KR101748244B1 - Liquid crystal display device, method of manufacturing the same, and polymer composition - Google Patents

Abstract

(Problems to be Solved by the Invention) Provided is a method for manufacturing a liquid crystal display element having a wide viewing angle, a high response speed of liquid crystal molecules, and excellent display characteristics and long-term reliability.
A method for producing a liquid crystal display element is provided by coating a polymer composition containing a polymer (A) and an organic solvent (B) on a conductive film of a pair of substrates having a conductive film to form a coating film A liquid crystal cell is formed by arranging a pair of substrates on which the coating film is formed so as to be opposed to each other through the layer of liquid crystal molecules so that the coating film is opposed to each other, A method for producing a liquid crystal display element through a step of irradiating light to a liquid crystal cell, wherein the polymer (A) is at least one of a structure generating radicals by light irradiation and a structure having a photosensitizing function, And a polymer having both unsaturated bonds.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device, a method of manufacturing the same,

The present invention relates to a method of manufacturing a liquid crystal display element. More particularly, the present invention relates to a novel method for manufacturing a liquid crystal display device having a wide viewing angle and a high response speed.

Among multi-domain vertical alignment (MVA) panels conventionally known as a vertical alignment mode, protrusions are formed in a liquid crystal panel, thereby restricting the tilting direction of the liquid crystal molecules. However, according to this method, insufficient transmittance and contrast derived from projections are inevitable, and there is also a problem that the response speed of liquid crystal molecules is slow.

In recent years, a PSA (Polymer Sustained Alignment) mode has been proposed to solve the problems of the MVA type panel. The PSA mode is a mode in which a gap between a pair of substrates comprising a substrate with a patterned conductive film and a substrate with a conductive film having no pattern or a gap between a pair of substrates comprising a substrate with two patterned conductive films, And then polymerizing the polymerizable compound by irradiating ultraviolet rays in a state where a voltage is applied between the conductive films to thereby control the alignment direction of the liquid crystal by expressing the pretilt angular characteristic Technology. According to this technique, the viewing angle can be increased and the response time of liquid crystal molecules can be increased by using a specific constitution of the conductive film, thereby solving the problem of lack of transmittance and contrast which is inevitable in the MVA type panel. However, in the PSA mode, for the polymerization of the polymerizable compound, a large amount of ultraviolet rays, for example, 100,000 J / m 2 is required to be irradiated, (Unreacted) compound which has not been left in the liquid crystal layer remains in the liquid crystal layer, and the display unevenness occurs due to mutual action thereof, which adversely affects the voltage holding property or the long-term reliability of the panel. It has not reached practical use.

In contrast, Non-Patent Document 1 proposes a method using a liquid crystal alignment film formed of a polyimide-based liquid crystal aligning agent containing a reactive mesogen. According to Non-Patent Document 1, in a liquid crystal display element having a liquid crystal alignment film formed by such a method, the response of liquid crystal molecules is said to be high. However, in the non-patent reference 1, there is no description as to what kind of reactive mesogen should be used at all, and the necessary amount of ultraviolet radiation is still large, so that concerns about display characteristics, in particular voltage preservation characteristics, .

This point has become extremely recent, and a technology relating to a more new display mode that replaces the PSA mode has been proposed (Patent Document 1). This technique is a technique of irradiating ultraviolet rays of unpolarized light to a polyimide thin film having a cinnamate structure having a photofunctionality and imparting a desired pretilt angle manifestation by using the rotation of the molecule by photoisomerization of the cinnamate structure It is intended. However, in order to impart desired tilt angles to the pretilt angle, it is necessary to irradiate a considerable amount of ultraviolet rays, which leads to a longer tact time in the production of a liquid crystal display device, or an electric characteristic of a liquid crystal alignment film formed due to intense ultraviolet rays, And damage such as damage is occurring.

U.S. Patent Application Publication No. 2009/0325453 Japanese Unexamined Patent Publication No. 5-107544

 Y.-J. Lee et al., SID 09 DIGEST, p. 666 (2009)  T. J. Scheffer et al., J. Appl. Phys. vo. 19, p. 2013 (1980)

An object of the present invention is to provide a method for manufacturing a liquid crystal display element having a wide viewing angle, a fast response speed of liquid crystal molecules, and excellent display characteristics and long-term reliability.

According to the present invention, the above-

On a conductive film of a pair of substrates having a conductive film,

(A) a polymer and

(B) an organic solvent

Is applied to form a coating film,

A pair of substrates on which the coating film is formed are disposed opposite to each other with the liquid crystal molecules interposed therebetween to form a liquid crystal cell,

A step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films of the pair of substrates,

Wherein the polymer (A)

(A1) a polymer having both a structure of generating a radical by light irradiation and a structure having a photosensitizing function and a polymerizable unsaturated bond, or

(A2-1) a polymer having at least one structure selected from the group consisting of a structure generating a radical by light irradiation and a structure having a photo-sensitization function, and

(A2-2) a polymer having a polymerizable unsaturated bond.

The liquid crystal display device manufactured by the method of the present invention has a wide viewing angle, a fast response time of liquid crystal molecules, a sufficient transmittance and contrast, exhibits excellent display characteristics, and does not impair the display characteristics even after continuous driving for a long time .

Further, according to the method of the present invention, since the amount of light required for irradiation is small, there is no problem of decomposition of liquid crystal molecules, which contributes to reduction of manufacturing cost of the liquid crystal display element.

Therefore, the liquid crystal display element manufactured by the method of the present invention is superior to the conventionally known liquid crystal display element in terms of performance and cost, and can be suitably applied to various applications.

Fig. 1 is an explanatory view showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film prepared in Examples and Comparative Examples. Fig.
Fig. 2 is an explanatory diagram showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film manufactured in the embodiment. Fig.
3 is an explanatory view showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film manufactured in the embodiment.

(Mode for carrying out the invention)

≪ Polymer composition >

The polymer composition used in the method of the present invention may be,

(A) a polymer and (B) an organic solvent,

However, the polymer (A)

(A1) a polymer having both a structure of generating a radical by light irradiation and a structure having a photosensitizing function and a polymerizable unsaturated bond (hereinafter referred to as " polymer (A1) ") Or

(A2-1) a polymer having at least one structure (hereinafter referred to as " polymer (A2-1) ") of a structure capable of generating a radical by light irradiation and a structure having a photosensitizing function, and

(A2-2) a polymer having a polymerizable unsaturated bond (hereinafter referred to as "polymer (A2-2)").

The photo-sensitization function refers to a function of quickly transiting to a triplet excitation state by causing an inter-beam crossing after becoming a singlet excited state by irradiation of light. When it collides with another molecule in this triplet excited state, it changes its partner into an excited state and returns to its base state by itself. This photo-sensitization function may coexist with a function of generating a radical by light irradiation.

Examples of the structure of at least one of the structure for generating a radical by light irradiation and the structure having a photosensitizing function include a benzophenone structure, a 9,10-dioxodihydroanthracene structure, a 1,3-dinitrobenzene structure Dioxocyclohexa-2,5-diene structure, that is, the following formulas (1) to (4):

, And may be at least one structure selected from these.

At least one structure or unsaturated bond selected from a structure generating a radical by light irradiation, a structure having a photosensitizing function, and a polymerizable unsaturated bond is referred to as " specific structure " .

[Polymer (A)]

Examples of the main skeleton of the polymer (A) in the present invention include polyamic acid, polyimide, polyamic ester, polyester, polyamide, polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative , A poly (styrene-phenylmaleimide) derivative, a poly (meth) acrylate derivative, and the like, and at least one polymer having a skeleton selected therefrom can be appropriately selected and used.

The polyamic acid having the above specific structure is, for example,

Can be synthesized by reacting a tetracarboxylic acid dianhydride with a diamine containing a specific structure and a compound having two amino groups. In addition, polyimide having a specific structure can be obtained by subjecting the obtained polyamic acid to dehydration ring closure.

The polyamic acid ester having a specific structure is, for example,

For example, a compound having a specific structure and an epoxy group, with a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine.

The polyorganosiloxane having a specific structure is, for example,

A method of hydrolyzing and condensing a hydrolyzable silane compound or a mixture thereof containing a silane compound having a specific structure and a hydrolyzable group; or

A polyorganosiloxane having an epoxy group obtained by hydrolysis and condensation of a hydrolyzable silane compound containing a silane compound having an epoxy group and a hydrolyzable group or a mixture thereof is first synthesized and then the polyorganosiloxane and the polyorganosiloxane having a specific structure and a carboxyl group A method of reacting a compound; or

And can be obtained by a combination of these.

The poly (meth) acrylate derivative having a specific structure can be prepared, for example, by first polymerizing a monomer raw material containing a monomer having an epoxy group to synthesize a poly (meth) acrylate derivative having an epoxy group, Can be obtained by reacting a compound having a specific structure and a carboxyl group.

As the polymer (A1) used in the present invention,

A polyorganosiloxane (hereinafter also referred to as " polyorganosiloxane (A1) ") having both a structure of generating a radical by light irradiation and a structure having a photosensitizing function and a polymerizable unsaturated bond ),

(Hereinafter also referred to as " polyamic acid (A1) ") having both a structure of generating a radical by light irradiation and a structure having a photosensitizing function and a polymerizable unsaturated bond, and

(Hereinafter, also referred to as " polyimide (A1) ") obtained by subjecting the polyamic acid to dehydration cyclization.

As the polymer (A2-1) used in the present invention,

(Hereinafter also referred to as " polyamic acid (A2-1) ") having at least one structure out of a structure capable of generating a radical by light irradiation and a structure having a photosensitizing function, and a polyamic acid (Hereinafter, also referred to as " polyimide (A2-1) ") is preferably used.

As the polymer (A2-2) used in the present invention,

It is preferable to use a polyorganosiloxane having a polymerizable unsaturated bond (hereinafter also referred to as " polyorganosiloxane (A2-2) ").

- polyorganosiloxane (A1) -

The polyorganosiloxane (A1) as the polymer (A1) used in the present invention is a polymer having at least one structure selected from the group consisting of a structure generating a radical by light irradiation and a structure having a photosensitizing function and a polymerizable unsaturated bond Lt; / RTI > Such a polyorganosiloxane (A1) may be synthesized by any synthesis method, but for example,

A silane compound having a polymerizable unsaturated bond and a hydrolyzable group (hereinafter referred to as " silane compound (1) ") and

A mixture of a silane compound containing an epoxy group and a silane compound having a hydrolyzable group (hereinafter referred to as " silane compound (2) ") is preferably hydrolyzed and condensed in the presence of an organic solvent, water and a catalyst to form a polymerizable unsaturated bond And a polyorganosiloxane having an epoxy group (hereinafter referred to as " precursor of polyorganosiloxane (A1) ") are first synthesized,

The polyorganosiloxane can be synthesized by reacting the polyorganosiloxane with a compound having a structure having at least one of a structure generating a radical by light irradiation and a structure having a photosensitizing function and a carboxyl group.

Examples of the silane compound (1) include 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, Acryloxyethyltrichlorosilane, 4 - (meth) acryloxyethyltrichlorosilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4- Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, Ethoxysilane, allyltriethoxysilane, and the like, and at least one selected from the above can be used.

Examples of the silane compound (2) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidylsilane, 3-glycidyloxypropyldimethylethoxysilane, 2- 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyl Glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldi 4-glycidyloxybutyldimethylmethoxysilane, 4-glycidyloxybutyldimethylethoxysilane, 2- (3,4-epoxide (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4 -Epoxycyclohexyl) propyltriethoxysilane, and the like, and at least one selected from these can be used.

The silane compound used for synthesizing the precursor of the polyorganosiloxane (A1) may be composed of only the silane compound (1) and the silane compound (2) as described above, or the silane compound (1) and the silane compound 2), other silane compounds (hereinafter referred to as " silane compound (3) ") may be contained.

Examples of the silane compound (3) that can be used herein include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyl But are not limited to, dichlorosilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, chlorodimethylsilane, methoxy There may be mentioned, for example, dimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethoxysilane and tetraethoxysilane. Can be used.

The silane compound used for synthesizing the precursor of the polyorganosiloxane (A1) preferably contains 20 to 80 mol%, more preferably 30 to 60 mol%, of the silane compound (1) More preferably, The silane compound (2) is preferably contained in an amount of 20 to 80 mol%, more preferably 30 to 60 mol%, based on the total silane compound. The use ratio of the silane compound (3) as described above is preferably 30 mol% or less, more preferably 10 mol% or less based on the total silane compound.

Examples of the organic solvent which can be used for synthesizing the precursor of the polyorganosiloxane (A1) include hydrocarbons, ketones, esters, ethers, and alcohols.

Examples of the hydrocarbons include toluene, xylene and the like;

Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and the like;

Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like;

Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;

Examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like, and at least one selected from the above can be used. Of these, it is preferable to select and use a non-water-soluble one.

The amount of the organic solvent to be used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound.

The amount of water used when synthesizing the precursor of the polyorganosiloxane (A1) is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, per 1 mole of the total amount of the silane compound.

As the catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound and the like can be used, and among them, an alkali metal compound or an organic base is preferably used. By using an alkali metal compound or an organic base as a catalyst, the formation of a three-dimensional structure is promoted, and a polyorganosiloxane having a small content of silanol groups is obtained. Therefore, when the condensation reaction between the silanol groups is suppressed even at the time of the reaction with the carbonic acid to be described later and the polymer composition containing the product of the reaction, and further the polymer composition contains the other polymer Condensation reaction of the silanol group and the other polymer is inhibited, so that a polymer composition excellent in storage stability can be obtained.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene;

And quaternary organic amines such as tetramethylammonium hydroxide. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used differs depending on the kind of the organic base, the reaction conditions such as the temperature, and the like, and is appropriately set. For example, the amount is preferably 0.01 to 3 moles per 1 mole of the total amount of the silane compound, Is 0.05 to 1 mol.

The hydrolysis and condensation reaction in the synthesis of the precursor of the polyorganosiloxane (A1) is carried out by dissolving the silane compounds (1) and (2) and, if necessary, the silane compound (3) in an organic solvent, And water, and heating by using a suitable heating device such as an oil bath, for example.

In the hydrolysis and condensation reaction, the heating temperature is preferably 130 占 폚 or lower, more preferably 40 to 100 占 폚, preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During the heating, the mixed solution may be stirred, the stirring may not be performed, or the mixed solution may be left under reflux.

After completion of the reaction, the organic solvent layer separated from the reaction mixture is preferably washed with water. At the time of this cleaning, it is preferable that the cleaning is carried out by washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 wt% or the like. The washing is carried out until the water layer after the washing becomes neutral. Thereafter, the organic solvent layer is dried with an appropriate drying agent such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain the objective polyorganosiloxane ( A1) can be obtained.

The precursor of the polyorganosiloxane (A1) thus obtained is then subjected to a treatment with at least one of a structure for generating radicals by light irradiation and a structure having a photosensitizing function in the presence of a catalyst and an organic solvent (Hereinafter referred to as " carbonic acid (1) "), a polyorganosiloxane (A1) can be obtained. At this time, one or more kinds selected from the group consisting of carbonic acid (1) and carbonic acid having a function of aligning liquid crystal molecules (hereinafter referred to as "carbonic acid (2)") and other carbonic acid may be used in combination.

Examples of the carbonic acid (1) include 3-benzoylbenzoic acid, 4-benzoylbenzoic acid, 3- (4-diethylamino-2-hydroxybenzoyl) benzoic acid, 4- (2-hydroxybenzoyl) Benzoic acid, 4- (4-methylbenzoyl) benzoic acid, 4- (4-methylbenzoyl) benzoic acid, 2- (2- Dioxo-9,10-dihydroanthracene-2-yl) phenoxy) propionic acid, ) Propionic acid, 3,5-dinitrobenzoic acid, 4-methyl-3,6-dioxo-cyclohexane- 5-dinitrobenzoic acid, 3- (3,5-dinitrophenoxy) propionic acid and 2-methyl-3,5-dinitrobenzoic acid.

The carbonic acid (2) is a compound having, for example, an alkyl or alkoxyl group having 4 to 20 carbon atoms, a group having a structure in which two or more 6-membered rings are connected or a group having a steroid structure and a carboxyl group, For example, 4-pentyloxybenzoic acid, 4-hexyloxybenzoic acid, 4-heptyloxybenzoic acid, 4-octyloxybenzoic acid, 4-nonyloxybenzoic acid, Benzoic acid, 4-heptadecane oxybenzoic acid, 4-heptadecane oxybenzoic acid, 4-heptadecane oxybenzoic acid, 4-tetradecane oxybenzoic acid, , 4-nonadecane oxybenzoic acid, icosane oxybenzoic acid, 4- (4-propylcyclohexyl) benzoic acid, 4- (4-butylcyclohexyl) benzoic acid, 4- , 4- (4-hexylcyclohexyl) benzoic acid, 4- (4-heptylcyclohexyl) benzoic acid, 4- Benzoic acid, 4- (4'-propylbicyclohexyl-4-yl) benzoic acid, 4- (4'-butylbicyclohexyl- (4'-heptylbicyclohexyl-4-yl) benzoic acid, 4- (4'-octylbicyclohexyl- Benzoic acid, succinic acid = 5? -Cholestan-3-yl, and the like.

The carbonic acid (3) is a carbonic acid other than the carbonic acids (1) and (2), and specific examples thereof include, for example, complex acids and propionic acids.

The use ratio of the carboxylic acid (1) is preferably 0.02 to 0.2 mol, more preferably 0.05 to 0.15 mol, per 1 mol of the epoxy group of the precursor of the polyorganosiloxane (A1).

The use ratio of the carboxylic acid (2) is preferably 0.7 mol or less, more preferably 0.2 to 0.6 mol, per 1 mol of the epoxy group of the precursor of the polyorganosiloxane (A1).

The use ratio of the carboxylic acid (3) is preferably 0.3 mol or less, more preferably 0.2 mol or less, per 1 mol of the epoxy group of the precursor of the polyorganosiloxane (A1).

The polyorganosiloxane (A1) in the present invention preferably has an epoxy equivalent of 5,000 g / mol or less, more preferably 500 to 3,000 g / mol. Therefore, it is preferable that the ratio of the total of the carbonic acids (1), (2) and (3) used is 0.8 mol or less based on 1 mol of the epoxy group of the precursor of the polyorganosiloxane (A1).

As the catalyst, known compounds can be used as so-called curing accelerators for promoting the reaction between an organic base or an epoxy compound and an acid anhydride.

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene;

And quaternary organic amines such as tetramethylammonium hydroxide. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine;

Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

Examples of the curing accelerator include tertiary amines, imidazole compounds, organic phosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, quaternary ammonium salts, boron compounds and metal halide compounds , There may be used those known as latent curing accelerators.

The catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the precursor of the polyorganosiloxane (A1).

Examples of the organic solvent include hydrocarbons, ethers, esters, ketones, amides, and alcohols. Of these, ethers, esters or ketones are preferable from the viewpoints of solubility of raw materials and products and ease of purification of products. The solvent is used in such a ratio that the solid concentration (the ratio of the weight of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5 to 50% by weight.

The reaction temperature is preferably 0 to 200 캜, more preferably 50 to 150 캜. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

In this way, a solution containing the polyorganosiloxane (A1) can be obtained. This solution may be directly supplied to the preparation of the polymer composition, but it is preferable to provide the solution after preparation of the polymer composition after removing the used catalyst from the solution or after isolating the polyorganosiloxane (A1). In order to remove the catalyst from the solution containing the polyorganosiloxane (A1), for example, the solution may be washed with water or the like. The isolation of the polyorganosiloxane (A1) can be preferably carried out by removing the organic solvent from the solution after washing.

- polyamic acid (A1) -

The polyamic acid (A1) as the polymer (A1) used in the present invention is a polymer having at least one structure selected from the group consisting of a structure generating a radical by light irradiation and a structure having a photosensitizing function and a poly It is mental. Such polyamic acid (A1) may be synthesized by any synthesis method, but for example,

Tetracarboxylic acid dianhydride,

(Hereinafter referred to as " diamine (1) ") having at least one structure and two amino groups among structures having a structure capable of generating a radical by light irradiation and a structure having a photosensitizing function,

Can be synthesized by reacting a diamine containing a polymerizable unsaturated bond and a compound having two amino groups (hereinafter referred to as " diamine (2) ").

Examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic dianhydride, and the like. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- , 5,8,10-tetralone, and the like;

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride and the like,

Tetracarboxylic acid dianhydride described in Japanese Patent Application No. 2009-157556 can be used.

As the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid (A1), those containing an alicyclic tetracarboxylic dianhydride are preferable, and 2,3,5-tricarboxycyclopentyl acetic acid 2 Anhydride and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and particularly preferably contains at least one selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. .

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid may be selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride. Is preferably contained in an amount of at least 60 mol%, more preferably at least 80 mol%, and more preferably at least one of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and And most preferably at least one selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride.

As the diamine (1), for example, {4- [2- (3,5-diaminophenoxy) -ethoxy] -phenyl} -phenyl- Phenyl} -p-tolyl-methanone, < / RTI > (4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl} -o-tolyl-methanone, and at least one selected from these can be used.

Examples of the diamine (2) include 3,5-diamino (2 '- (meth) acryloyloxyethyl) benzoate, 3,5-diamino (1' - (meth) acryloxymethyl) (4'- (meth) acryloyloxybutyl) benzoate, 3,5-diamino (3'- (meth) acryloyloxypropyl) benzoate, (Meth) acryloyloxyphenyl) benzoate, 3,5-diamino (6 '- (meth) acryloyloxyhexyl) benzoate, N ¹ , N ¹ -dialyl- 1,2,4-triamine, N, N-diallylbenzene-1,3,5-triamine and 2- (2,4-diaminophenoxy) ethyl (meth) acrylate. , And at least one selected from these can be used.

The diamine used for synthesizing the polyamic acid (A1) in the present invention may be composed only of the diamine (1) and the diamine (2) as described above, or may be a mixture of the diamine (1) and the diamine (2) Diamine (hereinafter referred to as " diamine (3) ").

Examples of the diamine (3) usable herein include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;

As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

As aromatic diamines, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9- 4,4'- (m-tert-butylphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 - diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole,

N, N'-bis (4-aminophenyl) benzidine, N, N'- Aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5- diaminobenzoic acid, dodecaneoxy- Oxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy- 2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecanoxy-2, 5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy- 2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, Bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1 (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, Heptylcyclohexane, 1,1-bis (4 - ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1-bis (4 - ((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane and the following formula (D-

(Formula (D-1) of, X ^I are also combined with the alkyl group having a carbon number of 1~3, ^* -O-, ^* -COO- or ^* -OCO- (However, the combined hand-diamino phenyl group attached to "*" ), H is 0 or 1, i is an integer of 0 to 2, and j is an integer of 1 to 20)

And the like;

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like,

Diamines described in Japanese Patent Application No. 2009-157556 may be used, and at least one selected from these diamines may be used.

X ^I in the above formula (D-1) is preferably an alkyl group having 1 to 3 carbon atoms, ^* -O- or ^* -COO- (provided that the bond with "*" is bonded to a diaminophenyl group) Do. Specific examples of the group C _j H _{2j + 1} - include a methyl group, an ethyl group, a n-propyl group, an n-butyl group, an n-pentyl group, a n-hexyl group, N-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-hexadecyl group, n-hexadecyl group, an n-nonadecyl group, and an n-eicosyl group. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-4)

And the like.

In the formula (D-1), it is preferable that h and i are not 0 at the same time.

The diamine used for synthesizing the polyamic acid (A1)

The diamine (1) is preferably contained in an amount of 0.1 to 10 mol%, more preferably 0.5 to 5 mol%, based on the total diamine,

The diamine (2) is preferably contained in an amount of 10 to 60 mol%, more preferably 20 to 50 mol%, based on the diamine. The proportion of the diamine (3) as described above is preferably 89.9 mol% or less, more preferably 30 mol% to 75 mol%, further preferably 30 mol% to 70 mol%, based on the total diamine.

The ratio of the tetracarboxylic dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid (A1) is preferably such that the ratio of the acid anhydride group of the tetracarboxylic acid dianhydride to the equivalent of 0.2 to 2 equivalents based on 1 equivalent of the amino group contained in the diamine compound , More preferably from 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid (A1) is preferably carried out in an organic solvent under a temperature condition of preferably -20 to 150 占 폚, more preferably 0 to 100 占 폚, preferably 0.5 to 24 hours, Preferably 2 to 10 hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid (A1) to be synthesized. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N- Aprotic polar solvents such as dimethylformamide, N, N-dimethylimidazolidinone, dimethylsulfoxide,? -Butyrolactone, tetramethylurea and hexamethylphosphoric triamide;

phenol-based solvents such as m-cresol, xylenol, phenol, halogenated phenol and the like. The amount (a) of the organic solvent to be used is preferably 0.1 to 50 wt%, more preferably 5 to 20 wt%, based on the total amount (a + b) of the reaction solution, 30% by weight.

As described above, a reaction solution obtained by dissolving the polyamic acid (A1) is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or the polyamic acid (A1) contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or the polyamic acid (A1) May be provided later for preparation of the liquid crystal aligning agent.

When the polyamic acid (A1) is dehydrated and ring-closed to form the polyimide (A1), the reaction solution may be directly supplied to the dehydration ring-closing reaction, or the polyamic acid (A1) contained in the reaction solution may be isolated, Or may be provided to the dehydration ring-closing reaction after the isolated polyamic acid (A1) is purified.

Isolation of the polyamic acid (A1) can be carried out by pouring the reaction solution into a large amount of a poor solvent to obtain a precipitate and drying the precipitate under reduced pressure, or a method of distilling off the organic solvent in the reaction solution under reduced pressure Method or the like. Further, the polyamic acid (A1) is dissolved again in an organic solvent and then precipitated with a poor solvent, or a solution obtained by dissolving the polyamic acid (A1) in an organic solvent is washed, and then the organic solvent in the solution is waxed The polyamic acid (A1) can be purified by, for example, a method of performing the step of distillation under reduced pressure with a purifier once or several times.

- polyimide (A1) -

The polyimide (A1) as the polymer (A1) used in the present invention is a polyimide having at least one structure selected from the group consisting of a structure generating a radical by light irradiation and a structure having a photosensitizing function, It is Meade. Such a polyimide (A1) can be synthesized by dehydration ring closure of the arboric acid structure having the above-mentioned polyamic acid (A1). At this time, all of the arctic structure may be completely imidized by dehydrating and ring closure, or only a part of the arctic structure may be dehydrated and cyclized to form a partial imide having an acid structure and an imide structure. The imidization ratio of the polyimide (A1) is preferably 40% or more, more preferably 50 to 80%.

The dehydration ring-closure of the polyamic acid (A1) can be carried out by a method comprising the steps of (i) heating the polyamic acid (A1) or (ii) dissolving the polyamic acid (A1) in an organic solvent, and adding a dehydrating agent and a dehydrating ring- And then heating it as necessary.

The reaction temperature in the method of heating the polyamic acid (A1) of (i) is preferably 50 to 200 캜, more preferably 60 to 170 캜. If the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the obtained polyimide (A1) may be lowered. The reaction time in the method of heating the polyamic acid (A1) is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.

On the other hand, in the method of adding the dehydrating agent and the dehydrating ring-closing catalyst to the solution of the polyamic acid (A1) of (ii), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride is used as the dehydrating agent . The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structural unit. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, the present invention is not limited thereto. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of the polyamic acid (A1). The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

The polyimide (A1) obtained in the above method (i) may be directly supplied to the preparation of the liquid crystal aligning agent or may be provided in the preparation of the liquid crystal aligning agent after the obtained polyimide (A1) is purified. On the other hand, in the above method (ii), a reaction solution containing the polyimide (A1) is obtained. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent. Alternatively, after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, the reaction solution may be added to the preparation of the liquid crystal aligning agent. After the polyimide (A1) May be added to the preparation of the liquid crystal aligning agent after the purified polyimide (A1) is purified. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent substitution can be applied. The isolation and purification of the polyimide (A1) can be carried out by performing the same operations as described above as a method for isolating and purifying the polyamic acid (A1).

- polyamic acid (A2-1) -

The polyamic acid (A2-1) as the polymer (A2-1) used in the present invention is a polyamic acid having at least one structure of a structure capable of generating a radical by light irradiation and a structure having a photo-sensitization function.

Such polyamic acid (A2-1) may be synthesized by any synthetic method, but for example,

Tetracarboxylic acid dianhydride,

Can be synthesized by reacting a diamine containing diamine (1).

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid (A2-1) is the same as the above-mentioned tetracarboxylic dianhydride used for synthesizing the polyamic acid (A1). Preferred tetracarboxylic acid dianhydrides and their preferable use ratios are also the same.

The diamine used for synthesizing the polyamic acid (A2-1) includes diamine (1), and may be composed only of diamine (1), or may contain diamine (1) in addition to diamine (1) . These diamines (1) and (3) are the same as the diamines (1) and (3) used for synthesizing the polyamic acid (A1), respectively.

The diamine used for synthesizing the polyamic acid (A2-1)

The amount of the diamine (1) is preferably 0.1 to 20 mol%, more preferably 0.5 to 10 mol%, based on the total diamine. The ratio of the diamine (3) to be used is preferably 99.9 mol% or less, more preferably 85 to 99.5 mol%, based on the total diamine.

The synthesis, isolation and purification of the polyamic acid (A2-1) can be carried out in the same manner as described for the synthesis, isolation and purification of the polyamic acid (A1).

- Polyimide (A2-1) -

The polyimide (A2-1) as the polymer (A2-1) used in the present invention is a polyimide having at least one structure of a structure capable of generating a radical by light irradiation and a structure having a photo-sensitization function. Such a polyimide (A2-1) can be synthesized by dehydration ring closure of the arboric acid structure having the above-mentioned polyamic acid (A2-1). The imidization ratio of the polyimide (A2-1) is preferably 40% or more, more preferably 50 to 80%.

The dehydration ring closure reaction of the polyamic acid (A2-1) and the isolation and purification of the obtained polyimide (A2-1) can be carried out by the dehydration ring closure reaction of the polyamic acid (A1) and the method described as the isolation and purification of the polyimide (A1) Can be performed in the same manner.

- polyorganosiloxane (A2-2) -

The polyorganosiloxane (A2-2) as the polymer (A2-1) used in the present invention is a polyorganosiloxane having a polymerizable unsaturated bond. Such a polyorganosiloxane (A2-2) may be synthesized by any synthesis method, but for example,

Can be synthesized by hydrolysis and condensation of a mixture of silane compounds containing silane compound (1), preferably in the presence of an organic solvent, water and a catalyst.

The silane compound used for synthesizing the polyorganosiloxane (A2-2) may be composed solely of the silane compound (1) as described above, or may be the silane compound (2) and the silane compound (3). ≪ / RTI > These silane compounds (1), (2) and (3) are the same as the silane compounds (1), (2) and (3) used for synthesizing the precursor of the polyorganosiloxane Do.

The silane compound used for synthesizing the polyorganosiloxane (A2-2) preferably contains the above silane compound (1) in an amount of 0.1 mol% or more, more preferably 0.1 to 20 mol% , More preferably from 0.1 to 10 mol%. The content of the silane compound (2) is preferably 70 mol% or less, more preferably 20 to 60 mol%, based on the total silane compound. The use ratio of the silane compound (3) as described above is preferably 70 mol% or less, more preferably 50 mol% or less, based on the total silane compound.

As is apparent from the above description, the polyorganosiloxane which is a precursor of the polyorganosiloxane (A1) may be used as the polyorganosiloxane (A2-2).

The synthesis and isolation of the polyorganosiloxane (A2-2) can be carried out in the same manner as described above as the synthesis and isolation of the precursor of the polyorganosiloxane (A1).

- Other polymers -

In the present invention, the polymer (A)

(A1), or

And both of the polymer (A2-1) and the polymer (A2-2).

(A) the polymer is composed only of the polymer (A1), or

May be composed solely of the polymer (A2-1) and the polymer (A2-2), or may contain other polymers in addition to them.

The other polymer is a polymer having no specific structure as described above. Examples of the other polymer include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyorganosiloxane, cellulose derivative, Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylate derivatives, and the like, and at least one selected from the above can be appropriately selected and used.

The other polymer in the present invention is preferably at least one selected from the group consisting of polyamic acid, polyimide and polyorganosiloxane.

The polyamic acid having no specific structure can be obtained by reacting the tetracarboxylic acid dianhydride with the diamine (3). By dehydrating and ring-closing the polyamic acid, a polyimide having no specific structure can be obtained. The polyorganosiloxane having no specific structure can be obtained by hydrolysis and condensation of at least one member selected from the group consisting of the silane compounds (2) and (3). Those skilled in the art will appreciate that these synthetic reactions, isolation and purification can be carried out in accordance with examples of polymers having a specific structure.

The use ratio of the other polymer in the polymer (A) is preferably 80% by weight or less, more preferably 70% by weight or less based on the total amount of the polymer.

The polymer (A) in the present invention is preferably any of the following embodiments.

(1) an embodiment comprising only polyorganosiloxane (A1);

(2) an embodiment wherein the other polymer is composed of a polyorganosiloxane (A1) and other polymer, and at least one selected from the group consisting of polyamic acid and polyimide having no specific structure;

(3) an embodiment comprising at least one selected from the group consisting of polyamic acid (A1) and polyimide (A1);

(4) A polymer comprising at least one member selected from the group consisting of a polyamic acid (A1) and a polyimide (A1) and other polymer, wherein the other polymer is selected from the group consisting of polyamic acid and polyimide having no specific structure ≪ / RTI > And

(5) An embodiment comprising at least one member selected from the group consisting of polyamic acid (A2-1) and polyimide (A2-1) and polyorganosiloxane (A2-2).

The proportion of each polymer in the embodiment (5) is preferably at least one selected from the group consisting of polyamic acid (A2-1) and polyimide (A2-1) and polyorganosiloxane (A2-2) Is preferably 2 to 30% by weight, more preferably 5 to 20% by weight, based on the total amount of the polyorganosiloxane (A2-2) and the polyorganosiloxane (A2-2). In this embodiment (5), it is preferable that no other polymer is contained.

The polymer (A) preferably contains 0.5 to 5 mmol / g of at least one structure selected from the group consisting of a structure which generates radicals by light irradiation and a structure having a photosensitizing function, / g is more preferable;

The polymerizable unsaturated bond is preferably contained in an amount of 1 to 15 mmol / g, more preferably 1 to 10 mmol / g.

[(B) Organic solvent]

Examples of the organic solvent (B) in the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, Acetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol Ethyl ether, ethylene glycol n-propyl ether ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, di Ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, Isoamyl isopropyl ether, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether and the like, and at least one selected from the above can be used.

[Polymer composition]

The polymer composition used in the present invention is preferably prepared as a solution prepared by dissolving the above-mentioned polymer (A) in the above-mentioned (B) organic solvent.

The ratio of the organic solvent (B) used is preferably such that the solid content of the polymer composition (the ratio of the weight of the polymer (A) in the polymer composition to the total weight of the polymer composition) is 1 to 15 wt% More preferably 1.5 to 8% by weight.

<Manufacturing Method of Liquid Crystal Display Element>

In the method of manufacturing a liquid crystal display element of the present invention,

A coating film is formed by applying the above-mentioned polymer composition on each of the conductive films of a pair of substrates having a conductive film,

A pair of substrates on which the coating film is formed are disposed opposite to each other with the liquid crystal molecules interposed therebetween to form a liquid crystal cell,

And a step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films of the pair of substrates.

Examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used.

As the conductive film, it is preferable to use a transparent conductive film. For example, a NESA (registered trademark) film made of SnO ₂ , an ITO film made of In ₂ O ₃ -SnO ₂ , or the like can be used. It is preferable that each of the conductive films is a patterned conductive film divided into a plurality of regions. With such a conductive film structure, it is possible to change the pretilt angle direction of the liquid crystal molecules for each region by applying a different voltage to each of these regions when a voltage is applied between the conductive films (described later) It becomes possible to make it wider.

The application of the polymer composition onto the conductive film of such a substrate can be carried out by a suitable application method such as a roll coater method, a spinner method, a printing method, or an ink jet method. After the application, the coated surface is preheated (prebaked) and then baked (post baked) to form a coated film. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 占 폚, the postbaking conditions are preferably 120 to 300 占 폚, more preferably 150 to 250 占 폚, preferably 5 to 200 minutes, Is 10 to 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

The thus formed coating film may be provided as it is in the production of the liquid crystal cell in the next step, or rubbing treatment may be performed on the coated film surface as necessary before the production of the liquid crystal cell. This rubbing treatment can be performed by rubbing the coating film surface in a predetermined direction with a roll of cloth made of fibers such as nylon, rayon, and cotton. Here, as described in Patent Document 2 (Japanese Unexamined Patent Publication (Kokai) No. 5-107544), a resist film is formed on a part of the coated film surface after rubbing once, and further, It is possible to further improve the visual characteristics of the resulting liquid crystal display element by carrying out a process of removing the resist film after the rubbing treatment and making the rubbing direction different for each region.

Subsequently, the pair of substrates on which the coating film is formed are opposed to each other with the liquid crystal molecules interposed therebetween to form the liquid crystal cell.

The liquid crystal molecules used herein are preferably nematic liquid crystals having negative dielectric anisotropy, and examples thereof include dicyanobenzene-based liquid crystals, pyridazine-based liquid crystals, shep base-based liquid crystals, A liquid crystal, a phenylcyclohexane-based liquid crystal, or the like can be used. The thickness of the liquid crystal molecule layer is preferably 1 to 5 mu m.

In order to manufacture a liquid crystal cell using such a liquid crystal, for example, the following two methods can be mentioned.

As a first method, two substrates are opposed to each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded to each other using a sealant, A liquid crystal is injected and filled in the cell gap defined by the liquid crystal cell, and then the injection hole is sealed. As a second method, for example, an ultraviolet curable sealant is applied to a predetermined position on one of the two substrates on which a liquid crystal alignment film is formed, and further liquid crystal is applied to a predetermined number of positions on the liquid crystal alignment film surface After the dropwise addition, the liquid crystal cell is formed by spreading the liquid crystal on the entire surface of the substrate while bonding the other substrate so as to face the liquid crystal alignment film and then curing the sealant by irradiating ultraviolet light to the entire surface of the substrate .

Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

The voltage to be applied here may be DC or AC of 5 to 50 V, for example.

As the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable. As the light source of the irradiation light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp and an excimer laser can be used. The ultraviolet ray of the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with a filter, a diffraction grating, or the like. The irradiation dose of light is preferably 1,000 J / m 2 or more and less than 100,000 J / m 2, and more preferably 1,000 to 50,000 J / m 2. In the conventionally known PSA mode liquid crystal display device, it is necessary to irradiate light of about 100,000 J / m 2. In the method of the present invention, however, the light irradiation amount is preferably 50,000 J / m 2 or less, more preferably 10,000 J / It is possible to obtain a desired liquid crystal display element, which contributes to the reduction of the production cost of the liquid crystal display element, and further, it is possible to avoid deterioration of electrical characteristics and deterioration of long-term reliability caused by strong light irradiation.

Then, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after performing the above-described processing. Examples of the polarizing plate used herein include a polarizing plate in which a polarizing film called &quot; H film &quot; in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state is sandwiched by a cellulose acetate protective film, or a polarizing plate made of the H film itself.

(Example)

Synthesis Example P1 < Synthesis of Polymer (A1) >

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride and 11 g (0.10 mole) of p-phenylenediamine as diamine, {4- [2- (0.30 mol) of 3,5-diamino (2'-methacryloyloxyethyl) benzoate and 0.35 g (0.30 mol) of 3,5-diamino-phenoxy) -ethoxy] -phenyl} (0.05 mol) of 2,2-bis (3,5-diaminobenzoyloxy) cholestane was dissolved in 750 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C for 6 hours to obtain a solution &Lt; / RTI &gt; A small amount of the obtained polyamic acid solution was collected, and the solution viscosity was measured to be 58 mPa · s as a solution containing 10 wt% of polyamic acid by adding NMP.

Then, 1,800 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring-closure reaction, the imidization ratio of the polymer (A1) of about 50% was obtained by solvent substitution of the solvent in the system with fresh NMP (by removing pyridine and anhydrous acetic acid used in the dehydration ring closure reaction out of the system by this operation, Of a polyimide (P-1) in an amount of about 15% by weight. A small amount of the obtained polyimide solution was collected, and NMP was added thereto to obtain a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 63 mPa · s.

Synthesis Example P2 < Synthesis of Polymer (A2-1) >

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride and 27 g (0.25 mole) of p-phenylenediamine as diamine, {4- [2- (0.05 mol) of 3- (3,5-diaminobenzoyloxy) cholestane were dissolved in 750 g of NMP, and 60 g (0.20 mol) of 3- Deg.] C for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected and NMP was added thereto to give a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 61 mPa · s.

Then, 1,800 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh NMP to obtain a solution containing about 15% by weight of polyimide (P-2) having an imidization rate of about 50% of the polymer (A2-1). A small amount of the obtained polyimide solution was collected, and NMP was added thereto to obtain a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 68 mPa · s.

Synthesis Example P3 < Synthesis of Other Polymer &

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 49 g (0.20 mole) of p-phenylenediamine as diamine, 38 g (0.25 g) of 3,5-diaminobenzoic acid, And 5ξ cholestan-3-yl-2,4-diaminophenyl ether (25 g, 0.05 mole) were dissolved in 750 g of NMP and reacted at 60 ° C for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected and NMP was added thereto to obtain a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 56 mPa · s.

Then, 1,800 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a fresh NMP solvent to obtain a solution containing about 15% by weight of polyimide (P-3) having an imidization rate of about 50% as another polymer. A small amount of the obtained polyimide solution was collected, and the solution viscosity was measured as a solution having a polyimide concentration of 10% by weight by adding NMP, and the solution viscosity was 69 mPa · s.

Synthesis Example P4 < Synthesis of Other Polymer &

(1.0 mole) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as tetracarboxylic dianhydride and 210 g (1.0 mole) of 2,2'-dimethyl-4,4'-diaminobiphenyl as a diamine, Was dissolved in a mixed solvent composed of 370 g of NMP and 3,300 g of? -Butyrolactone, and the reaction was carried out at 40 占 폚 for 3 hours to obtain a solution containing 10% by weight of polyamic acid (P-4) as another polymer. The solution viscosity of this polyamic acid solution was 160 mPa · s.

Synthesis Example S1 < Synthesis of Polymer (A2-2)

[Hydrolysis and condensation reaction]

123 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) as a hydrolyzable silane compound and 3 g of 3-methacryloxypropyl triethoxysilane were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube 124 g of methoxysilane (GMPTS) (ECETS: GMPTS = 50: 50 (molar ratio)), 500 g of methyl isobutyl ketone as a solvent and 10.0 g of triethylamine as a catalyst were added and mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted under reflux at 80 DEG C for 6 hours while stirring. After the completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous solution of ammonium nitrate until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a hydrolysis-condensation product having an epoxy group As a transparent liquid.

As a result of ¹ H-NMR analysis of this hydrolysis-condensation product, it was confirmed that a peak attributed to the epoxy group was obtained near the chemical shift (?) = 3.2 ppm as the theoretical intensity, and no side reaction of the epoxy group occurred during the reaction .

[Reaction of hydrolyzed condensate having an epoxy group with carbonic acid]

To a 200 mL three-necked flask was added 30.0 g of methyl isobutyl ketone as a solvent and 75.1 g of 4-octyloxybenzoic acid (OCTBA) as a carbonic acid (the total amount of the hydrolyzable silane compounds used as raw materials , And 0.10 g of UCAT 18X (trade name, manufactured by San A Pro Co., Ltd., which is a curing accelerator for an epoxy compound) as a catalyst were placed in a reactor equipped with a stirrer, The reaction was carried out with stirring at 100 DEG C for 48 hours. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed three times with water, dried over magnesium sulfate and then the solvent was distilled off to obtain a polyorganosiloxane (S-1) Was obtained. The polyorganosiloxane (S-1) had a weight average molecular weight Mw of 7,200 as measured by gel permeation chromatography (GPC) in terms of polystyrene.

Synthesis Examples S2 to S7 < Synthesis of polymer (A1) and other polymers >

In the same manner as in Synthesis Example S1 except that the kind and amount of the hydrolyzable silane compound and the carbonic acid shown in Table 1 were used in Synthesis Example S1, the hydrolysis and condensation reaction and the reaction with the hydrolyzed condensate and the carbonic acid were carried out (S-2) to (S-6) as the polymer (A1) and a polyorganosiloxane (S-7) as the other polymer were obtained. The yields and Mw of these polyorganosiloxanes are shown in Table 1.

The abbreviations of the respective compounds in Table 1 are as follows.

{Hydrolyzable silane compound}

ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

GMPTS: 3-methacryloxypropyltrimethoxysilane

GAPTS: 3-acryloxypropyltrimethoxysilane

{Carbonic acid}

OCTBA: 4-octyloxybenzoic acid

PCHBA: 4- (4-pentylcyclohexyl) benzoic acid

DAHBBA: 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid

DNBA: 3,5-dinitro-benzoic acid

SACY: succinic acid = 5? -Cholestan-3-yl

AQCA: Anthraquinone-2-carboxylic acid

The amount of the carbonic acid used in Table 1 is the molar ratio to the sum of the hydrolyzable silane compounds. In Synthesis Examples S2 to S6, two kinds of carbonic acid were used.

Example 1

In this embodiment, polyimide as the polymer (A1) was used as the polymer (A).

&Lt; Preparation of polymer composition >

N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added as an organic solvent to a solution containing the polyimide (P-1) obtained in Synthesis Example P1 as the polymer (A) A solution having a composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 6.0 wt% was prepared. This solution was filtered using a filter having a pore diameter of 1 탆 to prepare a polymer composition.

&Lt; Production of liquid crystal cell &

Six polymer liquid crystal display devices were manufactured by changing the pattern (two kinds) of transparent electrodes and the amount of ultraviolet irradiation (three levels) using the polymer composition prepared as described above and evaluated as follows.

[Production of liquid crystal cell having transparent electrode without pattern]

The polymer composition prepared above was applied onto the transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Shingen Co., Ltd.) After the solvent was removed by heating (prebaking), the film was heated on a hot plate at 150 ° C for 10 minutes (post baking) to form a coating film having an average film thickness of 600 Å.

The coating film was subjected to a rubbing treatment with a rubbing machine having a roll covered with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair pressing indentation length of 0.1 mm. Thereafter, the substrate was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

The rubbing treatment is a weak rubbing treatment for the purpose of controlling the inclination of the liquid crystal and performing the orientation division by a simple method.

Next, one of the pair of substrates was coated with an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 on the outer edge of the surface having the liquid crystal alignment film, and then a pair of substrates And the liquid crystal alignment film surfaces were opposed to each other and pressed, and the adhesive was cured. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to manufacture a liquid crystal cell.

The above operation was repeated to produce three liquid crystal cells each having a pattern-free transparent electrode. One of them was provided for the evaluation of the pre-tilt angle as will be described later. The remaining two liquid crystal cells were irradiated with light in a state in which a voltage was applied between the conductive films by the following method, and then provided for the evaluation of the pretilt angle and the voltage holding ratio.

Two of the liquid crystal cells obtained above were irradiated with an ultraviolet ray of 10,000 J / m &lt; 2 &gt; using an ultraviolet irradiation apparatus using a metal halide lamp as a light source, Or 100,000 J / m &lt; 2 &gt;. This irradiation dose is a value measured using a photometer which is measured at a wavelength of 365 nm.

[Evaluation of Pretilt Angle]

For each of the liquid crystal cells prepared above, He-Ne laser light was used in accordance with the method described in Non-Patent Document 2 (TJ Scheffer et al., J. Appl. Phys. And the value of the inclination angle of the liquid crystal molecules measured from the substrate surface by the crystal rotation method was defined as the pretilt angle.

Table 2 shows the pretilt angles of the liquid crystal cell of light irradiation, the liquid crystal cell of the dose of 10,000 J / m 2, and the liquid crystal cell of the irradiation dose of 100,000 J / m 2.

[Evaluation of Voltage Conservation Rate]

For each of the liquid crystal cells prepared above, a voltage of 5 V was applied at 23 DEG C for an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the release voltage was measured. As the measuring apparatus, VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

Table 2 shows the voltage holding ratios of the liquid crystal cell having an irradiation dose of 10,000 J / m 2 and the liquid crystal cell having an irradiation dose of 10,000 J / m 2.

[Production of liquid crystal cell having patterned transparent electrode]

The polymer composition prepared above was patterned in a slit shape as shown in Fig. 1, and a liquid crystal alignment film printing machine (Nippon Shanshin Insights Co., Ltd.) was formed on each electrode surface of two glass substrates each having ITO electrodes partitioned into a plurality of regions (Post-baking) on a hot plate at 80 DEG C for 1 minute to remove the solvent, and then heated on a hot plate at 150 DEG C for 10 minutes (post baking) to obtain a coating film having an average film thickness of 600 ANGSTROM . This coating film was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

Subsequently, with respect to one of the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied to the outer edge of the surface having the liquid crystal alignment film, and then the liquid crystal alignment film surface was opposed to the pair of substrates They were superimposed on each other and pressed, and the adhesive was cured. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to manufacture a liquid crystal cell.

The above operation was repeated to produce three liquid crystal cells having patterned transparent electrodes. One of them provided an evaluation of the response speed as will be described later. The remaining two liquid crystal cells were irradiated with light at an irradiation dose of 10,000 J / m 2 or 100,000 J / m 2 in a state where a voltage was applied between the conductive films by the same method as in the production of the liquid crystal cell having the patternless transparent electrode. After the investigation, it was provided to the evaluation of the response speed.

The electrode pattern used here is the same kind of pattern as the electrode pattern in the PSA mode.

[Evaluation of response speed]

After sandwiching each liquid crystal cell manufactured as described above with two polarizing plates arranged in a cross-Nicol state, a visible light lamp was irradiated without applying a voltage first, and the luminance of light transmitted through the liquid crystal cell was measured by a photomulti meter, This value was regarded as 0% relative transmittance. Next, the transmittance when an alternating current of 60 V was applied for 5 seconds between the electrodes of the liquid crystal cell was measured in the same manner as above, and the relative transmittance was set to 100%.

At this time, when the alternating current of 60 V was applied to each liquid crystal cell, the time from the relative transmittance to the transition from 10% to 90% was measured, and this time was defined as the response speed and evaluated.

Table 2 shows the response speeds of the liquid crystal cell of light irradiation, the liquid crystal cell of the dose of 10,000 J / m 2, and the liquid crystal cell of the irradiation dose of 100,000 J / m 2.

Example 2

In this example, a mixture of polyimide (P-2) as the polymer (A2-1) and polyorganosiloxane (S-1) as the polymer (A2-2) was used as the polymer (A).

(An amount corresponding to 80 parts by weight in terms of polyimide (P-2)) containing the polyimide (P-2) obtained in the above Synthesis Example P2 was added with N-methyl-2-pyrrolidone 20 parts by weight of the polyorganosiloxane (S-1) obtained in the above Synthesis Example S1 was added and the solvent composition was NMP: BC = 50: 50 (weight ratio) , And a solid content concentration of 6.0 wt%. This solution was filtered using a filter having a pore size of 1 탆 to prepare a polymer composition, and various liquid crystal cells were produced and evaluated.

The evaluation results are shown in Table 2.

Examples 3 to 8

In this embodiment, a mixture of polyorganosiloxane as polymer (A1) and polyimide or polyamic acid as other polymer was used as the polymer (A).

A solution containing the polymer (polyimide or polyamic acid) shown in Table 2 was used in place of the solution containing polyimide (P-2) in Example 2, and the polymer contained in the solution And a polyorganosiloxane of the type and amount described in Table 2 was used in place of the polyorganosiloxane (S-1), a polymer composition was prepared in the same manner as in Example 2, Various liquid crystal cells were produced and evaluated by using this.

The evaluation results are shown in Table 2.

Comparative Example 1

In this comparative example, only the other polymer, polyimide, was used as the polymer.

The procedure of Example 1 was repeated except that the solution containing polyimide (P-3) obtained in Synthesis Example P3 was used instead of the solution containing polyimide (P-1) And various liquid crystal cells were produced and evaluated by using these.

The evaluation results are shown in Table 2.

Comparative Example 2

In this Comparative Example, a mixture of polyimide and polyorganosiloxane, which are all other polymers, was used as the polymer.

In the second embodiment,

A solution containing the polyimide (P-4) obtained in the above Synthesis Example P4 was used instead of the solution containing the polyimide (P-2) so that the polyimide contained therein was 70 parts by weight, A polymer composition was prepared in the same manner as in Example 2 except that 30 parts by weight of the polyorganosiloxane (S-7) obtained in Synthesis Example S7 was used instead of the organosiloxane (S-1) Cells were prepared and evaluated.

The evaluation results are shown in Table 2.

From the results shown in Table 2, in the method of the present invention, when the ultraviolet irradiation amount is 100,000 J / m 2 (the value conventionally employed in the PSA mode), the degree of pretilt angle obtained becomes excessive, It can be understood that an appropriate pretilt angle is obtained at the irradiation amount below. Moreover, even when the dose is small, a sufficiently fast response speed is obtained and the voltage holding ratio is also excellent.

Therefore, according to the method of the present invention, it is possible to realize the advantages of the PSA mode with a small amount of light irradiation, and therefore, the viewing angle can be reduced without concern of occurrence of display irregularity due to high light amount, deterioration of voltage- It is possible to manufacture a liquid crystal display element which is wide, has a high response speed of liquid crystal molecules, high transmittance, and high contrast.

In addition, various liquid crystal cells were produced and evaluated in the same manner as in Example 1, except that the pattern of the ITO electrode of the glass substrate was changed by using various polymer compositions used in Examples 2 to 8. Both the polymer composition and the pattern shown in Fig. 2 and the pattern shown in Fig. 3 had the same effects as those of the first embodiment.

1: ITO electrode
2:
3:

Claims (7)

On a conductive film of a pair of substrates having a conductive film,
(A) a polymer and
(B) an organic solvent
Is applied to form a coating film,
A pair of substrates on which the coating film is formed are disposed opposite to each other with the liquid crystal molecules interposed therebetween to form a liquid crystal cell,
A step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films of the pair of substrates,
Wherein the polymer (A)
(A1) a polymer having both a structure of generating a radical by light irradiation and a structure having a photosensitizing function and a polymerizable unsaturated bond, or
(A2-1) a polymer having at least one structure selected from the group consisting of a structure generating a radical by light irradiation and a structure having a photo-sensitization function, and
(A2-2) a polymer having a polymerizable unsaturated bond,
The polymer (A), as a whole, is characterized by containing 0.5 to 5 mmol / g of at least one structure of a structure capable of generating a radical by light irradiation and a structure having a photosensitizing function How to. The method according to claim 1,
At least one structure of a structure capable of generating a radical by light irradiation and a structure having a photosensitizing function is selected from the group consisting of a benzophenone structure, a 9,10-dioxodihydroanthracene structure, a 1,3-dinitrobenzene structure, and a 1 , And a 4-dioxocyclohexa-2,5-diene structure. 3. The method according to claim 1 or 2,
Wherein the polymer (A)
A polyorganosiloxane (A1) having both of a structure of generating a radical by light irradiation and a structure having at least one of a structure having a photosensitizing function and a polymerizable unsaturated bond,
A polyamic acid (A1) having both a structure of generating a radical by light irradiation and a structure having a photo-sensitization function and a polymerizable unsaturated bond, and
And a polyimide (A1) obtained by subjecting the polyamic acid to dehydration ring closure. 3. The method according to claim 1 or 2,
Wherein the polymer (A)
(A2-1) having at least one structure out of a structure capable of generating a radical by light irradiation and a structure having a photosensitizing function, and a polyimide (A2-1) obtained by dehydration ring closure of the polyamic acid And at least one kind selected from
And a polyorganosiloxane (A2-2) having a polymerizable unsaturated bond. 3. The method according to claim 1 or 2,
Wherein each of the conductive films is a patterned conductive film divided into a plurality of regions. A polymer composition containing (A) a polymer and (B) an organic solvent,
Wherein the polymer (A)
(A1) a polymer having both a structure of generating a radical by light irradiation and a structure having a photosensitizing function and a polymerizable unsaturated bond, or
(A2-1) a polymer having at least one structure selected from the group consisting of a structure generating a radical by light irradiation and a structure having a photo-sensitization function, and
(A2-2) a polymer having a polymerizable unsaturated bond,
The polymer (A), as a whole, is characterized by containing 0.5 to 5 mmol / g of at least one structure of a structure capable of generating a radical by light irradiation and a structure having a photosensitizing function &Lt; / RTI &gt; A liquid crystal display element produced by the method according to claim 1 or 2.

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