 '-(allylbicyclo [2.2.1] hepto-5-ene2,3-dicarboxyimide) propoxy} ethane, 1,2-bis {3'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane, 1,2-bis {3 '-(metallylbicyclo [2.2.1] hepto-5-ene-2, 3-dicarboxyimide) propoxy} ethane, bis [2 '-{3'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether, Bis [2 '-{3'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether, 1,4-bis {3 '-( Allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} butane, 1,4-bis {3 '-(allylmethylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide) propoxy} butane,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-phenylene-bis (allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylbi Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-xylene-bis (Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (metallylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide ) Phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metallylmethylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- ( Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3- Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulfone, bis {4- (allylmethylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulfone,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulfone, 1,6-bis (allylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide) -3-hydroxy-hexane, 1,12-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -3,6- Dihydroxydodecane, 1,3-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -5-hydroxy-cyclohexane, 1,5-bis '-(Allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} -3-hydroxy-pentane, 1,4-bis (allylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-benzene,

1,4-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2,5-dihydroxybenzene, N, N'-p- (2-hydroxy Roxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p- (2-hydroxy) xylene-bis (arylmethylcyclo [ 2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene- 2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N , N'-p- (2,3-dihydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-phenoxy} phenyl] propane, bis {4 -(Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-phenyl} methane, bis {3- (allylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide) -4-hydroxy-phenyl} ether, bis {3- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)- 5-hydroxy-phenyl} sulfone, 1,1,1-tri {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)} phenoxymethylpropane, N , N ', N "-tri (ethylenemetallbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) isocyanurate, oligomers thereof and the like.

In addition, the alkenyl substituted nadimide compound used for this invention may be a compound represented by the following formula containing an asymmetric alkylene phenylene group.

Preferred compounds are shown below among alkenyl-substituted namidide compounds.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Trimethylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-hexamethylenebis (allylbicyclo [2.2.1] hepto-5- N-2,3-dicarboxyimide), N, N'-hexamethylenebis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dode Camethylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dodecamethylenebis (allylmethylbicyclo [2.2.1] hepto-5- N-2,3-dicarboxyimide), N, N'-cyclohexylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclo Hexylenebis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-phenylene-bis (allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylbi Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-xylene-bis (Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), 2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2- ratio [4- {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (metal Rylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metallylmethylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- ( Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3- Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulfone, bis {4- (allylmethylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulfone, bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} Sulfone.

Moreover, a preferable alkenyl substituted naimide compound is shown below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Trimethylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-hexamethylenebis (allylbicyclo [2.2.1] hepto-5- N-2,3-dicarboxyimide), N, N'-hexamethylenebis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dode Camethylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dodecamethylenebis (allylmethylbicyclo [2.2.1] hepto-5- N-2,3-dicarboxyimide), N, N'-cyclohexylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclo Hexylenebis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-phenylene-bis (allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylbi Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-xylene-bis (Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (metallylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide ) Phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metallylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metallylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane .

And as a particularly preferable alkenyl substituted nadimide compound, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by Formula (Ina-1) shown below Phenyl} methane, N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by formula (Ina-2), and formula (Ina N, N'-hexamethylenebis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by -3) is mentioned.

For example, the liquid crystal aligning agent of this invention may further contain the compound which has a radically polymerizable unsaturated double bond from a viewpoint of stabilizing the electrical characteristic of a liquid crystal display element for a long term. The compound which has a radically polymerizable unsaturated double bond may be 1 type of compounds, or 2 or more types of compounds may be sufficient as it. In addition, the alkenyl substituted naimide compound is not included in the compound having the radically polymerizable unsaturated double bond. As for content of the compound which has the said radically polymerizable unsaturated double bond, it is preferable that it is 0.01-1.00 by weight ratio with respect to a polyamic acid or its derivative from a viewpoint mentioned above, It is more preferable that it is 0.01-0.70, It is 0.01-0.50 Most preferred.

And the ratio of the compound which has a radically polymerizable unsaturated double bond with respect to an alkenyl substituted nadimide compound reduces the ion density of a liquid crystal display element, suppresses the time-dependent increase of ion density, and also From a viewpoint of suppressing afterimage, it is preferable that it is 0.1-10 in a weight ratio, and it is more preferable that it is 0.5-5.

As a compound which has a radically polymerizable unsaturated double bond, (meth) acrylic acid derivatives, such as (meth) acrylic acid ester and (meth) acrylic acid amide, and bismaleimide are mentioned. It is more preferable that the compound which has the said radically polymerizable unsaturated double bond is a (meth) acrylic acid derivative which has 2 or more of radically polymerizable unsaturated double bonds.

As a specific example of (meth) acrylic acid ester, (meth) acrylic-acid cyclohexyl, (meth) acrylic-acid 2-methylcyclohexyl, (meth) acrylic-acid dicyclopentanyl, (meth) acrylic-acid dicyclopentanyloxyethyl, (meth) Isobornyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate. (Meth) acrylic acid 2-hydroxyethyl, and (meth) acrylic acid 2-hydroxypropyl.

As a specific example of a bifunctional (meth) acrylic acid ester, For example, ethylene bisacrylate, Aronix M-210, Aronix M-240, and Aronix M-6200 which are products of Toa Synthetic Chemical Co., Ltd., Nippon Kayaku Co., Ltd. ) KAYARADHDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684, Osaka Organic Chemical Industry Co., Ltd. V260, V312 and V335HP, and Kyoesha Oil Chemical Co., Ltd. Light Acrylate BA-4EA, Light Acryl Rate BP-4PA and lightacrylate BP-2PA.

As a specific example of the trifunctional or more than trifunctional (meth) acrylic acid ester, For example, 4,4'- methylenebis (N, N- dihydroxy ethylene acrylate aniline), Aronix M which is a product made from Toa Synthetic Chemical Industries, Ltd. -400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Nippon Kayaku Co., Ltd. KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA- 30, KAYARAD DPCA-60, KAYARAD DPCA-120, and VGPT, a product of Osaka Organic Chemical Industry Co., Ltd.

As a specific example of a (meth) acrylic-acid amide derivative, N-isopropyl acrylamide, N-isopropyl methacrylamide, Nn-propyl acrylamide, Nn-propyl methacrylamide, N-cyclopropyl acrylamide, N, for example -Cyclopropyl methacrylamide, N-ethoxyethylacrylamide, N-ethoxyethyl methacrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N -Ethyl-N-methylacrylamide, N, N-diethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acrylic Loylpyrrolidine, N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide , N-phenyl methacrylamide, N-butyl methacrylamide, N- (i so-butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] meta Krillamide, N- (methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N'-methylenebismethacrylamide have.

Of the (meth) acrylic acid derivatives, N, N'-methylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, ethylenebisacrylate, and 4,4'-methylenebis (N, N-di Hydroxyethylene acrylate aniline) is particularly preferred.

As bismaleimide, for example, BMI-70 and BMI-80, manufactured by K-I Hwasung Co., Ltd., BMI-1000, BMI-3000, BMI-4000, BMI-5000, and BMI-, manufactured by Daiwa Chemical Co., Ltd. There are 7000.

For example, the liquid crystal aligning agent of this invention may contain the oxazine compound further from a viewpoint of the long-term stability of the electrical characteristic of a liquid crystal display element. The oxazine compound may be one kind of compound or two or more kinds of compounds. As for content of the said oxazine compound, it is preferable that it is 0.1-50 weight% with respect to the said polyamic acid or its derivative from a viewpoint mentioned above, It is more preferable that it is 1-40 weight%, It is most preferable that it is 1-20 weight% desirable.

An oxazine compound is soluble in the solvent which melt | dissolves a polyamic acid or its derivative, In addition, the oxazine compound which has ring-opening polymerization property is preferable.

In addition, the number of the oxazine structure in an oxazine compound is not specifically limited.

Various structures are known in the structure of an oxazine. Although the structure of an oxazine is not specifically limited in this invention, As an oxazine structure in the said oxazine compound, the oxazine structure which has aromatic groups containing condensed polycyclic aromatic groups, such as benzoxazine and naphthooxazine, is taken as an example. Can be mentioned.

As an oxazine compound, there exists a compound represented, for example by following formula (a)-(f). And in the following formula, the bond shown toward the center of a ring shows that it is couple | bonded with any one of carbon which can couple | bond a substituent, forming a ring.

In formula (a)-(c), R <^1> and R <^2> is a C1-C30 organic group. In addition, in Formula (a)-(f), R <^3> -R <^6> represents hydrogen or a C1-C6 hydrocarbon group. In formulas (c), (d) and (f), X is a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO- , -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, -S- (CH ₂ ) _m -S- to be. Where m is an integer of 1-6. In the formulas (e) and (f), Y is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- Or alkylene having 1 to 3 carbon atoms. Then, the expression (a)? A benzene ring in (f), hydrogen which is bonded to the naphthalene ring are, independently, _{-F, -CH 3, -OH, -COOH} , -SO 3 H, -PO 3 H 2 And may be substituted.

The oxazine compound includes oligomers and polymers having an oxazine structure in the side chain and oligomers and polymers having an oxazine structure in the main chain.

As an oxazine compound represented by Formula (a), the following oxazine compounds are mentioned, for example.

In formula, R <^1> has preferable C1-C30 alkyl, and its C1-C20 alkyl is more preferable.

As an oxazine compound represented by Formula (b), the following oxazine compounds are mentioned, for example.

In formula, R <^1> has preferable C1-C30 alkyl, and its C1-C20 alkyl is more preferable.

As an oxazine compound represented by Formula (c), the oxazine compound represented by following formula (c ') is mentioned.

Formula (c ') of, R ¹ and R ² are C 1 30 of the organic group, R ³ to R ⁶ is a hydrocarbon group, X is a single bond, a hydrogen or carbon number of _{1 6, -CH 2 -??} , -C ( CH ₃ ) _2- , -CO-, -O-, -SO ₂ -or C (CF ₃ ) _2- .

As an oxazine compound represented by said formula (c '), the following oxazine compound is mentioned, for example.

In the formula, R ¹ is a C 1? 30 alkyl, and more preferably a C 1? 20 alkyl.

As an oxazine compound represented by Formula (d), the following oxazine compounds are mentioned, for example.

As an oxazine compound represented by Formula (e), the following oxazine compounds are mentioned, for example.

As an oxazine compound represented by Formula (f), the following oxazine compounds are mentioned, for example.

Among these, More preferably, Formula (b-1), Formula (c-1), Formula (c-3), Formula (c-5), Formula (c-7), Formula (c-9), The oxazine compound represented by a formula (d-1)-a formula (d-6), a formula (e-3), a formula (e-4), a formula (f-2)-a formula (f-4) is mentioned, for example. Can be.

The oxazine compound mentioned above can be manufactured by the method similar to the method of international publication 2004/009708 pamphlet, Unexamined-Japanese-Patent No. 11-12258, and Unexamined-Japanese-Patent No. 2004-352670.

For example, the oxazine compound represented by formula (a) is obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication 2004/009708 pamphlet).

In addition, the oxazine compound represented by Formula (b) is obtained by reacting by adding a primary amine to formaldehyde gradually, and then adding and reacting the compound which has a naphthol type hydroxyl group (International Publication 2004/009708). Issue pamphlet).

In addition, the oxazine compound represented by Formula (c) is a secondary aliphatic amine which contains at least 2 mol or more of aldehydes and 1 mol of primary amines with respect to 1 mol of phenol compounds, 1 mol of phenolic hydroxyl groups in an organic solvent. Obtained by reacting in the presence of a tertiary aliphatic amine or an alkali-containing nitrogen heterocyclic compound (see International Publication 2004/009708 pamphlet and Japanese Patent Application Laid-open No. Hei 11-12258).

Moreover, the oxazine compound represented by Formula (d)-(f) is aldehydes, such as diamine and formalin, which have several benzene rings, such as 4,4'- diamino diphenylmethane, and the organic group which couples these, and phenol Is obtained by dehydrating condensation reaction at a temperature of 90 ° C. or higher in n-butanol (see Japanese Patent Application Laid-open No. 2004-352670).

For example, the liquid crystal aligning agent of this invention may contain the oxazoline compound further from a viewpoint of the long-term stability of the electrical characteristic in a liquid crystal display element. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one kind of compound or two or more kinds of compounds. As for content of the said oxazoline compound, it is preferable that it is 0.1-50 weight% with respect to the said polyamic acid or its derivative from a viewpoint mentioned above, It is more preferable that it is 1-40 weight%, It is most preferable that it is 1-20 weight% desirable. Alternatively, the content of the oxazoline compound is preferably from 0.1 to 40% by weight based on the polyamic acid or its derivative when the oxazoline structure in the oxazoline compound is converted to oxazoline.

The oxazoline compound may have only one type of oxazoline structure in one compound, and may have two or more types. Moreover, although the said oxazoline compound may have one said oxazoline structure in one compound, it is preferable to have two or more. In addition, an oxazoline compound may be a polymer which has an oxazoline structure in a side chain, and may be a copolymer. The polymer which has an oxazoline structure in a side chain may be a homopolymer of the monomer which has an oxazoline structure in a side chain, and may be a copolymer of the monomer which has an oxazoline structure in a side chain, and the monomer which does not have an oxazoline structure. The copolymer which has an oxazoline structure in a side chain may be a copolymer of 2 or more types of monomers which have an oxazoline structure in a side chain, and the monomer of two or more types of monomers which have an oxazoline structure in a side chain, and the monomer which does not have an oxazoline structure A copolymer may be sufficient.

The oxazoline structure is preferably a structure present in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure and the carbonyl group of the polyamic acid can react.

As an oxazoline compound, 2,2'-bis (2-oxazoline), 1,2, 4- tris (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-, 2-phenyl-4H-oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl ) Benzene, 2,3-bis (4-isopropenyl-2-oxazolin-2-yl) butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl) 2-oxazolin-2-yl) pyridine, 2,2'-isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2- Oxazoline), 2,2'-methylenebis (4-tert-butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline). In addition to these, polymers and oligomers having oxazolyl such as epochross (trade name, manufactured by Nippon Catalyst Co., Ltd.) may also be mentioned.

More preferable oxazoline compounds include 2,2'-bis (2-oxazoline) and 1,3-bis (4,5-dihydro-2-oxazolyl) benzene.

For example, the liquid crystal aligning agent of this invention may contain the epoxy compound further from a viewpoint of the long-term stability of the electrical characteristic in a liquid crystal display element. The said epoxy compound may be 1 type of compounds, or 2 or more types of compounds may be sufficient as it. It is preferable that content of the said epoxy compound is 0.1-50 weight% with respect to the said polyamic acid or its derivative (s) from the above-mentioned viewpoint, It is more preferable that it is 1-40 weight%, It is most preferable that it is 1-20 weight% Do.

As an epoxy compound, the various compound which has one or two or more epoxy rings in a molecule | numerator is mentioned. Examples of the compound having one epoxy ring in the molecule include phenylglycidyl ether, butylglycidyl ether, 3,3,3-trifluoromethylpropylene oxide, styrene oxide and hexafluoropropylene oxide. , Cyclohexene oxide, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-n- Butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N, N- diglycidylaniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene. Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether , 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate and 3- (N, N-diglycidyl) aminopropyltrimethoxysilane.

Examples of the compound having three epoxy rings in the molecule include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2, 3-epoxypropoxy] phenyl] ethyl] phenyl] propane (trade name "Texmore VG3101L", manufactured by Mitsui Chemicals Corporation).

As a compound which has four epoxy rings in a molecule | numerator, for example, 1,3,5,6- tetraglycidyl-2,4-hexanediol, N, N, N ', N'- tetraglycidyl- m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane , And 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane.

In addition to the foregoing, examples of the compound having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring. As a monomer which has an epoxy ring, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, and methylglycidyl (meth) acrylate are mentioned, for example.

As another monomer copolymerizing with the monomer which has an epoxy ring, it is (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth ) Acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

As a preferable specific example of the polymer of the monomer which has an epoxy ring, polyglycidyl methacrylate etc. are mentioned. Moreover, as a preferable specific example of the copolymer of the monomer which has an epoxy ring, and another monomer, N-phenylmaleimide- glycidyl methacrylate copolymer, N-cyclohexyl maleimide- glycidyl methacrylate copolymer, Benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl 3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer.

Among these examples, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N' , N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Texmore VG3101L", 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, Particular preference is given to N-phenylmaleimide-glycidyl methacrylate copolymers and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Systematically, as said epoxy compound, glycidyl ether, glycidyl ester, glycidyl amine, an epoxy-group containing acrylic resin, glycidyl amide, glycidyl isocyanurate, a chain | strand (鎖 狀) ) Aliphatic epoxy compounds, and cyclic aliphatic epoxy compounds. And an epoxy compound means the compound which has an epoxy group, and an epoxy resin means resin which has an epoxy group.

As glycidyl ether, for example, a bisphenol-A epoxy compound, a bisphenol F-type epoxy compound, a bisphenol S-type epoxy compound, a bisphenol-type epoxy compound, a hydrogenated bisphenol-A type epoxy compound, a hydrogenated bisphenol-F type epoxy compound, hydrogenation Bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolak type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolak type epoxy compound , Brominated cresol novolac epoxy compound, bisphenol A novolac epoxy compound, naphthalene skeleton-containing epoxy compound, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic Polyglycidyl Ether Compound, Polysulfide Type Diglycidyl ether compounds, and biphenol type epoxy compounds.

As glycidyl ester, there exist a diglycidyl ester compound and a glycidyl ester epoxy compound, for example.

As glycidylamine, there exists a polyglycidyl amine compound, for example.

Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having oxiranyl.

As glycidyl amide, there exists a glycidyl amide type epoxy compound, for example.

As a linear aliphatic epoxy compound, there exists a compound containing an epoxy group obtained by oxidizing the carbon-carbon double bond of an alkene compound, for example.

As a cyclic aliphatic epoxy compound, there exists a compound containing an epoxy group obtained by oxidizing the carbon-carbon double bond of a cycloalkene compound, for example.

As the bisphenol A epoxy compound, for example, 828, 1001, 1002, 1003, 1004, 1007, 1010 [all of which can be obtained as Japan's epoxy resin products (currently available as jER series products of Mitsubishi Chemical Corporation) ), Efototo YD-128 [manufactured by Toto Chemical Co., Ltd.], DER-331, DER-332, DER-324 (all from The Dow Chemical Company), epicron 840, epicron 850, epicron 1050 [All are manufactured by DIC Corporation], Epomic R-140, Epomic R-301, and Epomic R-304 (all are manufactured by Mitsui Chemical Co., Ltd.).

As a bisphenol F-type epoxy compound, for example, 806, 807, 4004P [all are the products made by Japan Epoxy Resin Co., Ltd.], Efototo YDF-170, Efototo YDF-175S, Efototo YDF-2001 [all Toto Hwasung Corporation], DER-354 (manufactured by The Dow Chemical Company), Epicron 830, and Epicron 835 (all manufactured by DIC Corporation).

As a bisphenol-type epoxy compound, the epoxide of 2, 2-bis (4-hydroxy phenyl) -1,1,1,3,3,3-hexafluoro propane is mentioned, for example.

Examples of the hydrogenated bisphenol-A epoxy compound include Santoto ST-3000 (manufactured by Toto Chemical Co., Ltd.), Licarazine HBE-100 (manufactured by Nippon Kasei), and Denacol EX-252 (manufactured by Nagase Chemtex Co., Ltd.). There is.

As a hydrogenated bisphenol-type epoxy compound, the epoxide of hydrogenated 2, 2-bis (4-hydroxyphenyl) -1, 1, 1, 3, 3, 3- hexafluoro propane is mentioned, for example.

Examples of the brominated bisphenol-A epoxy compound include 5050 and 5051 (all manufactured by Japan Epoxy Resin Co., Ltd.), Efototo YDB-360 and Efototo YDB-400 [all manufactured by Toto Chemical Co., Ltd.], DER-530, DER-538 (all from The Dow Chemical Company), epicron 152, and epicron 153 (all manufactured by DIC Corporation).

As a phenol novolak-type epoxy compound, for example, 152,154 (all are manufactured by Japan Epoxy Resin), YDPN-638 (made by Toto Kasei Co., Ltd.), DEN431, DEN438 (all are manufactured by The Dow Chemical Company), and epikron N, for example. -770 (manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.).

As a cresol novolak-type epoxy compound, for example, 180S75 [product made by Japan Epoxy Resin Co., Ltd.], YDCN-701, YDCN-702 [all Toto Kasei Co., Ltd. product], epicron N-665, and epicron N- 695 (all from DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all from Nippon Kayaku Co., Ltd. product).

As a bisphenol A novolak-type epoxy compound, there are 157S70 (made by Japan Epoxy Resin Co., Ltd.), and epicron N-880 (made by DIC Co., Ltd.), for example.

Examples of naphthalene skeleton-containing epoxy compounds include epicron HP-4032, epicron HP-4700, epicron HP-4770 (all manufactured by DIC Corporation), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.). have.

As an aromatic polyglycidyl ether compound, for example, hydroquinone diglycidyl ether (following formula E101), catechol diglycidyl ether (following formula E102), resorcinol diglycidyl ether (following formula E103) , Tris (4-glycidyloxyphenyl) methane (formula E105), 1031S, 1032H60 [all of Japan Epoxy Resin Co., Ltd.], TACTIX-742 (manufactured by The Dow Chemical Company), Denacol EX-201 [Nagase Chemtex Co., Ltd.], DPPN-503, DPPN-502H, DPPN-501H, NC6000 [All Nippon Kayaku Co., Ltd.], Tekmore VG3101L [Product of Mitsui Chemicals Co., Ltd.], the compound represented by following formula E106. And a compound represented by the following formula E107.

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by The Dow Chemical Company) and epiclon HP-7200 (manufactured by DIC Corporation).

As an alicyclic diglycidyl ether compound, there exist a cyclohexane dimethanol diglycidyl ether compound, and ligazine resin DME-100 (made by Nippon Kasei Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compounds include ethylene glycol diglycidyl ether (following formula E108), diethylene glycol diglycidyl ether (following formula E109), polyethylene glycol diglycidyl ether, and propylene glycol. Diglycidyl ether (following formula E110), tripropylene glycol diglycidyl ether (following formula E111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (following formula E112), 1, 4-butanediol diglycidyl ether (following formula E113), 1,6-hexanediol diglycidyl ether (following formula E114), dibromoneopentyl glycol diglycidyl ether (following formula E115), denacol EX-810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX- 313 [All Nagase Chemtex Co., Ltd.], DD-503 [ADEKA Co., Ltd.], Licar Resin W-100 [New Nippon Ewha Co., Ltd.], 1,3,5,6-tetra glycidyl -2,4-hexanediol (formula E116 below), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropanepolyglycidyl ether, pentaerythritol polyglycidyl ether, denacol EX-313 , Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all are manufactured by Nagase Chemtex Co., Ltd.).

Examples of the polysulfide diglycidyl ether compound include FLDP-50 and FLDP-60 (all manufactured by Dore Thiolol Co., Ltd.).

As a biphenol type epoxy compound, YX-4000, YL-6121H (all are manufactured by Japan Epoxy Resin Co., Ltd.), NC-3000P, and NC-3000S (all are Nippon Kayaku Co., Ltd. product) are mentioned, for example.

As a diglycidyl ester compound, for example, diglycidyl terephthalate (following formula 117), diglycidyl phthalate (following formula E118), bis (2-methyloxyranylmethyl) phthalate (following formula E119) , A compound represented by the following formula E121, a compound represented by the following formula E122, and a compound represented by the following formula E123.

As the glycidyl ester epoxy compound, for example, 871, 872 [all manufactured by Japan Epoxy Resin Co., Ltd.], epicron 200, epicron 400 [all DIC Co., Ltd.], Denacol EX-711, and dena Call EX-721 (all manufactured by Nagase Chemtex Co., Ltd.).

As a polyglycidyl amine compound, for example, N, N- diglycidyl aniline (following formula E124), N, N- diglycidyl o-toluidine (following formula E125), N, N-di Glycidyl m-toluidine (formula E126), N, N-diglycidyl-2,4,6-tribromoaniline (formula E127), 3- (N, N-diglycidyl) amino Propyltrimethoxysilane (formula E128), N, N, O-triglycidyl-p-aminophenol (formula E129), N, N, O-triglycidyl-m-aminophenol (formula E130) , N, N, N ', N'-tetraglycidyl-m-xylenediamine [TETRAD-X, Mitsubishi Gas Chemical Co., Ltd., following formula E132], 1,3-bis (N, N- digly Cydylaminomethyl) cyclohexane [TETRAD-C, Mitsubishi Gas Chemical Co., Ltd.], following formula E133), 1, 4-bis (N, N- diglycidylaminomethyl) cyclohexane (following formula E134) , 1,3-bis (N, N-diglycidylamino) cyclohexane (formula E135), 1,4-bis (N, N-diglycidylamino) cyclohexane (formula E136), 1 , 3-bis (N, N-diglycidylamino ) Benzene (formula E137), 1,4-bis (N, N-diglycidylamino) benzene (formula E138), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (formula E139), N, N, N ', N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (formula E140), 2,2'-dimethyl -(N, N, N ', N'-tetraglycidyl) -4,4'-diaminophenyl (formula E141), N, N, N', N'-tetraglycidyl-4,4 '-Diaminodiphenyl ether (formula E142), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene (formula E143), 2,4,4' -Tris (N, N-diglycidylamino) diphenylether (formula E144), tris (4- (N, N-diglycidyl) aminophenyl) methane (formula E145), 3,4, 3 ', 4'-tetrakis (N, N- diglycidylamino) biphenyl (formula E146 below), 3,4,3', 4'-tetrakis (N, N- diglycidylamino) Diphenyl ether (following formula E147), the compound represented by the following formula E148, and the compound represented by the following formula E149 are mentioned.

As a homopolymer of the monomer which has an oxiranyl, polyglycidyl methacrylate is mentioned, for example. As a copolymer of the monomer which has the said oxiranyl, for example, N-phenylmaleimide glycidyl methacrylate copolymer, N-cyclohexyl maleimide glycidyl methacrylate copolymer, benzyl methacrylate Glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-jade Cetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Examples of the monomer having oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methylglycidyl (meth) acrylate.

As monomers other than the monomer which has the said oxiranyl in the copolymer of the monomer which has oxiranyl, it is (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth), for example. ) Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, crawlmethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

As glycidyl isocyanurate, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (following) Formula E150), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (formula E151), and Glycidyl isocyanurate type epoxy resins.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and eporide PB3600 (manufactured by Daicel Chemical Industries, Ltd.).

Examples of the cyclic aliphatic epoxy compound include 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexyl carboxylate (formula E153), 2,3 -Epoxycyclopentane-2 ', 3'-epoxycyclopentane ether (formula E154 below), epsilon -caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, 1, 2: 8,9- diepoxylimonene [Celoxide 3000, the product made by Daicel Chemical Industries, Ltd.], 3, 4- epoxycyclohexenylmethyl-3 ', 4'- epoxycyclohexene carboxylate [celloxide 2021P] , Daicel Chemical Co., Ltd. product, the following formula E155, the compound represented by the following formula E156, CY-175, CY-177, CY-179 [all The Ciba-Geigy Chemical Corp. Products (available from Hanzman Japan), EHPD-3150 (manufactured by Daicel Chemical Industries, Ltd.), and cyclic aliphatic epoxy resins.

For example, the liquid crystal aligning agent of this invention may further contain various additives. As various additives, there exist high molecular compounds other than a polyamic acid and its derivatives, and a low molecular compound, for example, It can select and use according to each objective.

For example, the polymer compound is a polymer compound soluble in an organic solvent. It is preferable to add such a high molecular compound with the liquid crystal aligning agent of this invention from a viewpoint of controlling the electrical characteristic and orientation of the liquid crystal aligning film formed. Examples of the high molecular compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone modified polyurethane, and silicone modified polyester.

Further, as the low molecular weight compound, for example, 1) a surfactant according to the above-mentioned object when the applicability is desired, 2) an antistatic agent is required when the antistatic agent is required, and 3) when an adhesion with the substrate is desired. 4) In the case of advancing the imidization at a low temperature, there is an imidization catalyst.

As a silane coupling agent, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-, for example. Aminopropylmethyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N '-Bis [3- (trimethoxysilyl) propyl] ethylenediamine. Preferred silane coupling agents are 3-aminopropyltriethoxysilanes.

As an imidation catalyst, For example, aliphatic amines, such as trimethylamine, triethylamine, tripropylamine, and tributylamine; Aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl substituted aniline and hydroxy substituted aniline; Pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, etc. Cyclic amines. The imidation catalyst is one or two or more selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline. desirable.

The amount of the silane coupling agent added is usually 0 to 20% by weight of the total weight of the polyamic acid or its derivatives, and preferably 0.1 to 10% by weight.

The addition amount of an imidation catalyst is 0.01-5 equivalent normally with respect to the carbonyl group of polyamic acid or its derivative (s), and it is preferable that it is 0.05-3 equivalent.

Although the addition amount of another additive changes with the use, it is 0-100 weight% of the total weight of a polyamic acid or its derivative normally, and it is preferable that it is 0.1-50 weight%.

For example, the liquid crystal aligning agent of this invention is an acrylic acid polymer, an acrylate polymer, in the range which does not impair the effect of this invention (preferably within 20 weight% of the said polyamic acid or its derivative), And other polymer components such as polyamideimide, which is a reaction product of tetracarboxylic dianhydride, dicarboxylic acid or a derivative thereof and diamine.

For example, the liquid crystal aligning agent of this invention may contain the solvent further from a viewpoint of the coating property of a liquid crystal aligning agent, the density | concentration adjustment of the said polyamic acid, or its derivative (s). The solvent can be applied without particular limitation as long as it is a solvent having the ability to dissolve the polymer component. The said solvent contains the solvent normally used by the manufacturing process of a polymeric component, such as a polyamic acid and a soluble polyimide, and a use, and can be suitably selected according to a use purpose. The solvent may be one kind or two or more kinds of mixed solvents.

As a solvent, the solvent of the said polyamic acid or its derivative (s), and the other solvent for the purpose of improving applicability | paintability are mentioned.

As an aprotic polar organic solvent which is a solvent with respect to a polyamic acid or its derivative (s), N-methyl- 2-pyrrolidone, dimethyl imidazolidinone, N-methyl caprolactam, N-methyl propionamide, N, N- And lactones such as dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide and γ-butyrolactone.

Examples of other solvents for the purpose of improving coating properties include ethylene glycol monoalkyl ethers such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and ethylene glycol monobutyl ether, and diethylene glycol mono Diethylene glycol monoalkyl ethers such as ethyl ether, ethylene glycol monoalkyl or phenyl acetate, propylene glycol monoalkyl ethers such as triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethyl malonic acid, and the like. Ester compounds, such as dipropylene glycol monoalkyl ether, such as dialkyl dialkyl and dipropylene glycol monomethyl ether, and these acetates, are mentioned.

Among these solvents, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and propylene glycol Monomethyl ether and dipropylene glycol monomethyl ether are particularly preferable.

Although the density | concentration of the polymer component containing the said polyamic acid or its derivative in a liquid crystal aligning agent in this invention is not specifically limited, 0.1-40 weight% is preferable. When apply | coating the said liquid crystal aligning agent to a board | substrate, the operation which dilutes the polymer component contained for the film thickness adjustment with a solvent beforehand may be needed. It is preferable that the density | concentration of the said polymer component is 40 weight% or less from a viewpoint of adjusting the viscosity of a liquid crystal aligning agent to the viscosity suitable for mixing a solvent with respect to a liquid crystal aligning agent easily at this time.

In addition, the density | concentration of the said polymer component in a liquid crystal aligning agent may be adjusted with the coating method of a liquid crystal aligning agent. When the coating method of a liquid crystal aligning agent is a spinner method or the printing method, in order to maintain a favorable film thickness, the density | concentration of the said polymer component is usually made into 10 weight% or less in many cases. In other coating methods, for example, the dipping method or the inkjet method, the concentration may be further lowered. On the other hand, when the density | concentration of the said polymer component is 0.1 weight% or more, the film thickness of the liquid crystal aligning film obtained will be easily optimized. Therefore, the density | concentration of the said polymer component is 0.1 weight% or more, Preferably it is 0.5-10 weight% in normal spinner method, printing method, etc. However, depending on the coating method of a liquid crystal aligning agent, you may use at a lower density | concentration.

And when using for manufacture of a liquid crystal aligning film, the viscosity of the liquid crystal aligning agent of this invention can be determined according to the means or method of forming the film of this liquid crystal aligning agent. For example, when forming the film of a liquid crystal aligning agent using a printing machine, it is preferable that it is 5 mPa * s or more from a viewpoint of obtaining sufficient film thickness, and it is preferable that it is 100 mPa * s or less from a viewpoint of suppressing printing nonuniformity. More preferably, it is 10-80 mPa * s. When apply | coating a liquid crystal aligning agent by spin coating, and forming a film of a liquid crystal aligning agent, it is preferable that it is 5-200 mPa * s, More preferably, it is 10-100 mPa * s from a viewpoint similar to the above. The viscosity of a liquid crystal aligning agent can be reduced by curing by dilution with a solvent, and stirring.

The liquid crystal aligning agent of this invention may be the form containing one type of polyamic acid or its derivative (s), and may be the form of what is called polymer blend in which 2 or more types of polyamic acid or its derivative (s) are mixed.

Although the liquid crystal aligning film of this invention is a film formed by heating the coating film of the liquid crystal aligning agent of this invention, as mentioned above, linearly polarized light of an ultraviolet-ray is irradiated before or after heating a coating film.

The said coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to manufacture of a normal liquid crystal aligning film. The said board | substrate has a glass substrate which may be provided with electrodes, such as an ITO (Indium Tin Oxide) electrode, a color filter, etc.

As a method of apply | coating a liquid crystal aligning agent to a board | substrate, the spinner method, the printing method, the dipping method, the dropping method, the inkjet method, etc. are generally known. These methods can be similarly applied to the present invention.

The firing of the coating film can be carried out under conditions necessary for the polyamic acid or its derivative to undergo a dehydration / closing reaction. As the baking of the coating film, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods can be similarly applied in the present invention. Generally, it is preferable to carry out for 1 minute-3 hours at the temperature of about 150-300 degreeC.

The liquid crystal aligning film of this invention is obtained preferably by the method which further contains other processes other than the process mentioned above. As such another process, the process etc. which dry the said coating film are mentioned. And the liquid crystal aligning film of this invention does not need the process of wash | cleaning the film | membrane after baking or ultraviolet irradiation with a washing | cleaning liquid, but installing a washing | cleaning process is not prevented by the circumstances of another process.

As for the drying process, the method of heat-processing in oven or infrared, the method of heat-processing on a hotplate, etc. are generally known similarly to the said baking process. These methods can be similarly applied to the drying step. It is preferable to perform a drying process at the temperature within the range which a solvent can evaporate, and it is more preferable to carry out at the temperature comparatively low compared with the temperature of the said baking process.

As a washing | cleaning method with a washing | cleaning liquid, brushing, jet spray, steam washing | cleaning, ultrasonic washing | cleaning, etc. are mentioned, for example. These methods may be performed independently or may be used together. Examples of the cleaning liquid include pure water or various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, acetone and methyl ethyl ketone. Although ketones can be used, it is not limited to these. Of course, these washing | cleaning liquids are refine | purified sufficiently and the thing with few impurities is used. Such a cleaning method can be applied also to the said washing process in formation of the liquid crystal aligning film of this invention.

Although the film thickness of the liquid crystal aligning film of this invention is not specifically limited, It is preferable that it is 10-300 nm, and it is more preferable that it is 30-150 nm. The film thickness of the liquid crystal aligning film of this invention can be measured by well-known film thickness measuring devices, such as a stepmeter and an ellipsometer.

The liquid crystal display element of this invention contains a pair of board | substrates, a liquid crystal molecule, the liquid crystal layer formed between the said pair of board | substrates, the electrode which applies a voltage to a liquid crystal layer, and orients the said liquid crystal molecules in a predetermined direction. It has a liquid crystal aligning film to make. The liquid crystal aligning film of this invention mentioned above is used for the said liquid crystal aligning film.

The glass substrate mentioned above can be used for the board | substrate with the liquid crystal aligning film of this invention, and the ITO electrode formed in the glass substrate as mentioned above with the liquid crystal aligning film of this invention can be used for a board | substrate.

The liquid crystal layer is formed of a liquid crystal composition sealed in a gap between a pair of substrates facing each other so that a surface on which a liquid crystal alignment film in one of the pair of substrates is formed faces the other substrate.

There is no restriction | limiting in particular in a liquid crystal composition, The various liquid crystal composition whose dielectric anisotropy is plus or minus can be used. As preferred liquid crystal compositions having positive dielectric anisotropy, Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Publication No. Hei 5-501735, Japanese Patent Application Publication No. Hei 8-157826, and Japanese Patent Japanese Patent Application Laid-open No. Hei 8-231960, Japanese Patent Application Laid-open No. Hei 9-241644 (EP885272A1 specification), Japanese Patent Application Publication No. Hei 9-302346 (EP806466A1 specification), Japanese Patent Application Publication No. Hei 8- Japanese Patent Application Publication No. Hei 9-235552, Japanese Patent Application Publication No. Hei 9-255956, Japanese Patent Application Publication No. Hei 9-241643 (EP885271A1 Specification), Japanese Patent Application Japanese Patent Application Laid-open No. Hei 10-204016 (EP844229A1 specification), Japanese Patent Application Laid-open No. Hei 10-204436, Japanese Patent Application Laid-open No. Hei 10-231482, Japanese Patent Application Laid-open No. 2000-087040, There may be mentioned a liquid crystal composition that is disclosed in this Patent Application Laid-Open No. 2001-48822 as an example.

As a preferable liquid crystal composition whose dielectric anisotropy is negative, Unexamined-Japanese-Patent No. 57-114532, Unexamined-Japanese-Patent No. 2-4725, Unexamined-Japanese-Patent No. 4-224885, and Japan Patent Application Publication No. 8-40953, Japanese Patent Application Publication No. 8-104869, Japanese Patent Application Publication No. 10-168076, Japanese Patent Application Publication No. 10-168453, Japanese Patent Application Publication No. 10-236989, Japanese Patent Application Laid-Open No. 10-236990, Japanese Patent Application Laid-open No. 10-236992, Japanese Patent Application Laid-open No. 10-236993, Japanese Patent Application Publication No. 10-23 236994, Japanese Patent Application Publication No. Hei 10-237000, Japanese Patent Application Publication No. Hei 10-237004, Japanese Patent Application Publication No. Hei 10-237024, Japanese Patent Application Publication No. Hei 10-237035 Gazette, Japanese Patent Application Publication No. Hei 10-237075, Japanese Patent Application Publication No. Hei 10-237076, Japanese Patent Application Publication No. Hei 10-237448 (EP967261A1 specification), Japanese Patent Application Publication No. Hei 10-287874 Japanese Patent Application Publication No. Hei 10-287875, Japanese Patent Application Publication No. Hei 10-291945, Japanese Patent Application Publication No. Hei 11-029581, Japanese Patent Application Publication No. Hei 11-080049, The liquid crystal composition disclosed in Unexamined-Japanese-Patent No. 2000-256307, Unexamined-Japanese-Patent No. 2001-019965, Unexamined-Japanese-Patent No. 2001-072626, Unexamined-Japanese-Patent No. 2001-192657, etc. are mentioned. .

There is no problem even if one or more optically active compounds are added to the liquid crystal composition having a dielectric constant anisotropy plus or minus.

The liquid crystal display element of this invention forms the liquid crystal aligning film of this invention in at least one of a pair of board | substrate, and opposes a pair of board | substrates obtained which face a liquid crystal aligning film through a spacer in an inner direction, and forms a liquid crystal in the clearance gap formed between board | substrates. It is obtained by sealing a composition and forming a liquid crystal layer. In manufacturing of the liquid crystal display element of this invention, the new process, such as affixing a polarizing film to a board | substrate may be included as needed.

The liquid crystal display element of this invention can form the liquid crystal display element for various electric field systems. As such a liquid crystal display device for an electric field system, a liquid crystal display device for a transverse electric field system in which the electrode applies a voltage to the liquid crystal layer in a horizontal direction with respect to the surface of the substrate, or the electrode in a direction perpendicular to the surface of the substrate. The liquid crystal display element for the longitudinal electric field system which applies a voltage to this said liquid crystal layer is mentioned as an example.

The liquid crystal aligning film manufactured using the liquid crystal aligning agent of this invention as a raw material can be applied to the liquid crystal display element of various display drive systems by selecting the polymer which is this raw material suitably.

The liquid crystal display element of this invention may further have elements other than the component mentioned above. As such another component, the component normally used for liquid crystal display elements, such as a polarizing plate (polarizing film), a wavelength plate, a light scattering film, a drive circuit, may be mounted in the liquid crystal display element of this invention.

[Example]

Hereinafter, an Example demonstrates this invention. And the compound used in the Example is as follows.

Tetracarboxylic dianhydride

Acid dianhydride (A1): 1,2,3,4-cyclobutanetetracarboxylic dianhydride

Acid dianhydride (A2): pyromellitic dianhydride

Acid dianhydride (A3): 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride

<Diamine>

Diamine (D1): N, N'-bis (4-aminophenyl) -N, N'-dimethylethylenediamine

Diamine (D2): N, N'-bis (4-aminophenyl) piperazine

Diamine (D3): 4,4'-diaminodiphenylmethane

Diamine (D4): 3,3'-diaminodiphenylmethane

Diamine (D5): 1,4-phenylenediamine

Diamine (D6): 4,4'-diaminoazobenzene

Diamine (D7): 4,4'-diaminodiphenylamine

<Solvent>

N-methyl-2-pyrrolidone: NMP

Butyl cellosolve (ethylene glycol monobutyl ether): BC

<Additive>

Additive (Ad1): bis [4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl] methane

Additive (Ad2): N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

Additive (Ad3): 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

Additive (Ad4): 3-aminopropyltriethoxysilane

<1. Synthesis of Polyamic Acid>

Synthesis Example 1

In a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 3.397 g of diamine (D1) and 40.0 g of dehydrated NMP were placed and dissolved under stirring in a dry nitrogen stream. Subsequently, 1.232 g of acid dianhydride (A1), 1.370 g of acid dianhydride (A2) and 40.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. BC14.0g was added to this reaction solution, and the polyamic-acid solution of 6 weight% of polymer solid content concentration was obtained. This polyamic acid solution is called PA1. The weight average molecular weight of the polyamic acid contained in PA1 was 104,500.

The weight average molecular weight of the polyamic acid was measured by GPC method using a 2695 Separation Module 2414 Differential Refractometer (manufactured by Waters), and determined by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that a polyamic acid concentration might be about 2 weight%. The column was measured using HSPgel RT MB-M (manufactured by Waters) using the mixed solution as a developing agent under a column temperature of 50 ° C. and a flow rate of 0.40 mL / min. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.

Synthesis Example 2-19

Except having changed tetracarboxylic dianhydride and diamine as shown in Table 1, the polyamic-acid solution (PA2-PA19) whose polymer solid content concentration is 6 weight% based on the synthesis example 1 was prepared. Including the result of the synthesis example 1, the measurement result of the weight average molecular weight of the obtained polyamic acid was put together in Table 1.

[Table 1]

<2. Production of Substrate for Transmittance Evaluation>

Example 1

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to a polyamic acid solution (PA1) having a polymer solid content of 6 wt% prepared in Synthesis Example 1, and diluted to 4 wt% of a polymer solid content to form a liquid crystal aligning agent. . The board | substrate for transmittance | permeability evaluation was manufactured as follows using the obtained liquid crystal aligning agent.

<Method 1 for Manufacturing Substrate for Transmittance Evaluation>

The liquid crystal aligning agent was apply | coated to the glass substrate with the spinner. And in the following Example and the comparative example, the rotation speed of a spinner was adjusted according to the viscosity of a liquid crystal aligning agent, and the alignment film was made into the following film thickness. After coating and drying at 70 degreeC for 1 minute after coating, linearly polarized light of the ultraviolet-ray was irradiated through the polarizing plate from the perpendicular | vertical direction with respect to the board | substrate using Multilite ML-501C / B by Ushio Electric Co., Ltd. product. The exposure energy at this time is measured using a UV integrated photometer UIT-150 (receiver UVD-S365) manufactured by Ushio Electric Co., Ltd., and the exposure energy is exposed to 3.0 ± 0.1 J / cm ² at a wavelength of 365 nm. The time was adjusted. Irradiation of ultraviolet-ray covered the whole apparatus with the ultraviolet-ray prevention film, and was performed in room temperature and air. Subsequently, heat treatment was performed at 230 ° C. for 15 minutes to form an alignment film having a film thickness of 100 ± 10 nm.

[Examples 2 to 17]

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solution (PA2? PA17) having a polymer solid content concentration of 6 wt% prepared in Synthesis Examples 2 to 17, and diluted to 4 wt% of the polymer solid content concentration. To a liquid crystal aligning agent. The board | substrate for transmittance | permeability evaluation was manufactured by the method based on Example 1 using the obtained liquid crystal aligning agent.

[Example 18]

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, additive (Ad1) was added at a rate of 20 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. In addition, the weight of an additive is not included in calculation of the polymer solid content concentration at the time of using an additive including the following Example. The board | substrate for transmittance | permeability evaluation was manufactured by the method based on Example 1 using the obtained liquid crystal aligning agent.

[Example 19]

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, an additive (Ad2) was added at a rate of 20 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The board | substrate for transmittance | permeability evaluation was manufactured by the method based on Example 1 using the obtained liquid crystal aligning agent.

[Example 20]

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, additive (Ad3) was added at a rate of 10 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The board | substrate for transmittance | permeability evaluation was manufactured by the method based on Example 1 using the obtained liquid crystal aligning agent.

Example 21

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, an additive (Ad4) was added at a rate of 0.5 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The board | substrate for transmittance | permeability evaluation was manufactured by the method based on Example 1 using the obtained liquid crystal aligning agent.

[Example 22]

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to a polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, and diluted to 4 wt% of a polymer solid content to form a liquid crystal aligning agent. . The board | substrate for transmittance | permeability evaluation was manufactured as follows using the obtained liquid crystal aligning agent.

<Method 2 for Manufacturing Substrate for Transmittance Evaluation>

The liquid crystal aligning agent was apply | coated to the glass substrate with the spinner. After coating and heating at 70 degreeC for 1 minute, it heat-processed at 230 degreeC for 15 minutes. The glass substrate was irradiated with a linear polarized light of ultraviolet rays through a polarizing plate from the vertical direction with respect to the substrate using Multilite ML-501C / B manufactured by Ushio Electric Co., Ltd. (exposure energy: 3.0 ± 0.1 J at 365 nm). / cm ² ), an alignment film having a film thickness of 100 ± 10 nm was formed. The conditions of ultraviolet irradiation and adjustment of exposure energy were performed based on the method of Example 1.

[Comparative Examples 1 and 2]

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solutions (PA18 and PA19) having a polymer solid concentration of 6 wt% prepared in Synthesis Examples 18 and 19, and diluted to 4 wt% of the polymer solid concentration. To a liquid crystal aligning agent. The board | substrate for transmittance | permeability evaluation was manufactured by the method based on Example 1 using the obtained liquid crystal aligning agent.

[Comparative Example 3]

To a polyamic acid solution (PA19) having a polymer solid content of 6 wt% prepared in Synthesis Example 19, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and the polymer solid content was diluted to 4 wt% to obtain a liquid crystal aligning agent. . The board | substrate for transmittance | permeability evaluation was manufactured by the method based on Example 22 using the obtained liquid crystal aligning agent.

<3. Evaluation of transmittance>

The transmittance of the alignment film was measured using a UV-Vis spectral measuring apparatus (V-660 manufactured by Nippon Spectroscopy Co., Ltd.). A glass substrate on which no alignment film was formed was used as a control. The measurement was performed every 1 nm at the scanning speed of 400 nm / min in the range of wavelength 380-780 nm. The average value of the transmittance | permeability in the said wavelength range was made into the transmittance | permeability of an oriented film. The larger this value, the better the transmittance. The measurement results are shown in Table 2.

[Table 2]

"-" In a table | surface shows that an additive was not added.

Since the comparative example 1 uses the polyamic acid synthesize | combined using the diamine which has an azobenzene structure as a raw material, transmittance | permeability is remarkably inferior. The transmittance | permeability of the alignment film of this invention of Examples 1-22 is favorable, and it turns out that there is little coloring.

<4.Production of liquid crystal display element>

[Example 23]

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to a polyamic acid solution (PA1) having a polymer solid content of 6 wt% prepared in Synthesis Example 1, and diluted to 4 wt% of a polymer solid content to form a liquid crystal aligning agent. . The liquid crystal cell was produced as follows using the obtained liquid crystal aligning agent.

<Method 1 for Manufacturing Liquid Crystal Display Element>

The liquid crystal aligning agent was apply | coated by the spinner to the glass substrate which has two ITO electrodes. After coating and drying by heating at 70 ° C. for about 1 minute, linear polarization of ultraviolet rays was irradiated from the vertical direction with respect to the substrate through a polarizing plate using Multilite ML-501C / B manufactured by Ushio Electric Co., Ltd. (exposure energy: 3.0 ± 0.1 J / cm ² at 365 nm). The conditions of ultraviolet irradiation and the adjustment method of exposure energy were based on Example 1. Subsequently, heat treatment was performed at 230 ° C. for 15 minutes to form an alignment film having a film thickness of 100 ± 10 nm.

Opposing the surface on which the two alignment films on which the alignment film is formed is formed on the ITO electrode is formed so as to form a gap for injecting the liquid crystal composition between the opposite alignment films so that the polarization directions of the ultraviolet rays irradiated to each alignment film are parallel to each other. And a blank cell having a cell thickness of 4 µm was assembled. Moreover, the injection hole for injecting a liquid crystal into this empty cell was provided in the position so that the flow direction of a liquid crystal at the time of injection may be substantially parallel with the polarization direction of the ultraviolet-ray irradiated to the alignment film.

The liquid crystal composition A shown below was vacuum-injected into the empty cell manufactured as mentioned above, and the liquid crystal cell was produced.

<Liquid crystal composition A>

[Examples 24? 39]

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solution (PA2? PA17) having a polymer solid content concentration of 6 wt% prepared in Synthesis Examples 2 to 17, and diluted to 4 wt% of the polymer solid content concentration. To a liquid crystal aligning agent. The empty cell was assembled by the method based on Example 23 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into these empty cells, and the liquid crystal cell was produced.

Example 40

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, additive (Ad1) was added at a rate of 20 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 23 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

Example 41

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, an additive (Ad2) was added at a rate of 20 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 23 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

Example 42

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, additive (Ad3) was added at a rate of 10 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 23 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

Example 43

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, an additive (Ad4) was added at a rate of 0.5 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 23 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

Example 44

To a polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and the polymer solid content was diluted to 4 wt% to obtain a liquid crystal aligning agent. . The liquid crystal cell was produced as follows using the obtained liquid crystal aligning agent.

<Method 2 for Manufacturing Liquid Crystal Display Element>

The liquid crystal aligning agent was apply | coated by the spinner to the glass substrate which has two ITO electrodes. After coating and drying by heating at 70 degreeC for 1 minute, it heat-processed at 230 degreeC for 15 minutes. The glass substrate on which the alignment film was formed was irradiated with a linear polarized light of ultraviolet rays through a polarizing plate from the vertical direction with respect to the substrate using Multilite ML-501C / B manufactured by Ushio Electric Co., Ltd. (exposure energy: energy 3.0 at 365 nm). ± 0.1 J / cm ² ), and an alignment film having a film thickness of 100 ± 10 nm was formed. The conditions of ultraviolet irradiation and the adjustment method of exposure energy were based on Example 1.

The air gap for inject | pouring a liquid crystal composition between the opposing aligning films so that the surface in which the oriented films of the two board | substrates with which the oriented film was formed on the ITO electrode is formed may become parallel, and the polarization direction of the ultraviolet-ray irradiated to each aligning film will be parallel, It formed and joined, and the empty cell of cell thickness 4micrometer was assembled. Moreover, the injection hole for injecting a liquid crystal into this empty cell was provided in the position so that the flow direction of a liquid crystal at the time of injection may be substantially parallel with the polarization direction of the ultraviolet-ray irradiated to the alignment film. The liquid crystal composition A mentioned above was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

[Comparative Example 4]

To a polyamic acid solution (PA12) having a polymer solid content of 6 wt% prepared in Synthesis Example 19, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and the polymer solid content was diluted to 4 wt% to obtain a liquid crystal aligning agent. . The empty cell was assembled by the method based on Example 23 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

[Comparative Example 5]

To a polyamic acid solution (PA12) having a polymer solid content of 6 wt% prepared in Synthesis Example 19, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and the polymer solid content was diluted to 4 wt% to obtain a liquid crystal aligning agent. . The empty cell was assembled by the method based on Example 44 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

<5. Observation of Flow Orientation>

The liquid crystal cell produced as mentioned above was observed by visual observation by interposing into two polarizing plates arrange | positioned by cross nicol. In these liquid crystal cells, since the cyclobutane frame | skeleton of the polymer main chain which generally followed the polarization direction of an ultraviolet-ray cut | disconnected because of the ultraviolet-ray irradiated to the liquid crystal aligning film, a liquid crystal composition orientates in the direction substantially perpendicular to the polarization direction of an ultraviolet-ray. In the liquid crystal cell using the alignment film with favorable alignment property, the so-called flow orientation in which the liquid crystals were arranged along the direction in which the liquid crystals flow from the injection port was not observed at all. On the other hand, in the liquid crystal cell using the alignment film with poor orientation, flow orientation was observed. The observation result of the flow orientation is shown in Table 3.

<6. Observation of Orientation Defects>

The liquid crystal cell in which the flow orientation was observed was subjected to isotropic treatment at 110 ° C. for 30 minutes, and cooled to room temperature. When this liquid crystal cell was observed again with a polarizing microscope in the cross nicol state, the orientation defect of the liquid crystal was not observed in the liquid crystal cell using the orientation film with favorable orientation. On the other hand, in the liquid crystal cell using the alignment film with poor orientation, the orientation defect of the liquid crystal was observed. The observation result of the orientation defect is shown in Table 3.

[Table 3]

"-" In a table | surface shows that an additive was not added.

When the exposure energy of ultraviolet-ray was 3.0 +/- 0.1 J / cm <^2> , a defect was observed also in Examples 23-44, and the flow defect and the orientation defect were recognized together in Comparative Examples 4 and 5.

[Examples 45? 61]

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solution (PA1 to PA17) having a polymer solid concentration of 6 wt% prepared in Synthesis Examples 1 to 17, and diluted to 4 wt% of the polymer solid concentration. To a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the empty cell of the cell thickness of 4 micrometers was assembled by the method based on Example 23 except having changed the irradiation energy of ultraviolet-ray into 5.0 +/- 0.1 J / cm <^2> at 365 nm. And liquid crystal composition A was vacuum-injected into these empty cells, and the liquid crystal cell was produced.

Example 62

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, additive (Ad1) was added at a rate of 20 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 45 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

[Example 63]

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, an additive (Ad2) was added at a rate of 20 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 45 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

Example 64

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, additive (Ad3) was added at a rate of 10 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 45 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

[Example 65]

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, an additive (Ad4) was added at a rate of 0.5 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 45 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

[Example 66]

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to a polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, and diluted to 4 wt% of a polymer solid content to form a liquid crystal aligning agent. . Using the obtained liquid crystal aligning agent, the empty cell was assembled by the method according to Example 44 except having changed the irradiation energy of ultraviolet-ray into 5.0 +/- 0.1 J / cm <^2> at 365 nm. And liquid crystal composition A was vacuum-injected into these empty cells, and the liquid crystal cell was produced.

[Comparative Example 6]

To a polyamic acid solution (PA19) having a polymer solid content of 6 wt% prepared in Synthesis Example 19, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and the polymer solid content was diluted to 4 wt% to obtain a liquid crystal aligning agent. . The empty cell was assembled by the method based on Example 45 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

[Comparative Example 7]

To a polyamic acid solution (PA19) having a polymer solid content of 6 wt% prepared in Synthesis Example 19, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and the polymer solid content was diluted to 4 wt% to obtain a liquid crystal aligning agent. . The empty cell was assembled by the method based on Example 66 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

<Observation of flow orientation>

As described above, the liquid crystal cell was sandwiched between two polarizing plates arranged in cross nicol, and the flow orientation was observed by visual observation. The observation result of the flow orientation is shown in Table 4.

Observation of orientation defects

The liquid crystal cell in which the flow orientation was observed was subjected to isotropic treatment at 110 ° C. for 30 minutes, and cooled to room temperature. And this liquid crystal cell was observed again, making a polarizing microscope the cross nicol state. The observation result of the orientation defect is shown in Table 4.

[Table 4]

"-" In a table | surface shows that an additive was not added.

When the exposure energy of the ultraviolet rays was 5.0 ± 0.1 J / cm ² , the flow defects and the orientation defects were recognized together in Comparative Examples 6 and 7, but only Example 63 was observed in Examples 45 to 66.

[Examples 67? 83]

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solution (PA1 to PA17) having a polymer solid content concentration of 6 wt% prepared in Synthesis Examples 1 to 17, and diluted to 4 wt% of the polymer solid content concentration. To a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the empty cell was assembled by the method based on Example 23 except having changed the irradiation energy of ultraviolet-ray into 10.0 +/- 0.1 J / cm <^2> at 365 nm. And liquid crystal composition A was vacuum-injected into these empty cells, and the liquid crystal cell was produced.

Example 84

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, additive (Ad1) was added at a rate of 20 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 67 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

Example 85

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, an additive (Ad2) was added at a rate of 20 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 67 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

Example 86

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, additive (Ad3) was added at a rate of 10 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 67 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

Example 87

To the polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, an additive (Ad4) was added at a rate of 0.5 wt% per polymer weight. Then, the mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and it diluted to 4weight% of polymer solid content concentration, and was made into the liquid crystal aligning agent. The empty cell was assembled by the method based on Example 67 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

Example 88

A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to a polyamic acid solution (PA10) having a polymer solid content of 6 wt% prepared in Synthesis Example 10, and diluted to 4 wt% of a polymer solid content to form a liquid crystal aligning agent. . Using the obtained liquid crystal aligning agent, the empty cell of cell thickness 4 micrometers was assembled by the method based on Example 44 except the point which changed the irradiation energy of ultraviolet-ray to 10.0 +/- 0.1 J / cm <^2> at 365 nm. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

[Comparative Example 8]

To a polyamic acid solution (PA19) having a polymer solid content of 6 wt% prepared in Synthesis Example 19, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and the polymer solid content was diluted to 4 wt% to obtain a liquid crystal aligning agent. . The empty cell was assembled by the method based on Example 67 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

[Comparative Example 9]

To a polyamic acid solution (PA19) having a polymer solid content of 6 wt% prepared in Synthesis Example 19, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added, and the polymer solid content was diluted to 4 wt% to obtain a liquid crystal aligning agent. . The empty cell was assembled by the method based on Example 88 using the obtained liquid crystal aligning agent. And the liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was produced.

<Observation of flow orientation>

As described above, the liquid crystal cell was sandwiched between two polarizing plates arranged in cross nicol, and the flow orientation was observed by visual observation. The observation result of the flow orientation is shown in Table 5.

Observation of orientation defects

The liquid crystal cell in which the flow orientation was observed was subjected to isotropic treatment at 110 ° C. for 30 minutes, and cooled to room temperature. And this liquid crystal cell was observed again, making a polarizing microscope the cross nicol state. The observation result of the orientation defect is shown in Table 5.

[Table 5]

"-" In a table | surface shows that an additive was not added.

When the exposure energy of the ultraviolet ray was further strengthened to 10.0 ± 0.1 J / cm ² , orientation defects were still recognized in Comparative Example 8, whereas no defects were observed in Examples 67 to 88. From the results of Examples 23 to 88 and Comparative Examples 4 to 9, it is understood that the alignment film of the present invention has good orientation even at low energy ultraviolet irradiation, and the sensitivity of chemical change due to light irradiation is good.

Thus, when the orientation film of this invention is applied to the orientation film for liquid crystal display elements, it turns out that it has sufficient characteristic that transmittance | permeability and orientation can also be used practically. Moreover, the alignment film of this invention can fully photo-align with the ultraviolet-ray of the general-purpose wavelength, and can also photo-align with the ultraviolet irradiation of energy lower than conventionally known photo-alignment film.

Claims (51)

In the liquid crystal aligning agent for forming the liquid crystal aligning film for photoalignments containing the polyamic acid obtained by making tetracarboxylic dianhydride and diamine react, or its derivative (s),
The tetracarboxylic dianhydride contains tetracarboxylic dianhydride represented by the following formula (I);
Wherein said diamine comprises at least one selected from the group of diamines represented by the following formula (N-1) and the following formula (N-2):

In formula (I), R ^A -R ^D are independently hydrogen or alkyl having 1 to 4 carbon atoms,

In formula (N-1), R ^E is independently a monovalent organic group;
R ^F is independently hydrogen, a monovalent organic group or halogen; And,
Z is a divalent group containing alkylene having 1 to 5 carbon atoms,

In formula (N-2), R ^G is independently a monovalent organic group or halogen;
R ^H is independently a monovalent organic group;
m is independently an integer of 0-3; And,
n is an integer of 0-4. The method of claim 1,
Wherein R ^E is a independently selected from alkyl having a carbon number of 1? 3, wherein R ^F is independently hydrogen, C 1? A 3-alkyl, fluorine, chlorine, or bromine in the formula diamine or the diamine represented by the (N-1) The liquid crystal aligning agent containing the polyamic acid obtained by making the diamine mixture containing these react with tetracarboxylic dianhydride, or its derivative (s). The method of claim 1,
Polyamines or derivatives thereof obtained by reacting a diamine represented by the above formula (N-1) having a amino group at each para position in the phenyl at both ends of the molecule or a diamine mixture containing the diamine with tetracarboxylic dianhydride Liquid crystal aligning agent. The method of claim 1,
Polyamic acid or derivative thereof obtained by reacting at least one selected from the group of diamines represented by the following formulas (N-1-1)? (N-1-20) or a diamine mixture containing the diamine with tetracarboxylic dianhydride Liquid crystal aligning agent containing

. The method of claim 1,
Wherein R ^G is independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, carbamoyl, fluorine, chlorine, or bromine, and wherein R ^H is independently alkyl having 1 to 3 carbon atoms (N- The liquid crystal aligning agent containing the polyamic acid or its derivative (s) obtained by making the diamine represented by 2) or the diamine mixture containing the said diamine react with tetracarboxylic dianhydride. The method of claim 1,
Polyamines or derivatives thereof obtained by reacting a diamine represented by the formula (N-2) having an amino group at each para position in the phenyl at both ends of the molecule or a diamine mixture containing the diamine with a tetracarboxylic dianhydride Liquid crystal aligning agent. The method of claim 1,
Polyamic acid or derivative thereof obtained by reacting at least one selected from the group of diamines represented by the following formulas (N-2-1) to (N-2-15) or a diamine mixture comprising the diamine with tetracarboxylic dianhydride Liquid crystal aligning agent containing

. The method of claim 1,
The polyamic acid obtained by making the diamine mixture containing at least 1 or the said diamine of the said Formula (N-2-1) and said Formula (N-2-2) of Claim 7 react with tetracarboxylic dianhydride. Or liquid crystal aligning agent containing the derivative. The method of claim 1,
Liquid crystal aligning agent containing the polyamic acid or its derivative (s) obtained by reacting the diamine mixture further containing at least 1 chosen from the group of the diamine represented by following formula (III)? (IX) and (XV) with tetracarboxylic dianhydride. :

In formula (III), A ¹ is-(CH ₂ ) _m- , m is an integer of 1-6;
In formulas (V), (VII) and (IX), X is a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -NH-, -N ( CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- (CH _{2) m} ) -S-, m is an integer of 1-6;
In formula (VII), L ¹ and L ² are -H, but X is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) when ₂ -may be bonded to each other to form a single bond;
In formula (VIII) and formula (IX), Y is a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or 1 carbon number Alkylene of? 3;
In formula (XV), R ³³ and R ³⁴ are independently alkyl or phenyl having 1 to 3 carbon atoms; G is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10; And,
In each of the above formulas, -H of the cyclohexane ring or the benzene ring is substituted with -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , benzyl, or hydroxy benzyl. You may be. The method of claim 1,
The liquid crystal aligning agent containing the polyamic acid or its derivative (s) obtained by making the diamine mixture further containing the diamine which has a side chain structure react with tetracarboxylic dianhydride. The method of claim 10,
A liquid crystal aligning agent, wherein the diamine having the side chain structure is at least one selected from the group of diamines represented by the following formulas (X) to (XIV):

In formula (X),
Z ¹ is a single bond, -O-, -CO-, -COO-, -OCO- , -CONH-, -CH 2 O-, -OCH 2 -, -CF 2 O-, -OCF 2 -, or -(CH ₂ ) _m- , m is an integer of 1 to 6, and any -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH- or -C≡C- Become;
R ³ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 alkoxy as a substituent, or a group represented by the following formula (Xa): Arbitrary -CH ₂ -in the alkyl of -30 may be substituted with -O-, -CH = CH-, or -C≡C-;

In formula (Xa),
A ² and A ³ are independently a single bond, -O-, -COO-, -OCO-, -CONH-, -CH = CH-, or alkylene having 1 to 12 carbon atoms, and a and b are independently It is an integer of 0-4;
Ring B and Ring C are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5 -Diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
R ⁴ and R ⁵ are independently -F or CH ₃ , f and g are independently an integer of 0-2;
R ⁶ is -F, -OH, -CN, alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, or alkoxyalkyl having 2 to 30 carbon atoms, and in the alkyl, the alkoxy and the alkoxyalkyl, -H may be substituted with -F, and arbitrary -CH ₂ -may be substituted with -CF ₂ -or a divalent group represented by the following formula (s);

In formula (s), R ³⁵ and R ³⁶ are independently alkyl having 1 to 3 carbon atoms, m is an integer of 1 to 6;
c, d and e are each independently an integer of 0 to 3, and c + d + e ≧ 1,

In formulas (XI) and (XII),
R ⁷ is independently —H or —CH ₃ ;
R ⁸ is —H, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;
A ⁴ is independently a single bond, -CO- or -CH _2- ;
In formula (XII),
R ⁹ and R ¹⁰ are independently alkyl or phenyl having 1 to 20 carbon atoms,

In formulas (XIII) and (XIV), A ⁵ is independently —O— or alkylene having 1 to 6 carbon atoms;
In formula (XIII), R ¹¹ is -H or alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of the alkyl may be substituted with -O-, -CH = CH- or -C≡C-. Become;
A ⁶ is a single bond or alkylene having 1 to 3 carbon atoms;
Ring T is 1,4-phenylene or 1,4-cyclohexylene;
h is 0 or 1;
In formula (XIV), R ¹² is alkyl having 6 to 22 carbon atoms; And,
R ¹³ is alkyl having 1 to 22 carbons. The method of claim 1,
As a tetracarboxylic dianhydride made to react with the said diamine, the liquid crystal aligning agent which further uses at least 1 chosen from the group of the compound represented by following formula (An-1) (An-6):

In formulas (An-1), (An-4) and (An-5), X ¹ is independently a single bond or -CH _2- ;
In formula (An-2), G ¹ is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2- ;
In formula (An-2)? (An-4), Y ¹ is independently one selected from the group of the following trivalent groups;

In formula (An-3)? (An-5), ring E represents a group of a C3-C10 monocyclic hydrocarbon or a group of a C6-C20 condensed polycyclic hydrocarbon, and any hydrogen of the group is methyl May be substituted with ethyl or phenyl;
The bond connected to the ring is linked to any carbon constituting the ring, and two bonds may be linked to the same carbon;
In formula (An-6), X ¹¹ is alkylene having 2 to 6 carbon atoms;
Me represents methyl and Ph represents phenyl. The method of claim 1,
As the tetracarboxylic dianhydride reacted with the diamine, at least one selected from the group of aromatic tetracarboxylic dianhydrides represented by the following formulas (1), (2), (5) to (7) and (17) is further used. Liquid crystal aligning agent

. The method of claim 1,
As the tetracarboxylic dianhydride reacted with the diamine, an alicyclic compound represented by the following formulas (23), (25), (36) to (39), (44), (49) and (68) Liquid crystal aligning agent which further uses at least 1 chosen from the group of tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride.

. The method of claim 1,
As the tetracarboxylic dianhydride to be reacted with the diamine, at least one selected from the group of aromatic tetracarboxylic dianhydrides represented by the following formulas (1), (2), (5) to (7) and (17), and the following formula: At least one selected from the group of alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides represented by (23), (25), (36) to (39), (44), (49), and (68); Liquid crystal aligning agent to use:

. The liquid crystal aligning agent which mixed at least 2 from the liquid crystal aligning agent of any one of Claims 1-11. The liquid crystal aligning agent which mixed at least 2 from the liquid crystal aligning agent of any one of Claims 12-15. 12. The method according to any one of claims 1 to 11,
A liquid crystal aligning agent further comprising at least one selected from an alkenyl substituted nadimide compound, an epoxy compound, and a silane coupling agent. 19. The method of claim 18,
The alkenyl substituted naimide compound may be selected from the group consisting of bis [4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl] methane, N, N'-m-xylene-bis (Allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), and N, N'-hexamethylenebis (allylbicyclo [2.2.1] hepto-5-ene-2, Liquid crystal aligning agent which is at least 1 chosen from the group which consists of 3-dicarboxyimide). 19. The method of claim 18,
The said alkenyl substituted nadimide compound is bis [4- (allylbicyclo [2.2.1] hepto-5-ene-2,3- dicarboxyimide) phenyl] methane, The liquid crystal aligning agent. 19. The method of claim 18,
The liquid crystal aligning agent in which the said alkenyl substituted nadimide compound is contained 0.01-50 weight% with respect to the total amount of the said polyamic acid or its derivative (s). 19. The method of claim 18,
The epoxy compound is N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N- diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [ 4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-gly A liquid crystal aligning agent, which is at least one selected from the group consisting of a cyl methacrylate copolymer and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 19. The method of claim 18,
Liquid crystal whose said epoxy compound is N, N, N ', N'- tetraglycidyl-4,4'- diaminodiphenylmethane or 2- (3, 4- epoxycyclohexyl) ethyltrimethoxysilane. Aligning agent. The method of claim 18,
Liquid crystal aligning agent in which the said epoxy compound is contained 1-40 weight% with respect to the total amount of the said polyamic acid or its derivative (s). 19. The method of claim 18,
The said silane coupling agent is vinyl trimethoxysilane, vinyl triethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl Trimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N'-bis Liquid crystal, which is at least one selected from the group consisting of [3- (trimethoxysilyl) propyl] ethylenediamine Hyangje. 19. The method of claim 18,
The said silane coupling agent is 3-aminopropyl triethoxysilane, The liquid crystal aligning agent. 19. The method of claim 18,
The liquid crystal aligning agent with which a silane coupling agent is contained 0.1-10 weight% with respect to the total amount of the said polyamic acid or its derivative (s). The process of apply | coating the liquid crystal aligning agent in any one of Claims 1-11 to a board | substrate;
Heating and drying the substrate coated with the alignment agent; And
Process of irradiating polarized ultraviolet rays to the film
The liquid crystal aligning film for photoalignments formed through. Process of apply | coating the liquid crystal aligning agent in any one of Claims 12-15 to a board | substrate;
Heating and drying the substrate coated with the alignment agent; And
Process of irradiating polarized ultraviolet rays to the film
The liquid crystal aligning film for photoalignments formed through. Process of apply | coating the liquid crystal aligning agent of Claim 16 to a board | substrate;
Heating and drying the substrate coated with the alignment agent; And
Process of irradiating polarized ultraviolet rays to the film
The liquid crystal aligning film for photoalignments formed through. Process of apply | coating the liquid crystal aligning agent of Claim 17 to a board | substrate;
Heating and drying the substrate coated with the alignment agent; And
Process of irradiating polarized ultraviolet rays to the film
The liquid crystal aligning film for photoalignments formed through. The process of apply | coating the liquid crystal aligning agent in any one of Claims 1-11 to a board | substrate;
Heating and drying the substrate coated with the alignment agent;
Irradiating polarized ultraviolet rays to the dried film; And
Subsequently, heating and baking the film
The liquid crystal aligning film for photoalignments formed through. Process of apply | coating the liquid crystal aligning agent in any one of Claims 12-15 to a board | substrate;
Heating and drying the substrate coated with the alignment agent;
Irradiating polarized ultraviolet rays to the dried film; And
Subsequently, heating and baking the film
The liquid crystal aligning film for photoalignments formed through. Process of apply | coating the liquid crystal aligning agent of Claim 16 to a board | substrate;
Heating and drying the substrate coated with the alignment agent;
Irradiating polarized ultraviolet rays to the dried film; And
Subsequently, heating and baking the film
The liquid crystal aligning film for photoalignments formed through. Process of apply | coating the liquid crystal aligning agent of Claim 17 to a board | substrate;
Heating and drying the substrate coated with the alignment agent;
Irradiating polarized ultraviolet rays to the dried film; And
Subsequently, heating and baking the film
The liquid crystal aligning film for photoalignments formed through. The process of apply | coating the liquid crystal aligning agent in any one of Claims 1-11 to a board | substrate;
Heating and drying the substrate coated with the alignment agent;
Heating and baking the dried film; And
Subsequently, the step of irradiating polarized ultraviolet light to the film
The liquid crystal aligning film for photoalignments formed through. Process of apply | coating the liquid crystal aligning agent in any one of Claims 12-15 to a board | substrate;
Heating and drying the substrate coated with the alignment agent;
Heating and baking the dried film; And
Subsequently, the step of irradiating polarized ultraviolet light to the film
The liquid crystal aligning film for photoalignments formed through. Process of apply | coating the liquid crystal aligning agent of Claim 16 to a board | substrate;
Heating and drying the substrate coated with the alignment agent;
Heating and baking the dried film; And
Subsequently, the step of irradiating polarized ultraviolet light to the film
The liquid crystal aligning film for photoalignments formed through. Process of apply | coating the liquid crystal aligning agent of Claim 17 to a board | substrate;
Heating and drying the substrate coated with the alignment agent;
Heating and baking the dried film; And
Subsequently, the step of irradiating polarized ultraviolet light to the film
The liquid crystal aligning film for photoalignments formed through. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 28. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 29. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 30. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 31. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 32. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 33. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 34. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 35. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 36. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 37. The liquid crystal display element which has the liquid crystal aligning film for photoalignments of Claim 38. The liquid crystal display element which has a liquid crystal aligning film for photoalignments of Claim 39.