KR20100132436A - Method of manufacturing liquid crystal display device - Google Patents

Abstract

PURPOSE: A method for manufacturing a liquid crystal display device is provided to obtain a liquid crystal display device with excellent electrical property while enabling high-speed response at high brightness. CONSTITUTION: A method for manufacturing a liquid crystal display device comprises the steps of: forming a film consisting of a polymer with a structure represented by chemical formula (I) on a transparent pixel electrode, as a step for pinching nematic liquid crystals in which a dielectric anisotropy is negative between two substrates; and applying voltage the transparent pixel electrode to arrange the crystal and irradiating light.

Description

The manufacturing method of a liquid crystal display element {METHOD OF MANUFACTURING LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to the manufacturing method of a liquid crystal display element. More specifically, it is related with the manufacturing method of a liquid crystal display element suitable for manufacturing the liquid crystal display element of the MVA (Multi-domain Vertical Alignment) system which is excellent in liquid crystal orientation and electrical characteristics especially.

At present, as a liquid crystal display element, a liquid crystal aligning film is formed in the surface of the board | substrate with which the transparent conductive film is formed, and it is set as the board | substrate for liquid crystal display elements, the two sheets are opposed, and positive dielectric anisotropy exists in the clearance gap. TN type having a so-called TN (Twisted Nematic) type liquid crystal cell, in which a layer of nematic liquid crystal having a layer was formed to form a sandwich cell, and the long axis of the liquid crystal molecules was continuously twisted by 90 ° from one substrate to the other. A liquid crystal display element is known (patent document 1). In addition, STN (Super Twisted Nematic) type liquid crystal display element (Patent Document 2) capable of realizing a high contrast ratio compared to a TN type liquid crystal display element, has a low visual dependence and high-speed response of a video screen. Optically Compensated Bend (OCB) type liquid crystal display device (Patent Document 3) having excellent properties, and VA (Vertical Alignment) type liquid crystal display device using a nematic liquid crystal having negative dielectric anisotropy (Patent Document 4) IPS (In-Plane Switching) type liquid crystal display element (patent document 5) etc. with little visual dependence are known by orientation-regulating liquid crystal molecules in the plane horizontal to a board | substrate.

Among them, in the VA type liquid crystal display element, by forming an alignment control structure such as a linear protrusion or a slit structure on a substrate, the liquid crystal alignment direction at the time of voltage application is controlled in a plurality of orientations within the pixel, thereby wide viewing angle. The liquid crystal display element of the MVA system which realized this is known (patent document 6). Although the MVA type liquid crystal display element has an advantage of having excellent viewing angle characteristics, it also has a disadvantage of low display brightness and low display. It is thought that the main cause of this disadvantage is that the light transmittance of the entire pixel is lowered because the region on the structure for orientation regulation becomes a division boundary of the liquid crystal alignment and the region is visually darkly visible. In order to improve this, it is good to make the space | interval of an orientation regulation structure wide enough, but since the number of orientation regulation structures becomes relatively small, the time required to stabilize orientation becomes long, and a response speed becomes slow. Therefore, there is a limit to improvement by this measure.

In order to realize an MVA type liquid crystal display device capable of high-speed response at high luminance, a method of defining a pretilt angle of the liquid crystal molecules and an inclination direction when voltage is applied using a polymer has been proposed (Patent Document 6). ). The method of patent document 6 seals between two board | substrates the liquid crystal composition which mixed the monomer and liquid crystal superposed | polymerized by light or heat, applies a voltage between board | substrates, and liquid crystal molecules incline, and orientation is defined. In this state, light or heat is applied to the liquid crystal layer to thereby polymerize the monomer to form a polymer, thereby fixing the alignment direction and the pretilt angle of the liquid crystal molecules by the polymer. However, according to the technique of Patent Document 6, an unreacted polymerizable monomer remains in the liquid crystal, or a part of the polymerizable monomer is decomposed by light or heat, and the polymerizable monomer and / or its decomposition product is diffused in the liquid crystal. The side effect that the voltage retention is lowered sometimes occurs, and improvement is desired.

In recent years, the method which can improve some of the faults which the technique of patent document 6 has has been proposed (patent document 38). In this technique, a liquid crystal molecule is sandwiched between liquid crystal alignment films having a crosslinkable moiety, irradiated with ultraviolet light in a state in which an electric field is applied and the liquid crystal molecules are oriented to crosslink the crosslinkable moiety, It is a technique of fixing the orientation direction and pretilt angle of liquid crystal molecules. According to this technique, the problem caused by the remaining of the polymerizable monomer is certainly solved, but in addition to the large amount of ultraviolet irradiation required for crosslinking, there is a problem that the response speed of the liquid crystal molecules at the time of ON / OFF is slow. In the harsh field of today's liquid crystal display device, it cannot be provided for practical use.

Japanese Patent Application Laid-open No. Hei 4-153622 Japanese Laid-Open Patent Publication No. 60-107020 Japanese Patent Laid-Open No. 2009-48211 Japanese Patent Laid-Open No. 11-258605 Japanese Laid-Open Patent Publication No. 56-91277 Japanese Laid-Open Patent Publication 2002-23199 Japanese Patent Laid-Open No. 6-287453 Japanese Patent Publication No. 2003-520878 Japanese Patent Laid-Open No. 2007-286641 Japanese Laid-Open Patent Publication No. 57-114532 Japanese Patent Application Laid-open No. Hei 2-4725 Japanese Patent Application Laid-open No. Hei 4-224885 Japanese Patent Laid-Open No. 8-40953 Japanese Patent Application Laid-open No. Hei 8-104869 Japanese Patent Laid-Open No. 10-168076 Japanese Patent Application Laid-open No. Hei 10-168453 Japanese Patent Application Laid-open No. Hei 10-236989 Japanese Patent Laid-Open No. 10-236990 Japanese Patent Laid-Open No. 10-236992 Japanese Patent Application Laid-open No. Hei 10-236993 Japanese Patent Laid-Open No. 10-236994 Japanese Patent Application Laid-open No. Hei 10-237000 Japanese Patent Laid-Open No. 10-237004 Japanese Patent Laid-Open No. 10-237024 Japanese Patent Application Laid-Open No. 10-237035 Japanese Patent Application Laid-Open No. 10-237075 Japanese Patent Laid-Open No. 10-237076 Japanese Patent Laid-Open No. 10-237448 Japanese Patent Application Laid-open No. Hei 10-287874 Japanese Patent Laid-Open No. 10-287875 Japanese Patent Application Laid-Open No. 10-291945 Japanese Patent Application Laid-Open No. 11-029581 Japanese Patent Application Laid-Open No. 11-080049 Japanese Patent Laid-Open No. 2000-256307 Japanese Laid-Open Patent Publication 2001-019965 Japanese Patent Laid-Open No. 2001-072626 Japanese Laid-open Patent Publication 2001-192657 United States Patent Application Publication No. 2009/0325453

 T. J. Scheffer et. al., J. Appl. Phys. vo. 19, p. 2013 (1980)

This invention is made | formed in view of the said situation, and the objective is to provide the manufacturing method of the liquid crystal display element of especially the MVA system liquid crystal display element which is excellent in an electrical characteristic while being capable of high-speed response with high brightness.

According to the present invention, the above objects and advantages of the present invention,

Nematic liquid crystal with negative dielectric anisotropy between films of each of two substrates on which a film made of a polymer having a structure represented by the following formula (I) is formed on the transparent pixel electrode of the substrate having the transparent pixel electrode. And a process of irradiating light in a state in which a liquid crystal is oriented by applying a voltage between each of the transparent pixel electrodes of the two substrates, thereby achieving the liquid crystal display device manufacturing method.

(In formula (I), A <^1> and A <^3> are either a halogen atom, a cyano group, a nitro group, a C1-C12 alkyl group, and a C1-C12 alkoxy group (The alkyl group and the alkoxy group are each halogen. Or a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, 2,5, which may be substituted by one or more selected from the group consisting of -A thiophendiyl group, a 2, 5- franylene group or a CH group is a 1, 4- naphthylene group or 2, 6- naphthylene group which may be substituted by the nitrogen atom,

The other is a phenylene group which may be substituted by one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group, or a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, 2 1,4-naphthylene group or 2,6-naphthylene group or ^* -COO-, ^* -CONH-, ^* —CO—E— (herein, the number of bonds with “*” is bonded to —CH═CH—, and E is one or more selected from the group consisting of halogen atoms, cyano groups and nitro groups). A 1,4-phenylene group which may be substituted or a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a 2,5-thiophendiyl group, a 2,5-franylene group or a CH group 1,4-naphthylene group or 2,6-naphthylene group which may be substituted by nitrogen;

A ² is a 1,4-phenylene group which may be substituted by at least one member selected from the group consisting of a halogen atom, a cyano group and a nitro group, or a pyridine-2,5-diyl group and a pyrimidine-2,5 -Diyl group, 2,5-thiophendiyl group, 2,5-franylene group, trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group, or 1,4 -Piperidyl group;

Z ¹ is a single _{^{bond, * -CH 2 CH 2 -,}} * -COO-, * -OCO-, * -OCH 2 -, * -CH 2 O-, * -C≡C-, * - (CH 2 ^{_{) 4 -, * -O (CH}} 2) 3 - or ^* - (CH _{2) 3} O- or the trans form _{^{* -OCH 2 CH = CH-, *}} -CH = CHCH 2 O-, * - (CH 2 ) ₂ CH = CH- or ^* -CH = CH (CH ₂ ) _2- (wherein the number of bonds attached with "*" is bonded to A ² );

R ¹ is a hydrogen atom, a halogen atom, a cyano group, a nitro group or an NCS group or an alkyl group having 1 to 12 carbon atoms, wherein the alkyl group may be substituted by fluorine, and one or two non-contiguous —CH ₂ — The group may be substituted by an oxygen atom, —COO—, —OCO— or —CO—, and the —CH ₂ CH ₂ —group may be substituted by —CH═CH— or is a group having a steroid skeleton;

X and Y are each independently a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 12 carbon atoms, wherein the alkyl group may be substituted by a fluorine atom, and one or two non-contiguous —CH ₂ The group may be substituted by an oxygen atom, -COO-, -OCO- or -CO-;

n is an integer of 0 to 4,

However, when n is 0, R ¹ is not a hydrogen atom.)

According to this invention, the manufacturing method of the liquid crystal display element which is excellent in an electrical characteristic while being able to respond at high speed and high speed is provided. The liquid crystal display element manufactured by the method of this invention can be used especially suitably as a liquid crystal display element of MVA system.

Fig.1 (a) is the said schematic diagram which shows the structure of the pixel 2 which looked at the board | substrate surface in the normal line direction, and Fig.1 (b) is a partial sectional view in the A-A line of Fig.1 (a).
FIG. 2 is a partial cross-sectional view taken along line BB of FIG. 1A.
It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell manufactured in the Example.
It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell manufactured by the Example.

(Form to carry out invention)

In the method for producing a liquid crystal display device of the present invention, dielectric anisotropy is sandwiched between a film of each of two substrates on which a film made of a polymer having a structure represented by the formula (I) is formed. And applying a voltage between each transparent pixel electrode of the substrate to irradiate light in a state in which the liquid crystal is aligned.

It is preferable that the structure represented by said formula (I) is a structure which isomerized or dimerized by light or heat.

As for A <^1> and A <^3> in said Formula (I), one of these is a halogen atom, a cyano group, a nitro group, a C1-C12 alkyl group, and a C1-C12 alkoxy group (These alkyl group and an alkoxy group are respectively. Or a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, 2, or a phenylene group which may be substituted by at least one member selected from the group consisting of 5-thiophendiyl group, 2,5-franylene group, 1,4-naphthylene group, or 2,6-naphthylene group,

The other is a phenylene group which may be substituted by at least one member selected from the group consisting of a halogen atom, a cyano group and a nitro group, or ^* -COO- or ^* -CO-E- (wherein "*" is attached The bonding number is bonded to —CH═CH—, and E is a 1,4-phenylene group which may be substituted by at least one member selected from the group consisting of a halogen atom, a cyano group and a nitro group.

As Z ¹ in the formula (I), a single bond, ^* -CH ₂ CH _2- , ^* -COO-, ^* -OCH _2- , ^* -(CH ₂ ) _4- , ^* -O (CH ₂ ) ₃ — or ^* — (CH ₂ ) ₃ O—where the number of bonds appended with “*” is bonded to A ² ;

As R ¹ , a hydrogen atom, a halogen atom, a cyano group or a nitro group or an alkyl group having 1 to 12 carbon atoms, wherein the alkyl group may be substituted by fluorine, and one or two non-adjacent —CH ₂ — groups are oxygen. An atom, —COO — or —OCO— may be substituted, and —CH ₂ CH ₂ —group may be substituted by —CH═CH— or is a group having a steroid skeleton;

X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, wherein the alkyl group may be substituted by a fluorine atom;

Y is a hydrogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, wherein the alkyl group may be substituted by fluorine, or -COO-alkyl, wherein the alkyl group preferably has 1 to 3 carbon atoms.

As a structure represented by said Formula (I), More preferably, in said Formula (I),

A ¹ is selected from the group consisting of a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms (the alkyl group and the alkoxy group may each be substituted by a halogen atom). It is a phenylene group which may be substituted by 1 or more types, or a pyridine- 2, 5- diyl group, a pyrimidine- 2, 5- diyl group, a 2, 5- thiophendiyl group, a 2, 5- franylene group, 1 , 4-naphthylene group or 2,6-naphthylene group;

A <^3> is a phenylene group which may be substituted by 1 or more types chosen from the group which consists of a halogen atom, a cyano group, and a nitro group, or ^* -COO- or ^* -CO-E- (herein, attaching "*") The number of bonds is bonded to —CH═CH—, and E is a 1,4-phenylene group which may be substituted by at least one member selected from the group consisting of a halogen atom, a cyano group and a nitro group (hereinafter referred to as “structure (I-1) "or in the formula (I),

A ¹ is a 1,4-phenylene group which may be substituted by at least one member selected from the group consisting of a halogen atom, a cyano group and a nitro group, or ^* -COO- or ^* -CO-E- (wherein " The bond number to which ** is attached is -CH = CH-, and E is a 1,4-phenylene group which may be substituted by at least one member selected from the group consisting of a halogen atom, a cyano group and a nitro group);

1 in which A ³ is substituted by one or more selected from the group consisting of an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms (these alkyl groups and alkoxy groups may each be substituted by a halogen atom); 4-phenylene group, or pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, 2,5-thiophendiyl group, 2,5-franylene group, 1,4-naphthylene group, or It is a structure which is a 2, 6- naphthylene group (henceforth "a structure (I-2)").

When at least one of A <^1> and A <^3> in said Formula (I) is a phenylene group (including the case where it is substituted), the said phenylene group is a 1, 2- phenylene group, a 1, 3- phenylene group, or 1 , 4-phenylene group, of which 1,4-phenylene group is preferable.

Examples of the group having a steroid skeleton of R ¹ in the formula (I) include, for example, a cholestan-3 diary, a cholestan-5-en-3 diary, a cholestan-24-en-3 diary, Choletan-5,24-en-3 diary, lanostane-3 diary, etc. are mentioned. When R ¹ is a group having a steroid skeleton, n is preferably 0.

As an example of the said structure (I-1), the structure etc. which are represented by each of following formula (I-1-1) (I-1-10)-are mentioned, for example,

As an example of the said structure (I-2), the structure etc. which are represented by following formula (I-2-1) are mentioned, for example.

(In formula, R <^1> , A <^2> , Z <^1> and n are as defined in said Formula (I), respectively, R <^2> is a halogen atom, a cyano group, a nitro group, a C1-C12 alkyl group, or C1-C1 An alkoxy group of 12 (the alkyl group and the alkoxy group may each be substituted by a halogen atom), and m is an integer of 0 to 4).

(In formula (I-2-1), R <^1> , A <^2> , Z <^1> and n are as defined in said Formula (I), respectively, R <^2> is a halogen atom, a cyano group, a nitro group, C1-C1-C An alkyl group of 12 or an alkoxy group having 1 to 12 carbon atoms (these alkyl groups and alkoxy groups may each be substituted by halogen atoms), and m is an integer of 0 to 4;

The group R ^1- (A ² -Z ¹ ) _n -of the benzene ring in the formula (I- ¹ ) is 2nd, 3rd or 4th with respect to -CH = CH-COO-. It may be in the stomach, especially in the fourth place.

As a structure represented by said Formula (I), More preferably, it is a structure represented by each of said Formula (I-1-1) and said Formula (I-2-1), Especially a following formula (I-1-1) The structures represented by each of -1) to (I-1-1-3) and (I-2-1-1) to (I-2-1-4) are preferable.

(In formula, R <^1> , R <^2> and m are as having defined in said Formula (I-1-1) or (I-2-1), respectively.)

Preferably as a polymer film which has a structure represented by said Formula (I),

(Co) polymers of (meth) acrylic acid derivatives, styrene derivatives, vinyl ethers, vinyl esters or unsaturated carboxylic acid derivatives having a structure represented by formula (I);

Polyorganosiloxane which has a structure represented by said formula (I); And

It consists of at least 1 sort (s) chosen from the group which consists of a polyamic acid and its imidation polymer which have a structure represented by said Formula (I).

The polyorganosiloxane which has a structure represented by said formula (I) is, for example

Hydrolysis / (co) condensates of siloxanes having a structure represented by the formula (I) and a group capable of hydrolysis and condensation, or

Although it may be a reaction product of the polyorganosiloxane which has an epoxy group, and the carbonic acid which has a structure represented by said Formula (I), it is preferable that it is the latter among these.

The polyamic acid and its imidized polymer having a structure represented by formula (I) are, for example

Polyamic acid obtained by making tetracarboxylic dianhydride and diamine containing tetracarboxylic dianhydride which has a structure represented by said formula (I), and its imidation polymer, or

Although it may be polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing the diamine which has a structure represented by said formula (I), and its imidation polymer, the latter is preferable.

Among these, the reaction product of the (co) polymer of the (meth) acrylic acid derivative which has a structure represented by said Formula (I), the polyorganosiloxane which has an epoxy group, and the carbonic acid which has a structure represented by said Formula (I) is also tetra At least 1 sort (s) chosen from the group which consists of the polyamic acid obtained by making dicarboxylic acid dianhydride and the diamine containing the diamine which has a structure represented by said formula (I), and its imidation polymer are preferable.

The (co) polymer of the (meth) acrylic acid derivative having the structure represented by the formula (I) is a (meth) acrylic acid derivative having the structure represented by the formula (I) or a structure represented by the formula (I) It can obtain by polymerizing the mixture of the (meth) acrylic acid derivative which has, and another monomer.

As a (meth) acrylic acid derivative which has a structure represented by said formula (I), for example, methacryloyloxyethyl 3- (E)-[4-cyano-4'-biphenyl] acrylate and methacryl Loyloxyethyl 3- (E)-[3-cyanophenyl] acrylate, methacryloyloxyethyl 3- (E)-[4-chlorophenyl] acrylate, methacryloyloxyethyl 3-( E)-[4-methoxyphenyl] acrylate, methacryloyloxyethyl 3- (E)-[3-nitrophenyl] acrylate, 3-methacryloylaminopropyl (E) -3-[4 -Cyanophenyl] acrylamide, 1- [1-((E) -3- (4-methoxy-phenyl) -acryloyl] -piperidin-4-yloxycarbonyl] -1-methyl- Ethylene, methacryloyloxyethyl 3- (E) -biphenyl acrylate, etc. can be mentioned, The compound etc. which were described in patent document 7 (Unexamined-Japanese-Patent No. 6-287453) can be used suitably. There .

As said other monomer, For example, unsaturated monocarboxylic acid, such as acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid;

Unsaturated dicarboxylic acids and unsaturated carbonic anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;

Trivalent or higher unsaturated polyvalent carbonic acid and trivalent or higher unsaturated polyvalent carbonic anhydride;

Succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) Mono (2-acryloyloxyethyl) esters of the same non-polymerizable dicarboxylic acid and mono (2-acryloyloxyethyl) esters of the nonpolymerizable dicarboxylic acid;

unsaturated monomers having a carboxyl group such as? -carboxy-polycaprolactone monoacrylate and? -carboxy-polycaprolactone monomethacrylate;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-vinylbenzylmethyl Aromatic vinyl compounds such as ether and p-vinylbenzyl glycidyl ether;

Indenes such as indene, 1-methylindene and derivatives thereof;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, allyl acrylate, Allyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene Glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, article Unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate;

2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate , 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate (Meth) acrylic acid 5-hydroxypentyl ester, (meth) acrylic acid 6-hydroxyhexyl ester, (meth) acrylic acid 7-hydroxyheptyl ester, (meth) acrylic acid 8-hydroxyoctyl ester, (meth) acrylic acid 9-hydroxynonyl ester, (meth) acrylic acid 10-hydroxydecyl ester, (meth) acrylic acid 11-hydroxy undecyl Ester, (meth) acrylic acid 12-hydroxydodecyl ester, (meth) acrylic acid 2- (6-hydroxyethylhexanoyloxy) ethyl ester, (meth) acrylic acid 3- (6-hydroxyethylhexanoyloxy) propyl Ester, (meth) acrylic acid 4- (6-hydroxyethylhexanoyloxy) butyl ester, (meth) acrylic acid 5- (6-hydroxyethylhexanoyloxy) pentyl ester, (meth) acrylic acid 6- (6-hydr) Oxyethylhexanoyloxy) hexyl ester, (meth) acrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester, (meth) acrylic acid 3- (3-hydroxy-2) , 2-dimethyl-propoxycarbonyloxy) -propyl ester, (meth) acrylic acid 4- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -butyl ester, (meth) acrylic acid 5- ( 3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -pentyl Ste, (meth) acrylic acid 6- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -hexyl ester, (meth) acrylic acid 4-hydroxy-cyclohexyl ester, acrylic acid 4-hydroxymethyl -Cyclohexylmethyl ester, (meth) acrylic acid 4-hydroxyethyl-cyclohexylethyl ester, (meth) acrylic acid 3-hydroxy-bicyclo [2.2.1] hept-5 -ene-2-yl ester, (meth ) Acrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-ene-2-ylmethyl ester, (meth) acrylic acid 3-hydroxyethyl-bicyclo [2.2.1] hept-5-ene 2-ylethyl ester, (meth) acrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-ene-2-yl ester, (meth) acrylic acid 2-hydroxy-octahydro-4,7-meta No-inden-5-yl ester, (meth) acrylic acid 2-hydroxymethyl-octahydro -4,7-methano- inden-5-ylmethyl ester, (meth) acrylic acid 2-hydroxyethyl-octahydro-4,7-methano- inden-5-ylethyl ester, (meth) acrylic acid 3- Hydroxy-adamantane-1-yl ester, (meth) acrylic acid 3-hydroxymethyl-adamantane-1-ylmethyl ester, (meth) acrylic acid 3-hydroxyethyl-adamantane-1-ylethyl Unsaturated carboxylic acid hydroxyalkyl esters such as esters;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxylic acids such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate Aminoalkyl esters;

(Meth) acrylic acid glycidyl, (alpha)-ethyl acrylate glycidyl, the (alpha)-propyl acrylate glycidyl, the (alpha)-n-butyl acrylate glycidyl, (meth) acrylic acid -3, 4- epoxybutyl, ( Meta) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, (meth) acrylic acid-β-methylglycidyl, (meth) acrylic acid-β-ethylglycidyl, (meth) Acrylic acid (beta) -propylglycidyl, (alpha)-ethylacrylic acid (beta) -methylglycidyl, (meth) acrylic acid 3-methyl-3,4- epoxybutyl, (meth) acrylic acid 3-ethyl-3,4- Unsaturated carboxylic acid glycidyl esters such as epoxy butyl, (meth) acrylic acid-4-methyl-4,5-epoxypentyl, (meth) acrylic acid-5-methyl-5,6-epoxyhexyl;

Carbonic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methacryl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether ether;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Such as acrylamide, methacrylamide, α-chloroacrylamide, N-2 hydroxyethyl acrylamide, N-2 hydroxyethyl methacrylamide, N-methylol acrylamide, and N-methylol methacrylamide Unsaturated amides;

N-cyclohexyl maleimide, N-phenylmaleimide, N-o-hydroxyphenyl maleimide, N-m-hydroxyphenyl maleimide, N-p-hydroxyphenyl maleimide, N-o-methylphenyl maleimide N— such as N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide Substituted maleimides;

And aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.

Synthesis of the (co) polymer of a (meth) acrylic acid derivative having a structure represented by the formula (I) can be carried out according to a known radical polymerization method, for example, a structure represented by the above formula (I) A (meth) acrylic acid derivative having a compound or a mixture of a (meth) acrylic acid derivative having a structure represented by the formula (I) with another monomer can be obtained by reacting in a suitable solvent in the presence of a suitable polymerization initiator. have.

As a solvent which can be used here, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, etc. are mentioned, for example. The use ratio of a solvent becomes like this. Preferably it is 150-300 weight part with respect to a total of 100 weight part of the monomer to be used.

As a polymerization initiator which can be used here, for example, azobisisobutyronitrile (it is abbreviated generally to "AIBN" among those skilled in the art), 2,2'- azobis (2, 4- dimethylvaleronitrile) Radical polymerization initiators, such as these, are mentioned. The use ratio of the polymerization initiator is preferably 0.5 to 10 parts by weight based on 100 parts by weight in total of the monomers to be used.

The polymerization temperature is preferably 70 to 100 ° C, and the polymerization time is preferably 3 to 10 hours. About the (co) polymer of the (meth) acrylic acid derivative which has a structure represented by said formula (I), the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC; Gel Permeation Chromatography) becomes like this. Is 1,000 to 1,000,000, and more preferably 5,000 to 100,000.

As a (co) polymer of the (meth) acrylic acid derivative which has a structure represented by said formula (I), the homopolymer of the (meth) acrylic acid derivative which has a structure represented by said formula (I) is preferable, and especially poly (meth) Cryloyloxyethyl 3- (E)-[4-cyano-4'-biphenyl] acrylate), poly (methacryloyloxyethyl 3- (E)-[3-cyanophenyl] acrylate ), Poly (methacryloyloxyethyl 3- (E)-[4-chlorophenyl] acrylate), poly (methacryloyloxyethyl 3- (E)-[4-methoxyphenyl] acrylate) , Poly (methacryloyloxyethyl 3- (E)-[3-nitrophenyl] acrylate), poly (3-methacryloylaminopropyl (E) -3- [4-cyanophenyl] acrylamide ), Poly [1- [1-[(E) -3 (4-methoxy-phenyl) -acryloyl] -piperidin-4-yloxycarbonyl] -1-methyl-ethylene] and poly (Methacryloyloxye 3- (E) - to use at least one member selected from the group consisting of biphenyl acrylate) is preferred.

The polyorganosiloxane which has a structure represented by said formula (I), Preferably

A silane compound comprising a silane compound having an epoxy group and a hydrolyzable group is hydrolyzed and condensed in the presence of an organic solvent, water, and a catalyst, to first synthesize a polyorganosiloxane having an epoxy group, and then

It can synthesize | combine by making the polyorganosiloxane react with the carboxylic acid which has a structure represented by said Formula (I).

As a silane compound which has the said epoxy group and a hydrolysable group, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl methyldimethoxysilane, 3-glycidyloxypropyl methyldiethoxysilane, 3-glycidyloxypropyl dimethylmethoxysilane, 3-glycidyloxypropyl dimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimeth Oxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. are mentioned, One or more types selected from these can be used.

The silane compound used for synthesize | combining the polyorganosiloxane which has an epoxy group may consist only of the silane compound which has the above epoxy groups and a hydrolysable group, or may contain other silane compounds other than the said silane compound.

As another silane compound which can be used here, for example, methyl trichlorosilane, methyl trimethoxysilane, methyl triethoxysilane, phenyl trichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyldichlorosilane , Methyldimethoxysilane, methyldiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, chlorodimethylsilane, methoxydimethylsilane , Ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyl Trimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, egg Be a silane, an allyl-tree such as trimethoxysilane, allyl triethoxysilane trichloroethane, and may use one or more selected from these into.

The silane compound used for synthesizing the polyorganosiloxane having an epoxy group preferably contains 50 mol% or more of the silane compound having the epoxy group and the hydrolyzable group as described above with respect to the total silane compound, and is preferably from 60 to 100. It is more preferable to contain mol%.

As an organic solvent which can be used in synthesize | combining the polyorganosiloxane which has an epoxy group, hydrocarbon, ketone, ester, ether, alcohol, etc. are mentioned, for example.

As said hydrocarbon, For example, toluene, xylene, etc .;

As said ketone, For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, etc .;

As said ester, For example, ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .;

As said ether, For example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc .;

Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether. And propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like, and the like, and one or more selected from these can be used. It is preferable to select and use a water-insoluble thing among these.

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.

When synthesize | combining the polyorganosiloxane which has an epoxy group, the usage-amount of water becomes like this. Preferably it is 0.5-100 mol with respect to a total of 1 mol of a silane compound, More preferably, it is 1-30 mol.

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. can be used, for example, It is preferable to use an alkali metal compound or an organic base among these. By using an alkali metal compound or an organic base as a catalyst, formation of a three-dimensional structure is accelerated | stimulated and the polyorganosiloxane with few content ratio of a silanol group is obtained. For this reason, since the condensation reaction of silanol groups is suppressed also in the case of reaction with the carboxylic acid mentioned later and after making into the liquid crystal aligning agent containing the product of the said reaction, it is preferable at the point which can obtain the liquid crystal aligning agent excellent in storage stability. .

As said alkali metal compound, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc. are mentioned, for example.

Examples of the organic base include 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, diazabicycloundecene;

And quaternary organic amines such as tetramethylammonium hydroxide, and the like. Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine among these organic bases;

Preference is given to quaternary organic amines, such as tetramethylammonium hydroxide.

As the catalyst, an organic base is particularly preferable. Although the usage-amount of an organic base may differ suitably according to reaction conditions, such as the kind of organic base, temperature, etc., For example, Preferably it is 0.01-3 mol with respect to a total of 1 mol of a silane compound, More preferably, it is 0.05 It is-1 mol.

The hydrolytic condensation reaction in synthesizing the polyorganosiloxane having an epoxy group dissolves the silane compound and other silane compounds in an organic solvent, if necessary, and mixes the solution with an organic base and water, for example, an oil bath. It is preferable to carry out by heating using a suitable heating apparatus such as i).

At the time of hydrolysis condensation reaction, heating temperature becomes like this. Preferably it is 130 degrees C or less, More preferably, it is 40-100 degreeC, Preferably it is 0.5 to 12 hours, More preferably, it is preferable to heat 1 to 8 hours. During the heating, the mixed liquid may be stirred or not stirred, or the mixed liquid may be placed 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 washing | cleaning, it wash | cleans with water containing a small amount of salts, for example about 0.2 weight% of ammonium nitrate aqueous solution, etc., and is preferable at the point which a washing operation becomes easy. The washing is performed until the aqueous layer after washing is neutral, and then the organic solvent layer is dried with a suitable desiccant such as anhydrous calcium sulfate and molecular sieve, if necessary, and then the solvent is removed. Polyorganosiloxane which has an epoxy group can be obtained.

Thus, the structure represented by said formula (I) is made to react the polyorganosiloxane which has the epoxy group obtained by making it react with the carbonic acid which has a structure represented by said Formula (I), preferably in presence of a catalyst and an organic solvent. The polyorganosiloxane which has is obtained.

As carbonic acid which has a structure represented by said formula (I), it has a structure represented by said formula (I-1-1), for example, following formula (I-1 -C-1)-(I-1) The compound represented by each of -C-5);

As a compound which has a structure represented by said formula (I-2-1), the compound represented by each of following formula (I-2-C-1)-(I-2-C-5) can be mentioned, respectively. have.

(In the above formula, a is an integer of 1 to 12, and b is an integer of 0 to 12.)

(In the above formula, a is an integer of 1 to 12, and b is an integer of 0 to 12.)

As a usage ratio of the carbonic acid which has a structure represented by said formula (I), it is preferable to set it as 0.1-0.8 mol with respect to 1 mol of epoxy groups of the polyorganosiloxane which has an epoxy group, and it is more preferable to set it as 0.2-0.7 mol.

As said catalyst, a well-known compound can be used as an organic base or what is called a hardening accelerator which accelerates reaction of an epoxy compound and an acid anhydride.

Examples of the organic base include 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, diazabicycloundecene;

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

Preference is given to quaternary organic amines, such as tetramethylammonium hydroxide.

Examples of the curing accelerators include tertiary amines, imidazole compounds, organophosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, quaternary ammonium salts, boron compounds, metal halide compounds, and the like. In addition, what is known as a latent hardening accelerator can be used.

The catalyst is preferably used in an amount of 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane having an epoxy group.

As said organic solvent, hydrocarbon, ether, ester, ketone, amide, alcohol, etc. are mentioned, for example. Of these, ethers, esters or ketones are preferred from the viewpoint of solubility of the raw materials and the product, and ease of product purification. The solvent is used at a ratio such that the solid content concentration (a 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.

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

As tetracarboxylic acid dianhydride used for synthesize | combining the polyamic acid which has a structure represented by said Formula (I), and what is preferable as an imidation polymer thereof, For example, aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride And aromatic tetracarboxylic dianhydride. Specific examples thereof include aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, and for example, 1,2,3,4-butanetetracarboxylic dianhydride, Ethylene maleic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid 2 Anhydride, 3,5,6-tricarboxynorbornyl acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) Tetrahydronaphthalene-1,2-dicarboxylic acid anhydride Water, 5- (2,5-dioxotetrahydrofuran-3-yl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] octa-7-en 2,3,5,6-tetracarboxylic acid dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid dianhydride, 1,8-dimethylbicyclo [2.2.2] octa -7-en-2,3,5,6- tetracarboxylic dianhydride, etc .;

As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 4,4'- oxydiphthalic acid dianhydride, 3,3' , 4,4'-diphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3,4-furantetracarboxylic acid dianhydride, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis ( 3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, ethylene glycol bis (trimelitic acid) dianhydride, 4,4' 1,4-phenylene) bis (phthalic acid) dianhydride, 4,4 '-(1,3-phenylene) bis (phthalic acid) dianhydride, 4,4'-(hexafluoroisoph Filidene) diphthalic acid dianhydride, 4,4'-oxydi (1,4-phenylene) bis (phthalic acid) dianhydride, 4,4'-methylenedi (1,4-phenylene) bis (phthalic acid) 2 anhydrides, etc. are mentioned, respectively.

As a diamine which has a structure represented by said formula (I), it has a structure represented by said formula (I-1-1), for example, 3, 5- diamino benzoic acid 6- [3- (3-meth) Methoxy-4-butyloxyphenyl) acryloyloxy] hexyl ester, 2- (2,4-diaminophenyl) ethyl (2E) 3- ｛4-[(4- (4,4,4-trifluoro) Butoxy) benzoyl) oxy] phenyl acrylate;

As a compound which has a structure represented by said formula (I-2-1), the compound etc. which are represented by each of following formula (I-2-2D-1) (I-2D-5)-are respectively, for example. And at least 1 sort (s) selected from these can be used.

(In the above formula, a is an integer of 1 to 12, and b is an integer of 0 to 12.)

As the diamine used to synthesize the polyamic acid and the imidized polymer thereof, only diamines having a structure represented by the formula (I) may be used, or diamines and other diamines having a structure represented by the formula (I). You can also use together.

As other diamine which can be used here, an aliphatic diamine, an alicyclic diamine, and an aromatic diamine are mentioned, As an example, As aliphatic diamine to alicyclic diamine, it is ethylenediamine, 1, 3- propylene diamine, 1, 4-Butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, 1,7-heptylenediamine, 1,8-octylenediamine, 1,9-nonylenediamine, 1,10- Decylenediamine, 1,11-undecylenediamine, 1,12-dodecylenediamine, α, α'-diamino-m-xylene, α, α'-diamino-p-xylene, (5-amino-2 , 2,4-trimethylcyclopentyl) methylamine, 1,2-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis (methylamino) cyclohexane, 4,9-di Oxadodecane-1,12-diamine and the like;

As aromatic diamine, for example, 3, 5- diamino benzoic acid methyl ester, 3, 5- diamino benzoic acid hexyl ester, 3, 5- diamino benzoic acid dodecyl ester, 3, 5- diamino benzoic acid isopropyl ester, 4 , 4'-methylenedianiline, 4,4'-ethylenedianiline, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetramethylbenzidine, 4 , 4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4 ' -Diaminodiphenyl ether, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diamino-2,2'-dimethylbibenzyl, bis [4 (4 -Aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene , 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylenebis (2 -Chloroaniline), 4,4'-bis (4-aminophenoxy) biphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro -4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4 '-(1,4-phenylene iso Propylidene) bisaniline, 4,4 '-(1,3-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [ 3- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-amino-4-methylphenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane , 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl ) Biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -2,3,5,6,2 ', 3', 5 ', 6'-octafluorobi Phenyl etc. Can be.

When using together the diamine which has a structure represented by said formula (I), and other diamine, it is preferable to use 10 mol% or more of diamines which have a structure represented by said formula (I) with respect to all diamine, and it is 20 mol It is more preferable to use% or more.

The said polyamic acid and its imidation polymer can be synthesize | combined according to a well-known method. For example, the polyamic acid can be obtained by reacting a mixture of tetracarboxylic dianhydride and diamine as described above in a suitable solvent, preferably at 40 to 100 ° C, preferably for 1 to 6 hours. In addition, the imidized polymer can be obtained by dehydrating and ring-closing the polyamic acid obtained in this way. The dehydration ring closure reaction for synthesizing the imidized polymer can be carried out, for example, by heating (preferably at 2 to 6 hours at 60 to 250 ° C.) or by a suitable dehydrating agent (for example acetic anhydride, propionic anhydride, anhydrous). Phthalic acid, trifluoroacetic anhydride, etc.) and a dehydration catalyst (e.g., trimethylamine, triethylamine, tributylamine, pyridine, N, N-dimethylaniline, lutidine, collidine, etc.), preferably 90 Preferably at -120 degreeC, it can carry out by making it react for 2 to 4 hours easily.

When the polyamic acid and polyimide obtained as mentioned above are each made into the solution of 10 weight% of concentration, it is preferable to have a solution viscosity of 20-800 mPa * s, and it is more preferable to have a solution viscosity of 30-500 mPa * s. Do. The solution viscosity (mPa * s) of this polyamic acid and a polyimide was respectively prepared using the positive solvent of the said polymer (for example, (gamma) -butyrolactone, N-methyl- 2-pyrrolidone, etc.). It is the value measured in 25 degreeC using the E-type rotational viscometer about the polymer solution of 10 weight% of concentration.

In the manufacturing method of the liquid crystal display element of this invention, first, the film | membrane which consists of a polymer which has a structure represented by said Formula (I) obtained by the above as mentioned above is formed on a board | substrate.

As a board | substrate used here, the azimuth direction of the liquid crystal which inclines at the time of liquid crystal drive, such as represented by the stripe pattern electrode structure described, for example in patent document 9 (Unexamined-Japanese-Patent No. 2007-286641) can be regulated. And a substrate having a pixel electrode structure.

The structure of a preferable liquid crystal display element was shown to FIG. 1 and FIG. (A) is the said schematic diagram which shows the structure of the pixel 2 which looked at the board | substrate surface from the normal line direction, FIG. 1 (b) is a partial sectional view in the A-A line of FIG. 1 (a), and FIG. Is a partial cross sectional view taken along the line BB of FIG. The pixel electrode of the liquid crystal display element of Fig. 1 (a) is connected to an n-channel TFT 16, a drain bus line 6, a gate bus line 4 on an array substrate including a glass substrate 20. It consists of electrodes 12 and 14 and a plurality of stripe-shaped electrodes 8. On the opposing substrate including the glass substrate 30, a color filter layer 28 and a common electrode 26 are formed. As a board | substrate material, the glass substrate of about 0.7 mm in thickness is mentioned, for example. The plurality of stripe-shaped electrodes 8 are formed so as to extend in four directions (top right, bottom right, top left, bottom left) from the pixel center portion, respectively. The electrode width L of the stripe-shaped electrode 8 can be, for example, 3 m, and the width S of the space 10 can be, for example, 3 m.

In order to form a film made of a polymer on such a substrate, for example, a polymer having a structure represented by the above formula (I) is dissolved in a suitable solvent to form a solution-like composition (liquid crystal aligning agent). It may be by a method of removing the solvent after coating.

In addition to the polymer and solvent having the structure represented by the formula (I), the liquid crystal aligning agent used herein may contain other polymers, functional silane compounds, epoxy compounds and the like within a range that does not impair the desired physical properties. have.

The said other polymer is a polymer which does not have a structure represented by said Formula (I), For example, polyamic acid and its imidation polymer, polyamic acid ester, polyester, which do not have a structure represented by said Formula (I), Polyamides, polyorganosiloxanes, cellulose derivatives, polyacetal derivatives, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylate derivatives, and the like, and the like. You can choose to use it.

As another polymer in this invention, it is preferable that it is at least 1 sort (s) chosen from the group which consists of polyamic acid, its imidation polymer, and polyorganosiloxane.

Polyamic acid which does not have a structure represented by said formula (I) can be obtained by making tetracarboxylic dianhydride and the said other diamine react. By dehydrating and closing this polyamic acid, the imidation polymer which does not have a structure represented by said formula (I) can be obtained. The polyorganosiloxane which does not have a specific structure can be obtained by hydrolytically condensing at least 1 sort (s) chosen from the group which consists of a silane compound which has the above-mentioned epoxy group and a hydrolysable group, and other silane compounds. It will be apparent to those skilled in the art that these synthesis can be performed according to the above examples.

The preferable use ratio of another polymer changes with kinds of polymer which has a structure represented by said formula (I).

When the polymer having a structure represented by the formula (I) is a (co) polymer of a (meth) acrylic acid derivative, a styrene derivative, a vinyl ether, a vinyl ester, or an unsaturated carboxylic acid derivative having a structure represented by the formula (I) It is preferable that it is 30 weight% or less with respect to the sum total of the polymer and other polymer which have a structure represented by said Formula (I), and, as for the usage ratio of the other polymer in, it is more preferable that it is 15 weight% or less.

The use ratio of the other polymer in the case where the polymer which has a structure represented by said formula (I) is polyorganosiloxane which has a structure represented by said formula (I) has a structure represented by said formula (I) It is preferable that it is 95 weight% or less with respect to the sum total of a polymer and another polymer, It is more preferable that it is 90 weight% or less, It is preferable that it is especially 75 weight% or less. In this case, it is preferable that it is at least 1 sort (s) chosen from the group which consists of polyamic acid which does not have a structure represented by said Formula (I), and its imidation polymer as another polymer.

The use ratio of the other polymer in the case where the polymer which has a structure represented by said formula (I) is at least 1 sort (s) chosen from the group which consists of a polyamic acid and its imidation polymer which have a structure represented by said formula (I) is It is preferable that it is 50 weight% or less with respect to the sum total of the polymer which has a structure represented by said formula (I), and other polymer, It is more preferable that it is 20 weight%, It is preferable not to use other polymer especially.

The said functional silane compound and an epoxy compound can be used for the purpose of improving the adhesiveness to the board | substrate surface of a polymer film, respectively. As such a functional silane compound, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimeth Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3 , 6-diazononyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N Benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) 3-aminopropyl trimethoxysilane, N-bis (oxyethylene) 3-aminopropyl triethoxysilane, etc. are mentioned. As such an epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, 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, 3- (N-allyl-N-glycidyl) aminopropyl trimethoxysilane, 3- (N, N-diglycidyl) aminopropyl trimethoxysilane etc. are mentioned.

As a compounding ratio of these functional silane compounds and an epoxy group compound, it is 40 weight part or less with respect to a total of 100 weight part of polymers and other polymer which have a structure represented by said Formula (I), respectively, More preferably, 0.1-30 weight part.

As a solvent used here, when a polymer is a (co) polymer of the (meth) acrylic acid derivative which has a structure represented by said Formula (I), For example, alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, Diethylene glycol alkyl ether, dipropylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester, etc. are mentioned. As these specific examples, As alcohol, For example, methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl- 1-propanol etc .;

As the ether, for example, tetrahydrofuran and the like;

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetate, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol alkyl ether, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As dipropylene glycol alkyl ether, For example, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As propylene glycol alkyl ether acetate, For example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;

As propylene glycol alkyl ether propionate, For example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;

As aromatic hydrocarbon, For example, toluene, xylene, etc .;

As a ketone, For example, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl- 2-pentanone, etc .;

As the ester, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionate ethyl, 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate, hydroxyacetic acid Methyl, ethyl hydroxyacetic acid, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactic acid, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionic acid ethyl, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid Butyl, 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid propyl Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate Lopoxyacetic acid propyl, butyl propoxyacetate, butoxyacetic acid methyl, butoxyacetic acid ethyl, butoxyacetic acid propyl, butoxyacetic acid butyl, acetic acid 3-methoxybutyl, 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxy propyl propionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, Ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3 -Methyl ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxyprop Methyl Pionate, 3-propoxypropionate, 3-propoxypropionic acid propyl, 3-propoxypropionate butyl, 3-butoxypropionate methyl, 3-butoxypropionate ethyl, 3-butoxypropionic acid propyl, 3-butoxy Ester, such as butyl propionate, is mentioned, respectively.

Among these, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, dipropylene glycol alkyl ether, propylene glycol monoalkyl ether or propylene glycol alkyl ether acetate are preferable, and in particular, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether , Dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate or 3-methoxybutyl acetate are particularly preferred.

The said solvent can be used individually or in mixture of 2 or more types.

When the polymer is a polyorganosiloxane having a structure represented by the formula (I) and does not contain other polymer, or the other polymer is a polyorganosiloxane that does not have a structure represented by the formula (I), the organic As the solvent, for example, 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, Dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol Monohexyl ether, diethylene glycol, methyl cellosolve Tate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate I-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-acetic acid Hexyl, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, N-methyl-2-pyrrolidone, γ-butyrolactone, ethylene glycol-n-butyl ether (butyl cellosolve), and the like. .

When the polymer is at least one selected from the group consisting of polyamic acid having a structure represented by the formula (I) and an imidized polymer thereof, or as the polyorganosiloxane having the structure represented by the formula (I) In the case where the polymer is at least one member selected from the group consisting of polyamic acid having no structure represented by the formula (I) and an imidized polymer thereof, examples of the organic solvent include N-methyl-2-pyrrolidone. γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, lactic acid Butyl, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol -n-propyl ether, ethylene Glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy -N, N- dimethylpropanamide etc. are mentioned. Among them, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, and 3-hexyloxy-N, N-dimethylpropanamide show good printability. Particularly preferred.

As solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent) in the said liquid crystal aligning agent, it is preferable to set it as 1 to 15 weight%, and to set it as 1 to 10 weight% It is more preferable.

Applying a liquid crystal aligning agent on a board | substrate can be based on appropriate coating methods, such as a spinner method, the offset printing method, the dipping method, the dropping method, the inkjet printing method, for example. Thereafter, by heating to remove the solvent, a film made of a polymer can be formed on the substrate.

The heating performed here is prebaking performed at 50-120 degreeC, for example 0.1 to 5 minutes, for example, 80-300 degreeC, Preferably it is 120-250 degreeC, for example. For example, it is preferable to consist of postbaking performed for 5 to 200 minutes, preferably 10 to 100 minutes. Postbaking is preferably performed using a circulating clean oven, an IR oven, or a hot plate. After removing most of the solvent in the liquid crystal aligning agent in the prebaking, the solvent is completely removed by postbaking.

The film thickness of the coating film formed here becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

Thus, two board | substrates with a film | membrane which consists of a polymer are prepared, and the dielectric anisotropy denies the nematic liquid crystal between each film which two board | substrates have.

As an example of the dielectric anisotropy non-nematic liquid crystal which can be used here, the liquid crystal described in patent documents 10-37 etc. is mentioned, for example.

For sandwiching the nematic liquid crystals whose dielectric anisotropy is between the films made of polymers of two substrates, for example, a vacuum injection method and a liquid crystal dropping method (dropping the liquid crystal onto the substrate before bonding both substrates, And the method of joining the other substrate afterwards).

As thickness of the film | membrane which consists of a polymer, ie, the thickness of a liquid crystal layer, Preferably it is 2-6 micrometers, More preferably, it is 3-5 micrometers.

Subsequently, it can be set as a liquid crystal cell by irradiating light in the state which orientated liquid crystal by applying a voltage between each transparent pixel electrode of the said two board | substrates.

Although the voltage applied here differs also depending on the dielectric anisotropy value of the liquid crystal to be used, it is 10-50V, for example. The voltage applied here may be a DC voltage or an AC voltage.

The light to be irradiated is preferably unpolarized ultraviolet light using a high pressure mercury lamp or a metal halide lamp as a light source, and includes a bright line having a wavelength range of 280 to 350 nm. It is more preferable that it is external light. As an exposure amount, Preferably, the irradiation amount in wavelength 313nm is 1,000 J / m <2> or more and less than 100,000 J / m <2>, More preferably, it is 1,000-50,000 J / m <2>. In the method described in Patent Document 38 (US Patent Application Publication No. 2009/0325453), it is necessary to irradiate light of about 100,000 J / m 2, but in the method of the present invention, the light irradiation amount is 50,000 J / m 2 or less, Furthermore, even if it is set to 10,000 J / m <2> or less, a desired liquid crystal display element can be obtained, and it contributes to the reduction of the manufacturing cost of a liquid crystal display element, and also the fall of the electrical characteristic resulting from strong light irradiation, and the fall of long-term reliability. Can be avoided.

As temperature at the time of light irradiation, it is preferable to irradiate at the temperature below the isotropic temperature of a liquid crystal, For example, it is 20-60 degreeC, Preferably it is 25-50 degreeC.

Thus, the liquid crystal display element of this invention can be obtained by arrange | positioning a polarizing plate on both surfaces of the manufactured liquid crystal cell. In addition to the polarizing plate, a wavelength plate, a light scattering film, a drive circuit, etc. may be mounted in the liquid crystal display element of this invention further.

The liquid crystal display element of this invention manufactured as mentioned above is excellent in liquid crystal orientation and electrical property, and can be used suitably for the video display apparatus etc. which are represented by various apparatuses, for example, a liquid crystal television.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples.

In the following Examples, the weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.

Column: Tosoh Corporation, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf / ㎠

The epoxy equivalent was measured according to the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

<Synthesis of diamine having a structure represented by formula (I)>

3,5-diaminobenzoic acid 6- [3- (3-methoxy-4-butyloxyphenyl) acryloyloxy] hexyl ester (compound represented by a following formula) used by the following synthesis examples is patent document 8 It synthesize | combined according to the method as described in Unexamined-Japanese-Patent No. 2003-520878.

Synthesis Example 1

According to the following Reaction Scheme 1, compound (D-1) was synthesized.

<Scheme 1>

22.6 g (100 mmol) of 2,4-dinitrophenylacetic acid was dissolved in 150 mL of tetrahydrofuran, and 300 mL of THF solution (in the amount of borane THF complex) containing 1.0 mol / L of borane THF (tetrahydrofuran) complex. Equivalent to 300 mmol) was added dropwise over 2 hours. Then, after stirring at 25 degreeC for 3 hours, 200 mL of water was added slowly. Ethyl acetate was added to the resulting solution, followed by extraction. The organic layer was washed with water and dried over sodium sulfate, and then concentrated and dried by means of a rotary evaporator to obtain a crude product. The crude product thus obtained was purified by a column packed with 400 g of silica gel using a mixed solvent of toluene: ethyl acetate = 1: 1 (volume ratio) as a developing solvent, and further recrystallized from a mixed solution of ethyl acetate and hexane. 20.7 g of 2- (2,4-dinitrophenyl) ethanol were obtained (yield 98%).

2.5 g (11.8 mmol) of 2- (2,4-dinitrophenyl) ethanol obtained above, (2E) 3-X4-[(4- (4,4,4-trifluorobutoxy) benzoyl) 4.65 g (11.8 mmol) of oxy] phenyl vacrylic acid and 144 mg (1.2 mmol) of 4-dimethylaminopyridine were dissolved in 30 mL of dichloromethane and cooled to 0 ° C. At this temperature, 2.48 g (13.0 mmol) of hydrochloride of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide were added thereto and further stirred at 0 ° C for 1 hour. Thereafter, the reaction mixture was heated up to room temperature and reacted under stirring at room temperature for 22 hours. Dichloromethane and water were added to the obtained reaction solution, followed by extraction and washing. The organic layer was further washed with water and dried over sodium sulfate, and then concentrated and dried with a rotary evaporator to obtain a crude product. The crude product thus obtained was purified by a column packed with 200 g of silica gel using a mixed solvent of toluene: ethyl acetate = 95: 5 (volume ratio) as the developing solvent, and further recrystallized from a mixed solution of ethyl acetate and hexane. , Compound (D-1a) (2- (2,4-dinitrophenyl) ethyl (2E) 3- ｛4-[(4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl ｝ Acrylate) 4.93 g was obtained (yield 71%).

4.93 g (8.38 mmol) of the compound (D-1a) obtained above were dissolved in a mixed solution composed of 50 mL of N, N-dimethylformamide and 6 mL of water. Here, 13.9 g (51.4 mmol) of ferric chloride hexahydrate and 5.6 g (85.7 mol) of zinc powder were divided and added over 60 minutes, and reaction was performed at room temperature for 2 hours. Ethyl acetate and water were added to the reaction mixture, which was then extracted and washed. The resulting mixture was filtered to remove unwanted substances, and the organic layer was separated. The organic layer was washed with water and dried over sodium sulfate, and then concentrated and dried with a rotary evaporator to obtain a crude product. The crude product obtained was purified by a column packed with 200 g of silica gel using a mixed solvent of toluene: ethyl acetate = 1: 3 (volume ratio) as a developing solvent, and further recrystallized from a mixed solution of ethyl acetate and hexane. , Compound (D-1) (2- (2,4-diaminophenyl) ethyl (2E) 3- ｛4-[(4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl ｝ Acrylate) 3.01 g was obtained.

Synthesis Example 2

Compound (D-2) was synthesized according to the following Schemes 2 (1) and 2 (2).

<Scheme 2>

<Scheme 3>

In a 1 L three-necked flask equipped with a thermometer, a dropping lot, and a nitrogen introduction tube, 49 g of Compound (D-2A), 33 g of potassium carbonate, 6.4 g of tetrabutylammonium bromide, 200 mL of water, and 100 mL of tetrahydrofuran were added and ice-cooled to 5 ° C or lower. (Iii) While stirring this, the solution which consists of 60 mL of tetrahydrofuran and 19 g of acryloyl chlorides was dripped over 30 minutes or more from the dropping lot, and also reaction was performed under stirring for 1 hour. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed once with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a compound ( 60g of solid of D-2B) was obtained.

60 g of this compound (D-2B) was placed in a 3 L three-necked flask equipped with a thermometer, a nitrogen inlet tube and a cooling tube, and further 44 g of 4-iodophenol, 2 L of N, N-dimethylformamide and 28 mL of triethylamine. And 4.6 g of tetrakis triphenylphosphine palladium was added, and it stirred at 90 degreeC for 2 hours. After cooling to room temperature, the mixture was filtered, and the organic layer obtained by adding ethyl acetate to the filtrate was washed once with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and the solvent was removed under reduced pressure to obtain a compound (D A crude product of -2C) was obtained.

About 55 g of white crystals of a compound (D-2C) were obtained by recrystallizing from the mixed solvent which consists of ethanol and tetrahydrofuran about this crude product.

55 g of this compound (D-2C) was placed in a 1 L three-necked flask equipped with a thermometer, a nitrogen inlet tube, and a dropping lot. Further, 23 g of potassium carbonate, 4.5 g of tetrabutylammonium bromide, 100 mL of tetrahydrofuran and 200 mL of water were added. It was added and ice-cooled to 5 degrees C or less. While stirring this, 150 mL of the solution which consists of 32 g of 3, 5- dinitro benzoyl chlorides and tetrahydrofuran was dripped over 30 minutes or more from the dropping lot, and reaction was further performed under stirring for 1 hour or more. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed once with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a crude product of the compound (D-2D). Got it. 65 g of pale yellow crystals of the compound (D-2D) were obtained by recrystallization from the mixed solvent which consists of ethanol and tetrahydrofuran about this crude product.

65 g of this compound (D-2D) was placed in a 2 L eggplant flask equipped with a reflux tube and a nitrogen inlet tube, and 250 g of tin chloride dihydrate was added thereto and 1 L of ethyl acetate, followed by reaction at reflux for 4 hours. After completion of the reaction, the reaction mixture was washed twice with aqueous potassium fluoride solution and three times with water, and then the solvent was removed under reduced pressure to obtain a crude product. 23g of white crystals of a compound (D-2) were obtained by recrystallizing from the mixed solvent which consists of ethanol and tetrahydrofuran about this crude product.

<Synthesis of carboxylic acid having a structure represented by formula (I)>

Synthesis Example 3

Compound (C-1) was synthesized according to Scheme 3 below.

<Scheme 4>

7.8 g of a compound (D-2C) obtained in the same manner as in Scheme 2 (1) in Synthesis Example 2, 4.0 g of succinic anhydride, N, N in a 100 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube 0.30 g of -dimethylaminopyridine, 40 mL of ethyl acetate, and 3.4 mL of triethylamine were added thereto, and the reaction was carried out under reflux for 8 hours. After the completion of the reaction, the reaction mixture was washed once with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a crude product. About this crude product, 7.9 g of white crystals of compound (C-1) were obtained by recrystallization from ethyl acetate.

<Synthesis of polyorganosiloxane having an epoxy group>

Synthesis Example 4

Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine were added. Mix at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, followed by mixing at reflux for 6 hours while mixing under reflux. After the completion of the reaction, the organic layer was taken out of the reaction mixture, washed with 0.2% by weight ammonium nitrate aqueous solution until the water after washing was neutral, and then the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane (EPS). -1) was obtained as a viscous transparent liquid.

As a result of ¹ H-NMR analysis on this polyorganosiloxane (EPS-1), a peak based on an oxiranyl group was obtained at a chemical intensity (δ) of 3.2 ppm in the vicinity of the theoretical strength. V) It was confirmed that no reaction occurred.

The weight average molecular weight (Mw) of this polyorganosiloxane (EPS-1) was 2,200, and the epoxy equivalent was 186 g / mol.

<Synthesis of Polymer Having a Structure Represented by Formula (I)>

Synthesis Example 5

0.500 g (1.032 mmol) of 3,5-diaminobenzoic acid 6- [3- (3-methoxy-4-butyloxyphenyl) acryloyloxy] hexyl ester was dissolved in 3.1 mL of tetrahydrofuran, and 1 was added thereto. 182.1 mg (0.9285 mmol) of 2,3,4-cyclobutanetetracarboxylic dianhydride was added, and it stirred at 0 degreeC for 2 hours. Next, 20.2 mg (0.1030 mmol) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride was further added, and reaction was performed at room temperature (23 degreeC) for 22 hours. 3.5 mL of tetrahydrofuran was added to the obtained reaction mixture, the whole amount was thrown in 200 mL of diethyl ether, and the produced | generated deposit was collect | recovered. The resultant precipitate was redissolved in 10 mL of tetrahydrofuran, reprecipitated in 600 mL of water, and dried at room temperature for 24 hours under reduced pressure, whereby 0.61 g of polyamic acid (polymer A) having a structure represented by Formula (I) was used as a powder. Got it.

Synthesis Example 6

0.545 g (1.032 mmol) of compounds (D-1) obtained in Synthesis Example 1 in place of 3,5-diaminobenzoic acid 6- [3- (3-methoxy-4-butyloxyphenyl) acryloyloxy] hexyl ester ), 0.63 g of polyamic acid (polymer B) having a structure represented by the formula (I) was obtained as a powder in the same manner as in Synthesis Example 2 above.

Synthesis Example 7

In a 200 mL three-necked flask equipped with a reflux tube, 10 g of polyorganosiloxane (EPS-1) having an epoxy group obtained in Synthesis Example 4, 13 g of (C-1) obtained in Synthesis Example 3, 92 g of methyl isobutyl ketone, and 1.0 g of tetrabutylammonium bromide was added and reaction was performed at 80 degreeC for 12 hours. After the completion of the reaction, the reaction mixture was poured into a large amount of methanol, and the resulting precipitate was recovered. The solution obtained by dissolving it in ethyl acetate was washed three times with water, and then the solvent was removed under reduced pressure. Polyorganosiloxane (polymer C) which has a structure represented by this was obtained.

Synthesis Example 8

30 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 70 g of compound (D-2) obtained in Synthesis Example 2 as diamine were dissolved in 400 g of N-methyl-2-pyrrolidone. By reacting at 60 degreeC for 6 hours, the solution containing 20 weight% of polyamic acid (polymer D) which has a structure represented by said Formula (I) was obtained. The solution viscosity of this polyamic acid solution was 1,700 mPa * s.

Synthesis of Other Polymers

Synthesis Example 9

196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g (1.0 mol) of 2,2'-dimethyl-4,4'- diaminobiphenyl as diamine Was dissolved in 3670 g of N-methyl-2-pyrrolidone and reacted at 40 ° C for 3 hours to obtain a solution containing 10% by weight of polyamic acid (polymer r) which is another polymer. The solution viscosity of this polyamic acid solution was 170 mPa · s.

<Preparation of liquid crystal aligning agent, further manufacture and evaluation of liquid crystal display element>

Example 1

[Preparation of liquid crystal aligning agent]

The polymer A synthesized in Synthesis Example 5 was dissolved in N-methyl-2-pyrrolidone and butyl cellosolve, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 ( Weight ratio) and a solid content concentration of 3.0 wt%. The liquid crystal aligning agent was prepared by filtering this solution with the filter of 1 micrometer of pore diameters.

<Evaluation of Liquid Crystal Display Element (1)>

[Manufacture of Liquid Crystal Display Element]

On the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane with a stripe pattern, the liquid crystal aligning agent prepared in the said Example was apply | coated using a spinner, prebaking was performed for 1 minute on 80 degreeC hotplate, and (Iv) It heated in 200 degreeC for 1 hour in the oven which carried out the nitrogen substitution, and formed the film (liquid crystal aligning film) which consists of a polymer with a film thickness of 0.1 micrometer. The same operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

After screen-printing the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer on the outer periphery of the surface which has one liquid crystal aligning film of the said board | substrates, it may be so that the liquid crystal aligning film surface of a pair of board | substrates may oppose. The board | substrate was arrange | positioned and crimped | bonded, and the adhesive agent was thermosetted over 1 hour at 150 degreeC. Subsequently, after filling a negative liquid crystal (the Merck make, brand name "MLC-6608") in the clearance gap of both board | substrates from a liquid crystal injection hole, the liquid crystal injection hole was sealed with the epoxy adhesive. In addition, in order to eliminate the flow orientation at the time of liquid crystal injection, it heats at 150 degreeC, and then slowly cools to room temperature, and then applies a voltage (DC) 32V to it and irradiates unpolarized ultraviolet-ray using a high pressure mercury lamp, and a liquid crystal cell Furthermore, the liquid crystal display element was manufactured by bonding two polarizing plates to the outer both surfaces of a board | substrate so that their polarization directions may orthogonally cross.

This liquid crystal display device was evaluated as follows. The evaluation results are shown in Table 1.

(1) Evaluation of liquid crystal alignment

The liquid crystal display element manufactured above was observed by visually seeing the presence or absence of an abnormal domain in the change in contrast when the voltage of 5 V was turned ON and OFF (applied and released).

When no light leakage is observed from the cell when the voltage is OFF and no cell leakage is displayed when the cell drive region is white and no other light is applied when the voltage is applied, the liquid crystal alignment property is "good". The case where light leakage was observed from the cell or when light leakage was observed from regions other than the cell drive region at the time of voltage ON was evaluated as liquid crystal orientation "poor".

(2) Evaluation of voltage retention

After applying the voltage of 5V to 60 degreeC application time and 167 milliseconds span to the liquid crystal display element manufactured above, the voltage retention after 167 milliseconds after application | release cancellation was measured. As a measurement apparatus of the voltage retention, Toyo Technica Co., Ltd. make and model "VHR-1" were used.

The case where voltage retention was 98% or more was evaluated as voltage retention "good" and the following cases as "failure."

<Evaluation of the liquid crystal display element (2)>

Using the liquid crystal aligning agent prepared above, the pattern (two types) and ultraviolet irradiation amount (three levels) of a transparent electrode were changed, six liquid crystal display elements in total were manufactured, and the following evaluation was carried out.

[Production of Liquid Crystal Cell with Patternless Transparent Electrode]

The liquid crystal aligning agent prepared above was apply | coated on the transparent electrode surface of the glass substrate which has a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printing machine (made by Nippon Shashin Inc.), and for 1 minute on an 80 degreeC hotplate After heating (prebaking) to remove the solvent, the film was heated (postbaking) for 10 minutes on a 150 ° C. hot plate to form a coating film having an average film thickness of 600 kPa.

About this coating film, the rubbing process was performed by the rubbing machine which has the roll which wound the rayon spring, and it rolled at the roll rotation speed of 400 rpm, the stage moving speed of 3 cm / sec, and the total indentation length of 0.1 mm. Then, the board | substrate which has a liquid crystal aligning film was obtained by ultrasonic cleaning in ultrapure water for 1 minute, and then drying in a 100 degreeC clean oven for 10 minutes. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Moreover, the said rubbing process is a weak rubbing process performed in order to control the fall of a liquid crystal, and to perform orientation division by a simple method.

Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to the outer edge of the surface which has a liquid crystal aligning film, with respect to one sheet of the said pair of board | substrates, mutually so that a pair of board | substrates may face a liquid crystal aligning film surface. It was pressed by overlap and the adhesive was hardened. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was produced by sealing a liquid crystal injection port with an acryl-type photocuring adhesive agent.

The above operation was repeated to produce three liquid crystal cells having a transparent electrode without a pattern. One of them was used for evaluation of the pretilt angle mentioned later as it is. About the remaining two liquid crystal cells, light irradiation was carried out in the state which applied the voltage between electrically conductive films by the following method, respectively, and it used for evaluation of a pretilt angle.

Two of the liquid crystal cells obtained above were applied with an alternating current of 10 V at a frequency of 60 Hz between the electrodes, respectively, and in the state where the liquid crystal was being driven, using an ultraviolet irradiation device using a metal halide lamp as the light source, ultraviolet light was 10,000 J /. Irradiation was carried out at an irradiation dose of 2 m 2 or 100,000 J / m 2. In addition, this irradiation amount is the value measured using the photometer measured by the wavelength 365nm reference.

―Evaluation of pretilt angle―

For each of the liquid crystal cells produced above, He-Ne laser based on the method described in Non-Patent Document 1 (TJ Scheffer et. Al., J. Appl. Phys. Vo. 19, p. 2013 (1980)). The value of the inclination angle from the board | substrate surface of the liquid crystal molecule measured by the crystal rotation method using light was made into the pretilt angle.

Table 1 shows each pretilt angle of the liquid crystal cell of no ultraviolet irradiation, the liquid crystal cell of irradiation amount 10,000J / m <2>, and the liquid crystal cell of irradiation amount 100,000J / m <2>.

[Production of Liquid Crystal Cell with Patterned Transparent Electrode]

The liquid crystal aligning agent prepared above is patterned in the slit shape as shown in FIG. 3, and a liquid crystal aligning film printer (Nihonshashin Insatsu Corp.) is made on each electrode surface of two glass substrates which respectively have the ITO electrode divided into the several area | region. (Manufactured by Kaisha), and the solvent is removed by heating (prebaking) on an 80 ° C hot plate for 1 minute and then heating (postbaking) on a 150 ° C hot plate for 10 minutes to form a coating film having an average film thickness of 600 kPa. Formed. About this coating film, after performing ultrasonic cleaning in ultrapure water for 1 minute, it dried in a 100 degreeC clean oven for 10 minutes, and the board | substrate which has a liquid crystal aligning film was obtained. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Subsequently, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to the outer edge of the surface which has a liquid crystal aligning film, one board | substrate of the said pair of board | substrates is made so that a liquid crystal aligning film surface may face a pair of board | substrates. The adhesive was hardened by overlapping each other. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a patterned transparent electrode. One of them was used for evaluation of the response speed mentioned later as it is. The remaining two liquid crystal cells were irradiated at 10,000 J / m 2 or 100,000 J / m 2 with a voltage applied between the conductive films by the same method as in the manufacture of the liquid crystal cell having the transparent electrode without the pattern. After ultraviolet irradiation, it provided for evaluation of response speed.

-Evaluation of response speed-

The liquid crystal cells prepared above were sandwiched between a pair of polarizing plates arranged in cross nicols, and then first irradiated with a visible light lamp without applying a voltage to display the brightness of the light transmitted through the liquid crystal cell. It measured by the meter and made this value 0% of the relative transmittance | permeability. Next, the transmittance | permeability when AC 60V was applied for 5 second between electrodes of a liquid crystal cell was measured similarly to the above, and this value was made into 100% of the relative transmittance | permeability.

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

The response speed of each of the liquid crystal cell of unirradiated ultraviolet rays, the liquid crystal cell of irradiation amount 10,000J / m <2>, and the liquid crystal cell of irradiation amount 100,000J / m <2> was shown in Table 1.

Examples 2 and 4

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the polymer B synthesized in Synthesis Example 6 and the polymer D synthesized in Synthesis Example 8 were used instead of the polymer A in the preparation of the liquid crystal aligning agent. Using this, various liquid crystal display elements were manufactured and evaluated. The evaluation results are shown in Table 1.

Example 3

The solution containing the polymer r obtained in Synthesis Example 9 was converted into polymer r to reduce the amount corresponding to 90 parts by weight. To this, 10 parts by weight of the polymer C synthesized in Synthesis Example 7 was added, and N- Methyl-2-pyrrolidone and butyl cellosolve were added to obtain a solvent composition having a solution of N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio) and a solid content concentration of 3.0% by weight. The liquid crystal aligning agent was prepared by filtering this solution with the filter of 1 micrometer of pore diameters.

Various liquid crystal display elements were manufactured and evaluated using the liquid crystal aligning agent prepared above. The evaluation results are shown in Table 1.

Example 5

In the said Example 3, the liquid crystal aligning agent was prepared like Example 3 except having used the usage-amount of the polymer r and the polymer C as Table 1, respectively.

Various liquid crystal display elements were manufactured and evaluated using this liquid crystal aligning agent. The evaluation results are shown in Table 1.

Comparative Example 1

This comparative example is a comparative example based on patent document 6 (Unexamined-Japanese-Patent No. 2002-23199).

In manufacture of a liquid crystal display element, the liquid crystal made by Merck Corporation as a liquid crystal clamped between a pair of board | substrate further using the commercial item made from JAL Corporation, product name (JALS-684) as a liquid crystal aligning agent, MLC6608 'was manufactured and evaluated in the same manner as in Example 1 except that 0.3 wt% of a compound represented by the following formula was used. The evaluation results are shown in Table 1.

From the result of Table 1, in the method of this invention, when the ultraviolet irradiation amount is set to 100,000 J / m <2>, the degree of the pretilt angle obtained will become excess, and will become a suitable pretilt angle in the irradiation amount of 10,000 J / m <2> or less. It can be seen that. Moreover, even if the irradiation amount is small, a sufficiently fast response speed is obtained, and the voltage retention is also excellent.

In addition, the liquid crystal cell was produced and evaluated similarly to Example 1 except having changed the pattern of the ITO electrode which a glass substrate has using each polymer composition used in Examples 1-5. Even when all the polymer compositions were used, the same effects as in Examples 1 to 5 were obtained in both the pattern shown in FIG. 1 and the pattern shown in FIG. 4.

2: pixel
4: gate bus line
6: drain bus line
8: stripe shape electrode
10: space
12 and 14: connecting electrode
16: TFT
18: accumulated capacity bus line
20: array substrate side glass substrate
22: insulating film
24: liquid crystal layer
24a: liquid crystal molecules
26: common electrode
28 color filter layer
30: glass substrate on opposite substrate
32 and 34: alignment film
d: cell gap
100: ITO electrode
200: slit portion
300: light shielding film

Claims (6)

Nematic dielectric anisotropy is negative between each film of two substrates in which a film made of a polymer having a structure represented by the following formula (I) is formed on the transparent pixel electrode of the substrate having the transparent pixel electrode. Sandwich the liquid crystal,
And a step of irradiating light in a state in which the liquid crystal is aligned by applying a voltage between each of the transparent pixel electrodes of the two substrates.
<Formula 1>

(In formula (I), A <^1> and A <^3> are either a halogen atom, a cyano group, a nitro group, a C1-C12 alkyl group, and a C1-C12 alkoxy group (The alkyl group and the alkoxy group are each halogen. Or a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, 2,5, which may be substituted by one or more selected from the group consisting of -A thiophendiyl group, a 2, 5- franylene group or a CH group is a 1, 4- naphthylene group or 2, 6- naphthylene group which may be substituted by the nitrogen atom,
The other is a phenylene group which may be substituted by one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group, or a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, 2 1,4-naphthylene group or 2,6-naphthylene group or ^* -COO-, ^* -CONH-, ^* —CO—E— (herein, the number of bonds with “*” is bonded to —CH═CH—, and E is one or more selected from the group consisting of halogen atoms, cyano groups and nitro groups). A 1,4-phenylene group which may be substituted or a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a 2,5-thiophendiyl group, a 2,5-franylene group or a CH group 1,4-naphthylene group or 2,6-naphthylene group which may be substituted by nitrogen;
A ² is a 1,4-phenylene group which may be substituted by at least one member selected from the group consisting of a halogen atom, a cyano group and a nitro group, or a pyridine-2,5-diyl group and a pyrimidine-2,5 -Diyl group, 2,5-thiophendiyl group, 2,5-franylene group, trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group, or 1,4 -Piperidyl group;
Z ¹ is a single _{^{bond, * -CH 2 CH 2 -,}} * -COO-, * -OCO-, * -OCH 2 -, * -CH 2 O-, * -C≡C-, * - (CH 2 ^{_{) 4 -, * -O (CH}} 2) 3 - or ^* - (CH _{2) 3} O- or the trans form _{^{* -OCH 2 CH = CH-, *}} -CH = CHCH 2 O-, * - (CH 2 ) ₂ CH = CH- or ^* -CH = CH (CH ₂ ) _2- (wherein the number of bonds attached with "*" is bonded to A ² );
R ¹ is a hydrogen atom, a halogen atom, a cyano group, a nitro group or an NCS group or an alkyl group having 1 to 12 carbon atoms, wherein the alkyl group may be substituted by fluorine, and one or two non-contiguous —CH ₂ — The group may be substituted by an oxygen atom, —COO—, —OCO— or —CO—, and the —CH ₂ CH ₂ —group may be substituted by —CH═CH— or is a group having a steroid skeleton;
X and Y are each independently a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 12 carbon atoms, wherein the alkyl group may be substituted by a fluorine atom, and one or two non-contiguous —CH ₂ The group may be substituted by an oxygen atom, -COO-, -OCO- or -CO-;
n is an integer of 0 to 4,
Herein, when n is 0, R ¹ is not a hydrogen atom.) The method of claim 1,
The manufacturing method of the liquid crystal display element whose structure represented by said formula (I) is a structure represented by following formula (I-2-1).
<Formula 4>

(In formula (I-2-1), R <^1> , A <^2> , Z <^1> and n are as defined in said Formula (I), respectively, R <^2> is a halogen atom, a cyano group, a nitro group, C1-C1-C An alkyl group of 12 or an alkoxy group having 1 to 12 carbon atoms (these alkyl groups and alkoxy groups may each be substituted by halogen atoms), and m is an integer of 0 to 4; The method of claim 1,
The manufacturing method of the liquid crystal display element in which the structure represented by said formula (I) is group represented by a following formula (I-1-1).

(In formula (I-1-1), R <^1> , A <^2> , Z <^1> and n are as defined in the said Formula (I), respectively, R <^2> is a halogen atom, a cyano group, a nitro group, C1-C1-C An alkyl group of 12 or an alkoxy group having 1 to 12 carbon atoms (these alkyl groups and alkoxy groups may each be substituted by halogen atoms), and m is an integer of 0 to 4; 4. The method according to any one of claims 1 to 3,
The polymer is,
(Co) polymers of (meth) acrylic acid derivatives, styrene derivatives, vinyl ethers, vinyl esters or unsaturated carboxylic acid derivatives having a structure represented by formula (I);
Polyorganosiloxane which has a structure represented by said formula (I); And
The manufacturing method of the liquid crystal display element which is at least 1 sort (s) chosen from the group which consists of polyamic acid and its imidation polymer which have a structure represented by said Formula (I). 4. The method according to any one of claims 1 to 3,
The manufacturing method of the liquid crystal display element whose said light is unpolarized ultraviolet light containing the bright line of wavelength 280nm-350nm. The method of claim 4, wherein
The manufacturing method of the liquid crystal display element whose said light is unpolarized ultraviolet light containing the bright line of wavelength 280nm-350nm.

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