KR20100092390A - Radiation-sensitive polyorganosiloxane, method for producing the same and liquid crystal aligning agent - Google Patents

Abstract

PURPOSE: Radiation-sensitive polyorganosiloxane is provided to be conveniently manufactured using a stable raw material and to obtain a liquid crystal alignment film having a good expression property of a pretilt angle when the polyorganosiloxane is applied to a liquid crystal alignment agent. CONSTITUTION: Radiation-sensitive polyorganosiloxane has a structure which is marked by chemical formula 3. In chemical formula 3, R is hydrogen or a methyl group and n is an integer of 1-10. R^1 is a group which is marked by chemical formula (R1-1) and R^2 is fluorine or a cyano group. In chemical formula (R1-1), R^I is an alkyl group having a carbon number of 1-40 or a monovalent hydrocarbon group having a carbon number of 3-40.

Description

Radiation-sensitive polyorganosiloxane, preparation method thereof and liquid crystal aligning agent {RADIATION-SENSITIVE POLYORGANOSILOXANE, METHOD FOR PRODUCING THE SAME AND LIQUID CRYSTAL ALIGNING AGENT}

The present invention relates to a method for producing radiation-sensitive polyorganosiloxane. More specifically, it is related with the method of easily manufacturing the radiation sensitive polyorganosiloxane which can be contained preferably in the liquid crystal aligning agent used for a photo-alignment method.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy has a sandwich structure as a substrate with a transparent electrode having a liquid crystal alignment film, and if necessary, the long axis of the liquid crystal molecules is continuously twisted between 0 and 360 degrees between the substrates, if necessary, in TN (Twisted). BACKGROUND ART Liquid crystal display devices having liquid crystal cells such as Nematic type, STN (Super Twisted Nematic) type, and IPS (In Plane Switching) type are known (see Patent Documents 1 and 2).

In such a liquid crystal cell, it is necessary to provide a liquid crystal aligning film on the substrate surface in order to align the liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal aligning film is normally formed by the method (rubbing method) which rubs the surface of the organic film formed in the board | substrate surface with the cloth member, such as rayon, in one direction. However, when the liquid crystal alignment film is formed by a rubbing treatment, dust and static electricity are easily generated in the process, and thus there is a problem that dust adheres to the surface of the alignment film and causes display defects. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, there is also a problem that circuit breakdown of the TFT element occurs due to generated static electricity, which causes a decrease in yield. In addition, in the liquid crystal display device expected to be more precise in the future, irregularities are generated on the surface of the substrate due to the higher density of the pixels, which makes it difficult to perform the rubbing process uniformly.

As another means for orienting a liquid crystal in a liquid crystal cell, a photoalignment that imparts liquid crystal alignment ability by irradiating polarized or non-polarized radiation to a photosensitive thin film, such as polyvinylcinnamate, polyimide, or azobenzene derivative, formed on the substrate surface The law is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (see Patent Documents 3 to 13).

On the other hand, a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are orthogonal to a substrate as an operation mode of a liquid crystal display element separate from the above is also known. In this mode of operation, when the liquid crystal molecules are inclined toward a direction parallel to the substrate by applying a voltage between the substrates, the liquid crystal molecules need to be inclined toward one direction within the substrate surface from the substrate normal direction. As a means for this purpose, the liquid crystal molecules are slightly inclined from the substrate normal direction to one direction in the substrate surface by using a method of providing projections on the surface of the substrate, a method of providing stripes on the transparent electrode, and a rubbing alignment film (pretilt). And the like have been proposed.

It is known that the photo-alignment method is also useful as a method of controlling the tilt direction of liquid crystal molecules in the liquid crystal cell in the vertical alignment mode. That is, it is known that the inclination direction of the liquid crystal molecules at the time of voltage application can be uniformly controlled by using the liquid crystal alignment film of the vertical alignment which provided the orientation regulation ability and the pretilt angle expression property by the photo-alignment method (patent document 11-the 12 and 14 to 16).

Thus, the liquid crystal aligning film manufactured by the photo-alignment method can be effectively applied to various liquid crystal display elements. However, there existed a problem that the conventional photo-alignment film has a large amount of radiation irradiation required in order to obtain a large pretilt angle. For example, when the liquid crystal alignment ability is imparted to the thin film containing the azobenzene derivative by the photo alignment method, in order to obtain a sufficient pretilt angle, it is necessary that the optical axis has to irradiate at least 10,000 J / m 2 of radiation inclined from the substrate normal line. Have been reported (see Patent Documents 13 to 14 and Non-Patent Document 1). In addition, the liquid crystal aligning film formed by these techniques lacks stability over time of the pretilt angle because the phenomenon in which the pretilt angle developability disappears with time even if a good pretilt angle is initially displayed. It is pointed out that.

In order to solve these problems, the present inventors have recently introduced a group derived from a specific cinnamic acid derivative using a hydrosilylation reaction to hydrogen silsesquioxane to make a radiation-sensitive polysiloxane, and there are few liquid crystal aligning agents containing the same. It has been found and reported that a liquid crystal alignment film showing good liquid crystal alignment ability even by a photo-alignment method according to the radiation dose and exhibiting good pretilt angle expressability and stability over time of the pretilt angle is provided (Patent Documents 19 to 21). Reference). However, since hydrogen silsesquioxane used as a raw material in this technique is unstable with respect to moisture and the like, there is a problem of requiring special devices or considerations for its storage and handling.

Japanese Patent Laid-Open No. 56-91277 Japanese Patent Laid-Open No. 1-20528 Japanese Patent Publication No. 6-287453 Japanese Patent Publication No. 10-251646 Japanese Patent Publication No. 11-2815 Japanese Patent Laid-Open No. 11-152475 Japanese Patent Laid-Open No. 2000-144136 Japanese Patent Laid-Open No. 2000-319510 Japanese Patent Laid-Open No. 2000-281724 Japanese Patent Publication No. 9-297313 Japanese Patent Laid-Open No. 2003-307736 Japanese Patent Laid-Open No. 2004-163646 Japanese Patent Publication No. 2002-250924 Japanese Patent Laid-Open No. 2004-83810 Japanese Patent Laid-Open No. 9-211468 Japanese Patent Laid-Open No. 2003-114437 Japanese Patent Laid-Open No. 63-291922 Japanese Patent Publication No. 2003-520878 Japanese Patent Application No. 2007-305525 PCT / JP2008 / 065228 PCT / JP2008 / 065231

 J. of the SID 11/3, 2003, p.579  Journal of American Chemical Society, Vol. 92, No. 19, P.5586 (1970)  T. J. Scheffer et. al. J. Appl. Phys. vo. 19, p. 2013 (1980)  Chemical Reviews, Vol. 95, p. 1409 (1995).

This invention is made | formed in view of the said situation, The objective is the liquid crystal which shows favorable liquid-crystal orientation ability also by the photo-alignment method by a small irradiation amount, and shows the favorable pretilt angle expression property and the stability with time progress of a pretilt angle. It is providing the method of manufacturing easily the radiation sensitive polyorganosiloxane which can be contained preferably in the liquid crystal aligning agent which provides an oriented film using the raw material which is stable and easy to handle.

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

It is achieved by a method for producing a radiation-sensitive polyorganosiloxane in which a polyorganosiloxane having a structure represented by the following formula (1) and a compound represented by the following formula (2) are reacted in the presence of a heavy metal compound or a heavy metal complex.

(In Formula 1, R is a hydrogen atom or a methyl group, n is an integer of 1-10.)

In Formula 2, R ¹ is a group represented by the following general formula (R ¹ -1), R ² is a fluorine atom or a cyano group, b is an integer of 0 to 4, Z is a halogen atom, or 1 carbon atom An alkylsulfonate group having an alkyl group of 6 to 6 or an arylsulfonate group having an aryl group having 6 to 10 carbon atoms, provided that the alkyl group having the alkylsulfonate group may be substituted with a fluorine atom)

(In formula (R ^1-1 ), R ^I is a C1-C40 alkyl group or a C3-C40 monovalent hydrocarbon group containing an alicyclic group or a condensed cyclic group, provided that a hydrogen atom of said alkyl group Some or all may be substituted with a fluorine atom, R ^II is a single bond, an oxygen atom, * -COO- or * -OCO- (wherein the above-mentioned bond with "*" is bonded to R ^I ), R ^III is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, and R ^IV is a single bond, an oxygen atom, * -COO- or * -OCO- (wherein " Bond is attached to R ^III ) and a is an integer from 0 to 3).

According to the present invention, there is provided a method for producing a radiation-sensitive polyorganosiloxane simply by using a raw material which is stable and easy to handle. The radiation-sensitive polyorganosiloxane produced by the method of the present invention may be preferably contained in the liquid crystal aligning agent used in the photo-alignment method, the liquid crystal aligning agent containing the radiation-sensitive polyorganosiloxane, The liquid crystal aligning film which shows the favorable liquid-crystal orientation ability also by the photo-alignment method by a small irradiation amount, and shows the favorable pretilt angle expression property and the stability with time progress of a pretilt angle can be provided.

Method for producing a radiation-sensitive polyorganosiloxane of the present invention, a polyorganosiloxane having a structure represented by the formula (1) (hereinafter referred to as "polyorganosiloxane having a (meth) acryloxy group"),

The compound represented by the formula (2) (hereinafter referred to as "compound (2)") is characterized in that the reaction in the presence of a heavy metal compound or heavy metal complex.

<Polyorganosiloxane having a (meth) acryloxy group>

As polyorganosiloxane which has a structure represented by the said Formula (1), For example, 1 selected from the group which consists of a polyorganosiloxane which has a repeating unit represented by following formula (1 '), its hydrolyzate, and a hydrolyzate condensate. You can do it more than species.

<Formula 1 '>

(In Formula 1 ', R and n are the same meanings as in Formula 1, respectively, and Y ¹ 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.)

In Formula 1, R is preferably a hydrogen atom. It is preferable that n in General formula (1) is an integer of 1-6, and it is especially preferable that it is 1-3.

As said C1-C10 alkoxyl group of Y <^1> in the said General formula (1 '), For example, a methoxyl group, an ethoxyl group, etc .; Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octade Real groups, n-nonadecyl groups, n-eicosyl groups and the like; As a C6-C20 aryl group, a phenyl group etc. are mentioned, for example.

As for the polyorganosiloxane which has a (meth) acryloxy group, it is preferable that the weight average molecular weights of polystyrene conversion measured by the gel permeation chromatography (GPC) are 500-100,000, It is more preferable that it is 1,000-10,000, It is 1,000-1,000 More preferably 5,000.

The polyorganosiloxane having such a (meth) acryloxy group is preferably a silane compound having a (meth) acryloxy group or a mixture of a silane compound having a (meth) acryloxy group and another silane compound. It can synthesize | combine by hydrolysis or hydrolysis-condensation in presence of water, a catalyst, and water.

As a silane compound which has the said (meth) acryloxy group, 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane, 3-methacryl, for example. Oxypropyltriethoxysilane, etc. are mentioned.

As said other silane compound, for example, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec -Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane , Fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec -Butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyl Tri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorocysilane, 2- (triple Oromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri -i-propoxysilane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 3-glycidyloxypropyltrime Methoxysilane, 3-glycidyloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane,

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- (purple Fluoro-n-octyl) ethyltrimethoxysilane, 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, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxy Silane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxy Silane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyl Triethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxy Silane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, methyldichlorosilane, methyldimeth Methoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysilane, methyldi-sec- Silane,

Dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro R-n-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-i-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) diethoxysilane, (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, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane , Divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyl Di-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane , Iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane , (Chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) In addition to the silane compound which has one silicon atom, such as diphenylsilane, (methoxy) (methyl) diphenylsilane, and (ethoxy) (methyl) diphenylsilane,

As a brand name, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X- 22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40- 2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, manufactured by Shin-Etsu Chemical Co., Ltd.); Glass resin (manufactured by Showa Denko Co., Ltd.); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray Dow Corning Corporation); FZ3711 and FZ3722 (above, manufactured by Nippon Unicar Co., Ltd.); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS- 227, PSD-0332, PDS-1615, PDS-9931, and XMS-5025 (above, manufactured by Chisso Corporation); Methyl silicate MS51 and methyl silicate MS56 (above, manufactured by Mitsubishi Chemical Corporation); Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, manufactured by Colcot Co., Ltd.); And partial condensates such as GR100, GR650, GR908, and GR950 (above, manufactured by Showa Denko Co., Ltd.).

Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- Preference is given to (3,4-epoxycyclohexyl) ethyltriethoxysilane or dimethyldiethoxysilane.

It is preferable that it is 0.1-10 mmol / g, and, as for the content rate of the (meth) acryloxy group in the polyorganosiloxane which has a (meth) acryloxy group used for this invention, it is more preferable that it is 1-7.5 mmol / g. Therefore, when synthesize | combining the polyorganosiloxane which has a (meth) acryloxy group, the content rate of the (meth) acryloxy group in the polyorganosiloxane which obtains the use ratio of the silane compound which has a (meth) acryloxy group and another silane compound is obtained. It is preferable to adjust and set so that it may become the said range.

As an organic solvent which can be used when synthesize | combining the polyorganosiloxane which has a (meth) acryloxy group, a hydrocarbon, a ketone, ester, an ether, an alcohol, etc. are mentioned, for example.

As said hydrocarbon, toluene, xylene, etc. are mentioned, for example;

As said ketone, For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, etc .; As said ester, For example, ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .; As said ether, For example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc .; Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. It is preferable that they are water-insoluble among these.

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

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

The amount of water used when producing the polyorganosiloxane having a (meth) acryloxy group is preferably 0.5 to 100 times mole, and more preferably 1 to 30 times mole, based on the total silane compounds.

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

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

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene; And quaternary organic amines such as tetramethylammonium hydroxide, and the like. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Preference is given to quaternary organic amines, such as tetramethylammonium hydroxide.

As a catalyst in manufacturing the polyorganosiloxane which has a (meth) acryloxy group, an alkali metal compound or an organic base is preferable.

The liquid crystal aligning agent containing the radiation sensitive polyorganosiloxane manufactured using the polyorganosiloxane which has the (meth) acryloxy group synthesize | combined using the alkali metal compound or the organic base as a catalyst is very excellent in storage stability. It is preferable because of that. The reason is that, as pointed out in Non-Patent Document 4 (Chemical Reviews, Vol. 95, p. 1409 (1995)), the use of alkali metal compounds or organic bases as catalysts in hydrolysis and condensation reactions , A random structure, a ladder structure, or a cage structure are formed, and it is presumed that this is because a polyorganosiloxane having a small content ratio of silanol groups is obtained. Since the condensation reaction of silanol groups is suppressed because the content ratio of silanol groups is small, and when said liquid crystal aligning agent contains another polymer, the condensation reaction of a silanol group and another polymer is suppressed, and therefore the result which was excellent in storage stability It is assumed to be.

As the catalyst, an organic base is particularly preferable. The use ratio of the organic base is different depending on the type of organic base, reaction conditions such as temperature, and the like, but should be appropriately set. For example, the use ratio of the organic base is preferably 0.01 to 3 times mole, more preferably 0.05 To 1 mole.

The hydrolysis or hydrolysis / condensation reaction when producing a polyorganosiloxane having a (meth) acryloxy group is a silane compound having a (meth) acryloxy group and, if necessary, another silane compound is dissolved in an organic solvent. It is preferable to carry out by mixing a solution with an organic base and water, for example by heating with an oil bath or the like.

In the case of the hydrolysis-condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., preferably 0.5 to 12 hours, more preferably 1 to 8 hours. Do. During the heating, the mixed liquid may be stirred or placed under reflux.

It is preferable to wash | clean the organic solvent layer fractionated from the reaction liquid after completion | finish of reaction with water. At the time of this washing | cleaning, washing | cleaning using water containing a small amount of salts, such as about 0.2 weight% of ammonium nitrate aqueous solution, etc., is preferable at the point which can perform washing operation easily. The washing is performed until the aqueous layer after washing is neutral, and then the organic solvent layer is dried with a suitable drying agent such as calcium sulfate anhydride and molecular sieve, if necessary, and then the solvent is removed to have a target (meth) acryloxy group. Polyorganosiloxane can be obtained.

In this invention, what is marketed can also be used as a polyorganosiloxane which has a (meth) acryloxy group. As such a commercial item, AC-SQ, MC-SQ (all are manufactured by Toagosei Co., Ltd.) etc. are mentioned, for example.

<Compound (2)>

Compound (2) used in the method for producing a radiation-sensitive polyorganosiloxane of the present invention is a compound represented by the above formula (2).

R ¹ in the formula ( ² ) is a group represented by the formula (R ¹ -1).

As a C1-C40 alkyl group of R <^I> in the said General formula (R <^1> -1), it is preferable that it is a C1-C20 alkyl group, and it is more preferable that it is a C4-C20 alkyl group. It is preferable that this alkyl group is a linear alkyl group, and some or all of the hydrogen atoms which this alkyl group has may be substituted by the fluorine atom. Examples of such a group include, for example, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n -Tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 4,4, 4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4, 4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group And 2- (perfluorooctyl) ethyl group and 2- (perfluorodecyl) ethyl group.

As a C3-C40 monovalent organic group containing the alicyclic group or condensed cyclic group of R <^1> , a cholesteryl group, a cholestanyl group, an adamantyl group, etc. are mentioned, for example.

Examples of the divalent aromatic group R ^III, for example, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene group, a 2,3,5,6 -Tetrafluoro-1,4-phenylene group; As a bivalent alicyclic group of R ^III , a 1, 4- cyclohexylene group etc. are mentioned, for example;

As a bivalent heterocyclic group of R ^III , a 1, 4- pyridylene group, a 2, 5- pyridylene group, a 1, 4- furanylene group etc. are mentioned, for example; As the fused ring group of a divalent R ^III, for example, a naphthylene group, and the like, respectively.

It is preferable that a is 0 or 1.

It is preferable that it is 0 or 1, and, as for b, it is more preferable that it is zero.

As a halogen atom of Z, a chlorine atom, a bromine atom, an iodine atom, etc .;

As an alkylsulfonate group which has a C1-C6 alkyl group (However, the alkyl group which this alkylsulfonate group has may be substituted by a fluorine atom), For example, a methylsulfonate group, an ethylsulfonate group, a trifluoromethylsulfo Nate group etc .; As an arylsulfonate group which has a C6-C10 aryl group, a phenyl group, p-tolyl group, etc. are mentioned, respectively. As Z in the said Formula (2), a bromine atom, an iodine atom, a methylsulfonyl group, a trifluoromethylsulfonyl group, or p-tolylsulfonyl group is preferable among the above.

As a preferable example of a compound (2), the compound etc. which are respectively represented by following General formula (2-1)-(2-9) are mentioned, for example.

(In Formulas (2-1) to (2-9), each of R ^I has the same meaning as in Formula (R ¹ -1), and Z is the same meaning as in Formula 2, respectively.

The use ratio of the compound (2) in the method of the present invention is preferably 0.001 to 1.5 mol, more preferably to 1 mol of the (meth) acryloxy group of the polyorganosiloxane having a (meth) acryloxy group. 0.01 to 1 mol, more preferably 0.05 to 0.9 mol.

<Heavy metal compound or heavy metal complex>

As a heavy metal compound or heavy metal element contained in the heavy metal compound or heavy metal complex used for the manufacturing method of the radiation sensitive polyorganosiloxane of this invention, palladium is preferable.

In this invention, it is preferable to use a bivalent palladium compound or a 0-valent palladium complex as a heavy metal compound or a heavy metal complex, It is more preferable to use a bivalent palladium compound, It is especially preferable to use palladium acetate.

As a heavy metal compound or a heavy metal complex in this invention, when using a bivalent palladium compound, it is preferable to coexist at least 1 type selected from the group which consists of a compound and a base which have a phosphorus atom with this. As a compound which has a phosphorus atom, triphenyl phosphine, tri (o-tolyl) phosphine, etc. are mentioned, for example; As a base, triethylamine, potassium carbonate, etc. are mentioned, respectively. When using a divalent palladium compound as a heavy metal compound or a heavy metal complex, it is more preferable to coexist both a compound and a base which have a phosphorus atom with this.

The use ratio of the heavy metal compound or the heavy metal complex in the method of the present invention is preferably 0.0005 to 1 mole, more preferably 0.005 to 0.1 mole with respect to 1 mole of the compound (2). When using the compound which has a phosphorus atom together, the use ratio is preferably 0.001-1 mol, More preferably, it is 0.01-0.5 mol with respect to 1 mol of compound (2). When using a base, the use ratio is 1 mol-100 mol with respect to 1 mol of compound (2), More preferably, it is 2-10 mol.

<Production of radiation-sensitive polyorganosiloxane>

The method for producing a radiation-sensitive polyorganosiloxane of the present invention is preferably in the presence of a heavy metal compound or a heavy metal complex of the polyorganosiloxane having a (meth) acryloxy group and the compound (2) as described above. Preferably, the reaction is carried out in a suitable organic solvent. This reaction applies the reaction generally called "Heck reaction."

As an organic solvent which can be used for the method of this invention, for example, toluene, xylene, diethyl ether, tetrahydrofuran, anisole, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N, N -Dimethylacetamide, N-methyl-2-pyrrolidone, gamma -butyrolactone, ethyl acetate, etc. are mentioned. It is preferable that it is 5,000 weight part or less with respect to 100 weight part of compounds (2), and, as for the usage ratio of a solvent, it is more preferable that it is 200-2,000 weight part.

Reaction temperature becomes like this. Preferably it is 20-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 0.1 to 48 hours, more preferably 0.5 to 12 hours.

<Radiation Polyorganosiloxane>

The radiation sensitive polyorganosiloxane prepared by the method of the present invention has a structure represented by the following formula (3). Since this structure is easily isomerized according to the polarization direction of radiation by irradiating a radiation, the said radiation sensitive polyorganosiloxane can be used suitably as a component of the liquid crystal aligning agent used for the photo-alignment method.

(In Formula 3, R and n are the same meanings as in Formula 1, respectively, and R ¹ , R ² and b are the same meanings as in Formula 2, respectively.)

Hereinafter, although the preferable aspect of the liquid crystal aligning agent manufactured using the radiation sensitive polyorganosiloxane manufactured by the method of this invention is demonstrated, this invention is not limited to this.

<Liquid crystal aligning agent>

Although the liquid crystal aligning agent containing the radiation sensitive polyorganosiloxane manufactured by the method of this invention contains the said radiation sensitive polyorganosiloxane as a main component, it may contain other components as needed.

As such other components, for example, polymers other than the radiation-sensitive polyorganosiloxane produced by the method of the present invention (hereinafter referred to as "other polymers"), compounds having one or more epoxy groups in the molecule (hereinafter, " Epoxy compounds ", functional silane compounds, curing agents, curing catalysts, curing accelerators, surfactants, and the like.

[Other polymers]

As said other polymer, 1 or more types chosen from the group which consists of a condensate of the at least 1 sort (s) of polymer chosen from the group which consists of polyamic acid and polyimide, the polysiloxane represented by following formula (4), its hydrolyzate, and hydrolyzate, for example (Hereinafter referred to as “other polysiloxanes”), polyamic acid esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like. have.

In Formula 4, X ² is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y ² is a hydroxyl group or an alkoxyl group having 1 to 10 carbon atoms. )

As another polymer, 1 or more types of polymers chosen from the group which consists of a polyamic acid and a polyimide, or another polysiloxane are preferable.

Polyamic Acid

The said polyamic acid can be obtained by making tetracarboxylic dianhydride and diamine react.

As said tetracarboxylic acid, an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, etc. are mentioned, for example, As these specific examples, for example, butane Tetracarboxylic 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- (tetrahydro-2,5-dioxo-3-furanyl) -8-methyl-naphtho [ 1,2-c] -furan-1,3-dione, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride Water, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, and the like.

As said diamine, aromatic diamine, aliphatic diamine, alicyclic diamine, etc. are mentioned, As a specific example of these, p-phenylenediamine, 4,4'- diamino diphenylmethane, 1, 5- dia, for example. Minonaphthalene, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4 -Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) Phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy C] -octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-dia Minobenzene, 1-cholestanyloxy-2,4-diaminobenzene, hexadecyloxy (3,5-diaminobenzoyl), octadecyl When the like (3,5-diamino-benzoylamino), cholesteryl oxy (3,5-diamino-benzoylamino), Collet star carbonyl oxy (3,5-diamino benzoyl).

Synthesis reaction of polyamic acid (reaction of tetracarboxylic dianhydride and diamine as described above) is preferably a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C in a suitable organic solvent. Underneath, preferably 0.5 to 24 hours, more preferably 2 to 10 hours.

[Polyimide]

The polyimide can be produced by dehydrating and ring closing the amic acid structure of the polyamic acid obtained as described above to imidize it.

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

The method (i) can be carried out by heating at a temperature of, for example, 50 to 200 ° C, for example, for 0.5 to 48 hours.

As an example of the dehydrating agent in the method of said (ii), For example, acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride; As an example of a dehydration ring-closure catalyst, tertiary amines, such as pyridine, collidine, lutidine, and triethylamine, etc. are mentioned, for example. This dehydration ring-closure reaction is performed at the temperature of 0-180 degreeC, for example for 0.5 to 20 hours.

[Other Polysiloxanes]

The other polysiloxane is, for example, at least one silane compound (hereinafter also referred to as "raw silane compound") selected from the group consisting of an alkoxysilane compound and a halogenated silane compound, preferably selected from the group consisting of water and a catalyst It can manufacture by hydrolysis or hydrolysis and condensation in presence.

As a raw material silane compound used here, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, Dimethyl diethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, etc. are mentioned.

As a catalyst which can be used in the synthesis | combination of another polysiloxane, a metal chelate compound, an organic acid, an inorganic acid, etc. are mentioned, for example.

The preparation of other polysiloxanes is carried out, for example, at a temperature of 0 to 100 ° C., for example for 0.5 to 24 hours.

Epoxy Compound

As said epoxy compound, N, N, N ', N'- tetraglycidyl-m-xylenediamine, 1, 3-bis (N, N- diglycidyl aminomethyl) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'-diaminodiphenylmethane, N, N- diglycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane, etc. It is mentioned as a preferable thing.

[Liquid crystal aligning agent]

Although the liquid crystal aligning agent containing the radiation sensitive polyorganosiloxane manufactured by the method of this invention contains a radiation sensitive polyorganosiloxane and other components used as needed, Preferably each component is an organic solvent. It is prepared as a solution phase composition dissolved in. The solid content concentration of the liquid crystal aligning agent, that is, the ratio of the weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is appropriately selected depending on the coating method used in consideration of viscosity, volatility, and the like. It is the range of 1 to 10 weight%.

<Formation Method of Liquid Crystal Alignment Film>

Next, the method to form a liquid crystal aligning film using the liquid crystal aligning agent as mentioned above is demonstrated.

As a method of forming a liquid crystal aligning film, the method of apply | coating the said liquid crystal aligning agent on the transparent substrate with a patterned transparent conductive film, for example, forms a coating film, and then gives a liquid crystal aligning ability to the said coating film by the photo-alignment method. Can be mentioned.

Coating is performed by the appropriate coating methods, such as a roll coater method, a spinner method, the printing method, and the inkjet method, for example. After application | coating, a coating film can be formed by preheating (prebaking) and then baking (post-baking). The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-baking conditions are 5 to 200 minutes at 120 to 300 ° C., for example. The film thickness of the coating film after post-baking becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

Subsequently, the liquid crystal aligning ability is provided by irradiating linearly or partially polarized radiation or unpolarized radiation to the said coating film. Here, as the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable.

The irradiation amount of the radiation is preferably 1 J / m 2 or more and less than 10,000 J / m 2, more preferably 10 to 3,000 J / m 2. In addition, the liquid crystal aligning agent containing the radiation-sensitive polyorganosiloxane manufactured by the method of this invention is good even if the radiation dose at the time of photo-alignment method is 3,000 J / m <2> or less and 1,000 J / m <2> or less. Performance can be provided, and it is effective in reducing the manufacturing cost of a liquid crystal display element.

The liquid crystal aligning film formed as mentioned above can be preferably applied to various liquid crystal display elements. Manufacture of a liquid crystal display element can be performed by a well-known method using the board | substrate which has a liquid crystal aligning film formed as mentioned above.

[Example]

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

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

Column: Toso Corporation, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68 kgf / ㎠

In addition, in the following example, the synthesis | combination of a raw material compound and a polymer was repeated as needed on the following synthesis scale, and the required amount in the following example was ensured.

Synthesis Example of Compound (2)

Synthesis Example 1 (Synthesis of Compound (2-4-1))

According to Scheme 1 below, compound (2-4-1) was synthesized.

91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate, and 320 mL of N-methyl-2-pyrrolidone were added to a 1 L branched flask, followed by stirring at room temperature for 1 hour, followed by 4,4, 99.7 g of 4-trifluoro-1-iodobutane were added and stirred at 100 ° C. for 5 hours. After the reaction was completed, reprecipitation was carried out with water. 48 g of sodium hydroxide and 400 mL of water were added to the obtained precipitate, and the mixture was refluxed for 3 hours to undergo a hydrolysis reaction. After completion of the reaction, neutralization was performed by adding hydrochloric acid to the reaction mixture, and the resultant precipitate was recrystallized from ethanol to give 102 g of white crystals of the compound (2-4-1A).

23 g of this compound (2-4-1A) were taken in a reaction vessel, and 200 mL of thionyl chloride and 144 μL of N, N-dimethylformamide were added thereto, and the mixture was stirred at 80 ° C. for 1 hour. Subsequently, thionyl chloride was distilled off under reduced pressure, and the organic layer obtained by adding methylene chloride was washed with an aqueous sodium hydrogen carbonate solution, then dried over magnesium sulfate, the solvent was distilled off, and tetrahydrofuran was added to make a solution.

Subsequently, 19 g of 4-bromophenol, 11 g of triethylamine, and 100 mL of tetrahydrofuran were added to a 500 mL three-neck flask separate from the above. This solution was ice-cooled, and the said tetrahydrofuran solution was slowly dripped, and reaction was performed at room temperature for 2 hours, stirring. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was separated and washed three times with water. Subsequently, the organic layer was dried over magnesium sulfate, concentrated and dried, and then recrystallized with ethanol to obtain 28 g of compound (2-4-1).

<Production of radiation-sensitive polyorganosiloxane>

Example S-1

16.5 g of AC-SQ (manufactured by Toagosei Co., Ltd.) in a 500 mL three-necked flask equipped with a nitrogen inlet tube, a thermometer, and a reflux tube (Compound (2-9-1) -1)) 15.5 g, 0.11 g of palladium acetate, 0.61 g of tri (o-tolyl) phosphine, 27.8 mL of triethylamine and 100 mL of N, N-dimethylacetamide were added and the reaction was carried out at 115 ° C. for 3 hours. It was. After completion of the reaction, the reaction mixture was filtered to remove the insoluble fraction, and the organic layer obtained by adding ethyl acetate to the filtrate was separated and washed twice with dilute hydrochloric acid and then three times with water, and then concentrated under reduced pressure. It was. By reprecipitating the obtained concentrate with methanol, 15 g of radiation-sensitive polyorganosiloxane (S-1) was obtained.

¹ H-NMR analysis of the radiation-sensitive polyorganosiloxane (S-1) revealed that 38 mol% of the acryloxy groups of AC-SQ as the starting material react to react with the compound (2-9-1) It confirmed that it was converted into the group derived from.

The weight average molecular weight Mw of this radiation sensitive polyorganosiloxane (S-1) was 6,200.

Example S-2

Radiation-sensitive by performing the same operation as in Example S-1, except that 16.5 g of Compound (2-4-1) obtained in Synthesis Example 1 was used instead of Compound (2-9-1) in Example S-1. 16 g of polyorganosiloxane (S-2) was obtained.

¹ H-NMR analysis of the radiation-sensitive polyorganosiloxane (S-2) showed that 33 mol% of the acryloxy groups of the raw material AC-SQ reacted to react with the compound (2-4-1) It confirmed that it was converted into the group derived from.

The weight average molecular weight Mw of this radiation sensitive polyorganosiloxane (S-2) was 6,600.

Example S-3

Radiation-sensitive by performing the same operation as in Example S-1, except that 33 g of Compound (2-4-1) obtained in Synthesis Example 1 was used instead of Compound (2-9-1) in Example S-1. 18 g of polyorganosiloxane (S-3) was obtained.

¹ H-NMR analysis of the radiation-sensitive polyorganosiloxane (S-3) showed that 48 mol% of the acryloxy groups of AC-SQ as the starting material reacted to give the compound (2-4-1) It confirmed that it was converted into the group derived from.

The weight average molecular weight Mw of this radiation sensitive polyorganosiloxane (S-3) was 7,500.

Synthesis of Other Polymers

[Synthesis of Polyamic Acid]

Synthesis Example PA-1

109 g (0.50 mol) of pyromellitic dianhydrides as tetracarboxylic dianhydride and 98 g (0.50 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4-diamino as diamine 200 g (1.0 mole) of diphenyl ether was dissolved in 2,290 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours, followed by adding 1,350 g of N-methyl-2-pyrrolidone. About 4,000 g of a solution containing 10 wt% of mymic acid (PA-1) was obtained. The solution viscosity of this polyamic acid solution was 210 mPa · s.

Synthesis Example PA-2

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 14.23 g (0.1 mol) of cyclohexanebis (methylamine) as diamine are N-methyl-2-pi It melt | dissolved in 329.3 g of rolidones, and reaction was performed at 60 degreeC for 6 hours. The reaction mixture was then poured into very excess methanol and the reaction product precipitated out. The precipitate was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to give 32 g of polyamic acid (PA-2).

Synthesis Example PA-3

1,96 g (1.0 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine (1.0 mol) was dissolved in 4,050 g of N-methyl-2-pyrrolidone and reacted at 40 ° C for 3 hours to obtain about 3,700 g of a solution containing 10% by weight of polyamic acid (PA-3). The solution viscosity of this polyamic acid solution was 170 mPa · s.

Synthesis of Polyimide

Synthesis Example PI-1

As tetracarboxylic dianhydride 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra 157 g (0.50 mol) of hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 95 g (0.88 p-phenylenediamine as diamine) Moles), 2,2-ditrifluoromethyl-4,4-diaminobiphenyl 32 g (0.10 mole), 3,6-bis (4-aminobenzoyloxy) cholestane 6.4 g (0.010 mole) and octa 4.0 g (0.015 mol) of decanoxy-2,5-diaminobenzene was dissolved in 960 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 9 hours. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 58 mPa · s.

2,740 g of N-methyl-2-pyrrolidone, 396 g of pyridine and 409 g of acetic anhydride were added to the obtained polyamic acid solution, and dehydration ring-closure reaction was performed at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was substituted with fresh N-methyl-2-pyrrolidone (by this operation, the pyridine and acetic anhydride used for the dehydration ring closure reaction were removed to the outside of the system), whereby the imidation ratio was about 95 About 2,500 g of a solution containing 15% by weight of polyimide (PI-1) in% was obtained.

A small amount of this polyimide solution was removed, the solvent was removed under reduced pressure, and then dissolved in γ-butyrolactone, and the solution viscosity measured as a solution having a polymer concentration of 8.0 wt% was 33 mPa · s.

Synthesis Example PI-2

20.9 g (0.093 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 9.2 g (0.085 mol) of p-phenylenediamine as diamine and represented by the following general formula (D-6) 4.9 g (0.009 mol) of the compound was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing polyamic acid. A little aliquot of the obtained polyamic-acid solution was added, N-methyl- 2-pyrrolidone was added, and the solution viscosity was measured as a solution of 10 weight% of polymer concentration, and it was 126 mPa * s.

Subsequently, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 7.4 g of pyridine and 9.5 g of acetic anhydride were added to dehydrate and close the ring at 110 ° C. for 4 hours. After dehydration ring closure, about 220 g of a solution containing 16.1% by weight of polyimide (PI-2) having an imidization rate of about 54% was obtained by solvent substitution of the solvent in the system with fresh N-methyl-2-pyrrolidone. .

The solution viscosity measured as a small amount of this polyimide solution, the addition of N-methyl- 2-pyrrolidone, and the solution of 10 weight% of polymer concentrations was 75 mPa * s.

[Synthesis of Other Polysiloxanes]

Synthesis Example PS-1

20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated to 60 ° C and stirred. The aqueous maleic anhydride solution in which 0.26 g of maleic anhydride prepared in a separate flask having a volume of 20 mL was dissolved in 10.8 g of water was added thereto, and the reaction was carried out by heating and stirring at 60 ° C for 4 hours. The solvent was distilled off from the obtained reaction mixture, 1-ethoxy-2-propanol was added, and it concentrated again, and the polymer solution containing 10 weight% of polyorganosiloxane (PS-1) was obtained. The weight average molecular weight Mw of PS-1 was 5,100.

Example A-1

<Production of Liquid Crystal Alignment Agent>

The amount equivalent to 1,000 parts by weight of the solution containing the polyamic acid (PA-1) obtained in Synthesis Example PA-1 as the other polymer in terms of the polyamic acid (PA-1) contained therein is taken. 100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in Example S-1 was added, and additionally N-methyl-2-pyrrolidone and butyl cellosolve were added to give a solvent composition of N-methyl. 2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio), and solid content concentration was set as the solution which is 3.0 weight%. The liquid crystal aligning agent (A-1) was manufactured by filtering this solution with the filter of 1 micrometer of pore diameters.

This liquid crystal aligning agent (A-1) was stored at -15 degreeC for 6 months. The viscosity was measured by the E-type viscosity meter at 25 degreeC before and after storage. The storage stability of the liquid-crystal aligning agent (A-1) was "good" when the change rate before and after storage of the solution viscosity evaluated less than 10% as storage stability "good" and 10% or more.

<Formation of Liquid Crystal Alignment Film and Production of Liquid Crystal Display Element>

The liquid crystal aligning agent (A-1) prepared above was apply | coated using the spinner on the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO film, and it preliminarily baked on 80 degreeC hotplate for 1 minute, and then in-system Was heated (post-baked) at 200 ° C. for 1 hour in an oven substituted with nitrogen to form a coating film having a thickness of 0.1 μm. Subsequently, 200 J / m <2> of polarized ultraviolet-ray containing 313 nm bright line was irradiated to the surface of this coating film from the direction normal to 40 degrees from the board | substrate normal line using a Hg-Xe lamp and a glan tailor prism, and it was set as the liquid crystal aligning film. The same operation was repeated and a pair (two sheets) of board | substrates which have a liquid crystal aligning film were manufactured.

After screen-printing the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer on the outer peripheral part of the surface which has one liquid crystal aligning film among the said board | substrates, the liquid crystal aligning film surface of a pair of board | substrate is made to oppose, and the ultraviolet-ray of each board | substrate is It crimp | bonded so that the projection direction of an optical axis to the board | substrate surface might become antiparallel, and the adhesive agent was thermosetting at 150 degreeC over 1 hour. Subsequently, after filling a negative liquid crystal (MLC-6608 by Merck Co., Ltd.) in the clearance gap between board | substrates from a liquid crystal injection hole, the liquid crystal injection hole was sealed with the epoxy adhesive. In addition, in order to remove the flow orientation at the time of liquid crystal injection, after heating to 150 degreeC, it cooled gradually to room temperature. Next, the liquid crystal display element was manufactured by bonding the polarizing plates to the outer both surfaces of a board | substrate so that the polarization directions orthogonal to each other, and may make an angle of 45 degrees with the projection direction to the board | substrate surface of the ultraviolet optical axis of a liquid crystal aligning film.

This liquid crystal display device was evaluated by the following method. The evaluation results are shown in Table 2.

<Evaluation Method of Liquid Crystal Display Element>

(1) Evaluation of liquid crystal alignment

With respect to the liquid crystal display device manufactured above, the presence or absence of an abnormal domain in the change in contrast when the voltage of 5 V is turned ON / OFF (applied or released) is observed by an optical microscope, and the case where there is no abnormal domain is found. "Good".

(2) Evaluation of the pretilt angle

Regarding the liquid crystal display device manufactured above, literature [T. J. Scheffer et. al. J. Appl. Phys. vol. 19, p. 2013 (1980)], the pretilt angle was measured by the crystal rotation method using He-Ne laser light.

(3) Evaluation of voltage retention

After applying the voltage of 5 V to the liquid crystal display element manufactured above by the application time of 60 microseconds, and the span of 167 milliseconds, the voltage retention after 167 milliseconds after application | release cancellation was measured. The measurement apparatus used VHR-1 by Toyo Technica.

(4) Evaluation of Stability of Pretilt Angle

After storing the liquid crystal display element manufactured above for 30 days at 23 degreeC, the pretilt angle was measured again. When the amount of change from the beginning was less than 1 °, the pretilt angle stability was "good".

Example A-2

1,000 parts by weight of polyamic acid (PA-2) obtained in Synthesis Example PA-2 as a polymer different from 100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in Example S-1 was added to N. N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio) and solid content concentration of 3.0 weight% by addition of methyl-2-pyrrolidone and butyl cellosolve It was. The liquid crystal aligning agent (A-2) was manufactured by filtering this solution with the filter of 1 micrometer of pore diameters.

About this liquid crystal aligning agent, various evaluation was performed like Example A-1. The evaluation results are shown in Table 1 and Table 2.

Examples A-3 to A-6, A-8 to A-10, A-12 and A-14 to A-16

In Example A-1, 100 parts by weight of each of the kind shown in Table 1 as a radiation-sensitive polyorganosiloxane was used, using a solution containing the kind and amount of the polymer shown in Table 1 as the solution containing the other polymer. A liquid crystal aligning agent was produced similarly to the said Example A-1 except having used each, and various evaluation was performed. The evaluation results are shown in Table 1 and Table 2.

Examples A-7 and A-13

In Example A-2, except having used 100 weight part of each of the kind shown in Table 1 as a radiation sensitive polyorganosiloxane, it carried out similarly to Example A-2, and produced the liquid crystal aligning agent. Each evaluation was performed similarly to the said Example A-1 using these liquid crystal aligning agents. The evaluation results are shown in Table 1 and Table 2.

Example A-11

As another polymer, the solution containing the other polysiloxane (PS-1) obtained by the said synthesis example PS-1 was converted into the polysiloxane (PS-1) contained in this, and the quantity equivalent to 2,000 weight part is taken, 100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in Example S-1 was added, and 1-ethoxy-2-propanol was further added to obtain a solution having a solid content of 4.0% by weight. The liquid crystal aligning agent (A-7) was manufactured by filtering this solution with the filter of 1 micrometer of pore diameters.

About this liquid crystal aligning agent, various evaluation was performed like Example A-1. The evaluation results are shown in Table 1 and Table 2.

Claims (5)

A radiation sensitive polyorganosiloxane, which has a structure represented by the following formula (3).
<Formula 3>

In formula (3), R is a hydrogen atom or a methyl group, n is an integer of 1 to 10, R ¹ is a group represented by the following formula (R ¹ -1), R ² is a fluorine atom or a cyano group, b Is an integer from 0 to 4)

(In formula (R ^1-1 ), R ^I is a C1-C40 alkyl group or a C3-C40 monovalent hydrocarbon group containing an alicyclic group or a condensed cyclic group, provided that a hydrogen atom of said alkyl group Some or all may be substituted with a fluorine atom, R ^II is a single bond, an oxygen atom, * -COO- or * -OCO- (wherein the above-mentioned bond with "*" is bonded to R ^I ), R ^III is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, and R ^IV is a single bond, an oxygen atom, * -COO- or * -OCO- (wherein " Bond is attached to R ^III ) and a is an integer from 0 to 3). A method for producing a radiation-sensitive polyorganosiloxane, comprising reacting a polyorganosiloxane having a structure represented by the following formula (1) with a compound represented by the following formula (2) in the presence of a heavy metal compound or a heavy metal complex.
<Formula 1>

(In Formula 1, R and n each have the same meaning as in Formula 3 described in claim 1)
<Formula 2>

(In Formula 2, R <^1> , R <^2> and b are respectively the same meaning as in Formula (3) of Claim 1, and Z is a halogen atom or the alkylsulfonate group or C6 which has a C1-C6 alkyl group To an arylsulfonate group having an aryl group of 10, provided that the alkyl group having the alkylsulfonate group may be substituted with a fluorine atom) The method for producing a radiation sensitive polyorganosiloxane according to claim 2, wherein the radiation sensitive polyorganosiloxane has a structure represented by the formula (3) according to claim 1. The method for producing a radiation sensitive polyorganosiloxane according to claim 2 or 3, wherein the radiation sensitive polyorganosiloxane is used for a liquid crystal aligning agent. A radiation sensitive polyorganosiloxane which has a structure represented by General formula (3) of Claim 1,
At least one polymer selected from the group consisting of polyamic acids and polyimides
It contains, The liquid crystal aligning agent characterized by the above-mentioned.