JP5354161B2 - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

PURPOSE: A liquid crystal alignment material is provided to ensure good liquid crystal alignment property and excellent electrical property, and to form a liquid crystal alignment film with excellent voltage holding rate and afterimage property. CONSTITUTION: A liquid crystal alignment material comprises one or more kinds selected from the group consisting of polyorganosiloxane having a repeating unit represented by chemical formula 1, hydrolysate thereof, and condensate of the hydrolysate. In chemical formula 1, R^I is a group having a steroid skeleton or a group represented by chemical formula 1a; Z is a sulfur atom or oxygen atom; R^II is a hydrogen atom or methyl group; A^I is a methylene group or C2-10 alkylene group; Y^I is a hydroxyl group, C1-10 alkoxyl group, C1-20 alkyl group or C6-20 aryl group.

Description

  The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal aligning agent that can provide a liquid crystal alignment film having excellent liquid crystal alignment properties and electrical characteristics, and excellent printability, and a liquid crystal display element excellent in display quality.

Conventionally, as a liquid crystal display element, a liquid crystal alignment film is formed on the surface of a substrate on which a transparent conductive film is provided to form a substrate for a liquid crystal display element. A nematic liquid crystal layer having a directivity is formed into a sandwich cell, and the long axis of the liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other substrate. There are TN type liquid crystal display elements having a (Nematic) liquid crystal cell, VA (Vertical Alignment) type liquid crystal display elements using nematic liquid crystal having negative dielectric illegality and having less viewing angle dependency than TN type liquid crystal display elements. It is known (see Patent Documents 1 to 6 and Non-Patent Documents 1 to 4).
In such a liquid crystal display element, the alignment of liquid crystal molecules is controlled by a liquid crystal alignment film mainly composed of a polymer such as polyamic acid or polyimide. Such a liquid crystal alignment film is required to have good liquid crystal alignment performance, high voltage holding ratio, and performance such as no afterimage.
By the way, recent liquid crystal display elements are mainly used for television, and high-speed liquid crystal is used. However, it is known that when a conventionally known liquid crystal alignment film is applied to a liquid crystal with high response speed, it is known that the electrical characteristics such as voltage holding ratio and afterimage characteristics are insufficient. For this reason, there is a demand for a liquid crystal alignment film that is further excellent in electrical characteristics as compared with conventional ones, but such a liquid crystal alignment film is not yet known.
JP-A-4-153622 Japanese Patent Laid-Open No. 62-165628 JP 2002-327058 A JP-A-6-222366 JP-A-6-281937 JP-A-5-107544 “Liquid Crystal” vol. 3, no. 2, 117 (1999) “Liquid Crystal” vol. 3, no. 4, 272 (1999) “Jpn Appl. Phys.” Vol. 36, 428 (1997) “SID '94 Digest” 927 (1997) Chemical Reviews, Volume 95, 1409 (1995)

The present invention has been made in view of the above circumstances, and an object thereof is a liquid crystal aligning agent that provides a liquid crystal alignment film that exhibits excellent liquid crystal alignment performance and excellent electrical characteristics, and particularly excellent in voltage holding ratio and afterimage characteristics. Another object is to provide a liquid crystal display element having excellent display quality.
Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are as follows.
Following formula (1)

(In the formula (1), R ^I represents a group having a steroid skeleton or the following formula (1A)

(In Formula (1A), R is an alkyl group which may be substituted with fluorine having 4 to 20 carbon atoms, A ^II is a cyclohexylene ring or a phenylene group, and X is a single bond, an oxygen atom or a sulfur atom. , -COO- or -OCO-, a is an integer of 0 to 3, and when a plurality of A ^II are present, they may be the same or different.
Z is a sulfur atom or an oxygen atom, R ^II is a hydrogen atom or a methyl group, A ^I is a methylene group or an alkylene group having 2 to 10 carbon atoms, and Y ^I is a hydroxyl group , An alkoxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. )
It is achieved by a liquid crystal aligning agent comprising at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the formula:
The above objects and advantages of the present invention are secondly,
This is achieved by a liquid crystal display element comprising a liquid crystal alignment film formed from the above liquid crystal aligning agent.

  The liquid crystal aligning agent of the present invention is excellent in liquid crystal aligning performance and exhibits excellent electrical characteristics that surpass conventionally known liquid crystal aligning films, and provides a liquid crystal aligning film particularly excellent in voltage holding ratio and afterimage characteristics. The liquid crystal display element of the present invention comprising the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention is excellent in display quality and high-speed response, and various devices such as desk calculators, watches, table clocks, counting display boards, word processors. It can be suitably applied to personal computers, liquid crystal televisions, and the like.

The liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (1), a hydrolyzate thereof and a condensate of the hydrolyzate (hereinafter referred to as “ Polyorganosiloxane (1) ").
<Polyorganosiloxane (1)>
Examples of the group having a steroid skeleton in ^{R I} in the above formula (1) is preferably a 17 to 30 carbon atoms. Specific examples thereof include, for example cholestane-3-yl group, cholest-5-en-3-yl Group, cholesta-24-en-3-yl group, cholesta-5,24-dien-3-yl group, lanostane-3-yl group and the like.
When R ^I is a group represented by the above formula (1A), examples of R in the above formula (1A) include n-dodecyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl Group, n-nonadecyl group, n-eicosyl group, 4,4,4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl group and the like. The cyclohexylene group and the phenylene group of A ^II in the above formula (1A) are each preferably a 1,4-cyclohexylene group or a 1,4-phenylene group.
The ^{A I} in the above formula (1), such as methylene group, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene group, 1,6-hexylene originally And so on.
Examples of the alkoxy group having 1 to 10 carbon atoms of Y ^I in the above formula (1) include a methoxyl group and an ethoxyl group;
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group and an ethyl group;
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a tolyl group.
In addition to the structure represented by the above formula (1), the polyorganosiloxane (1) is further represented by the following formula (2)

(In the formula (2), R ^II , A ^I and Y ^I have the same meanings as in the above formula (1).)
It is preferable that it is at least 1 sort (s) selected from the group which consists of polyorganosiloxane which has a repeating unit represented by these, its hydrolyzate, and the condensate of a hydrolyzate. In this case, the (meth) acrylic equivalent of the polyorganosiloxane (1) is preferably 150 to 10,000 g / mol, and more preferably 300 to 3,000 g / mol.
The polyorganosiloxane (1) has a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography (GPC), preferably 1,000 to 100,000, more preferably 2,000 to 50,000. is there. Use of the polyorganosiloxane (1) within this range is preferable because the storage stability and electrical properties of the liquid crystal aligning agent are further improved.
The structure of the polyorganosiloxane (1) is preferably a random structure, a ladder structure, or a cage structure. Since the polyorganosiloxane (1) having such a structure has a small content ratio of silanol groups, the condensation reaction between the silanol groups is suppressed, and the liquid crystal aligning agent of the present invention has other polymers described later. When it is contained, the condensation reaction between the silanol group and the other polymer is suppressed, so that the storage stability is excellent, which is preferable.
[Synthesis of Polyorganosiloxane (1)]
The polyorganosiloxane (1) in the present invention is, for example, at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (2), a hydrolyzate thereof, and a condensate of the hydrolyzate. (Hereinafter referred to as “polyorganosiloxane (2) having a (meth) acryloyl group”) and the following formula (3)

(In the formula (3), R ^I and Z have the same meanings as in the above formula (1).)
It can obtain by making it react with the compound (henceforth "compound (3)") represented by these.
-Polyorganosiloxane having (meth) acryloyl group (2)-
The (meth) acryl equivalent in the polyorganosiloxane (2) having the (meth) acryloyl group is preferably 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol.
For the polyorganosiloxane (2) having a (meth) acryloyl group, the polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography (GPC) is preferably 500 to 100,000, and preferably 1,000 to It is more preferably 10,000, and further preferably 1,500 to 5,000.
Such a polyorganosiloxane (2) having a (meth) acryloyl group is preferably a silane compound having a (meth) acryloyl group or a mixture of a silane compound having a (meth) acryloyl group and another silane compound. Can be synthesized by hydrolysis or hydrolysis / condensation in the presence of a suitable organic solvent, water and catalyst.
Examples of the silane compound having the (meth) acryloyl group include the following formula (2-1):

(In the formula ^{(2-1), R II} and ^{A I} are each the same as in the formula (2), ^{B I} is a hydroxyl group or an alkoxyl group having 1 to 10 carbon ^{atoms, B II} is carbon An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and b is an integer of 1 to 3)
The compound represented by these can be mentioned.
In the above formula (2-1), b is preferably 2 or 3, and specific examples of those in which b is 2 include 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Acryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and the like;
As specific examples of those in which b is 3, for example, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Can be mentioned.
In the above formula (2-1), a compound in which b is 3 is more preferable.

  Examples of the other silane compounds include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, Tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, trimethoxy Silane, 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, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) ethylto Methoxysilane, 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) ethyltrimethoxy Silane, 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, hydroxyethyltrimethoxy Silane, hydroxymethylto -n- propoxysilane, hydroxymethyl tri -i- propoxysilane, hydroxymethyl tri -n- butoxysilane, hydroxymethyl tri -sec- butoxysilane,

3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 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, allyltrichlorosilane, allyltrimethoxysilane, allylto Ethoxysilane, 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- -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-n-octyl) ethyl] diemethoxysilane, (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-butoxy Silane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (methyl ) (3-mercaptopropyl) dichlorosilane,

(Methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) diethoxysilane, (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-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di -N-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichloro Silane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxy Silane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, Bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxyto Methylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) In addition to silane compounds having one silicon atom such as (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl) diphenylsilane,

Product names such as KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X -21-5848, 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-41-10 3, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (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 Toray Dow Corning Co., Ltd.); FZ3711, FZ3722 (above, manufactured by Nihon Unicar Co., Ltd.); DMS-S1 , 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, XMS-5025 (above, manufactured by Chisso Corporation); methyl silicate MS51, methyl silicate MS56 (above, manufactured by Mitsubishi Chemical Corporation); ethyl silicate 28, ethyl silicate 40, Examples thereof include partial condensates such as ethyl silicate 48 (manufactured by Colcoat Co., Ltd.); GR100, GR650, GR908, GR950 (manufactured by Showa Denko Co., Ltd.).

Among these other silane compounds, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, Tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethyl Kishishiran, phenyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane are preferred.
In synthesizing the polyorganosiloxane (2) having a (meth) acryloyl group, the use ratio of the silane compound having a (meth) acryloyl group and another silane compound is determined based on the (meth) acryl equivalent of the resulting polyorganosiloxane. Is preferably adjusted and set so as to be within the above-mentioned preferable range.

Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane (2) having (meth) acryloyl include hydrocarbons, ketones, esters, ethers, and alcohols.
Examples of the hydrocarbon include toluene and xylene;
Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone;
Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate;
Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;
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, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl. Examples include ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like. Of these, water-insoluble ones are preferred.
These organic solvents can be used alone or in admixture of two or more.
The amount of the organic solvent used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total silane compounds.
The amount of water used in synthesizing the polyorganosiloxane (2) having (meth) acryloyl is preferably 0.5 to 100 times mol, more preferably 1 to 30 times mol, based on the total silane compound. .

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. can be used, for example.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.
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;
A quaternary organic amine such as tetramethylammonium hydroxide can be used. Among these organic bases, there are tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide. preferable.

As a catalyst for synthesizing the polyorganosiloxane (2) having a (meth) acryloyl group, an alkali metal compound or an organic base is preferable. The liquid crystal aligning agent of the present invention containing a reaction product of a polyorganosiloxane (2) having a (meth) acryloyl group synthesized using an alkali metal compound or an organic base as a catalyst and the compound (3) has storage stability. It is convenient because it is extremely excellent. The reason for this is that, as pointed out in Non-Patent Document 5 (Chemical Reviews, Vol. 95, 1409 (1995)), when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis / condensation reaction, a random structure, a ladder It is assumed that a polyorganosiloxane having a mold structure or a cage structure and having a low silanol group content is obtained. Since the content of silanol groups is small, the condensation reaction between silanol groups is suppressed, and when the liquid crystal aligning agent of the present invention contains other polymers described later, silanol groups and other polymers Since the condensation reaction is suppressed, it is presumed that the storage stability is excellent.
As the catalyst, an organic base is particularly preferable. The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate. For example, the amount is preferably 0.01 to 3 moles relative to the total silane compound, More preferably, it is 0.05-1 times mole.

The hydrolysis / condensation reaction when synthesizing the polyorganosiloxane (2) having a (meth) acryloyl group involves dissolving a silane compound having a (meth) acryloyl group and, if necessary, another silane compound in an organic solvent. The solution is preferably mixed with an organic base and water and heated by, for example, an oil bath.
During the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixed solution may be stirred or refluxed.
After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by weight is preferred because the washing operation is facilitated. Washing is carried out until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with an appropriate desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the solvent is removed to remove the solvent. A polyorganosiloxane (2) having a (meth) acryloyl group can be obtained.
In the present invention, a commercially available polyorganosiloxane having a (meth) acryloyl group may be used. As such a commercial item, AC-SQ, MC-SQ, etc. (above, Toagosei Co., Ltd. product) can be mentioned, for example.

-Compound (3)-
The compound (3) is a compound in which R ^I is a group having a steroid skeleton in the above formula (3) or the following formula (3A)

(In the formula (3A), R, X, A ^II and a have the same meanings as in the above formula (1A), and Z has the same meaning as in the above formula (1).)
It is a compound represented by these. Group having a steroid skeleton of the R ^I are the same as for the group having a steroid skeleton in R ^I in formula (1A).
Examples of the compound (3) include the following formulas (3-1) to (3-23)

(In the above formula, m is an integer of 4 to 20, k is an integer of 1 to 20, n is an integer of 0 to 6, provided that k + n is an integer of 4 to 20.)
And the like, and the like.
[Synthesis of Polyorganosiloxane (1)]
The polyorganosiloxane (1) in the present invention is an addition reaction between the polyorganosiloxane (2) having the (meth) acryloyl group and the compound (3), preferably in an organic solvent, preferably in the presence of a catalyst. It can be synthesized by performing below. This addition reaction is generally called Michael addition.
In the above addition reaction, the proportion of compound (3) used should be appropriately set according to the content of the desired (meth) acryloyl group in polyorganosiloxane (1) and the reactivity of the addition reaction. For example, with respect to 1 mol of the (meth) acryloyl group that the polyorganosiloxane (2) having a (meth) acryloyl group has, it is preferably 0.01 to 2.0 mol, more preferably 0.1 to 1. mol. The amount is 0 mol, and more preferably 0.2 to 0.8 mol.
The above addition reaction can be performed in the presence of an organic solvent, if necessary. Examples of such organic solvents include hydrocarbon compounds, ether compounds, ester compounds, amide compounds, and nitrile compounds. Of these, ether compounds, ester compounds, and nitrile compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of the products. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 5 to 100% by weight.
In the above addition reaction, a catalyst can be added as necessary. Examples of such catalysts include tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, potassium carbonate, sodium hydroxide, water An alkali metal compound such as potassium oxide can be used. The use ratio of the catalyst is preferably 0.001 to 1.5 mol, and more preferably 0.1 to 1.1 mol, relative to 1 mol of the compound (3).
The reaction temperature is preferably 0 to 200 ° C, more preferably 10 to 100 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 10 hours.
The addition reaction between the polyorganosiloxane (2) having a (meth) acryloyl group for synthesizing the polyorganosiloxane (1) and the compound (3) is a method in which a part of the compound (3) can be added by Michael. It may be carried out by replacing with at least one compound selected from monohydric alcohol and other monovalent thiols. Examples of such compounds include thioglycolic acid and mercaptopropionic acid. The use ratio of at least one compound selected from other monohydric alcohols and other monovalent thiols is 50 mol% or less based on the total of compound (3) and other monohydric alcohols and other monovalent thiols. It is preferable that

<Other ingredients>
Although the liquid crystal aligning agent of this invention contains the above polyorganosiloxane (1) as an essential component, in addition to this, unless the effect of this invention is impaired, it contains the other component. Also good. Examples of such other components include polymers other than polyorganosiloxane (1) (hereinafter referred to as “other polymers”), compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compounds”). And a functional silane compound, a surfactant, a radical polymerization initiator, and the like.
[Other polymers]
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 property of the liquid crystal aligning film obtained. Examples of such other polymers include at least one polymer selected from the group consisting of polyamic acid and polyimide, and the following formula (S):

(In the formula ^{(S), X II} is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group or an aryl group having 6 to 20 carbon atoms having 1 to 6 carbon ^{atoms, Y II} is a hydroxyl group or a carbon (It is an alkoxyl group of formula 1 to 10.)
At least one selected from the group consisting of polysiloxanes, hydrolysates thereof and condensates of hydrolysates (hereinafter referred to as “other polysiloxanes”), polyamic acid esters, polyesters, polyamides, celluloses Derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like can be mentioned.

-Polyamic acid-
The polyamic acid can be obtained by reacting tetracarboxylic dianhydride and diamine.
Examples of tetracarboxylic dianhydrides that can be used for the synthesis of polyamic acid include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2-dimethyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxyl Lopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic 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- 5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -7-methyl-5- (tetrahydro-2 , 5-Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-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, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl- 5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, -C] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2,2,2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 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 anhydride, 3,5,6-tri Carboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone The following formulas (TI) and (T-II)

(Wherein R ¹ and R ³ are each a divalent organic group having an aromatic ring, R ² and R ⁴ are each a hydrogen atom or an alkyl group, and a plurality of R ² and R ^{4 are present.} May be the same or different.)
An aliphatic or alicyclic tetracarboxylic dianhydride such as a compound represented by each of the following:
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicar Boxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 , 2 ′, 3,3′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis ( Triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis ( Anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate) Retate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis ( Anhydrotrimellitate), the following formulas (T-1) to (T-4)

And aromatic tetracarboxylic dianhydrides such as compounds represented by each of the above. These may be used alone or in combination of two or more.
Among tetracarboxylic dianhydrides used in the synthesis of polyamic acid, among the above, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic 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, 1,3,3a, 4 , 5,9b- Xahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2,2,2] -oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, 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 anhydride, 3,5,6-tricarboxy- 2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyro Mellitic acid dianhydride, 3,3 ', 4,4'-benzoph Non-tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 1,4,5 , 8-Naphthalenetetracarboxylic dianhydride, among the compounds represented by the above formula (TI), the following formulas (T-5) to (T-7)

And the following formula (T-8) among the compounds represented by formula (T-II):

It is preferable to use at least one selected from the group consisting of the compounds represented by the above from the viewpoint that the liquid crystal alignment film to be formed can exhibit better liquid crystal alignment.
Particularly preferably, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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-tricarbo Shi-carboxylate norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10- tetraone , Pyromellitic dianhydride and at least one selected from the group consisting of compounds represented by the above formula (T-5).

  Examples of the diamine used for the synthesis of the polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4 , 4′-diaminodiphenylsulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditri Fluoromethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophen ) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4 Aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 1,4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′- Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoro) Oromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, the following formulas (D-1) to (D-5)

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5.)
An aromatic diamine such as a compound represented by each of the following:
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 , 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4 Aliphatic or cycloaliphatic diamines such as 1,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane;
2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4 -Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3 , 5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl -S-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6 Phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl -3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-di (4-aminophenyl) -benzidine, the following formula (DI)

(In the formula (DI), R ⁵ is a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ¹ is a divalent organic group. R ⁶ is an alkyl group having 1 to 4 carbon atoms, and a1 is an integer of 0 to 3.)
A compound represented by formula (D-II):

(In Formula (D-II), R ⁷ is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ² is a divalent organic group, respectively. A plurality of X ² may be the same or different, R ⁸ is an alkyl group having 1 to 4 carbon atoms, and a2 is an integer of 0 to 3 respectively. is there.)
A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in a molecule such as a compound represented by:
The following formula (D-III)

(In the formula (D-III), R ⁹ represents —O—, —COO— ^* , —OCO— ^* , —NHCO— ^* , —CONH— ^* (in the above, the bond indicated by “*” is R ¹⁰ is bonded to R ¹⁰ ) or —CO—, and R ¹⁰ is a monovalent organic group or carbon having a skeleton or group selected from a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group An alkyl group having 6 to 30 carbon atoms, R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a3 is an integer of 0 to 3.)
Monosubstituted phenylenediamines such as compounds represented by:
The following formula (D-IV)

(In the formula (D-IV), each R ¹² is a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ¹² may be the same or different, and p is each 1 is an integer of 1 to 3, and q is an integer of 1 to 20.)
And diaminoorganosiloxanes such as compounds represented by the formula: These diamines can be used alone or in combination of two or more.
The benzene ring of the aromatic diamine may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). In the above formulas (DI), (D-II) and (D-III), R ⁶ , R ⁸ and R ¹¹ are each preferably a methyl group, and a1, a2 and a3 are each 0 Or it is preferable that it is 1, and it is more preferable that it is 0.
Specific examples of the group having a steroid skeleton of R ^{10 in} the above formula (D-III) include, for example, cholestane-3-yl group, cholesta-5-en-3-yl group, and cholesta-24-en-3-yl. Group, cholesta-5,24-dien-3-yl group, lanostane-3-yl group and the like.

  Among the above, diamines used for the synthesis of polyamic acid are p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, and 2,2′-dimethyl. -4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 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, 1,4-cyclohexanediamine, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, compounds represented by the above formulas (D-1) to (D-5), 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′-di (4-aminophenyl) -benzidine, represented by the above formula (DI) Formula of that compound (D-6)

Of the compounds represented by formula (D-II), the following formula (D-7)

Of the compounds represented by formula (D-III), dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy- 2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, the following formula (D-8) ~ (D-16)

And at least one selected from the group consisting of 1,3-bis (3-aminopropyl) -tetramethyldisiloxane among the compounds represented by each of the above and the compounds represented by the above formula (D-IV) It is preferable that it is included.
The proportion of tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is 0.2 to 0.2 acid anhydride groups of tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of the diamine. A ratio of 2 equivalents is preferable, and a ratio of this value of 0.3 to 1.2 equivalents is more preferable.
The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 to 150 ° C., more preferably 0 to 100 ° C., preferably 1 to 48 hours, more preferably 2 to 10 hours. Is called. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide; phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol Can do. The amount of the organic solvent used (a: when the organic solvent and the poor solvent described later are used in combination) means the total amount of tetracarboxylic dianhydride and diamine compound (b). The amount is preferably 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution.

For the organic solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc., which are generally believed to be poor solvents for polyamic acid, may be used in combination as long as the resulting polyamic acid does not precipitate. it can. Specific examples of such poor solvents include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, and methyl ethyl ketone. , Methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether Ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, Lenglycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4 -Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoamylisobutyrate, diisopentyl ether and the like.
When a polyamic acid is used in combination with a poor solvent as described above in the organic solvent, the use ratio can be appropriately set within a range in which the produced polyamic acid does not precipitate, but preferably 50% by weight of the total solvent. % Or less, more preferably 20% by weight or less.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. Polyamic acid can be isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. it can. Further, the polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the step of distilling under reduced pressure with an evaporator once or several times.

-Polyimide-
The polyimide can be synthesized by dehydrating and ring-closing and imidizing polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine.
Examples of the tetracarboxylic dianhydride used for the synthesis of the polyimide include the same compounds as the tetracarboxylic dianhydride used for the synthesis of the polyamic acid described above.
As a tetracarboxylic dianhydride used for the synthesis | combination of the polyimide which can be used for this invention, it is preferable to use the tetracarboxylic dianhydride containing an alicyclic tetracarboxylic dianhydride. Particularly preferred alicyclic tetracarboxylic dianhydrides include 2,3,5-tricarboxycyclopentylacetic acid 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 anhydride, 3,5,6 -Tricarboxy-2-carbox Norbornane -2: 3,5: 6-dianhydride or 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10- tetraone and the like.
In synthesizing the polyimide, an alicyclic tetracarboxylic dianhydride and other tetracarboxylic dianhydrides may be used in combination. In this case, the ratio of the alicyclic tetracarboxylic dianhydride in the total tetracarboxylic dianhydrides is preferably 10 mol% or more, more preferably 50 mol% or more.

Examples of the diamine used for the synthesis of the polyimide include the same compounds as the diamine used for the synthesis of the polyamic acid described above.
As the diamine used for the synthesis of the polyimide of the present invention, it is preferable to use a diamine containing a diamine represented by the above formula (D-III). Preferable specific examples include dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy- among the compounds represented by the formula (D-III). 2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene and the above formula (D-8) The compound represented by each of-(D-16) can be mentioned.

  In the synthesis | combination of the said polyimide, you may use together the diamine represented by the said Formula (D-III), and another diamine. Among the other diamines, preferred are p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4 ′. -Diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 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) hexafluoro Propane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m Phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4′-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) Biphenyl, compounds represented by the above formulas (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, N , N′-di (4-aminophenyl) -benzidine, N, N′-di (4-aminophenyl) -N, N′-dimethyl-benzidine, among the compounds represented by the above formula (DI) Of the compound represented by the above formula (D-6), the compound represented by the above formula (D-7) among the compounds represented by the above formula (D-II), and the above formula (D-IV) 1,3-bis of the compound (3-aminopropyl) - can be given tetramethyldisiloxane. When the diamine represented by the above formula (D-III) and other diamine are used in combination, the diamine represented by the above formula (D-III) is preferably 0.5% by weight or more based on the total diamine, Particularly preferably, 1% by weight or more is used.

The dehydration ring closure reaction of polyamic acid for synthesizing the polyimide that can be used in the present invention includes (i) a method of heating polyamic acid, or (ii) dissolving polyamic acid in an organic solvent, and dehydrating agent in this solution And it can carry out by the method of adding a dehydration ring closure catalyst and heating as needed.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease.
On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the amic acid structure. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC, Reaction time becomes like this. Preferably it is 0.5-24 hours, More preferably, it is 1-10 hours. .

The polyimide that can be used in the present invention may be a completely imidized product in which all of the amic acid structure is dehydrated and closed, and a part of the amic acid structure is dehydrated and closed, and the imide ring structure and the amic acid structure May be a partially imidized product.
The imidation ratio in the polyimide that can be used in the present invention is preferably 80% or more, and more preferably 85% or more. Here, the “imidization rate” is a percentage of the number of imide rings to the total number of amic acid structures and the number of imide rings in the polymer. At this time, a part of the imide ring may be an isoimide ring. The imidation ratio is obtained by the following formula (i) from the result of ¹ H-NMR measurement at room temperature using tetramethylsilane as a reference substance by dissolving polyimide in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide). be able to.

Imidation rate (%) = (1-A ¹ / A ² × α) × 100 (i)

(In Formula (i), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a polyimide precursor (polyamic acid). The number ratio of other protons to one proton of NH group in
The reaction solution obtained as described above may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. The polyimide may be isolated and used for preparation of a liquid crystal aligning agent, or the isolated polyimide may be purified and then used for preparation of a liquid crystal aligning agent. In order to remove the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. Polyimide can be isolated and purified by the same method as the polyamic acid isolation and purification method.

-End-modified polymer-
The polyamic acid and the polyimide may each be a terminal-modified polymer having a molecular weight adjusted. Such a terminal-modified polymer can be synthesized by adding a molecular weight regulator to the reaction system when synthesizing the polyamic acid. As said molecular weight regulator, an acid monoanhydride, a monoamine compound, a monoisocyanate compound etc. can be mentioned, for example.
Here, examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl. A succinic anhydride etc. can be mentioned. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, Examples include n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine. it can. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The molecular weight regulator is preferably used in an amount of 20 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid. .
-Solution viscosity-
The polyamic acid and polyimide obtained as described above preferably have a solution viscosity of 20 to 800 mPa · s, and a solution viscosity of 30 to 500 mPa · s, respectively, when a solution having a concentration of 10% by weight is obtained. It is more preferable that it has.
The solution viscosity (mPa · s) of the polymer is a value measured at 25 ° C. using an E-type viscometer for a polymer solution having a concentration of 10% by weight using a good solvent for the polymer.

[Other polysiloxanes]
The other polysiloxane that can be used in the present invention is at least one selected from the group consisting of a polysiloxane having a repeating unit represented by the above formula (S), a hydrolyzate thereof, and a condensate of the hydrolyzate. It is. Other polysiloxanes, it is preferable X ^II in the above formula (S) is a polyorganosiloxane is an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms.
Such other polysiloxane is, for example, at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter also referred to as “raw silane compound”), preferably in a suitable organic solvent. And can be synthesized by hydrolysis or hydrolysis / condensation in the presence of water and a catalyst.
Examples of the raw material silane compound that can be used here include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and 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-propoxy Lan, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; dimethyldimethoxysilane, dimethyldiethoxysilane, Examples include dimethyldichlorosilane; trimethylmethoxysilane, trimethylethoxysilane, and trimethylchlorosilane. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane are preferred.

Examples of organic solvents that can optionally be used in the synthesis of other polysiloxanes include alcohol compounds, ketone compounds, amide compounds or ester compounds, and other aprotic compounds. These can be used alone or in combination of two or more.
Examples of the alcohol compound include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol , Phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, monoalcohol compounds such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol compounds such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, etc. partial ethers of polyhydric alcohol compounds, such as dipropylene glycol monopropyl ether. These alcohol compounds can be used alone or in combination of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-. Monoketone compounds such as hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fencheon;
Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5 -Methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, etc. The β-diketone compound and the like can be mentioned respectively. These ketone compounds may be used alone or in combination of two or more.
Examples of the amide compound include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-ethyl. Acetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide compounds can be used alone or in combination of two or more.

  Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, acetic acid. i-butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, acetic acid n-nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene acetate monoethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, vinegar Acid diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples thereof include amyl, diethyl malonate, dimethyl phthalate, and diethyl phthalate. These ester compounds can be used alone or in combination of two or more.

Examples of the other aprotic compounds include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N— Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N -Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone and the like can be mentioned.
Of these solvents, polyhydric alcohol compounds, partial ethers or ester compounds of polyhydric alcohol compounds are particularly preferred.
The amount of water used in the synthesis of the other polysiloxane is preferably 0.5 to 100 mol, more preferably 1 to 100 mol, based on 1 mol of the total of the alkoxyl group and halogen atom of the starting silane compound. It is preferably 30 mol, and more preferably 1 to 1.5 mol.

Examples of catalysts that can be used in the synthesis of other polysiloxanes include metal chelate compounds, organic acids, inorganic acids, organic bases, ammonia, alkali metal compounds, and alkaline earth metal compounds.
Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Natto) titanium, di-t-butoxy Su (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n -Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri -S c-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis ( Ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy・ Tris (ethyl aceto Acetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Titanium chelate compounds such as acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetate) Acetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis ( Ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di- sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n- Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) Zirconium, mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium;
Examples thereof include aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum.

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, and gallic acid. Acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples thereof include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.
Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclo. Nonane, diazabicycloundecene, tetramethylammonium hydroxide, and the like can be given.
Examples of the alkali metal compound or alkaline earth metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.
These catalysts may be used alone or in combination of two or more.
Of these catalysts, metal chelate compounds, organic acids or inorganic acids are preferred, and titanium chelate compounds or organic acids are more preferred.
The amount of the catalyst used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the raw material silane compound.
Water added during the synthesis of other polysiloxanes can be added intermittently or continuously in the raw material silane compound or in a solution of the silane compound dissolved in an organic solvent.
The catalyst may be added in advance to a raw material silane compound or a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.
The reaction temperature at the time of synthesizing other polysiloxane is preferably 0 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

[Content ratio of other polymers]
When the liquid crystal aligning agent of this invention contains another polymer with the above-mentioned polyorganosiloxane (1), as a content rate of another polymer, it is 100 weight part of polyorganosiloxane (1). The amount is preferably 10,000 parts by weight or less. The more preferable content of the other polymer varies depending on the type of the other polymer.
Total use ratio of polyamic acid and polyimide when the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of polyorganosiloxane (1) and polyamic acid and polyimide Is more preferably 100 to 5,000 parts by weight, more preferably 200 to 2,000 parts by weight, based on 100 parts by weight of the polyorganosiloxane (1).
On the other hand, when the liquid crystal aligning agent of the present invention contains polyorganosiloxane (1) and another polysiloxane, the proportion of other polysiloxane used is 100 parts by weight of polyorganosiloxane (1). And more preferably 100 to 2,000 parts by weight.
When the liquid crystal aligning agent of this invention contains another polymer with polyorganosiloxane (1), as a kind of other polymer, at least 1 sort (s) selected from the group which consists of a polyamic acid and a polyimide. It is preferable that the polymer or other polysiloxane.

[Epoxy compound]
The said epoxy compound can be contained in the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness with respect to the substrate surface of the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention.
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 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′-tetra Glycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodi Enirumetan, N, N-diglycidyl - benzylamine, N, N-diglycidyl - such as aminomethyl cyclohexane may be mentioned as preferred. The use ratio of these epoxy compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the total of the polymers (referring to the total amount of the polyorganosiloxane (1) and other polymers. The same shall apply hereinafter). More preferably, it is 0.1 to 30 parts by weight.

-Functional silane compounds-
Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N- Benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis ( Examples thereof include oxyethylene) -3-aminopropyltrimethoxysilane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.
The use ratio of these functional silane compounds is preferably 4 parts by weight or less with respect to 100 parts by weight of the total polymer.
-Surfactant-
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. it can.
When the liquid crystal aligning agent of this invention contains surfactant, as the content rate, Preferably it is 10 weight part or less with respect to 100 weight part of the whole liquid crystal aligning agent, More preferably, it is 1 weight part or less. is there.

-Radical polymerization initiator-
The radical polymerization initiator is a repeating unit in which the polyorganosiloxane (1) contained in the liquid crystal aligning agent of the present invention is further represented by the above formula (2) in addition to the structure represented by the above formula (1). When it is at least one selected from the group consisting of a polyorganosiloxane having a hydrolyzate thereof, a hydrolyzate thereof and a condensate of the hydrolyzate (that is, having a (meth) acryloyl group), And it can contain in the liquid crystal aligning agent of this invention in order to improve durability of the liquid crystal aligning film formed.
Examples of such radical polymerization initiators include thermal radical polymerization initiators and photo radical polymerization initiators. Of these, thermal radical polymerization initiators are preferred.
Examples of the thermal radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2). , 4-dimethylvaleronitrile), acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds, and the like. .
Specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropanone-1, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1, 2-benzyl. -2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethanone-1, and the like. Of these, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1 and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 are preferable. The acetophenone compounds can be used alone or in admixture of two or more.

Specific examples of the biimidazole compound include 2,2′-bis (2-
Chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5, 5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6) -Trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'- Examples include tetraphenyl-1,2'-biimidazole, and of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,4) 6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferred, especially 2,2'-bis (2,4-dichlorophenyl) -4,4', 5 , 5′-Tetraphenyl-1,2′-biimidazole is preferred. The above biimidazole compounds can be used alone or in admixture of two or more.
Examples of commercially available radical polymerization initiators include Irgacure 369 and 407 (all manufactured by Ciba Specialty Chemicals Co., Ltd.) as trade names.
The use ratio of the radical polymerization initiator in the liquid crystal aligning agent of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the polyorganosiloxane (1). .

<Liquid crystal aligning agent>
As described above, the liquid crystal aligning agent of the present invention contains polyorganosiloxane (1) as an essential component, and additionally contains other components as necessary. Preferably, each component is an organic solvent. It is prepared as a dissolved solution composition.
The organic solvent that can be used for preparing the liquid crystal aligning agent of the present invention is preferably one that dissolves the polyorganosiloxane of the present invention and other components optionally used and does not react with them.
The organic solvent preferably used for the liquid crystal aligning agent of this invention changes with kinds of the other polymer added arbitrarily.
As a preferred organic solvent in the case where the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of polyorganosiloxane (1) and polyamic acid and polyimide, a synthetic reaction of polyamic acid The solvent illustrated as what is used for can be mentioned. Here, the poor solvent illustrated as what can be used together in the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together.
Particularly preferred organic solvents that can be used in this case include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4 -Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, Ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol di Examples thereof include methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, and diisopentyl ether. These can be used alone or in admixture of two or more.

  On the other hand, when the liquid crystal aligning agent of the present invention contains only the polyorganosiloxane (1) as a polymer, or a case where it contains the polyorganosiloxane (1) and another polysiloxane, a preferred organic material Examples of the solvent include 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene. Glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Pill ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, Propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, acetic acid Methylpentyl, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, Such as isoamyl, and the like. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate and the like can be mentioned.

The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is selected in consideration of viscosity, volatility, and the like. A preferable solid content concentration is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal aligning film. When the solid content concentration is less than 1% by weight, When the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive. The viscosity of the aligning agent increases, resulting in poor coating properties.
The particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by weight is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature at which the liquid crystal aligning agent of the present invention is prepared is preferably 0 ° C to 200 ° C, more preferably 20 ° C to 60 ° C.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention as described above.
The liquid crystal display element of the present invention can be produced, for example, by the following method.
(1) First, the liquid crystal alignment film of the present invention is applied onto a pair of substrates, and the solvent is removed to form a coating film. Here, when the display mode of the liquid crystal display element to be manufactured is a vertical electric field system such as a TN type, an STN type, or a VA type, two substrates on which a transparent conductive film patterned on one side is provided. Are used as a pair of substrates. On the other hand, when the display mode of the liquid crystal display element to be manufactured is a horizontal electric field method, a pair of a substrate provided with a transparent conductive film having a comb-like pattern and a substrate not having a transparent conductive film is used. Used as a substrate.
In any of the above cases, when the substrate has a transparent conductive film, the liquid crystal aligning agent is applied to the surface of the substrate having the transparent conductive film. In the case of a substrate that does not have a transparent conductive film, the liquid crystal aligning agent is applied to one side of the substrate. Here, as the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. Examples of the transparent conductive film provided on one surface of the substrate include an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), and the like. Can be used. In addition, in order to obtain these patterned transparent conductive films, a method of forming a pattern by a photo-etching method after forming a transparent conductive film without a pattern, and a mask having a desired pattern when forming the transparent conductive film. For example, a method of directly forming a patterned transparent conductive film can be employed.

The liquid crystal aligning agent is applied onto the substrate by an appropriate application method such as a roll coater method, a spinner method, a printing method, or an ink jet method. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, or the like is applied in advance to the coated surface of the substrate. You may keep it.
In the case where the liquid crystal display element to which the liquid crystal aligning agent of the present invention is applied is a VA type liquid crystal display element, for example, a projecting structure as described in Patent Document 3 (Japanese Patent Laid-Open No. 2002-327058) is used. A viewing angle characteristic may be improved by applying a liquid crystal aligning agent after forming an object on a substrate.
After the application, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied alignment agent.
When the liquid crystal aligning agent of this invention does not contain a thermal radical polymerization initiator, Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. The pre-bake time is preferably 0.1 to 10 minutes, more preferably 0.5 to 3 minutes. On the other hand, when the liquid crystal aligning agent of this invention contains a thermal radical polymerization initiator, it is preferable to set the prebaking temperature within the above range to a temperature at which the thermal radical polymerization initiator does not function at the prebaking stage.

Next, after pre-baking, a baking (post-baking) step is performed for the purpose of completely removing the solvent. In this case, the post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 180 minutes, more preferably 10 to 100 minutes.
The film thickness of the coating film formed here is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(2) When the display mode of the liquid crystal display element to be manufactured is the VA type, the coating film formed as described above can be used as a liquid crystal alignment film as it is. The rubbing process described may be performed.
On the other hand, when the display mode of the liquid crystal display element to be manufactured is a vertical electric field method other than the VA type or a horizontal electric field method, for example, nylon, rayon, cotton or the like on the formed coating film surface A rubbing treatment is performed by rubbing in a certain direction with a roll wound with a cloth made of the above fibers. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. Furthermore, for the coating film after the rubbing treatment, for example, a part of the liquid crystal alignment film as shown in Patent Document 4 (Japanese Patent Laid-Open No. 6-222366) or Patent Document 5 (Japanese Patent Laid-Open No. 6-281937). Or a part of the surface of the liquid crystal alignment film as disclosed in Patent Document 6 (Japanese Patent Laid-Open No. 5-107544) By forming a resist film on the top and performing a rubbing treatment in a direction different from the previous rubbing treatment, and then removing the resist film so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region, It is possible to improve the visibility characteristics of the obtained liquid crystal display element.

(3) When a pair of substrates on which a liquid crystal alignment film is formed as described above is manufactured and rubbed, the two rubbing directions in each liquid crystal alignment film are orthogonal or antiparallel. A liquid crystal cell is configured by disposing a liquid crystal in a gap (cell gap) in which the substrates are arranged to face each other so that the liquid crystal alignment film faces each other. For example, the following two methods can be used to arrange the liquid crystal in the gap between the pair of substrates.
The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.
In any of the above methods, it is desirable to remove the flow alignment at the time of filling the liquid crystal by heating the liquid crystal cell to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooling it to room temperature.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl. Cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck) A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.
As a polarizing plate bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between protective films of cellulose acetate The polarizing plate which consists of itself can be mentioned.
The liquid crystal display element of the present invention produced as described above is very excellent particularly in terms of electrical characteristics, and can realize extremely high display quality.
The liquid crystal aligning agent of the present invention is preferably applied to the liquid crystal aligning film of the VA type liquid crystal display element because the advantages of the present invention can be maximized.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
The weight average molecular weight Mw of the polymer measured below is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.

Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²

The imidation ratio of polyimide is calculated from the above formula from ¹ H-NMR spectrum obtained by thoroughly drying polyimide at room temperature under reduced pressure, then dissolving in deuterated dimethyl sulfoxide and measuring tetramethylsilane as a reference material at room temperature. Calculated according to (i).
The solution viscosity of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.

<Synthesis of polyorganosiloxane (2) having (meth) acryloyl group>
Synthesis example 1
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 50 g of 3-acryloxypropyltrimethoxysilane, 50 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10 g of triethylamine was charged and mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer is taken out, washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure, whereby a polyorgano having an acryloyl group is obtained. Siloxane (APS-1) was obtained as a viscous transparent liquid.
The weight average molecular weight Mw of the polyorganosiloxane (APS-1) having this acryloyl group was 2,000.
Synthesis example 2
The same procedure as in Synthesis Example 1 was carried out except that 80 g of 3-acryloxypropyltrimethoxysilane and 20 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were used as raw material silane compounds, and they had an acryloyl group. Polyorganosiloxane (APS-2) was obtained as a viscous transparent liquid.
The weight average molecular weight Mw of this polyorganosiloxane (APS-2) having an acryloyl group was 1,900.

<Synthesis of polyorganosiloxane (1)>
Example 1
To a 300 mL three-necked flask equipped with a thermometer, 30 g of dodecanethiol, 50 g of AC-SQ (manufactured by Toagosei Co., Ltd.) and 80 g of acetonitrile as polyorganosiloxane having an acryloyl group were added and dissolved uniformly. Next, 7.6 g of triethylamine was added thereto and reacted at 50 ° C. for 3 hours. After completion of the reaction, 500 mL of butyl acetate and 500 mL of dilute hydrochloric acid are added to the reaction mixture, the organic layer is washed with 500 mL of water three times, and then the solvent is distilled off to make polyorganosiloxane (S-1) as a transparent viscous liquid. Obtained.
Mw of this polyorganosiloxane (S-1) was 14,000.
Example 2
To a 300 mL three-necked flask equipped with a thermometer, 43 g of octadecanethiol, 50 g of AC-SQ (manufactured by Toagosei Co., Ltd.) and 93 g of acetonitrile as polyorganosiloxane having an acryloyl group were added and dissolved uniformly. Next, 7.6 g of triethylamine was added thereto and reacted at 50 ° C. for 3 hours. After completion of the reaction, 500 mL of butyl acetate and 500 mL of dilute hydrochloric acid are added to the reaction mixture, the organic layer is washed with 500 mL of water three times, and then the solvent is distilled off to make polyorganosiloxane (S-2) as a transparent viscous liquid. Obtained.
Mw of this polyorganosiloxane (S-2) was 15,000.
Example 3
To a 300 mL three-necked flask equipped with a thermometer, 64 g of octadecanethiol, 50 g of AC-SQ (manufactured by Toagosei Co., Ltd.) and 114 g of acetonitrile as polyorganosiloxane having an acryloyl group were added and dissolved uniformly. Next, 11 g of triethylamine was added thereto and reacted at 50 ° C. for 3 hours. After completion of the reaction, 500 mL of butyl acetate and 500 mL of dilute hydrochloric acid are added to the reaction mixture, and the organic layer is washed 3 times with 500 mL of water and then the solvent is distilled off to make polyorganosiloxane (S-3) as a transparent viscous liquid. Obtained.
Mw of this polyorganosiloxane (S-3) was 16,000.

Example 4
In a 300 mL three-necked flask equipped with a thermometer, 43 g of octadecanethiol and 50 g of APS-1 obtained in Synthesis Example 1 as a polyorganosiloxane having an acryloyl group and 93 g of acetonitrile were uniformly dissolved. Next, 7.6 g of triethylamine was added thereto and reacted at 50 ° C. for 3 hours. After completion of the reaction, 500 mL of butyl acetate and 500 mL of dilute hydrochloric acid are added to the reaction mixture, the organic layer is washed 3 times with 500 mL of water, and then the solvent is distilled off to make polyorganosiloxane (S-4) as a transparent viscous liquid. Obtained.
Mw of this polyorganosiloxane (S-4) was 16,000.
Example 5
In a 300 mL three-necked flask equipped with a thermometer, 43 g of octadecanethiol and 50 g of APS-2 obtained in Synthesis Example 2 above as polyorganosiloxane having an acryloyl group and 93 g of acetonitrile were uniformly dissolved. Next, 7.6 g of triethylamine was added thereto and reacted at 50 ° C. for 3 hours. After completion of the reaction, 500 mL of butyl acetate and 500 mL of dilute hydrochloric acid are added to the reaction mixture, the organic layer is washed with 500 mL of water three times, and then the solvent is distilled off to make polyorganosiloxane (S-5) as a transparent viscous liquid. Obtained.
Mw of this polyorganosiloxane (S-5) was 16,000.
Example 6
To a 300 mL three-necked flask equipped with a thermometer, add 43 g of octadecanethiol, 50 g of AC-SQ (manufactured by Toagosei Co., Ltd.) as a polyorganosiloxane having an acryloyl group, 5.5 g of thioglycolic acid and 93 g of acetonitrile, and uniformly Dissolved. Next, 7.6 g of triethylamine was added thereto and reacted at 50 ° C. for 3 hours. After completion of the reaction, 500 mL of butyl acetate and 500 mL of dilute hydrochloric acid are added to the reaction mixture, the organic layer is washed 3 times with 500 mL of water, and the solvent is distilled off to make polyorganosiloxane (S-6) as a transparent viscous liquid. Obtained.

<Synthesis of other polymers>
[Synthesis of polyamic acid]
Synthesis example 3
Pyromellitic dianhydride 109 g (0.50 molar equivalent) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 molar equivalent) as tetracarboxylic dianhydride and 4,4 as diamine 200 g (1.0 molar equivalent) of 4-diaminodiphenyl ether is dissolved in 2,290 g of N-methyl-2-pyrrolidone, reacted at 40 ° C. for 3 hours, and then 1,350 g of N-methyl-2-pyrrolidone is added. As a result, about 3,590 g of a solution containing 10% by weight of polyamic acid (PA-1) was obtained.
The solution viscosity of this polyamic acid solution was 210 mPa · s.
Synthesis example 4
196 g (1.0 molar equivalent) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g (1 of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine) (0.0 molar equivalent) was dissolved in 3,670 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours to obtain 3,700 g of a solution containing 10% by weight of polyamic acid (PA-2). .
The solution viscosity of this polyamic acid solution was 170 mPa · s.

[Synthesis of polyimide]
Synthesis example 5
1,9.9 g (0.089 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 6.8 g (0.063 mol) of p-phenylenediamine as diamine, 4,4 ′ -3.6 g (0.018 mol) of diaminodiphenylmethane and 4.7 g (0.009 mol) of the compound represented by the above formula (D-10) were dissolved in 140 g of N-methyl-2-pyrrolidone and dissolved at 60 ° C. Reaction was performed for 4 hours to obtain a solution containing polyamic acid. A small amount of the resulting polyamic acid solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 115 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 14 g of pyridine and 18 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (in this operation, pyridine and acetic anhydride used in the dehydration ring-closing reaction were removed from the system), thereby imido. About 220 g of a solution containing 15.4% by weight of polyimide (PI-1) having a conversion rate of about 77% was obtained.
A small amount of this polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 84 mPa · s.
[Synthesis of other polysiloxanes]
Synthesis Example 6
A 200 mL three-necked flask equipped with a condenser was charged with 20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol, heated to 60 ° C. and stirred. A maleic anhydride aqueous solution prepared by dissolving 0.26 g of maleic anhydride in 10.8 g of water prepared in another flask having a capacity of 20 mL was added thereto, and the reaction was performed by heating and stirring at 60 ° C. for further 4 hours. The solvent was distilled off from the resulting reaction mixture, 1-ethoxy-2-propanol was added, and the mixture was concentrated again to obtain a polymer solution containing 10% by weight of polyorganosiloxane (PS-1).
The weight average molecular weight Mw of this polyorganosiloxane (PS-1) was 5,100.

<Preparation of liquid crystal aligning agent and evaluation of storage stability>
Example 7
A solution containing 100 parts by weight of the polyorganosiloxane (S-1) obtained in Example 1 and the polyamic acid PA-1 obtained in Synthesis Example 3 as another polymer was converted to PA-1. Combined with the amount corresponding to 1,000 parts by weight, N-methyl-2-pyrrolidone and butyl cellosolve were added thereto, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio), solid content A solution having a concentration of 3.0% by weight was obtained. The liquid crystal aligning agent (A-1) was prepared by filtering this solution with a filter having a pore diameter of 1 μm.
A part of the liquid crystal aligning agent (A-1) was taken and stored at −15 ° C. for 6 months. Viscosity measured with an E-type viscometer at 25 ° C. was measured before and after storage. When the change rate of the viscosity of the solution before and after storage was less than 10%, the storage stability was evaluated as “good”. The property was “good”.
Examples 8-14
In Example 7, the same procedure as in Example 7 was carried out except that the type of polyorganosiloxane (1) and the type and amount of other polymers were as shown in Table 1, respectively. A-2) to (A-8) were respectively prepared.
Table 1 shows the storage stability evaluation results for each liquid crystal aligning agent examined in the same manner as in Example 7.
Example 15
A solution containing 100 parts by weight of the polyorganosiloxane (S-6) obtained in Example 6 and the polyamic acid (PA-2) obtained in Synthesis Example 4 as another polymer (PA-1) In combination with an amount corresponding to 1,000 parts by weight, an epoxy compound represented by the following formula (E-1)

200 parts by weight of a compound represented by the formula: N-methyl-2-pyrrolidone and butyl cellosolve are added thereto, and the solvent composition is N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio), solid content concentration Was a 3.0 wt% solution. A liquid crystal aligning agent (A-9) was prepared by filtering this solution through a filter having a pore size of 1 μm.
Table 1 shows the evaluation results of the storage stability of this liquid crystal aligning agent (A-9) examined in the same manner as in Example 7.
Example 16
A solution containing the other polysiloxane (PS-1) obtained in Synthesis Example 6 as another polymer was converted to PS-1, and an amount corresponding to 500 parts by weight was taken. 100 parts by weight of the obtained polyorganosiloxane (S-2) was added, and 1-ethoxy-2-propanol was further added to obtain a solution having a solid content concentration of 4.0% by weight. A liquid crystal aligning agent (A-10) was prepared by filtering this solution through a filter having a pore size of 1 μm.
Table 1 shows the evaluation results of the storage stability of this liquid crystal aligning agent (A-10) examined in the same manner as in Example 7.

<Manufacture and evaluation of VA type liquid crystal cell>
Example 17
[Manufacture of VA liquid crystal cell]
The liquid crystal aligning agent (A-1) prepared in Example 7 was applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a spinner, and prebaked at 80 ° C. for 1 minute on a hot plate. After performing, it heated at 200 degreeC for 1 hour in the oven which substituted the inside with nitrogen, and formed the coating film (liquid crystal aligning film) with a film thickness of 0.1 micrometer.
This operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film on the transparent conductive film.
After applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing, the liquid crystal alignment film surfaces of the pair of substrates are opposed to each other. The adhesive was thermally cured at 150 ° C. for 1 hour. Next, after filling the gap between the substrates from the liquid crystal injection port with negative type liquid crystal (MLC-6608, manufactured by Merck), the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 150 ° C. for 10 minutes and then gradually cooled to room temperature, thereby producing a VA liquid crystal cell.
This liquid crystal cell was evaluated by the following method. The evaluation results are shown in Table 2.

[Evaluation of VA liquid crystal cell]
(1) Evaluation of liquid crystal orientation The liquid crystal cell produced above was sandwiched between two polarizing plates orthogonal to each other, observed with a microscope, and evaluated as “good” when there was no light leakage.
(2) Evaluation of voltage holding ratio After applying a voltage of 5 V to the liquid crystal cell produced above at 60 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, the voltage is held 167 milliseconds after the application release. The rate was measured.
In addition, the model "VHR-1" by Toyo Technica Co., Ltd. was used as a measuring apparatus.
(3) Evaluation of burn-in (measurement of residual DC voltage)
The residual voltage (residual DC voltage) in the liquid crystal cell immediately after the DC voltage was turned off by applying a 30 Hz, 3 V rectangular wave with a direct current of 4 V to the liquid crystal cell manufactured above for 5 hours at an ambient temperature of 60 ° C. Was determined by the flicker elimination method.

Examples 18-26
In Example 17, the VA liquid crystal cell was produced and evaluated in the same manner as in Example 17 except that the liquid crystal aligning agents shown in Table 2 were used.
The evaluation results are shown in Table 2.
Comparative Example 1
N-methyl-2-pyrrolidone and butyl cellosolve were added to the solution containing polyimide (PI-1) obtained in Synthesis Example 5, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio). It was set as the solution whose solid content concentration is 3.0 weight%. The liquid crystal aligning agent (R-1) was prepared by filtering this solution through a filter having a pore size of 1 μm.
A VA liquid crystal cell was produced and evaluated in the same manner as in Example 17 except that the liquid crystal aligning agent (R-1) prepared above was used as the liquid crystal aligning agent.
The evaluation results are shown in Table 2.

Claims (7)

Following formula (1)

(In the formula (1), R ^I represents a group having a steroid skeleton or the following formula (1A)

(In Formula (1A), R is an alkyl group which may be substituted with fluorine having 4 to 20 carbon atoms, A ^II is a cyclohexylene ring or a phenylene group, and X is a single bond, an oxygen atom or a sulfur atom. , -COO- or -OCO-, a is an integer of 0 to 3, and when a plurality of A ^II are present, they may be the same or different.
Z is a sulfur atom or an oxygen atom, R ^II is a hydrogen atom or a methyl group, A ^I is a methylene group or an alkylene group having 2 to 10 carbon atoms, and Y ^I is a hydroxyl group , An alkoxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. )
A liquid crystal aligning agent comprising at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the formula: At least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (1), a hydrolyzate thereof and a condensate of the hydrolyzate is represented by the following formula (2)

(In the formula (2), R ^II , A ^I and Y ^I have the same meanings as in the above formula (1).)
At least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the following formula, a hydrolyzate thereof and a condensate of the hydrolyzate:

(In the formula (3), R ^I and Z have the same meanings as in the above formula (1).)
The liquid crystal aligning agent of Claim 1 obtained by making it react with the compound represented by these.   The proportion of the compound represented by the above formula (3) in the above reaction is selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (2), a hydrolyzate thereof, and a condensate of the hydrolyzate. The liquid crystal aligning agent of Claim 2 which is 0.2-0.8 mol% with respect to the (meth) acryloyl group which has at least 1 sort (s) selected.   Furthermore, the liquid crystal aligning agent as described in any one of Claims 1-3 containing the at least 1 sort (s) of polymer selected from the group which consists of a polyamic acid and a polyimide. Furthermore, the following formula (S)

(In the formula ^{(S), X II} is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group or an aryl group having 6 to 20 carbon atoms having 1 to 6 carbon ^{atoms, Y II} is a hydroxyl group or a carbon (It is an alkoxyl group of formula 1 to 10.)
The liquid crystal aligning agent as described in any one of Claims 1-3 containing at least 1 sort (s) selected from the group which consists of polysiloxane represented by these, its hydrolyzate, and the condensate of a hydrolyzate.   A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1.   Polyorganosiloxane represented by the above formula (1).