KR20120054522A - Liquid crystal aligning agent, method for forming liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent is provided to provide orientation-restraining force of liquid crystal molecules, and to have excellent balance of vertical orientation-restraining force and spreadability. CONSTITUTION: A liquid crystal alignment agent contains a radiation-sensitive polymer having structure in chemical formula A', and additionally contains at least one kind of polymer selected from a group consisting of polyamic acids, and polyimides, but the polymer does not have the structure in chemical formula A'. A forming method of a liquid crystal alignment film comprises: a step of forming a coating by coating the liquid crystal alignment film, and a step of irradiating radiation to the coating. A liquid crystal display device comprises a liquid crystal alignment film formed by the liquid crystal alignment agent.

Description

Liquid crystal aligning agent, the formation method of a liquid crystal aligning film, and a liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT, METHOD FOR FORMING LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, it relates to the liquid crystal aligning agent which gives the liquid crystal aligning film excellent in the orientation regulation force of liquid crystal molecules, and the liquid crystal display element excellent in the display quality.

In a liquid crystal display element, in order to orient liquid crystal molecules with respect to a board | substrate surface in a predetermined direction, the liquid crystal aligning film is formed in the board | substrate surface. This liquid crystal aligning film is normally formed by the method (rubbing method) which rubs the organic film surface formed in the surface of the board | substrate in one direction with cloth, such as rayon. However, when the liquid crystal aligning film is formed by a rubbing process, dust and static electricity are easily generated during the rubbing process, so that dust adheres to the surface of the alignment film, causing display defects. In addition, TFT (Thin Film Transistor) In the case of a substrate having an element), there is a problem that circuit breakdown of the TFT element occurs due to the generated static electricity, which causes a decrease in product yield. Then, as another means of orienting a liquid crystal in a liquid crystal cell, the photo-alignment method which provides the liquid-crystal orientation ability by irradiating the radiation-sensitive organic thin film formed in the surface of the board | substrate with polarization or non-polarization radiation is proposed (patent document 1). ? 6). According to this photo-alignment method, uniform liquid crystal orientation can be formed without generating dust and static electricity during a process.

As a liquid crystal display element, in addition to the liquid crystal display element of the horizontal orientation mode using the nematic type liquid crystal which has positive dielectric anisotropy represented by TN (Twisted-Nematic) type, STN (Super-Twisted-Nematic) type | mold, etc., it is negative. BACKGROUND ART A VA (Vertical Alignment) type liquid crystal display element of a vertical (homeotropic) alignment mode using a nematic liquid crystal having dielectric anisotropy of is known. In the vertical alignment mode, when a liquid crystal molecule is inclined toward a direction parallel to the substrate by applying a voltage between the substrates, it is necessary to incline the liquid crystal molecules toward a constant direction from the substrate normal direction. Said photo-alignment method is also useful as a method of controlling the inclination direction of a liquid crystal molecule in the liquid crystal display element of a vertical alignment mode (patent document 1, 2, and 4-6).

Thus, the liquid crystal aligning film manufactured by the photo-alignment method can be effectively applied to various liquid crystal display elements.

However, when it tries to form the liquid crystal aligning film applied to TN type, STN type, or a vertical alignment type liquid crystal display element by the photo-alignment method, the liquid crystal aligning agent which stably expresses liquid crystal aligning control force of industrially sufficient grade is sufficient. , Not known at this time. In particular, in the case of application to a vertically aligned liquid crystal display element, in order to express the liquid crystal alignment regulating force in the vertical direction with respect to the substrate surface, the polymer serving as the liquid crystal alignment film must have a rigid liquid crystal like structure, There exists a problem that the coating property or printability of the liquid crystal aligning agent containing this is impaired, and the vertically-aligned liquid crystal aligning agent for the photo-alignment method which has both favorable liquid crystal aligning property and favorable applicability | coating so far is unknown.

By the way, recently, the liquid crystal display element of the transverse electric field system (IPS mode) was proposed (patent document 7). This transverse liquid crystal display element is a liquid crystal display element of the system which forms an electrode only on one side of a pair of opposing board | substrates, and produces an electric field in the direction parallel to a board | substrate, and forms an electrode in both board | substrates, Compared with the liquid crystal display element of the conventional electric field system which generate | occur | produces an electric field in a vertical direction, it is known that it has a wide viewing angle characteristic, and high quality display is possible. Since the liquid crystal molecules respond to electric fields only in the direction parallel to the substrate, the transverse electric field type liquid crystal display element is visually recognized by the observer even when the viewing angle is changed without changing the refractive index in the major axis direction of the liquid crystal molecules. There is little change in the contrast and the color of the display color, so that high quality display is possible regardless of the time of day.

Since the liquid crystal aligning film in the liquid crystal display element of such a transverse electric field system is also normally formed by the rubbing method, there exists a problem as mentioned above and application of the photo-alignment method is examined. However, when the liquid crystal aligning film applied to the liquid crystal display element of a transverse electric field system is formed by the photo-alignment method, it is pointed out that the orientation regulation force of liquid crystal molecules is not enough, and improvement is calculated | required.

Japanese Laid-Open Patent Publication No. 2003-307736 Japanese Laid-Open Patent Publication No. 2004-163646 Japanese Laid-Open Patent Publication No. 2002-250924 Japanese Laid-Open Patent Publication No. 2004-83810 Japanese Patent Laid-Open No. 9-211468 Japanese Laid-Open Patent Publication 2003-114437 US Patent No. 5,928,733 Japanese Laid-Open Patent Publication No. 2010-97188 Japanese Laid-Open Patent Publication No. 63-291922

 「Science of the Sol-Gel Method」, Published by Agnesho Fusha, 1988, pp 154-161

This invention is made | formed in view of the said situation, The objective can provide the orientation control force of a liquid crystal molecule by the photo-alignment method, and when it applies to a vertical alignment type liquid crystal display element, It is excellent in the balance with applicability | paintability, and when applying to the liquid crystal display element of a TN type, STN type, or a transverse electric field system, it is providing the liquid crystal aligning agent which gives the liquid crystal aligning film excellent in the orientation regulation force.

Another object of the present invention is to provide a liquid crystal display device which is excellent in liquid crystal alignment regulating force and excellent in display quality.

Still other objects and advantages of the present invention will become apparent from the following description.

The above object and advantages of the present invention are first, the following formula (A '):

It is achieved by the liquid crystal aligning agent containing the radiation sensitive polymer which has a structure represented by

Secondly, it is achieved by a liquid crystal display device having a liquid crystal alignment film formed of the above liquid crystal aligning agent.

The liquid crystal aligning agent of this invention can provide the orientation control force of a liquid crystal molecule by the photo-alignment method, and when it is applied to a liquid crystal display element of a vertical alignment type, it is excellent in the balance of the vertical alignment control force of a liquid crystal molecule and applicability | paintability. On the other hand, when it applies to the liquid crystal display element of a TN type, STN type, or a transverse electric field system, the liquid crystal aligning film excellent in the orientation regulation force of a liquid crystal molecule can be provided.

Since the liquid crystal display element of this invention provided with the liquid crystal aligning film formed from such a liquid crystal aligning agent of this invention is possible to display high quality, and also cheap, it can be effectively applied as various display apparatuses.

Moreover, the coating film formed from the liquid crystal aligning agent of this invention can be used suitably also as an insulating film in an electronic material.

(Form to carry out invention)

The liquid crystal aligning agent of this invention contains the radiation sensitive polymer which has a structure represented by said formula (A '). In said Formula (A '), it is preferable that the benzyl position carbon adjacent to the benzene ring of the right side has at least 1 hydrogen atom.

As the skeleton of the radiation-sensitive polymer, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose and its derivatives, polyacetal, polystyrene and its derivatives, poly (styrene- Phenylmaleimide) and derivatives thereof, poly (meth) acrylate, and the like, but polyorganosiloxanes are preferred among them. That is, it is preferable that it is a radiation sensitive polyorganosiloxane which has a structure represented by said formula (A ') as a radiation sensitive polymer which the liquid crystal aligning agent of this invention contains.

<Radiation Polyorganosiloxane>

The radiation sensitive polyorganosiloxane contained preferably in the liquid crystal aligning agent of this invention has a structure represented by said formula (A ').

It is preferable that the content rate of the structure represented by said formula (A ') in the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention is 0.2-6 mmol / g-polymer, and 0.3-5 mmol It is more preferable that it is / g-polymer.

It is preferable that the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention has an epoxy group in addition to the structure represented by said formula (A '). In this case, the epoxy equivalent of the radiation sensitive polyorganosiloxane becomes like this. Preferably it is 150 g / mol or more, More preferably, it is 200-10,000 g / mol, More preferably, it is 200-2,000 g / mol. By using the radiation-sensitive polyorganosiloxane of such an epoxy equivalent, the liquid crystal aligning agent of this invention forms the liquid crystal aligning film which was more excellent in liquid-crystal orientation and excellent in afterimage characteristics, without impairing the storage stability of a liquid crystal aligning agent. It becomes possible, and is preferable.

It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography about the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention is 1,000-200,000, and it is more preferable that it is 2,000-100,000. Especially, it is preferable that it is 3,000-30,000.

<Synthesis of radiation-sensitive polyorganosiloxane>

As long as the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention is the same as the above, you may use what was synthesize | combined by any method. As a synthesis | combining method of the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention, for example,

A method of hydrolyzing and condensing a hydrolyzable silane compound having a structure represented by formula (A '), or a mixture of the hydrolyzable silane compound and other hydrolyzable silane compounds,

It can be based on the method etc. which make the polyorganosiloxane which has an epoxy group, and the compound (henceforth "carboxylic acid (A)") represented by a following formula (A) react.

[In Formula (A), R is respectively independently a C1-C4 alkyl group, a halogen atom, or a cyano group,

n1 is an integer of 0-3, n2 is an integer of 0-4,

R <^1> is group represented by following formula (R-1) or (R-2), R <^2> and R <^3> is group represented by following formula (R-3), respectively, and exists in a formula (A) One of Z is a carboxyl group and the other is a hydrogen atom:

^* -R ⁵ -Z (R-2)

^* -X ² -R ⁶ -Z (R-3)

(Formula (R-1) of X ¹ is a single bond, -O- ^+, -COO- or -OCO- ^{+ + (single,} combined hand R ⁴ cheukim tagged "+"), R ⁴ represents a single bond Is a methylene group or an alkylene group having 2 to 5 carbon atoms, R is an alkyl group having 1 to 4 carbon atoms, a halogen atom or a cyano group, n3 is an integer of 0 to 4,

R <^5> in Formula (R-2) is a methylene group or a C2-C5 alkylene group,

Formula (R-3) of X ² is a single bond, -O- ^+, -COO- or -OCO- ^{+ + (Note,} however, that this combination hand tagged "+" R ⁶ cheukim) and, R ⁶ represents a single bond, A methylene group or an alkylene group having 2 to 5 carbon atoms,

"*" In formula (R-1)? (R-3) represents a bonding hand, respectively).

Among these, it is preferable by the latter method from a viewpoint of the ease of synthesis of a raw material compound, the ease of reaction, etc.

Hereinafter, the reaction method of the polyorganosiloxane which has an epoxy group, and carbonic acid (A) which is a preferable method for synthesize | combining the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention is demonstrated.

[Polyorganosiloxane with Epoxy]

The epoxy group in the polyorganosiloxane having an epoxy group is bonded to a silicon atom via an alkylene group in which the ethylene oxide skeleton or the 1,2-epoxycycloalkane skeleton may be interrupted by an oxygen atom either directly or in the middle. It is preferable to exist in polyorganosiloxane as contained in the group (group which has an epoxy group). As group which has such an epoxy group, it is following formula (EP-1) or (EP-2):

("*" Represents a bond in formula (EP-1) and (EP-2).)

The group represented by is mentioned.

The epoxy equivalent of the polyorganosiloxane which has an epoxy group becomes like this. Preferably it is 100-10,000 g / mol, More preferably, it is 150-1,000 g / mol.

It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography about the polyorganosiloxane which has an epoxy group is 500-100,000, It is more preferable that it is 1,000-10,000, It is especially preferable that it is 1,000-5,000. Do.

Such polyorganosiloxane having an epoxy group is, for example, hydrolyzed a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and other silane compounds in the presence of a suitable organic solvent, water and a catalyst. And condensation.

As a silane compound which has the said epoxy group, 3-glycidyloxy propyl trimethoxysilane, 3-glycidyl oxypropyl triethoxy silane, 3-glycidyl oxypropyl methyl dimethoxy silane, 3-glycol, for example Cydyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane etc. are mentioned.

Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane and tetra-sec. -Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane , Fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec -Butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyl Tri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (triflu Rhomethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri -i-propoxysilane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n- Hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n- Hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane , 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltri Methoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane,

2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl ) Ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxymethyltrie Methoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- ( Meta) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane , 3- (meth) acryloxypropyltri-i-propoxysilane, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3 -Me Lecaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-pro Foxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyl trichloro Rosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane , Phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri- i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi- i-propoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi- i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane,

(Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro Rho-n-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-i-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) die Methoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di -n-butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) Diethoxysilane, (methyl) (vinyl) di-n-propoxy Silane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, di Vinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane , Diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyl Di-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxy Trimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (Methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl) diphenyl In addition to the silane compound which has one silicon atom, such as a silane,

As a brand name, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X- 22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40- 2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR-212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, manufactured by Shin-Etsu Chemical Co., Ltd.); Glass resin (manufactured by Showa Denko KK); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Torre Dow Corning Co., Ltd.); FZ3711 and FZ 3722 (above, manufactured by Nippon Unicar Co., Ltd.); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS- 227, PSD-0332, PDS-1615, PDS-9931, and XMS-5025 (above, manufactured by Tosso Corp.); Methyl silicate MS51 and methyl silicate MS56 (above, manufactured by Mitsubishi Chemical Co., Ltd.); Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, manufactured by Colcot Co., Ltd.); Partial condensates, such as GR100, GR650, GR908, GR950 (above, Showa Denko KK) are mentioned, One or more of these can be used.

As other silane compounds, among these, tetramethoxysilane, tetraethoxysilane, methyl trimethoxysilane, methyl triethoxysilane, 3- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryloxy Propyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Allyltrimethoxysilane, Allyltriethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, 3-mercaptopropyltrimethoxy Using at least one selected from the group consisting of silane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane desirable.

In synthesizing the polyorganosiloxane having an epoxy group in the present invention, the use ratio of the silane compound having an epoxy group and other silane compounds is adjusted so that the epoxy equivalent of the obtained polyorganosiloxane is in the above preferred range. It is preferable to set it.

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. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. It is preferable that they are water-insoluble.

These organic solvents can be used individually or in mixture of 2 or more types.

The amount of the organic solvent used is preferably 10 to 10,000 parts by weight, based on 100 parts by weight of the total of the silane compounds (the sum of the silane compound having an epoxy group and other silane compounds optionally used, hereinafter the same). Preferably it is 50-1,000 weight part.

The amount of water used when synthesizing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, based on 1 mole of the total of the silane compounds.

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. can be used, for example.

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; Quaternary organic amines, such as tetramethylammonium hydroxide, etc. are mentioned, respectively. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organics such as tetramethylammonium hydroxide; Amine is preferred.

As a catalyst at the time of synthesize | combining the polyorganosiloxane which has an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, the desired polyorganosiloxane can be obtained at a high hydrolysis and condensation rate without generating side reactions such as ring opening of an epoxy group, so that the production stability is excellent, which is preferable. Do. Moreover, the liquid crystal aligning agent of this invention containing the reaction material of the polyorganosiloxane which has the epoxy group synthesize | combined using the alkali metal compound or the organic base as a catalyst and carbonic acid (A) is suitable since it is very excellent in storage stability. . The reason is, as pointed out in Non-Patent Document 1 ("Science of the Sol-Gel Method", Published by Agnessho Fuchsia, 1988, pp 154-161), alkali as a catalyst in hydrolysis and condensation reactions. When a metal compound or an organic base is used, only some of the alkoxysilanes are intensively hydrolyzed to generate polyfunctional species, and consequently, condensation polymerization proceeds three-dimensionally, resulting in a crosslinked polymer. It is guessed whether polyorganosiloxane with a small content rate of a silanol group is obtained. That is, since the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention has a small content rate of a silanol group, condensation reaction of silanol groups is suppressed, and the liquid crystal aligning agent of this invention contains the other polymer mentioned later In the case where it is used, the condensation reaction between the silanol group and other polymers is also suppressed, which is inferred to be the result of excellent storage stability.

As the catalyst, an organic base is particularly preferable. The amount of the organic base used varies depending on the type of organic base, reaction conditions such as temperature and the like, and should be appropriately set. It is 0.05-1 mol.

Hydrolysis and condensation reaction in synthesizing polyorganosiloxane having an epoxy group include dissolving a silane compound having an epoxy group and other silane compounds in an organic solvent, if necessary, and mixing the solution with an organic base and water. For example, it is preferable to carry out by heating using suitable heating apparatuses, such as an oil bath.

At the time of hydrolysis and condensation reaction, heating temperature becomes like this. Preferably it is 130 degrees C or less, More preferably, it is 40-100 degreeC, It is preferable to heat 0.5 to 12 hours, More preferably, it is 1 to 8 hours. . During 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. In this washing | cleaning, it is preferable at the point by which washing operation becomes easy by washing with water containing a small amount of salts, for example, about 0.2 weight% of ammonium nitrate aqueous solution. The washing is performed until the aqueous layer after washing is neutral, and then the organic solvent layer is dried with a suitable drying agent such as anhydrous calcium sulfate and molecular sieve, if necessary, and then the solvent is removed to remove the polyol having the target epoxy group. Ganosiloxane can be obtained.

In this invention, you may use what is marketed as polyorganosiloxane which has an epoxy group. As such a commercial item, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, Chisso Corp. make) etc. are mentioned, for example.

[Carbonic Acid (A)]

Carbonic acid (A) in this invention is a compound represented by said formula (A).

R in the formulas (A) and (R-1) is preferably a methyl group, a fluorine atom or a cyano group;

N1 and n2 in the formula (A) and n3 in the formula (R-1) are each preferably 0 or 1, and more preferably 0;

The formula (R-1) X ² in the formula X ¹ and (R-3) in the is preferably a single bond, respectively. Moreover, Especially preferably, X <^1> and R <^{4> in} said Formula (R-1) and X <^2> and R <^{6> in} said Formula (R-3) are respectively a compound which is a single bond.

As a specific example of a carboxylic acid (A), for example, following formula (A-1)? (A-15):

(In the formula, n and m are each an integer of 1 to 5)

The compound represented by each of these is mentioned, One or more types selected from these can be used. Among these, compounds represented by each of (A-1), (A-2) and (A-5) to (A-8) are preferable, and of (A-1) and (A-2) The compound represented by each is more preferable.

Carbonic acid (A) can be synthesize | combined by combining suitably the organic chemical method.

For example, the compound represented by said formula (A-1) or (A-2) makes 2-hydroxybenzophenone react with sodium hydride to make a sodium salt, and also 3- (halomethyl) benzoic acid alkyl or 4- After reacting with (halomethyl) benzoic acid alkyl, the ester bonds are hydrolyzed, respectively.

[Synthesis of radiation sensitive polyorganosiloxane]

The radiation-sensitive polyorganosiloxane preferably contained in the liquid crystal aligning agent of the present invention is preferably a polyorganosiloxane having an epoxy group as described above and a carbonic acid (A), preferably a catalyst and an organic solvent. By reacting in presence, it can obtain easily.

Here, carbonic acid (A) has the sum total with respect to 1 mol of epoxy groups which polyorganosiloxane has, Preferably it is 0.01-5 mol, More preferably, it is 0.05-2 mol, More preferably, it is 0.1-0.8 Used in molar ratios.

In the present invention, the following formula (B) together with the carboxylic acid (A) in a range that does not impair the effects of the present invention.

R ^I -R ^II -COOH (B)

(In Formula (B), R ^I is an alkyl group or alkoxy group having 8 to 20 carbon atoms or a fluoroalkyl group or fluoroalkoxy group having 4 to 21 carbon atoms, and R ^II is a single bond, a 1,4-cyclohexylene group or 1,4-phenylene group)

You may use together the compound represented by. In this case, synthesis | combination of a radiation sensitive polyorganosiloxane is performed by making the polyorganosiloxane which has an epoxy group, and the mixture of a carbonic acid (A) and the compound represented by said Formula (B) react.

As a preferable example of a compound represented by said formula (B), it is following formula (B-1)? (B-4):

(In the above formula, f is an integer of 1 to 3, g is an integer of 3 to 18, h is an integer of 5 to 20, i is an integer of 1 to 3, j is an integer of 0 to 18, k is an integer from 1 to 18)

The compound represented by each of these is mentioned, Among these, following formula (B-3-1)? (B-3-3)

The compound represented by each of is preferable, and 1 or more types chosen from these can be used.

Since the compound represented by said formula (B) is a compound which becomes a site | part which gives pretilt angle expression property to the liquid crystal aligning film obtained by reacting with the polyorganosiloxane which has an epoxy group with carbonic acid (A), When applying a liquid crystal aligning agent to a vertical alignment type liquid crystal display element, it can use preferably. In this specification, the compound represented by said formula (B) is called "other carbonic acid" hereafter.

In the present invention, in the case of using other carbonic acid together with the carbonic acid (A), the use ratio of the sum of the carbonic acid (A) and the other carbonic acid is preferably based on 1 mole of the epoxy group of the polyorganosiloxane. 0.001-1.5 mol, More preferably, it is 0.01-1 mol, More preferably, it is 0.05-0.9 mol. In this case, the other carbonic acid is preferably used in a range of 50 mol% or less, more preferably 25 mol% or less, based on the total amount of the carbonic acid (A). When the use ratio of other carbonic acid exceeds 50 mol%, the problem that an abnormal domain generate | occur | produces may arise when turning a liquid crystal display element ON.

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.

As said hardening accelerator, For example, tertiary amines, such as benzyl dimethylamine, 2,4,6- tris (dimethyl aminomethyl) phenol, cyclohexyl dimethylamine, and triethanolamine;

2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methyldi Midazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl)- 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2- Cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimelli Tate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s Triazine, 2,4-di Mino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, 2-phenylimidazole Imidazole compounds such as isocyanuric acid adducts of isocyanuric acid adducts of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine; Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine and triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium Iodine, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium, O, O-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazoleate, tetra-n-butylphosphonium tetrafluoro Quaternary phosphonium salts such as loborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 or organic acid salts thereof;

Organometallic compounds such as zinc octylate, octylate tin, and aluminum acetylacetone complex;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;

Boron compounds such as boron trifluoride and triphenyl borate;

Metal halide compounds such as zinc chloride and tin tin;

High-melting-point dispersion | distribution type latent hardening accelerators, such as an amine addition type | mold promoter, such as an adduct of dicyandiamide, an amine, and an epoxy resin;

Microcapsule-type latent curing accelerators in which a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;

Amine salt type latent curing accelerators;

And latent curing accelerators such as high-temperature dissociation-type thermal cationic polymerization-type latent curing accelerators such as Lewis salts and Bronsted salts.

Among them, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride are preferable.

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.

Reaction of the polyorganosiloxane which has an epoxy group, and carbonic acid (A) can be performed in presence of an organic solvent as needed. As such an organic solvent, hydrocarbon, ether, ester, ketone, amide, alcohol, etc. are mentioned, for example. Of these, ethers, esters or ketones are preferred in view of solubility of raw materials and products and ease of purification of the products. The solvent is used at a ratio such that the solid content concentration (a ratio of the weight of 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.

Synthesis | combination of a radiation sensitive polyorganosiloxane as mentioned above is a method of introduce | transducing the structure represented by said formula (A ') by ring-opening addition of the epoxy which the polyorganosiloxane which has an epoxy group has. This synthesis method is simple and is a very suitable method in that the introduction ratio of the structure represented by the formula (A ') can be increased.

<Other components>

The liquid crystal aligning agent of this invention contains such a radiation sensitive polymer, Preferably a radiation sensitive polyorganosiloxane.

The liquid crystal aligning agent of this invention may contain other components other than the above radiation sensitive polymer, Preferably it is a radiation sensitive polyorganosiloxane, unless the effect of this invention is impaired. As such other components, for example, a polymer other than a radiation sensitive polymer (hereinafter referred to as "other polymer"), a curing agent, a curing catalyst, a curing accelerator, and a compound having at least one epoxy group in a molecule (wherein the radiation sensitive Except those corresponding to the sex polyorganosiloxane, hereinafter referred to as "epoxy compound", functional silane compounds (except those corresponding to the radiation-sensitive polyorganosiloxane), and surfactants Can be.

[Other polymers]

The said other polymer can be used in order to improve the solution characteristic of the liquid crystal aligning agent of this invention, and the electrical characteristic of the obtained liquid crystal aligning film further. Such other polymers are polymers having no structure represented by the formula (A '), for example, polyamic acid, polyimide; Polyorganosiloxanes other than the above-mentioned radiation-sensitive polyorganosiloxanes (hereinafter referred to as "other polyorganosiloxanes"): polyamic acid esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrenes) -Phenyl maleimide) derivatives, poly (meth) acrylates, and the like are preferably selected, and one or more of them can be used.

As the other polymer in the present invention, it is preferable to use at least one polymer selected from the group consisting of polyamic acid, polyimide and other polyorganosiloxane, and at least one selected from the group consisting of polyamic acid and polyimide. It is more preferred to use one polymer or other polyorganosiloxane.

{Polyamic acid}

The said polyamic acid can be obtained by making tetracarboxylic dianhydride and diamine react. Tetracarboxylic dianhydride and diamine used here do not have the structure represented by said formula (A ').

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid in this invention, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butanetetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3- Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3 -Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornan-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3 , 5,8,10-tetraon and the like;

As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride etc. are mentioned, respectively, In addition, tetracarboxylic dianhydride described in patent document 8 (Unexamined-Japanese-Patent No. 2010-97188) can be used. .

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, what contains alicyclic tetracarboxylic dianhydride among these is preferable, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, and 1 It is more preferable that it contains at least 1 sort (s) chosen from the group which consists of a 2,3, 4- cyclobutane tetracarboxylic dianhydride, and especially contains 2,3,5- tricarboxy cyclopentyl acetic dianhydride. It is preferable.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid is selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride. It is preferable to contain 10 mol% or more with respect to all tetracarboxylic dianhydride, It is more preferable to contain 20 mol% or more, More preferably, 2,3,5-tricarboxycyclopentyl It is most preferable that it consists only of at least 1 sort (s) chosen from the group which consists of an acetic dianhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride.

As a diamine used for synthesize | combining a polyamic acid, an aliphatic diamine, an alicyclic diamine, an aromatic diamine, diamino organosiloxane, etc. are mentioned, for example. As these specific examples, As an aliphatic diamine, For example, 1, 1- metha xylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1, 5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7- Diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene ) Bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl , 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3, 6-diaminocarbazole, N-ethyl- 3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl)- N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid,

Cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diamino Benzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethyl Benzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((amino Phenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl ) Methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane, N, N-dial Ryldiaminoaniline, ω-aminoalkylaniline and the following formula (D-0)

In formula (D-0), X ^I is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, ^* -O-, ^* -COO-, ^* -OCO-, ^* -X'-R-, ^* -R-X'- or ^* -X'-R-X'- (where X 'is ⁺ -O-, ⁺ -COO- or ⁺ -OCO- (where "+" is a bond attached to this) The hand is pointing toward the left side of the formula (D-0), R is an alkylene group having 2 or 3 carbon atoms, and the bond hand with "*" is bonded to the diaminophenyl group),

Ring ¹ and Ring ² are each independently a cyclohexylene group or a phenylene group,

X "is a single bond, ⁺ -O-, ⁺ -COO- or ⁺ -OCO- (where" + "indicates that the bonding hand to which it is attached is directed toward the left side of the formula (D-0)),

a is 0 or 1, b is an integer of 0-3,

When b is 2 or more, two or more X "and Ring ² may mutually be same or different, and when a is 0, X" located in the leftmost part of Formula (D-0) is a single bond,

c is an integer of 0-20, (alpha) and (beta) are integers of 0-2c + 1, respectively, except that alpha + beta = 2c + 1, and

a compound represented by a case where c is 0 when a + b = 0, and the like;

As diamino organosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be cited,

The diamine described in patent document 8 (Unexamined-Japanese-Patent No. 2010-97188) can be used.

As X <^I> in said Formula (D-0), it is preferable that it is ^* -O-, ^* -COO-, or ^* -OCO- (But the bond which attached "*" couple | bonds with a diaminophenyl group). .

As a cyclohexylene group and a phenylene group of Ring ¹ and Ring ² , it is preferable that they are 1, 4- cyclohexylene group and 1, 4- phenylene group, respectively. As Ring ¹ , it is preferable that it is a 1, 4- phenylene group, and as Ring ² it is preferable that it is a 1, 4- cyclohexylene group.

As X ", it is preferable that it is a single bond.

It is preferable that α is 2c + 1 and β is 0, that is, the group C _c H _α F _β − is the group C _c H _{2c +1} −.

It is preferable that a + b is an integer of 2-4, or a + b is 0 or 1 and c is 6 or more. Among these, it is preferable that a + b is an integer of 2-4.

As a preferable structure of the compound represented by said Formula (D-0), it is following formula (D-1):

(In formula (D-1), X ^I is ^* -O-, ^* -COO- or ^* -OCO-, provided that the bond to which "*" is attached is combined with a diaminophenyl group.), And a is 0 or 1, b is an integer from 0 to 2, c is an integer from 1 to 20)

The compound represented by this is mentioned.

As a specific example of a compound represented by said formula (D-1), For example, dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-dia Minobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecaneoxy-2,5-diaminobenzene , Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, the following formula (D-1-1)? (D- 1-3)

The compound etc. which are represented by each of these are mentioned. In said Formula (D-1), it is preferable that a and b do not become zero simultaneously.

These diamines can be used individually or in combination of 2 or more types.

As for the use ratio of tetracarboxylic dianhydride and diamine provided for the synthesis reaction of polyamic acid, the ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.2-2 equivalent with respect to 1 equivalent of amino group contained in diamine, More preferably, it is a ratio which becomes 0.3-1.2 equivalent.

Synthesis reaction of polyamic acid, Preferably in an organic solvent, Preferably it is -20-150 degreeC, More preferably, under the temperature conditions of 0-100 degreeC, Preferably it is 0.5 to 24 hours, More preferably, It is performed for 2 to 10 hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Aprotic polar solvents such as N, N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphotriamide;

Phenolic solvents, such as m-cresol, a xylenol, a phenol, and a halogenated phenol, etc. are mentioned. As for the usage-amount (a) of an organic solvent, the total amount (b) of tetracarboxylic dianhydride and a diamine compound becomes like this. Preferably it is 0.1-50 weight% with respect to the total amount (a + b) of a reaction solution, More preferably, it is 5-30 weight It is an amount which becomes%.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after isolating the polyamic acid contained in a reaction solution, or after refine | purifying the isolated polyamic acid, preparation of a liquid crystal aligning agent You may provide to.

When polyamic acid is dehydrated and closed, and it is set as polyimide, the said reaction solution may be used for a dehydration ring-closure reaction as it is, may be used for dehydration ring-closure reaction after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid After purification, the dehydration ring-closure reaction may be used.

Isolation of the polyamic acid can be performed by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, drying the precipitate under reduced pressure, or distilling off the organic solvent in the reaction solution with an evaporator under reduced pressure. have. The polyamic acid is again dissolved in an organic solvent, and then precipitated with a poor solvent, or the solution obtained by dissolving polyamic acid in an organic solvent again is washed, and the organic solvent in the solution is distilled under reduced pressure with an evaporator. Polyamic acid can be refine | purified by the method of performing the removal process once or several times.

{Polyimide}

The said polyimide can be synthesize | combined by dehydrating and ring-closing the dark acid structure which the polyamic acid which does not have a structure represented by said formula (A ') obtained as mentioned above has. At this time, all of the dark acid structure may be dehydrated and completely imidized, or only a part of the dark acid structure may be dehydrated and closed to be a partial imide cargo in which the dark acid structure and the imide structure coexist.

The dehydration ring closure of polyamic acid may be carried out by (i) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. This can be done by.

The reaction temperature in the method of heating the polyamic acid of said (i) becomes like this. Preferably it is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, but when reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide obtained may fall. The reaction time in the method of heating a polyamic acid becomes like this. Preferably it is 0.5 to 48 hours, More preferably, it is 2 to 20 hours.

On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the polyamic acid of said (ii), acid anhydrides, such as acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of polyamic acid structural units. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to these. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C, and the reaction time is preferably 0.5 to 20 hours, and more preferably 1 to 8 hours.

The polyimide obtained in the said method (i) may be provided as it is to preparation of a liquid crystal aligning agent, or may be provided to preparation of a liquid crystal aligning agent after refine | purifying the polyimide obtained. On the other hand, in the said method (ii), the reaction solution containing a polyimide is obtained. This reaction solution may be provided as it is to preparation of a liquid crystal aligning agent as it is, may be provided to preparation of a liquid crystal aligning agent after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, and after isolation of a polyimide to preparation of a liquid crystal aligning agent You may provide, or after refine | purifying an isolated polyimide, you may provide for preparation of a liquid crystal aligning agent. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of a polyimide can be performed by performing the same operation as the above as an isolation | purification and purification method of polyamic acid.

{Other Polyorganosiloxane}

Other polyorganosiloxanes in the present invention are polyorganosiloxanes other than the above-mentioned radiation-sensitive polyorganosiloxanes, that is, polyorganosiloxanes having no structure represented by the formula (A '). Such other polyorganosiloxane is, for example, at least one silane compound (hereinafter also referred to as "raw silane compound") selected from the group consisting of an alkoxysilane compound and a halogenated silane compound, preferably in a suitable organic solvent. And hydrolysis and condensation in the presence of water, a catalyst and the like.

As a raw material silane compound used here, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec- Butoxysilane, tetra-tert-butoxysilane, tetrachlorosilane; Methyltrimethoxysilane, Methyltriethoxysilane, Methyltri-n-propoxysilane, Methyltri-iso-propoxysilane, Methyltri-n-butoxysilane, Methyltri-sec-butoxysilane, Methyltri -tert-butoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyl tree -n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane; Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, etc. are mentioned, It is preferable to use 1 or more types of these, Especially, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyl tri Preference is given to using at least one selected from the group consisting of ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane. .

The other polyorganosiloxane in this invention can be synthesize | combined as mentioned above as a synthesis | combining method of the polyorganosiloxane which has an epoxy group except using the above-mentioned raw material silane compound.

It is preferable that it is 1,000-100,000, and, as for the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography about other polyorganosiloxane, it is more preferable that it is 5,000-50,000.

{Rate of use of other polymers}

When the liquid crystal aligning agent of this invention contains another polymer with the radiation sensitive polymer mentioned above, it is preferable that it is 10,000 weight part or less with respect to 100 weight part of radiation sensitive polymers as a use ratio of another polymer. The more preferable use ratio of other polymer changes with kinds of polymer contained in the liquid crystal aligning agent of this invention.

The more preferable use ratio of both when the liquid crystal aligning agent of this invention contains at least 1 sort (s) of polymer chosen from the group which consists of a radiation sensitive polyorganosiloxane, polyamic acid, and polyimide is radiation sensitive It is preferable that it is 100-5,000 weight part as a total amount of polyamic acid and polyimide with respect to 100 weight part of sex polyorganosiloxanes, and also it is 200-2,000 weight part.

On the other hand, when the liquid crystal aligning agent of this invention contains a radiation sensitive polyorganosiloxane and other polyorganosiloxane, the more preferable use ratio of both is 100 weight part of radiation sensitive polyorganosiloxanes. The amount of other polyorganosiloxane relative to 100 to 2,000 parts by weight.

Curing Agents and Curing Catalysts

The curing agent and curing catalyst may be contained in the liquid crystal aligning agent of the present invention for the purpose of further strengthening the crosslinking reaction of the radiation-sensitive polymer, preferably the radiation-sensitive polyorganosiloxane, wherein the curing accelerator is carried by the curing agent. It may be contained in the liquid crystal aligning agent of this invention for the purpose of promoting hardening reaction.

As said hardening | curing agent, the hardening | curing agent generally used for hardening of the curable composition containing the curable compound which has an epoxy group, or the compound which has an epoxy group can be used, For example, polyhydric amine, polyhydric carboxylic acid anhydride, polyhydric carboxylic acid can be illustrated. Can be.

As said polyhydric carboxylic acid anhydride, anhydride of cyclohexane tricarboxylic acid and other polyhydric carboxylic acid anhydride are mentioned, for example.

As a specific example of cyclohexane tricarboxylic acid anhydride, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4- anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5- anhydride And cyclohexane-1,2,3-tricarboxylic acid-2,3-acid anhydride. Examples of other polyvalent carboxylic anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadic acid anhydride, Dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, formula (CA-1):

(Q is an integer of 1-20 in Formula (CA-1).)

Diels? Alder reaction products of alicyclic compounds having conjugated double bonds such as α-terpinene and allocymen and maleic anhydride, in addition to tetracarboxylic dianhydrides generally used for the synthesis of compounds and polyamic acids Hydrogenated substance etc. are mentioned.

As said curing catalyst, an antimony hexafluoride compound, a phosphorus hexafluoride compound, aluminum tris acetylacetonate, etc. can be used, for example. These catalysts can promote cationic polymerization of epoxy groups by heating.

As said hardening accelerator, it is an imidazole compound, for example;

Quaternary phosphorus compounds;

Quaternary amine compounds;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and its organic acid salts;

Organometallic compounds such as zinc octylate, octylate tin and aluminum acetylacetone complex;

Boron compounds such as boron trifluoride and triphenyl borate; Metal halide compounds such as zinc chloride and tin tin;

High melting point latent cure accelerators such as dicyanidiamides, amine addition accelerators such as amines and adducts of epoxy resins:

Microcapsule-type latent curing accelerators coated with polymers such as quaternary phosphonium salts:

Amine salt type latent hardening accelerator:

High temperature dissociation type | mold thermal cationic polymerization type latent hardening accelerator, such as a Lewis acid salt and Bronsted acid salt, etc. are mentioned.

[Epoxy Compound]

The said epoxy compound can be contained in the liquid crystal aligning agent of this invention from a viewpoint of further improving the adhesiveness to the board | substrate surface of the liquid crystal aligning film formed.

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, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycid Diyl-aminomethylcyclohexane etc. are mentioned as a preferable thing.

When the liquid crystal aligning agent of this invention contains an epoxy compound, as the content rate, it is 40 weight part or less with respect to a total of 100 weight part of said radiation sensitive polymer and the other polymer arbitrarily used, More Preferably it is 0.1-30 weight part.

Moreover, when the liquid crystal aligning agent of this invention contains an epoxy compound, you may use together base catalysts, such as 1-benzyl- 2-methylimidazole, in order to raise the crosslinking reaction efficiently.

[Functional silane compound]

The said functional silane compound can be used for the purpose of improving the adhesiveness with the board | substrate of the liquid crystal aligning film obtained further. As a functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3, 6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminoprop Triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N- Bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. As described in Patent Document 9 (Japanese Laid-Open Patent Publication No. 63-291922), a reaction product of a tetracarboxylic dianhydride and a silane compound having an amino group can be used.

When the liquid crystal aligning agent of this invention contains a functional silane compound, it is 50 weight part or less with respect to a total of 100 weight part of said radiation-sensitive polymer and the other polymers arbitrarily used as the content rate. More preferably, it is 20 weight part or less.

[Surfactants]

As said surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant etc. are mentioned, for example.

When the liquid crystal aligning agent of this invention contains surfactant, it is 10 weight part or less with respect to all 100 weight part of liquid crystal aligning agents as the content rate, More preferably, it is 1 weight part or less.

<Liquid crystal aligning agent>

Although the liquid crystal aligning agent of this invention contains a radiation sensitive polymer as an essential component as mentioned above, and contains other components as needed in addition, Preferably it is a solution composition which each component melt | dissolved in the organic solvent. As prepared.

As an organic solvent which can be used in order to prepare the liquid crystal aligning agent of this invention, it is preferable to melt a radiation sensitive polymer and other components used arbitrarily, and to not react with these.

The organic solvent which can be used suitably for the liquid crystal aligning agent of this invention changes with kinds of the polymer which the liquid crystal aligning agent of this invention contains.

When the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation-sensitive polyorganosiloxane and polyamic acid and polyimide, and radiation-sensitive polyorganosiloxane and polyamic acid and poly Preferred organic solvents in the case of containing other polyorganosiloxane in addition to at least one polymer selected from the group consisting of mead include the organic solvents exemplified above as being used for the synthesis of polyamic acid. Can be. These organic solvents can be used individually or in combination of 2 or more types.

On the other hand, when the liquid crystal aligning agent of this invention contains only radiation-sensitive polyorganosiloxane as a polymer, or contains radiation-sensitive polyorganosiloxane and other polyorganosiloxane, it is a group which consists of polyamic acid and polyimide. As a preferable organic solvent in the case of not containing at least 1 sort (s) of polymer chosen from, for example, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methylmethoxypropionate, ethyl ethoxy Propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether (Butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, methanol, ethanol, Pro Ol, butanol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, monoethylene glycol, diethylene glycol, monopropylene glycol, monohexylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, methyl acetate And ethyl acetate, ethyl lactate, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol and the like.

The preferable solvent used for preparation of the liquid crystal aligning agent of this invention is obtained by combining 1 type (s) or 2 or more types of said organic solvent according to the presence or absence of use of the other polymer, and its kind, and it is at the following preferable solid content concentration It is a solvent in which each component contained in the liquid crystal aligning agent does not precipitate, and the surface tension of a liquid crystal aligning agent becomes the range of 25-40 mN / m.

Solid content concentration of the liquid crystal aligning agent of this invention, ie, the ratio which the weight of all components other than the solvent in a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., Preferably it is 1-10. It is the range of weight%. Although the liquid crystal aligning agent of this invention forms on the surface of a board | substrate and forms the coating film used as a liquid crystal aligning film, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes less and it is difficult to obtain a favorable liquid crystal aligning film. have. On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and it is difficult to obtain a favorable liquid crystal aligning film, and the viscosity of a liquid crystal aligning agent may increase, and coating characteristics may be lacking. The range of especially preferable solid content concentration changes with the method employ | adopted when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% is especially preferable. In the case of the printing method, the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is particularly preferably in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1-5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 0-40 degreeC.

<Formation method of liquid crystal aligning film>

The liquid crystal aligning agent of this invention can be used suitably in order to form the liquid crystal aligning film used for the liquid crystal aligning film, TN type, STN type, transverse electric field system (IPS type), or VA type liquid crystal display element by the photo-alignment method. . When the liquid crystal aligning agent of this invention is applied to the liquid crystal display element of a TN type, STN type, or a transverse electric field system, when it is especially applied to the liquid crystal display element of a transverse electric field system, the effect of this invention is exhibited to the maximum, desirable.

In order to form a liquid crystal aligning film using the liquid crystal aligning agent of this invention, it can be based on the method of apply | coating the liquid crystal aligning agent of this invention on a board | substrate, forming a coating film, and passing the process of irradiating a radiation to the said coating film.

Here, when applying the liquid crystal aligning agent of this invention to the liquid crystal display element of a TN type, STN type, or VA type, two board | substrates with which the patterned transparent conductive film is formed are paired, and each said transparent conductive film On the formation surface, the liquid crystal aligning agent of this invention is apply | coated and a coating film is formed. On the other hand, when the liquid crystal aligning agent of this invention is applied to the liquid crystal display element of a transverse electric field system, the board | substrate which has the electrode in which the transparent conductive film or the metal film was patterned in the shape of comb on one side, and the counter substrate in which the electrode is not formed Are made into a pair, the liquid crystal aligning agent of this invention is apply | coated to the formation surface of a comb-tooth shaped electrode, and the single side | surface of a counter substrate, respectively, and a coating film is formed.

In either case, as the substrate, for example, a glass such as float glass, glass such as soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, or a plastic such as polycarbonate can be used. As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ -SnO ₂ , an NESA (registered trademark) film made of SnO ₂ , and the like can be used. As said metal film, the film which consists of metals, such as chromium, can be used, for example. For the patterning of the transparent conductive film and the metal film, for example, a method of forming a pattern by a photo-etching method, a sputtering method or the like after forming a transparent conductive film without a pattern, or using a mask having a desired pattern when forming the transparent conductive film The method can be used.

In the application of the liquid crystal aligning agent on the substrate, in order to further improve the adhesion between the substrate or the conductive film or the electrode and the coating film, a functional silane compound, titanate, or the like may be applied on the substrate and the electrode in advance. .

Coating of the liquid crystal aligning agent on a substrate, Preferably, it can be performed by appropriate coating methods, such as an offset printing method, a spin coating method, a roll coater method, and an inkjet printing method, Then, pre-heating (prebaking) a coating surface Subsequently, a coating film is formed by baking (postbaking). Prebaking conditions are 0.1-5 minutes in 40-120 degreeC, for example, Preferably the postbaking conditions are 120-300 degreeC, More preferably, it is 5-200 minutes in 150-250 degreeC. More preferably, it is 10-100 minutes. The film thickness of the coating film after postbaking becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

The liquid crystal aligning ability is provided to the coating film formed in this way by irradiating linearly or partially polarized radiation or unpolarized radiation. Here, as the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an oblique direction to impart a pretilt angle, or may be performed in combination. In the case of irradiating non-polarized radiation, the direction of irradiation needs to be oblique.

As a light source to be used, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer-laser, etc. can be used, for example. Ultraviolet rays in the above preferred wavelength region can be obtained by means of using the light source together with a filter, a diffraction grating, or the like, for example.

As an irradiation amount of radiation, Preferably they are 1 J / m <2> or less than 10,000 J / m <2>, More preferably, it is 10-3,000 J / m <2>. Moreover, when providing liquid-crystal orientation capability by the photo-alignment method to the coating film formed from the liquid crystal aligning agent known conventionally, the irradiation amount of 10,000 J / m <2> or more was required. However, when the liquid crystal aligning agent of this invention is used, even if the irradiation amount at the time of the photo-alignment method is 3,000 J / m <2> or less, and 1,000 J / m <2> or less can provide favorable liquid-crystal orientation ability, productivity improvement and manufacture of a liquid crystal display element are possible. Contribute to cost reduction

<Method of Manufacturing Liquid Crystal Display Element>

The liquid crystal display element formed using the liquid crystal aligning agent of this invention can be manufactured as follows, for example.

First, a pair of board | substrates with which the liquid crystal aligning film was formed as mentioned above is prepared, and the liquid crystal cell of the structure by which the liquid crystal was clamped between this pair of board | substrates is manufactured. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method. First, two substrates are arranged to face each other via a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealing agent and partitioned by the substrate surface and the sealing agent. After the liquid crystal is injected and filled into the cell gap, the liquid crystal cell can be manufactured by sealing the injection hole.

The second method is a method called an ODF (One Drop Drop) method. An ultraviolet-ray curable sealing compound is apply | coated to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, and a liquid crystal aligning film opposes after dropping a liquid crystal in several places on the liquid crystal aligning film surface further. A liquid crystal cell can be manufactured by bonding another board | substrate so that a liquid crystal may be spread widely on a board | substrate, then irradiating an ultraviolet light to the whole surface of a board | substrate, and hardening a sealing compound.

Also in any case, it is preferable to remove the liquid orientation at the time of liquid crystal filling by heating gradually to the temperature which the liquid crystal which used the liquid crystal cell takes an isotropic phase, and then gradually cools to room temperature.

And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. Here, the desired liquid crystal display element can be obtained by adjusting the angle which the polarization direction of the irradiated linearly polarized radiation and the angle of each board | substrate and a polarizing plate in two board | substrates with a liquid crystal aligning film formed suitably.

As said sealing agent, the epoxy resin etc. which contain the aluminum oxide sphere as a spacer, a hardening | curing agent, etc. can be used, for example.

As said liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. can be used, for example. Nematic liquid crystals having positive dielectric anisotropy are preferable, and for example, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, and dioxane-based liquid crystals. Liquid crystals, bicyclooctane-based liquid crystals, kuban-based liquid crystals and the like are used. Moreover, for the said liquid crystal, For example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate;

Chiral agent sold as brand name "C-15", "CB-15" (above, Merck make);

Strong dielectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.

As a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate which consists of H film itself, etc. are mentioned. .

Since the liquid crystal display element of this invention manufactured in this way is excellent in the orientation regulation force of a liquid crystal molecule, it is excellent in display characteristics.

(Example)

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

The weight average molecular weight (Mw) in the following synthesis examples is the polystyrene conversion value measured by the gel permeation chromatography of the following conditions, respectively.

Column: Tosoh Corp., TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf / cm2

<Synthesis example of polyorganosiloxane having an epoxy group>

Synthesis Example ES-1

In 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 as a raw silane compound, 500 g of methyl isobutyl ketone as a solvent, and a catalyst 10.0 g of triethylamines were put, and it mixed at room temperature.

Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, mixing under reflux. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the water after washing became neutral, followed by distilling off the solvent and water under reduced pressure, thereby obtaining polyorganosiloxane (ES). -1) was obtained as a viscous transparent liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane having this epoxy group, a peak based on the epoxy group was obtained according to the theoretical strength near the chemical shift (δ) = 3.2 ppm, and no side reaction of the epoxy group occurred during the reaction. Was confirmed.

Mw of the polyorganosiloxane (ES-1) which has this epoxy group was 2,200, and the epoxy equivalent was 186g / mol.

Synthesis Example ES-2 and ES-3

Except having made input material as shown in Table 1, it carried out similarly to synthesis example ES-1, and obtained the polyorganosiloxane (ES-2) and (ES-3) which have an epoxy group as a viscous transparent liquid, respectively.

Table 1 shows the Mw and epoxy equivalents of the polyorganosiloxanes having these epoxy groups.

In addition, in Table 1, abbreviated-name of a raw material silane compound is the following meanings, respectively.

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

MTMS: Methyltrimethoxysilane

PTMS: Phenyltrimethoxysilane

<Synthesis example of compound (A)>

Scheme 1:

According to the above formula (A-1) (hereinafter referred to as "compound (A-1)") and the compound represented by formula (A-2) (hereinafter referred to as "compound (A-2)"). Synthesized

Synthesis Example A-1

A three-necked flask equipped with a reflux condenser and a calcium chloride tube was taken with NaH oil dispersion (amount equivalent to 1.2 equivalents in NaH), washed with hexane, and then anhydrous tetrahydrofuran (THF) was added thereto. . 1.1 equivalent of 2-hydroxybenzophenone dissolved in THF was dripped here, and it stirred at room temperature for 15 minutes. After the generation of hydrogen from the reaction system was completed, the calcium chloride tube was exchanged with an argon balloon, 1.0 equivalent of methyl 3- (bromomethyl) benzoate dissolved in THF was added dropwise, stirred at room temperature for 1 hour, and further 2 hours. Reflux was performed. Then, after cooling to room temperature, THF was removed by the evaporator. Water and ethyl acetate were added to this residue, and the organic layer was separated. Subsequently, in order to remove unreacted 2-hydroxybenzophenone, the organic layer was wash | cleaned with NaOH aqueous solution of 1 mol / L of concentration. The organic layer was further washed sequentially with water and saturated brine, dried over anhydrous magnesium sulfate, and then the residue obtained by removing the solvent under reduced pressure was mixed with silica gel column chromatography (developing solvent: hexane and ethyl acetate mixed). Separation with a solvent (hexane: ethyl acetate = 10: 1 (volume ratio)), followed by removal of the solvent from the fraction, yielded intermediate 3-((2-benzoylphenoxy) methyl) benzoate (compound (A-1a)). ) Was obtained (yield 60%).

Subsequently, the compound (A-1a) is dissolved in a mixed solvent (methanol: THF = 10: 1 (volume ratio)) consisting of methanol and THF to prepare a solution, and the potassium hydroxide equivalent to an aqueous potassium hydroxide solution having a concentration of 2 mol / L is added thereto. An amount equivalent to 2 equivalents was added and the reaction was carried out at 50 ° C. overnight under stirring. After completion of the reaction, ether and water were added to the reaction mixture to separate an aqueous phase. After hydrochloric acid was added to the aqueous phase to make it acidic, the mixture was washed sequentially with water and saturated brine, and then the solvent was distilled off under reduced pressure to obtain a mixed solvent consisting of THF and hexane (THF: hexane = 10: 1 (volume ratio). By recrystallization from)), the compound (A-1) was obtained (yield 83%).

Synthesis Example A-2

In Synthesis Example A-1, 1.0 equivalent of 4- (bromomethyl) benzoate methyl instead of 3- (bromomethyl) benzoate was used in the same manner as in Synthesis Example A-1, except that 4- ( (2-Benzoylphenoxy) methyl) methylbenzoate (Compound (A-2a)) was obtained in a yield of 55% to give Compound (A-2) (yield 82%).

<Comparative synthesis example of carboxylic acid>

Synthesis Example R-1

Scheme 2 below

According to this, comparative carbonic acid (R-1) was synthesized.

11.21 g of 4-hydroxychalcone, 8.35 g of ethyl bromoacetate, 13.8 g of potassium carbonate, and 100 mL of dimethylacetamide were put into a 200 mL three-neck flask, and the reaction was carried out at 120 ° C. for 7 hours with stirring. After the reaction was completed, the reaction solution was cooled at room temperature, and then 100 mL of ethyl acetate was added. After washing the organic layer with water, the solid obtained by removing the solvent under reduced pressure was recrystallized from a mixed solvent consisting of ethanol and water (ethanol: water = 4: 1 (volume ratio)) to give an intermediate compound (R-1a) 11.4. g was obtained.

Subsequently, 6.2 g of said compound (R-1a), 2 g of sodium hydroxide, 200 mL of ethanol, and 50 mL of water were put into the 500 mL three necked flask equipped with a cooling tube, and reaction was performed under reflux for 3 hours. After completion | finish of reaction, after cooling the reaction mixture, it made acidic by adding diluted hydrochloric acid, 500 mL of ethyl acetate was added and liquid-liquid extraction was performed. After washing the obtained organic layer with water, 4.1 g of compounds (R-1) were obtained by removing a solvent under reduced pressure.

<Synthesis example of radiation sensitive polyorganosiloxane>

Synthesis Example S-1

9.3 g of polyorganosiloxane (ES-1) having an epoxy group obtained in Synthesis Example ES-1, 26 g of methyl isobutyl ketone, and carbonic acid (A) in a 100 mL three-necked flask were obtained in Synthesis Example A-1. 7.64 g of Compound (A-1) and 0.10 g of UCAT # 18X (the quaternary amine salt manufactured by San Apro Co., Ltd.) were added thereto, and the reaction was performed at 80 ° C under stirring for 12 hours. After completion of the reaction, methanol was added to the reaction mixture to recover the precipitate. The solution obtained by dissolving this in ethyl acetate was washed with water three times, and then the solvent was distilled off to remove radiation-sensitive polyorganosiloxane (S-1). 10 g was obtained as a white powder. The weight average molecular weight (Mw) of the radiation sensitive polyorganosiloxane (S-1) was 5,600.

Synthesis Example S-2 and S-3

In the said Synthesis Example S-1, the radiation sensitive property was carried out similarly to the Synthesis Example S-1 except having made the kind and usage-amount of the polyorganosiloxane and carbonic acid (A) which have an epoxy group as Table 2, respectively. Polyorganosiloxanes (S-2) and (S-3) were obtained, respectively. The yield and weight average molecular weight (Mw) of these radiation-sensitive polyorganosiloxanes were also shown in Table 2, respectively.

<Comparative synthesis example of radiation sensitive polyorganosiloxane>

Synthesis Example RS-1

In the said synthesis example S-1, the compound (R-1) obtained by the said synthesis example R-1 instead of compound (A-1) was made into 11.4 g of polyorganosiloxane (ES-1) which has an epoxy group. ) Was used in the same manner as in Synthesis Example S-1 to obtain 9.1 g of radiation-sensitive polyorganosiloxane (RS-1). Table 2 shows the weight average molecular weight (Mw) of the radiation-sensitive polyorganosiloxane (RS-1).

<Synthesis example of other polymer>

[Synthesis example of polyamic acid]

Synthesis Example PA-1

19.61 g (0.1 mole) of cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mole) of 4,4'-diamino-2,2'-dimethylbiphenyl are dissolved in 367.6 g of N-methyl-2-pyrrolidone. And reaction was performed at room temperature for 6 hours. The reaction mixture was then poured into excess methanol to precipitate the reaction product. The precipitate was recovered, washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 35 g of polyamic acid (PA-1).

Synthesis Example PA-2

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g (0.1 mol) of cyclohexanebis (methylamine) were dissolved in 329.3 g of N-methyl-2-pyrrolidone, and 60 The reaction was carried out at 占 폚 for 6 hours. The reaction mixture was then poured into excess methanol to precipitate the reaction product. 32g of polyamic acid (PA-2) was obtained by wash | cleaning a deposit with methanol and drying at 40 degreeC under reduced pressure for 15 hours.

This polyamic acid (PA-2) provided the one part for preparation of a liquid crystal aligning agent in the Example mentioned later, and provided the remainder for the synthesis | combination of the following polyimide.

Synthesis Example of Polyimide

Synthesis Example PI-1

17.5 g of polyamic acid (PA-2) obtained in Synthesis Example PA-2 was taken, and 232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine, and 4.9 g of acetic anhydride were added thereto, and the mixture was stirred at 120 DEG C for 4 hours. The imidation reaction was performed. The obtained reaction mixture was poured into a large excess of methanol to precipitate the reaction product. 15g of polyimide (PI-1) was obtained by wash | cleaning a deposit with methanol and drying under reduced pressure for 15 hours.

Example 1

<Preparation of liquid crystal aligning agent>

100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in Example S-1 and 1,000 parts by weight of polyamic acid (PA-1) obtained in Synthesis Example PA-1 as the other polymer, N-methyl- It was dissolved in a mixed solvent consisting of 2-pyrrolidone and butyl cellosolve (N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio)) to give a solution having a solid concentration of 3.0% by weight. did. The liquid crystal aligning agent was prepared by filtering this solution with the filter of 1 micrometer of pore diameters.

<Manufacture of Liquid Crystal Display Element>

The liquid crystal aligning agent prepared above was apply | coated using the spinner to the electrode formation surface of the glass substrate which has the metal electrode made from chrome patterned in comb shape, and the opposite glass substrate in which the electrode is not formed, respectively, After 1 minute prebaking on a hot plate, the inside of the tube was postbaked at 200 ° C. for 1 hour in an oven substituted with nitrogen to form a coating film having a film thickness of 0.1 μm. Subsequently, 600 J / m <2> of polarization ultraviolet-rays containing 313 nm bright line were irradiated to this coating film surface in the normal line direction of a board | substrate using a Hg-Xe lamp and a glan tailor prism, respectively, and the pair of board | substrates which have a liquid crystal aligning film was obtained.

After screen-coating an aluminum oxide sphere containing epoxy resin adhesive of 5.5 micrometers in diameter on the outer periphery of the surface in which the liquid crystal aligning film of the board | substrate which has a chromium metal electrode was formed among the said pair of board | substrates, the liquid crystal of a pair of board | substrate The oriented film surface was faced and crimped | bonded, and it heated at 150 degreeC for 1 hour, and thermosetting the adhesive agent. Next, after filling the liquid crystal made by Merck and MLC-7028 in the clearance gap between board | substrates from a liquid crystal injection hole, the liquid crystal injection hole was sealed with the epoxy adhesive. In addition, in order to remove the flow orientation at the time of liquid crystal injection, after heating at 150 degreeC, it cooled gradually to room temperature. Next, the liquid crystal display element of the transverse electric field system was produced by bonding the polarizing plate to the outer both surfaces of a board | substrate so that the polarization directions may orthogonally cross, and orthogonal to the projection direction to the board surface of the optical axis of the ultraviolet-ray of a liquid crystal aligning film. .

<Evaluation of Liquid Crystal Display Element>

This liquid crystal display device was evaluated by the following method. The evaluation results are shown in Table 3.

(1) Evaluation of liquid crystal alignment

When the above-mentioned liquid crystal display element WHEREIN: The presence or absence of the abnormal domain in the change of the contrast at the time of turning ON / OFF (deactivation) of the voltage of 5V is observed with an optical microscope, and the abnormal domain was not observed. Was made into liquid crystal orientation "quantity", and the case where an abnormal domain was observed was evaluated as liquid crystal orientation "poor".

(2) evaluation of voltage holding ratio

After applying the voltage of 5V to 60 microseconds of application time and the span of 167 milliseconds to the liquid crystal display element manufactured above, the voltage retention rate after 167 milliseconds after application | release cancellation was measured. As a measuring device, VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

Examples 2-8 and Comparative Example 1

In the said Example 1, the liquid crystal aligning agent was prepared like Example 1 except having changed the kind of radiation sensitive polyorganosiloxane, and the kind and quantity of other polymer as shown in Table 3, respectively. The liquid crystal display element of the transverse electric field system was produced and evaluated. The evaluation results are shown in Table 3.

In addition, in the comparative example 1, the amount of polarized ultraviolet irradiation at the time of liquid crystal display element manufacture was 1,000 J / m <2>.

Claims (7)

Formula (A '):

The radiation sensitive polymer which has a structure represented by this is contained, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 1,
Liquid crystal aligning agent whose said radiation sensitive polymer is a radiation sensitive polyorganosiloxane which has a structure represented by said formula (A '). The method of claim 2,
The radiation-sensitive polyorganosiloxane,
Polyorganosiloxane which has an epoxy group, the compound represented by following formula (A),
Liquid crystal aligning agent which is a reaction product of:

[In Formula (A), R is respectively independently a C1-C4 alkyl group, a halogen atom, or a cyano group,
n1 is an integer of 0-3, n2 is an integer of 0-4,
R <^1> is group represented by following formula (R-1) or (R-2), R <^2> and R <^3> is group represented by following formula (R-3), respectively, and exists in a formula (A) One of Z is a carboxyl group and the other is a hydrogen atom:

^* -R ⁵ -Z (R-2)
^* -X ² -R ⁶ -Z (R-3)
(Formula (R-1) of X ¹ is a single bond, -O- ^+, -COO- or -OCO- ^{+ + (single,} combined hand R ⁴ cheukim tagged "+"), R ⁴ represents a single bond Is a methylene group or an alkylene group having 2 to 5 carbon atoms, R is an alkyl group having 1 to 4 carbon atoms, a halogen atom or a cyano group, n3 is an integer of 0 to 4,
R <^5> in Formula (R-2) is a methylene group or a C2-C5 alkylene group,
Formula (R-3) of X ² is a single bond, -O- ^+, -COO- or -OCO- ^{+ + (Note,} however, that this combination hand tagged "+" R ⁶ cheukim) and, R ⁶ represents a single bond, A methylene group or an alkylene group having 2 to 5 carbon atoms,
"*" In formula (R-1)? (R-3) represents a bonding hand, respectively). 4. The method according to any one of claims 1 to 3,
Furthermore, the liquid crystal aligning agent containing at least 1 sort (s) of polymer chosen from the group which consists of a polyamic acid and a polyimide, but this polymer does not have a structure represented by said Formula (A '). 4. The method according to any one of claims 1 to 3,
Furthermore, the liquid crystal aligning agent containing polyorganosiloxane (However, this polyorganosiloxane does not have a structure represented by said formula (A ').). A method of forming a liquid crystal aligning film, comprising: applying a liquid crystal aligning agent according to any one of claims 1 to 3 on a substrate to form a coating film and irradiating the coating film with radiation. The liquid crystal aligning film formed from the liquid crystal aligning agent of any one of Claims 1-3 is provided. The liquid crystal display element characterized by the above-mentioned.