WO2009051273A1 - Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane which is obtained by reacting a cinnamic acid derivative having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R represents a hydrogen atom or an alkyl group having 1-6 carbon atoms), -CH=CH2 and -SO2Cl with a polyorganosiloxane having an oxethane ring.

Description

 Technical Field

 The present invention relates to a liquid crystal aligning agent, a method for producing a liquid crystal aligning film, and a liquid crystal display element.

Background art

 Light

 Conventionally, nematic liquid crystal with positive dielectric anisotropy has been converted to transparent with liquid crystal alignment film.

Sandwich structure with electrode-attached substrate, and the long axis of liquid crystal molecules is written between the substrates as necessary.

 0-360 ° liquid crystal that twists continuously, such as TN (Tw isted Nematic) type, STN (Super Twisted Nematic) type, I PS (In P Lane Switching) type, etc. A liquid crystal display element having a cell is known (see Japanese Patent Application Laid-Open No. 56-91277 and Japanese Patent Application Laid-Open No. 11-12528).

 In such a liquid crystal cell, it is necessary to provide a liquid crystal alignment film on the substrate surface in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon. However, when the liquid crystal alignment film is formed by rubbing, dust and static electricity are likely to be generated in the process, and there is a problem that dust adheres to the alignment film surface and causes display defects. In particular, in the case of a substrate having TFT (Thin Film Trns sistor) elements, there is a problem that the circuit damage of the TFT elements occurs due to the generated static electricity, resulting in a decrease in yield. Furthermore, liquid crystal display elements with higher definition in the future will have unevenness on the substrate surface as the pixel density increases, making uniform rubbing difficult.

As another means of aligning the liquid crystal in the liquid crystal cell, polarized light is applied to photosensitive thin films such as polyvinyl cinnamate, polyimide, and azobenzene derivatives formed on the substrate surface. Alternatively, a photo-alignment method that imparts liquid crystal alignment ability by irradiating non-polarized radiation is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (Japanese Patent Laid-Open No. 6-287453, Japanese Patent Laid-Open No. 10-251646, Japanese Patent Laid-Open No. 11-2815, JP-A-11-152475, JP-A-2000-144136, JP-A-2000-319510, JP-A-2000-281724, JP-A-9-297313, JP2003-307736, JP open 2004- 163646 and JP-open 2002- see JP _250924) ς

 By the way, in liquid crystal cells such as TN (Twisted Nematic) and STN (Super Twisted Nematic) types, the liquid crystal alignment film tilts the liquid crystal molecules at a predetermined angle with respect to the substrate surface. It must have pre-tilt angle characteristics. In the case of forming a liquid crystal alignment film by the photo-alignment method, the pretilt angle is usually given by tilting the incident direction of the irradiated radiation to the substrate surface from the substrate normal.

 On the other hand, as an operation mode of a liquid crystal display element different from the above, a vertical (homeotope pick) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known. In this operation mode, when a voltage is applied between the substrates and the liquid crystal molecules are tilted in the direction parallel to the substrate, the liquid crystal molecular force is tilted in the direction normal to the substrate from the normal direction of the substrate. There is a need. As a means for this, for example, a method of providing protrusions on the substrate surface, a method of providing stripes on the transparent electrode, and using a rubbing alignment film, liquid crystal molecules are slightly directed from the substrate normal direction to one direction in the substrate surface. There have been proposed methods of tilting (pre-tilting).

The photo-alignment method is known to be useful as a method for controlling the tilt direction of liquid crystal molecules in a vertical alignment mode liquid crystal cell. In other words, it is known that the tilt direction of liquid crystal molecules when a voltage is applied can be uniformly controlled by using a vertical alignment film imparted with alignment regulating ability and pretilt angle expression by a photo-alignment method (Japanese Patent Laid-Open No. 2003-307736). No. 2004, No. 2004-163646, No. 20 04-83810, No. JP-A-911468 and No. 2003- 114437).

Thus, the liquid crystal alignment film produced by the photo-alignment method can be effectively applied to various liquid crystal display elements. However, the conventional photo-alignment film has a problem that a large amount of radiation is required to obtain a large pretilt angle. For example, when liquid crystal alignment ability is imparted to a thin film containing an azobenzene derivative by the photo-alignment method, radiation with the optical axis tilted from the substrate normal is 10,000 JZm ² or more in order to obtain a sufficient pretilt angle. It has been reported that it has to be irradiated (see JP 2002-250924 A and JP 2004-83810 A and J. oft he S ID 1 1/3, 2003, ρ 579). Disclosure of the invention

 An object of the present invention is to provide a liquid crystal alignment agent that provides a liquid crystal alignment film having a good liquid crystal alignment ability even with a small exposure amount by irradiation with polarized or non-polarized radiation without rubbing, and a method for producing the liquid crystal alignment film Another object of the present invention is to provide a liquid crystal display device excellent in various properties such as display characteristics and reliability.

 Still other objects and advantages of the present invention will become apparent from the following description. According to the present invention, the above object of the present invention is as follows.

Power Rupokishiru group, a hydroxyl group, one SH, one NCO, -NHR (where R was or hydrogen atom is an alkyl group having 1 to 6 carbon atoms), - CH = CH ₂ and - S_〇 group consisting of ₂ C 1 A cinnamic acid derivative having at least one group selected from

A polyorganosiloxane having an oxetane ring and

This is achieved by a liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane obtained by reacting the above.

 The above object of the present invention is secondly,

This is achieved by a method for forming a liquid crystal alignment film in which the liquid crystal aligning agent is applied onto a substrate to form a coating film, and the coating film is irradiated with radiation.

Thirdly, the above object of the present invention is as follows. It is achieved by a liquid crystal display device comprising a liquid crystal alignment film formed from the above liquid crystal aligning agent. BEST MODE FOR CARRYING OUT THE INVENTION

The liquid crystal aligning agent of the present invention includes a carboxyl group, 7j <acid group, —SH, —NCO, 1 NH R (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —CH═CH ₂ and A cinnamic acid derivative having at least one group selected from the group consisting of S0 ₂ C 1 and

A polyorganosiloxane having an oxetane ring (hereinafter referred to as “polyorganosiloxane having an oxetane ring”) and

Contains a radiation-sensitive polyorganosiloxane obtained by reacting

 [Cinnamic acid derivatives]

 Powerful loxyl group used in the present invention, hydroxyl group, —SH, 1 NCO, —NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —CH═CH

₂ and — a cinnamic acid derivative having at least one group selected from the group consisting of SO ₂ C 1 is represented by the following formula (A-1)

(In the formula (A-1), R ¹ is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, provided that one of the hydrogen atoms of the alkyl group is Part or all may be substituted with a fluorine atom, R ² is a single bond, an oxygen atom, —C 0— or —OCO—, R ³ is a divalent aromatic group, a divalent aromatic group, An alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, provided that part or all of the hydrogen atoms of the divalent aromatic group may be substituted with fluorine atoms, R ⁴ is a single bond, oxygen atom, —COO— or —OC〇1, R ⁵ is a single bond, methylene group, carbon An alkylene group of 2 to 10 or a divalent aromatic group; when R ⁵ is a single bond, R ⁶ is a hydrogen atom; and when R ⁵ is a methylene group, an alkylene group or a divalent aromatic group R ⁶ is a force lpoxyl group, a hydroxyl group, —SH, one NCO, —NHR, —CH = CH ₂ or one S0 ₂ C 1, where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁷ is a fluorine atom, a methyl group or a cyano group, a is an integer of 0 to 3, and b is an integer of 0 to 4. )

Or a compound represented by the following formula (A-2)

(A-2)

(In the formula (A-2), R ⁸ is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group or aromatic group, provided that the alkyl group Some or all of the hydrogen atoms may be substituted with fluorine atoms, R ⁹ is a single bond, oxygen atom, 1 COO— or 1 OCO—, R ^1Q is a methylene group, alkylene having 2 to 10 carbon atoms A divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group, provided that one of the hydrogen atoms of the divalent aromatic group is Part or all may be substituted with a fluorine atom, and R ¹¹ is a single bond, one OCO— (CH ₂ ) _e —, —COO— (CH ₂ ) _g — or —Oichi (CH ₂ ) i— Where e, g and i are each an integer from 1 to 10, R ¹² is a force lpoxyl group, a hydroxyl group, one SH, — NCO, — NHR, one CH = CH ₂ or — SO ₂ C 1 However, however Serial R is a hydrogen atom or an alkyl group of carbon number. 1 to 6, R ¹³ is fluorine atom, a methyl group or Shiano group, c is an integer of 0 to 3, d is an integer of 0 to 4 is there.)

It is preferable that the compound is represented by the formula:

Examples of the alkyl group having 1 to 40 carbon atoms of R ^{1 in} the above formula (A-1) include, for example, an alkyl group having 1 to 20 carbon atoms, provided that a part of hydrogen atoms of the alkyl group or It is preferable that all of them may be substituted with a fluorine atom. Examples of such alkyl groups 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-dode. Decyl 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— pendefluoropentyl, 4, 4, 5, 5, 6, 6, 6—heptofluor group hexyl group, 3, 3, 4, 4, 5, 5, 5—hepteven fluoropentyl group, 2, 2, 2— trifluoroethyl group, 2, 2, 3, 3, 3—pentafluoropropyl group, 2- (Perfluorobutyl) ethyl group, 2- (perfluorooctyl) ethyl group, 2 (perfluorodecyl) ethyl group and the like. Examples of the monovalent organic group having 3 to 40 carbon atoms including the alicyclic group of R ¹ include a cholestenyl group, a cholesterol group, an adamantyl group, and the like.

Examples of the divalent aromatic group of R ³ include, for example, 1,4-phenylene group, 2-fluoro-1,1,4-monophenylene group, 3-fluoro-1,4_phenylene group, 2, 3 , 5, 6-1 tetrafluoro-1, 4-phenylene group and the like; and the divalent alicyclic group R ³ is, for example 1, 4 Shikuro xylene based on the; 2 R ³ Examples of the valent heterocyclic group include 1,4_pyridylene group, 2,5-pyridylene group, 1,4-furylene group, and the like. Examples of the divalent condensed cyclic group for R ³ include, for example, A naphthylene group can be mentioned respectively.

For example, the divalent aromatic group of R ⁵ can include 1,4 monophenylene groups.

Examples of the compound represented by the above formula (A-1) include cinnamic acid derivatives having a strong lpoxyl group, for example, the following formulas (A-1—CI) to (A-1-C24)

Three R CH = CH— COO- (CH ₂ ) -COOH (A-1-C22)

^R1Q ~ ^ ^COO- ^ CH = CH— ^COO- (CH ₂ ) -COOH (A-1-C23)

R ¹ COO— ^ ^ -COO-^^ — CH = CH— COO- (CH ₂ ) -COOH (A-1-C24)

(In the formula, R ¹ has the same meaning as in the above formula (A-1), and f is an integer of 1 to 10.)

A compound represented by each of the above;

As the cinnamic acid derivative having a hydroxyl group, for example, the following formulas (A— 1— Ol) to (A— 1 1 O 13)

R ¹ -0— ^ CH = CH— CO- <-° ^H (A-1-01)

R ¹ — COO- -CH = CH— CO- -OH (A-1-02)

Five)

CH = CH— COO- (CH ₂ ) — OH (A-1-08)

CH = CH— COO (CH ₂ ) — OH (A-1-09)

R ¹ COO— ^ ~ CH = CH— COO- (CH ₂ ) — OH (A-1-O10)

(In the formula, R ¹ has the same meaning as in the above formula (A-1), and ί is an integer of 1 to 10).

The compounds represented by each of the above can be mentioned.

In the above formula (Α-2), the alkyl group having 1 to 40 carbon atoms of R ⁸ is, for example, an alkyl group having 1 to 20 carbon atoms, provided that part or all of the hydrogen atoms of this alkyl group are fluorine atoms. It is preferable that it may be substituted by. Examples of such an alkyl group include those exemplified as the alkyl group for R ¹ in the above formula (Α-1). Examples of the monovalent organic group having 3 to 40 carbon atoms including the alicyclic group of R ⁸ include a cholestenyl group, a cholestenyl group, and an adamantyl group. Examples of the monovalent organic group having 3 to 40 carbon atoms including the aromatic group of R ⁸ include

(In the above formula, R ¹ is an alkyl hexyl having an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, or an alkyl group having 1 to 20 carbon atoms. Or a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms.)

Or a group represented by any of the above.

Examples of the divalent aromatic group, divalent alicyclic group, divalent heterocyclic group or divalent fused cyclic group of R ^{1 Q} include, for example, R ^{3 in} the above formula (A-1). Examples thereof include those exemplified as a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group and a divalent condensed cyclic group.

 Examples of the compound represented by the above formula (A-2) include cinnamic acid derivatives having a strong lpoxyl group, for example, the following formulas (A-2—C 1) to (A-2—C 6):

R ⁸ -OCO— CH = CH-/) — OCO— (CH ₂ ) _a -COOH (A-2-C1)

R ⁸ — (/) — CO— CH = CH ~ ^ — OQ (A-2-C2)

r ⁸ ° ~ ^ ~ CO— CH = CH ~ COOH (A-2-C3)

R ⁸ — </) — CO— CH = CH ~ ^ OCO— (CH ₂ ) _a -COOH (A-2-C4)

R ⁸ 0— <\ /> — CO— CH = CH ~ (\ /)-OCO- (CH ₂ ) _a -COOH (A-2-C5) R ⁸ OCO-CH = CH ~, ^ -OCO- ^ ^ -OOC- (CH ₂ ) -COOH (A-2-C6)

(In the above formula, R ⁸ has the same meaning as in the above formula (A-2), and a is an integer of 1 to 10).

 A compound represented by each of the above;

 Examples of cinnamic acid derivatives having a hydroxyl group include the following formulas (Α-2-Ol) to (A-2 -05)

(In the above formula, R ⁸ has the same meaning as in the above formula (A-2), and h is an integer of 1 to 10).

 The compounds represented by each of the above can be mentioned.

 The compound represented by the above formula (A-1) or (A-2) can be synthesized by a conventional method of organic chemistry.

For example, the compound represented by the above formula (A-1-C 1) includes, for example, hydroxycinnamic acid and an alkyl halide having an alkyl group corresponding to R ¹ such as potassium carbonate. The reaction can be carried out by heating in the presence of an appropriate base, and then hydrolyzing with an appropriate aqueous solution such as sodium pentoxide.

The compound represented by the above formula (A-1 1 C 2) can be prepared in the presence of a suitable base such as hydroxycinnamic acid and an alkyl-powered ruponic acid chloride having an alkyl group corresponding to R ¹ , such as carbonated power. It can be obtained by reacting at 0 ° C to room temperature.

The compound represented by the above formula (A-1—C 4) is obtained by combining, for example, methyl hydroxybenzoate with an alkyl halide having an alkyl group corresponding to R ¹ or a tosylated alkyl, such as a suitable carbonic acid lithium. After reacting at room temperature to 100 ° C. in the presence of a base, it is hydrolyzed with an appropriate aqueous alkali solution such as sodium hydroxide, and this is converted to acid chloride with thionyl chloride, which is then carbonated. It can be obtained by reacting with hydroxycinnamic acid at a temperature of 0 ° C. to room temperature in the presence of a suitable base such as potassium.

The compound represented by the above formula (A_l-C 5) is prepared by, for example, combining hydroxybenzoic acid and an alkyl carboxylic acid chloride having an alkyl group corresponding to R ¹ in the presence of a suitable base such as triethylamine. After reacting at room temperature, acid chloride is obtained with thionyl chloride, and this can be obtained by reacting with hydroxycinnamic acid at 0 to room temperature in the presence of a suitable base such as potassium carbonate.

 The compound represented by the above formula (A-1—C 6) is obtained by converting, for example, 4 monoalkylbenzoic acid to acid chloride with thionyl chloride, and then reacting with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate. It can be obtained by reacting at a temperature of C to room temperature.

Examples of the compound represented by the above formula (A-1 C7) include, for example, methyl 4-hydroxycyclohexyl carboxylate and halogenated alkyl having an alkyl group corresponding to R ¹ , such as sodium hydrogenated or metal sodium. After reacting in the presence of an appropriate strength of ether, it is converted to ether, hydrolyzed with an aqueous strength solution of sodium hydroxide or the like, and further converted to acid chloride with thionyl chloride, and then this is converted to an appropriate amount of potassium carbonate or the like. By reacting with hydroxycinnamic acid in the presence of the appropriate base at a temperature between 0 and room temperature. Can be obtained.

The compound represented by the above formula (A-1-C8) is, for example, a compound obtained by converting 4-alkylcyclohexylcarboxylic acid having an alkyl group corresponding to R ¹ into acid chloride with thionyl chloride, potassium carbonate, etc. Can be obtained by reacting with hydroxycinnamic acid at a temperature of 0 ° C. to room temperature in the presence of a suitable base.

The compound represented by the above formula (A-1-C9) is formed by reacting halogenated alkyl corresponding to R ¹ with hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond, and then 4-acetyl. It can be obtained by subjecting benzoic acid to aldol condensation in the presence of sodium hydroxide. Compounds represented by the above formulas (A-1-C10) to (A-11-C15) can also be obtained by a method analogous thereto.

The compound represented by the above formula (A-2-C 1) can be reacted with, for example, 4-alkylphenol and an alkyl alcohol U having an alkyl group corresponding to R ¹ using palladium and amine as catalysts ( In general, this is referred to as “Heck reaction.”) Then, the reaction product can be obtained by ring-opening addition of a desired cyclic acid anhydride such as succinic anhydride or daltaric anhydride.

The compound represented by the above formula (A-2-C2) can be obtained by aldol condensation of 4-alkylacetophenone corresponding to R ¹ and 4-formylbenzoic acid in the presence of sodium hydroxide. A compound represented by the above formula (A-2-C3) can also be obtained by a method analogous thereto.

The compound represented by the above formula (A-2-C4) can be obtained by subjecting a 4-alkyl alkylphenphenone corresponding to R ¹ and 4-hydroxybenzaldehyde to a vinyl condensation in the presence of sodium hydroxide. A compound represented by the above formula (A-2-C5) can also be obtained by a method according to this.

The compound represented by the above formula (Α-1-Ol) is obtained by reacting an alkyl halide having an alkyl group corresponding to R ¹ with 4-hydroxybenzaldehyde in the presence of a base such as carbonic acid rhium. After the bond is formed, 4-hydroxyacetophenone can be obtained by aldol condensation in the presence of sodium hydroxide. The compounds represented by the above formulas (A-1-02) to (A-1-07) can also be obtained by a method similar to the above.

The compound represented by the above formula (A-2-01) is obtained by reacting, for example, 4-iodophenol with an alkyl acrylate having an alkyl group corresponding to R ¹ using palladium and an amine as catalysts (generally “He It is called “ck reaction”.)

The compound represented by the above formula (A-2-02) can be obtained by aldol condensation of 4-alkylacetophenone corresponding to R ¹ and 4-hydroxybenzaldehyde in the presence of sodium hydroxide. The compound represented by the above formula (A-2-03) can also be obtained by a method similar to the above.

[Polyorganosiloxane with oxene ring]

 The polyorganosiloxane having the above oxetane ring is represented by the following formula (S-1)

(In the formula (S-1), X is the following formula (X-1)

(In the formula (X-1), R ¹⁴ is an alkyl group having 1 to 6 carbon atoms, and “*” indicates a bond.)

Y ¹ is a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. ) The polyorganosiloxane having a repeating unit represented by the formula (1) is preferably at least one selected from the group consisting of a hydrolyzate thereof and a hydrolyzate condensate.

The alkyl group of the group R ¹⁴ in the group X in the formula (S-1) is preferably a methyl group, an ethyl group, an n-propyl group or an n-butyl group.

 The group X in the formula (S-1) is preferably the following formula (X-2)

(In the formula (X-2), R ^{1 4} has the same meaning as in the above formula (X-1), ⁵ is a methylene group or an intermediate force S 2 C alkylene optionally interrupted by an oxygen atom. Group, "*" indicates a bond.)

In addition, the following formula (X-3)

(X-3)

It is preferable that it is a group represented by

Examples of the alkoxyl group having 1 to 20 carbon atoms of Y ¹ include, for example, a methoxyl group, an ethoxyl group, an n-propoxyl group, an i-propoxyl group, an n-butoxyl group, an s-butoxyl group, and a t-butoxyl group; Examples of the alkyl group having 1 to 10 include, for example, 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, etc. can be mentioned respectively.

Polyorganosiloxanes with oxetane rings are gel permeation chromatography. The polystyrene equivalent weight average molecular weight measured by matography (GPC) is preferably 500 to 100,000, more preferably 1,000 to L 0,000, and more preferably 1,000 to 6, A power of 000 S is preferred. Such polyorganosiloxane having an oxetane ring is preferably a silane compound having an oxetane ring, or a mixture of a silane compound having an oxetane ring and another silane compound, preferably an appropriate organic solvent. It can be synthesized by hydrolysis or hydrolysis / condensation in the presence of water and a catalyst.

 Examples of the silane compound having an oxetane ring include the following formula (3-1)

(In the formula (3-1), R ¹⁶ is a methyl group or an ethyl group.)

The compound etc. which are represented by these can be mentioned.

Examples of the other silane compounds include 3-daricidyloxypropyltrimethoxysilane, 3-daricidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropylmethylgesidioxypropyldimethyl. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 monoepoxycyclohexyl) ethyltriethoxysilane, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane , Tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tree i-propoxysilane Shishiran, tree n- butoxysilane, tri one sec - butoxysilane, full O b trichlorosilane, full O b trimethoxysilane, Fluorotriethoxysilane, Fluorotri n-Proboxysilane, Fluorotri i-Proboxysilane, Fluorotri-n-Butoxysilane, Fluorotri sec-Butoxysilane, Methyltrichlorosilane, Methyltrimethoxysilane, Methyltriethoxysilane, Methyltri n —Propoxy silane, methyl tri—i—Propoxy silane, methyl tri-n-butoxy silane, methyl tri sec-butoxy silane, 2— (trifluoromethyl) ethyl trichlorosilane, 2-— (trifluoromethyl) ethyl trimethoxy silane , 2— (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethylyltri-n-propoxysilane, 2— (trifluoromethyl) ethylylsilane i-propoxysilane, 2— ( Rifluoromethyl) ethyltri n-butoxysilane, 2- (trifluoromethyl) ethyl retley sec-butoxysilane, 2- (perfluoro n-hexyl) ethyltrichlorosilane, 2- (perfluoro n-hexyl) ethyltrimethoxy Silane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2 _ (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2-(perfluoro-n-hexyl) ethylil i-propoxysilane, 2— (Perfluoro-n-hexyl) ethyltri n-butoxy silane, 2-— (Perfluoro-n-hexyl) ethyltri sec—butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (para-) Fluoro-n-octyl) ethyltrimethoxysilane, 2— ( -Fluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri n-propoxysilane, 2- (perfluoro-n-octyl) ethyltri- i-propoxysilane, 2- (perfluoro-n-octyl) N-butoxysilane, 2- (perfluoro-n-octyl) ethyltril sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxy Silane, hydroxymethyl tree i-propoxysilane, hydroxymethyl tree n-butoxysilane, hydroxymethyltri sec sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3 1- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltree i—propoxysilane, 3— (meth) acryloxypropyltree n—butoxysilane, 3— (meth) acryloxypropyltree sec—butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxy Silane, 3-Mercaptopropyltriethoxysilane, 3-Mercaptopropyltree n-Proxoxysilane, 3-Mercaptopropyltree i-Proxoxysilane, 3-Mercaptopropyltri-n-butoxysilane, 3-Mercaptopropyltree sec —Butoxy Silane, Merca Tomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltree i-propoxysilane, vinyltri-n-butoxysilane, vinyltree sec- Toxisilane, allylic trichlorosilane, allylic trimethoxysilane, allylic triethoxysilane, allylic tri-n-propoxy silane, allylic tri-i-propoxy silane, allylic n-butoxy silane, allylic sec sec-butoxy silane, phenyltrichlorosilane, phenyl Trimethoxysilane, phenyl triethoxysilane, phenyltree n-propoxysilane, phenyltree i—propoxysilane, phenyltree n Butoxy silane, phenyl tri sec sec butoxy silane, methyl dichloro silane, methyl dimethoxy silane, methyl diethoxy silane, methyl di n-propoxy silane, methyl di i monopropoxy silane, methyl di n-butoxy silane, methyl di sec-butoxy silane, dimethyl dichloro silane , Dimethyldimethoxysilane, dimethyljetoxysilane, dimethylzie n-propoxysilane, dimethylzie i monopropoxysilane, dimethylzie n-butoxysilane, dimethylzie sec-butoxysilane, (methyl) [2- (perfluoron- Diethylsilane] (Methyl) [Methyl] [Methyl] [2- (Perfluoro-n-Octyl) Ethyl] Dimethoxysilane, (Methyl) [2- (Perfluoro-N-octyl) Ethyl] Di Methoxysilane, (meth ) [2— (Perfluoro-n-octyl) ethyl] G-n-propoxysilane, (methyl) [2— (Perfluoro-n-year-old octyl) ethisole] Di-i-propoxysilane, (methyl) [2- (Perfluoro-n— Octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec sec-butoxysilane, (methyle) (3-mercaptopropinole) dichlorosilane, (methyl) ( 3-Mercaptopropyl) Dimethoxysilane, (Methyl) (3-Mercaptopropyl) Diethoxysilane, (Methyl) (3-Mercaptopropyl) G-n-Propoxysilane, (Methyl) (3-Mercaptopropyl) Di-i-propoxy Sisilane, (Methyl) (3-Mercaptopropyl) G-N-Butoxysilane, (Methyl) (3-Mercaptopropyl) G sec-Butoxysilane, (Methyl) (Vinyl) Dichlorosilane, (Methyl) (Vinyl) Dimethoxysilane, (Methyl) (Vinyl) Jetoxysilane, (Methyl) (Vinyl) Dione n-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) G-n-butoxysilane, (methyl) (vinyl) G sec-butoxysilane, divinyldiclonal silane, divinyldimethoxysilane, divinyl N-propoxysilane, divinyldi i-propoxysilane, divinyldi n-butoxysilane, divinyldi sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyljetoxysilane, diphenyldi-n Propoxy silane, Diphenyl silane i—Propoxy silane, Diphenyl diol n-Butoxy silane, Diphenyl oxy sec—Poxy silane, Chlorodimethyl silane, Methoxy dimethyl silane, Ethoxy dimethyl silane, Chloro trimethyl silane, Promo trimethyl silane, Yoodo trimethyl silane , Methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i—propoxytrimethylesilane, n-butoxytrimethylylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (black mouth) (vinyl) Dimethylsilane, (Methoxy) (Vinyl) Dimethylsilane, (Ethoxy) (Vinyl) Dimethylsilane, (Black) (Methyl) Diphenylsilane, (Methoxy) (Methyl) Di Et two Rushiran, the Kei atom such as (ethoxy) (methyl) Jifuenirushiran Besides having one silane compound,

For example, KC 1 89, KC 1 89 S, X 1 2 1 1 3 1 5 3, X -2 1-

5 841, X— 21— 5842, X -21 -58 43, X ― 2 1 5 8 44, X 1 2 1— 5845, X -21 -58 46, X-2 1― 58 4 7, X ― 2 1 -58 4 8, X-22- 1 6 OAS, X— 22- 1 70 B, X-2 2— 1 7 0 BX, X 1 22-1 70D, X -22- 1 7 0DX, X-22 1 1 7 6 B, X ― 22-1

7 6D, X-22- 1 76DX, X -22- 1 7 6 F, X ― 40 ― 2 3 0 8, X

― 40—265 1, X -40-26 55 A, X—40 1 2 6 7 1, X 1 40-2

6 7 2, X-40-9 220, X— 40-922 5, X-4 0— 9 2 2 7, X— 4 0— 9246, X— 40-924 7, X-40 1 9 25 0, X ― 4 0-932

3, X-41-105 3, X-41 1 10 56, X—41 ― 1 8 0 5, X—41 1 1 8 10, KF 60 0 1, F 6 002, KF 60 03, KR 2 1 2 , KR-

2 13, KR_ 2 17, KR 2 20 L, KR242 A, KR27 1, KR282, KR300, KR3 1 1, KR40 1N, KR 500, KR 5 1 0, KR 520 6, KR 5230, KR 523 5, KR 92 1 8, KR 9706 (Shin-Etsu Chemical Co., Ltd.); Glass Resin (Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR241 0, SR241 1, SR 2416, SR2420 (above, manufactured by Toray Dow Corning Co., Ltd.); FZ 37 1 1, FZ 3 722 (above, made by Nippon Nichiichi Co., Ltd.); DMS—S 1 2, DMS—S 1 5, DMS—S 2 1, DMS 1 S 27, DMS—S 3 1, DMS—S 32, DMS—S 33, D SS 35, DMS—S 38, DMS-S 42, DMS-S 45, DMS -S 51, DMS— 2 27, PSD— 0332, PDS— 1 6 1 5, PDS— 993 1, X S-5 025 (above, manufactured by Chisso Corp.); Methyl Silicate MS 51, Methyl Silicate MS 56 (Mitsubishi Chemical Corporation); Ethyl silicate 28, Ethyl silicate — 卜 40, Ethyl silicate 48 (above, manufactured by Colcoat Co.); partial condensates such as GR 100, GR650, GR908, GR950 (above, manufactured by Showa Denko KK). Of these, tetramethoxysilane, tetraethoxysilane, methyl ^ / trimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyl-trimethoxysilane, phenyltriethoxysilane, 3-mercaptoprovir trimethoxysilane, 3-mercaptopropyltriethoxysilane, mercapto Methyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, dimethyljetoxycyclohexyl) ethyltrimethoxysilane and the like are preferable.

 In the polyorganosiloxane having an oxetane ring preferably used in the present invention, the weight of the polyorganosiloxane corresponding to 1 mol of the oxetane ring is preferably from 100 to 2,000 gZ mol. It is more preferably 0 to 1, OOO g / mol. Therefore, when synthesizing a polyorganosiloxane having an oxetane ring, the use ratio of the silane compound having an oxetane ring and another silane compound is adjusted so that the concentration of the oxetane ring of the obtained polyorganosiloxane falls within the above range. Is preferably set.

 Examples of organic solvents that can be used to synthesize polyorganosiloxanes having an oxetane ring include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, 2-butanone, and methylisobutyl ketone; Tetrahydrofuran, toluene, 1,4-dioxane, hexane, rigin and the like can be mentioned. The amount of the organic solvent used is preferably 10 to: L 0, 00 parts by weight, more preferably 50 to: L, 0,000 parts by weight with respect to 100 parts by weight of the total silane compound. is there.

 The amount of water used in synthesizing the polyorganosiloxane having an oxetane ring is preferably 0.1 to 1,000 times mol, more preferably 1, 0 to; Double moles.

Catalyst used in the synthesis of polyorganosiloxane having oxetane ring Examples of preferred compounds include basic compounds such as ammonia, quaternary ammonium salts, and organic amines. As the organic amine, tertiary amine is preferable. The catalyst is particularly preferably a quaternary ammonium salt or a tertiary amine amine. Specific examples thereof include triethylamine, tripropylamine, diazabicycloundecene, tetramethylammonium hydroxide, and the like. Can be mentioned. The amount of the catalyst used is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the total silane compound.

 As the reaction conditions for synthesizing the polyorganosiloxane having an oxene ring, the appropriate conditions can be adopted, but the total number of hydrolyzable groups in all silane compounds (of hydroxyl groups, halogen atoms and alkoxyl groups). It is preferable that at least 90 mol% or more of the total number) is condensed, and 95 mol% or more is preferably condensed. In order to obtain such polyorganosiloxane, the reaction conditions are preferably 10 to 120 ° C., more preferably 20 to 80 ° C., preferably 0.1 to 30 hours. More preferably, the reaction time can be 1 to 10 hours.

 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 power becomes easy. 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 A polyorganosiloxane having an oxetane ring can be obtained.

 In the present invention, a commercially available polyorganosiloxane having an oxetane ring may be used. Examples of such commercially available products include “X-SQ”, a trade name of Toagosei Co., Ltd.

[Radiation sensitive polyorganosiloxane]

The radiation-sensitive polyorganosiloxane used in the present invention is cinnamic acid as described above. It can be synthesized by reacting a derivative with a polyorganosiloxane having an oxetane ring, preferably in the presence of a catalyst. Here, the cinnamic acid derivative is preferably 0.001 to 3 mol, more preferably 0 ::! With respect to 1 mol of the oxetanyl group of the polyorganosiloxane. To 1 mol, more preferably 0.2 to 0.9 mol.

 In the present invention, a part of the cinnamic acid derivative is represented by the following formula (5) as long as the effects of the present invention are not impaired.

_R 18_ _R 19_ _R 20 (5)

(In the formula (5), R ¹⁸ is an alkyl group having 4 to 20 carbon atoms, an alkoxyl group, or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, provided that the alkyl group or alkoxyl Some or all of the hydrogen atoms in the group may be substituted with fluorine atoms, and R ¹⁹ is a single bond or a phenylene group, provided that when R ¹⁸ is an alkoxy group, R ¹⁹ is a phenylene group. R ^2Q is a force lpoxyl group, a hydroxyl group, one SH, one NCO, —NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), one CH—CH ₂ and one S0. ₂ is at least one group selected from the group consisting of C 1)

It may be used by replacing with a compound represented by In this case, the synthesis of the radiation-sensitive polyorganosiloxane is carried out by reacting a polyorganosiloxane having an oxene ring with a mixture of a cinnamic acid derivative and a compound represented by the above formula (5). .

In the above formula (5), R ¹⁸ is preferably an alkyl group having 8 to 20 carbon atoms or an alkoxyl group, or a fluoroalkyl group having 4 to 21 carbon atoms or a fluoroalkoxyl group, and R ¹⁹ is a single bond or It is preferable that it is a 1,4 monophenylene group, and it is preferable that R ^2G be a strong loxyl group.

Preferred examples of the compound represented by the above formula (5) include, for example, the following formula (5-1) ~ (5-4)

C _h F _{2h +}广 CiH _2i —COOH (5-1)

(In the above formula, h is an integer from 1 to 3, i is an integer from 3 to 18, j is an integer from 5 to 20, k is an integer from 1 to 3, and m is from 0 to : L is an integer of 8, and n is an integer of 1 to 18.)

Or a compound represented by the following formula (5-3-

1) to (5-3-3)

C ₂ F ₅ — C ₃ H ₆ — 0 COOH (5-3-3) A compound force represented by either

 The compound represented by the above formula (5) is a compound that reacts with a polyorganosiloxane having an oxenyl group together with the cinnamic acid derivative and becomes a site that imparts pretilt angle expression to the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (5) is hereinafter referred to as “another pretilt angle developing compound”.

 In the present invention, when another pretilt angle-expressing compound is used together with the cinnamic acid derivative, the total use ratio of the cinnamic acid derivative and the other pretilt angle-expressing compound is 1 mol of oxenayl group possessed by the polyorganosiloxane. Is preferably from 0.001 to 1.5 mol, more preferably from 0.01 to 1 mol, and even more preferably from 0.05 to 0.5 mol. In this case, the other pretilt angle-expressing compound is preferably used in a range of 50 mol% or less, more preferably 25 mol% or less, based on the total with the cinnamic acid derivative. If the proportion of other pretilt angle-expressing compounds exceeds 50 mol%, there may be a problem that an abnormal domain occurs when the liquid crystal display element is turned on.

 Examples of the catalyst include aluminum oxide, tetrabutoxy titanium, tetraisopropoxy titanium, zinc octylate, tin octylate, aluminum acetyl acetone complex, titanium acetyl acetylacetone complex, zirconium acetyl acetylene complex, benzyl dimethyl diamine. Min, paratoluenesulfonic acid, tetraphenylphosphine promide, etc. can be used. The amount of the catalyst used is preferably 0.01 to 100 parts by weight, more preferably 0.0 :! with respect to 100 parts by weight of the polyorganosiloxane having an oxetane ring. ~ 20 parts by weight.

 The reaction temperature is preferably 0 to 300 ° C, more preferably 10 to 25 ° C, and the reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. It is.

In the synthesis of the radiation-sensitive polyorganosiloxane, organic solvents such as hydrocarbons, ethers, esters, ketones, amides and alcohols can be used as necessary. Ethers, esters or ketones are preferred from the standpoints of solubility of raw materials and products, ease of purification, and the like. Specific examples of particularly preferred organic solvents include Ruen, xylene, jetylbenzene, mesitylene, methylethylketone, methyliso RY s—I

 2 1 tilketone, 2 heptanone and hexanone

wear. Organic o-solvent is a solid content concentration (ratio in which the weight of components other than the solvent in the reaction solution occupies the total weight of the solution) force preferably 0.1% by weight or more, more preferably 5 to 50% by weight Used in.

[Other ingredients]

 The liquid crystal aligning agent of the present invention contains the radiation sensitive polyorganosiloxane as described above.

 In addition to the radiation-sensitive polyorganosiloxane as described above, the liquid crystal aligning agent of the present invention may further contain other components as long as the effects of the present invention are not impaired. Examples of such other components include polymers other than radiation-sensitive polyorganosiloxanes (hereinafter referred to as “other polymers”), heat-sensitive cross-linking agents, functional silane compounds, and surface active agents. Can be mentioned.

 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. Such other polymer includes, for example, at least one polymer selected from the group consisting of polyamic acid and polyimide; the following formula (S-2)

(S-2)

(In the formula (S-2), R ¹⁷ is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, Y ² is a hydroxyl group, a halogen atom, or 1 carbon atom. A polyorganosiloxane having a repeating unit represented by: a hydrolyzate thereof and a condensate of the hydrolyzate. At least one type (hereinafter “other Also called “polyorganosiloxane”. ); Polyamic acid ester, Polyester, Polyamide, Cell mouth derivative, Polyacetal, Polystyrene derivative, Poly

(Styrene monophenylmaleimide) derivatives, poly (meth) acrylates, and the like. One polyamic acid

 The polyamic acid can be obtained by reacting tetra force ruponic dianhydride with a diamine compound.

Examples of tetracarboxylic dianhydrides that can be used in the synthesis of polyamic acid include 2, 3, 5-trioxyloxycyclopentyl acetic acid dianhydride, butantetracarboxylic dianhydride, 1, 2, 3, 4 -Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3 , 5, 6 1 Tricarpoxynorpolnan 1-acetic acid dianhydride, 2, 3, 4, 5—tetrahydrofurantetracarboxylic dianhydride, 1, 3, 3 a, 4, 5, 9 b— Hexahi Draw 5 -— (Tetrahydro-2,5-dioxo-3-furanyl) One-naphtho [1, 2-c] One furan 1,3-Dione 1, 3, 3 a, 4, 5, 9b-Hexahydride Rho 5— (Tetrahydro-2, 5-dioxo-3-furanyl) 1-8-methylnaphtho [ 1, 2 c] —furan 1,3-dione, 5- (2,5-dixotetrahydrofuranyl) 1 3-methyl-3-cyclohexene-1,2-dicarbonoic acid anhydrous, bicyclo [2.2 2] —Octo 7—En 1, 2, 3, 5, 6—Tetra force Rubonic dianhydride, following formula (T 1 1) to (T 1 14)

An aliphatic or alicyclic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of

Pyromellitic dianhydride, 3, 3 ', 4, 4'-biphenylsulfonetetracarboxylic dianhydride, 1, 4, 5, 8-naphthalenetetracarboxylic dianhydride, 2, 3, 6, 7-naphthalene tetracarboxylic dianhydride, 3, 3,, 4, 4 '— biphenyl ether tetracarboxylic dianhydride, 3, 3', 4, 4 '— dimethyldiphenylsilane tetracarboxylic acid Dianhydride, 3, 3,, 4, 4, -tetraphenyl silane tetracarboxylic dianhydride, 1, 2, 3, 4-furantetracarboxylic dianhydride, 4, 4 'one bis (3,4 -Dicarboxyphenoxy) diphenylsulfide anhydride, 4, 4, —bis (3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4, 4 ′ monobis (3,4-dicarboxyphenoxy) Ii) Diphenylpropane dianhydride, 3, 3,, 4, 4, monoperfluoroisopropyl Ridentetracarboxylic dianhydride, 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene monobis (triphenyl) Phthalic acid) dianhydride, m-phenylene monobis (triphenyl phthalic acid) dianhydride, bis (triphenyl phthalic acid) mono 4,4'-diphenyl terternary anhydride, bis (triphenyl phthalic acid) Acid) 1, 4, 4-diphenyl methane dianhydride, following formula (T 1 15) to (T 1 18)

An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of the above.

Of these, 1, 3, 3 a, 4, 5, 9 b-hexahydrone 5-- (tetrahydro-2,5-dioxo-3-furanyl) 1-naphtho [1,2-c] -furan 1,3-dione, 1,3,3 a, 4, 5, 9b-Hexahydro-5- (tetrahydro-2,5-dioxo-1-furanyl) 1-8-methyl-naphth [1, 2-c] —furan 1,3-dione, 2, 3,5-tricarpoxy-pentyl acetic acid dianhydride, butantecola carboxylic dianhydride, 1,3-dimethyl 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3, 3 ', 4, 4, bibiphenyl sulfone Tetracarboxylic acid dianhydride, 1, 4, 5, 8-Naphthalene tetracarboxylic acid dianhydride, 2, 3, 6, 7-Naphthalene tetraforce dianhydride, 3, 3 ', 4 , 4, -biphenyl ether tetracarboxylic acid dihydrate and tetracarboxylic acid represented by each of the above formulas (T-1), (T-2) and (T-15) to (T-18) Mention may be made of dianhydrides.

 These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

Examples of diamine compounds that can be used for the synthesis of polyamic acid include P-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl. Nilsulfide, 4, 4'-diaminodiphenylsulfone, 3,3'-dimethyl 1,4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-Diaminonaphthalene, 3,3-Dimethyl-1,4,4'-diaminobiphenyl, 5-Amino 1- (4'-aminophenyl) 1,1,3,3-Trimethylindane, 6-Amino 1 1 (4, 1-aminophenyl) 1 1, 3, 3-trimethylindane, 3, 4, 1-diaminodiphenyl 1 ter, 2, 2-bis (4 1-aminophenoxy) propane, 2, 2— [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4 (4-1aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Lopropane, 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) One 10-Hydroanthracene, 2,7-Diaminofluorene, 9, 9-Bis (4-Aminophenyl) Full Orene, 4, 4, monomethylene monobis (2-chloroaniline), 2, 2,, 5, 5, monotetrachloro-4, 4, diaminobiphenyl, 2, 2'-dichloro-4, 4'-diamino 5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4, 1-diaminobiphenyl, 4, 4, 1 (p-phenylene isopropylidene) bisaniline, 4, 4, 1 (m-phenyl) Lenisopropylidene) Bisaniline, 2, 2-bis [4 (4-amino_2-trifluoromethylphenoxy) phenyl] Hexafluoropropan, 4, 4, 1-diamino-2,2,1bis (trifluoromethyl) ) Biphenyl, 4, 4, 1 bis [(4 1-amino-2-trifluoromethyl) phenoxy] Monofluor fluorbiphenyl, 6- (4 1-conconyloxy) hexyloxy (2, 4-diaminobenzene) , 6_ (4 , Monofluoro-4 force hexyloxy) hexyloxy (2, 4-diaminobenzene), 8- (4 force luconyloxy) octyloxy (2, 4-diaminobenzene), 8-— (4, fluor-4 monocalconyloxy) octyloxy (2,4-diaminobenzene), 1-dedecyloxy-2, 4-diaminobenzene, 1-tetradecyloxy 2,4-diaminobenzene, 1-pentadecyloxy 2,4-diaminobenzene, 1-hexadecyl Oxy-2,4-diaminobenzene, 1-octadecyloxy 2,4-diaminobenzene, 1-cholesteryloxy-1,2,4-diaminobenzene, 1-cholesyloxyloxy 2,4-diaminobenzene, dodecyloxy (3, 5 —Diaminobenzoyl), Tetradecyloxy (3,5-Diaminobenzoyl), Pen Oxy (3,5-diaminobenzol), hexadecyloxy (3,5-diaminobenzol), decyloxy (3,5-diaminobenzol), cholesteryloxy (3,5-diaminobenzol) , Cholesyloxy (3,5-diaminophenoxy), (2,4-diaminophenoxy) palmitate, (2,4-diaminophenoxy) stearylate, (2,4-diaminophenoxy) Trifluoromethylbenzoate, represented by the following formula (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

Aromatic diamines having heteroatoms such as diaminotetraphenylthiophene; metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene Diamine, Octamethylenediamine, Nonamethylenediamine, 1,4-Diaminocyclohexane, Isophoronediamine, Tetrahydrodicyclopentanegenylenediamine, Hexahydro-1,4_ Evening in tick range methylenediamine, tricyclo

[6. 2. 1. 0 ² ' ⁷ ] —aliphatic or cycloaliphatic diamines such as undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine);

Examples include diaminoorganosiloxanes such as diaminohexamethyldisoxyhexane.

Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4,1 diaminodiphenyl ether, 4, 4, 1 (p-phenylene sopropylidene) Bisaniline, 2, 2-bis [4 1 (4 aminophenoxy) [Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4 (4- (amino-1-trifluoromethylphenoxy) phenyl] hexafluoro Propane, 4,4, -diamino-2,2, -bis (Trif J-rero-methyl) Bifu-ni J-re, 4,4'-bis [(4-Amino-1-2-trifluoromethyl) phenoxy] -octaful Orobiphenyl, 1-Hexadecyloxy-1,4-diaminobenzene, 1-year-old Kutadecyloxy _ 2,4-Diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1- Cholestanyloxy-2,4-diaminobenzene, hexadecyloxy (3,5-diaminobenzoyl), decoctyldecyloxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzene) Zoyl), cholesylnitroxyl (3,5-diaminobenzoyl) and diamine compounds represented by the above formulas (D-1) to (D-5).

 These diamine compounds can be used alone or in combination of two or more. The ratio of tetracarboxylic dianhydride and diamine compound used for the polyamic acid synthesis reaction is as follows: 1 equivalent of amino group contained in diamine compound; Is preferably a ratio of 0.2 to 2 equivalents, more preferably a ratio of 0.3 to 1.2 equivalents.

The polyamic acid synthesis reaction is preferably carried out in an organic solvent, preferably at a temperature of −20 to 150 ° C., more preferably at a temperature of 0 to 100 ° C., preferably 0.5 to 24. The time is more preferably 2 to 10 hours. 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 , N-dimethylimidazolidinone, dimethylsulfoxide, aptilolactone, tetramethylurea, hexamethylphosphortriamide and other aprotic polar solvents; m-cresol, xylenol, phenol, halogenated phenol, etc. The following phenolic solvents can be mentioned. The amount of organic solvent used (a: When an organic solvent is used in combination with a poor solvent described later, it means the combined amount of both) • Total amount of tetracarboxylic dianhydride and diamine compound The amount (b) is preferably 0.1 to 50% by weight, more preferably 5 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, should be used in combination as long as the resulting polyamic acid does not precipitate. Can do. Specific examples of such poor solvents include, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4 monobutane diol, triethylene glycol, ethylene glycol monomethyl ether, lactic acid ethyl, ethyl lactyl, Acetone, Methyl ethyl ketone, Methyl isobutyl ketone, Cyclohexanone, Methyl acetate, Ethyl acetate, Butyl acetate, Methyl methoxypropionate, Ethyl ethoxypropionate, Jetyl oxalate, Jetyl malonate, Jetyl ether, Ethylene glycol Methyl ether, ethylene Daricol ether ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol Butyl ether, ethylene dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl 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, black benzene, o-dichloro benzene, hexane, heptane, octane, benzene, toluene, xylene, etc. Can be mentioned.

 When a polyamic acid is used in combination with a poor solvent such as the above in an organic solvent, the proportion of the solvent used can be appropriately set within a range in which the produced polyamic acid does not precipitate; 50% by weight or less.

As described above, the reaction solution strength S obtained by dissolving the polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution. In addition, after purifying the polyamic acid, it may be used for preparing a liquid crystal aligning agent. Polyamic acid can be isolated by pouring the reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure with an evaporator. Can be performed. In addition, the polyamic acid can be purified by a method in which the polyamic acid is dissolved again in an organic solvent and then precipitated in a poor solvent, or a method in which the step of evaporating under reduced pressure in an evaporator is performed once or several times. . One polyimide

 The polyimide can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid obtained as described above. At this time, all of the amic acid structure may be dehydrated and cyclized to completely imidize, or only a part of the amic acid structure may be dehydrated and cyclized to form a partially imidized product in which an amic acid structure and an imido structure coexist. Also good.

 Dehydration and ring closure of polyamic acid can be achieved by either (1) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and dehydrating ring closure catalyst to this solution and heating as necessary. By the method.

 The reaction temperature in the method of heating the polyamic acid of U) is preferably 50 to 20 ° C., more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C, the dehydration and ring-closing reaction force does not proceed sufficiently, and if the reaction temperature exceeds 20 ° C, the molecular weight of the imidized polymer obtained may be lowered. The reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.

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. it can. The amount of the dehydrating agent used is preferably 0.1 to 20 mol per mol of the polyamic acid structural unit. Also, examples of the dehydrating ring closure catalyst include pyridine, collidine, lutidine, and triethylamine. Can be used. However, it is not limited to these. The amount of dehydration ring closure catalyst used is 0 per mol of the dehydrating agent used. A power of 0 to 10 mol is preferable. Examples of the organic solvent used for the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration cyclization reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 ~ 8 hours.

 The polyimide obtained in the above method (i) may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after purifying the obtained polyimide. On the other hand, in the above method (i i), a reaction solution containing polyimide is obtained. This reaction solution 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. It may be used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after purifying the isolated polyimide. In order to remove the dehydrating agent and the dehydrating ring closure catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. The isolation and purification of the polyimide can be performed by performing the same operations as described above as the method for isolating and purifying the polyamic acid. One other polyorganosiloxane

 At least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (S-2), a hydrolyzate thereof, and a condensate of the hydrolyzate (other polyorganosiloxane) is GPC. It is preferable that the weight average molecular weight of polystyrene conversion measured by the above is from 100 to 100,000. Such other polyorganosiloxane 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 an appropriate organic compound. It can be synthesized by hydrolysis or hydrolysis / condensation in a solvent in the presence of water and a catalyst.

Examples of raw material silane compounds that can be used here include tetramethoxysilane, Tetraethoxysilane, tetra_n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrachlorosilane; methyltrimethoxysilane, methyltriethoxysilane, Methyltri-n-propoxysilane, methyltri-iso iso-propoxysilane, methyltri_n-butoxysilane, methyltree sec-butoxysilane, methyltree tert-butoxysilane, methylethyltriethoxysilane, etyltri n-propoxysilane, etyltri-iso- Propoxy silane, Ethyl tri-n-Butoxy silane, Ethyl tri sec-Butoxy silane, Ethyl tri tert-Butoxy silane, Ethyl trichlorosilane, Phenyltrimethoxy silane Phenylene ^ / triethoxysilane, Hue sulfonyl trichlorosilane; dimethyldimethoxysilane, dimethyl jet silane, dimethyldichlorosilane, Bok trimethyl methoxy silane, trimethyl E butoxy Sila emissions, and the like trimethylchlorosilane. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethylsilane, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, lan or trimethylethoxysilane are preferred.

 Organic solvents that can optionally be used in the synthesis of other polyorganosiloxanes include, for example, alcohol compounds, ketone compounds, amide compounds and 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-pen alcohol, i-Pen Yunol, 2-Methylbuenol, sec-Pen Yunol, t-Pen Yunol, 3-Methoxybutenol, n-Hexanol, 2-Methylpenonol, sec-Hexanol, 2-Ech Lubutanol, sec-Hep Yunol, Hep Yunol 1-3, n-Yu Yu Yunol, 2-Ethylhexanol, sec-octanol, n-nonyl alcohol, 2, 6-dimethylheptano-luo 4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-hept Monoalcohol compounds such as decyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;

Ethylene glycol, 1,2_propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-1,2, hexandiol 2,5, heptanediol- Polyhydric alcohol compounds such as 2,4,2-ethylhexenediol 1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene dallicol;

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, Dethylene glycol monomethyl ether, Dethylene 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 mono Propyl ether, propylene glycol monobutyl ether, Propylene glycol one Rumonomechirue one ether, dipropylene glycol monomethyl E Ji ethers, partial ethers of a polyhydric alcohol compounds such as dipropylene glycol monopropyl ether, etc., can be exemplified respectively. These alcohol compounds may 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-propyl ketone, jetyl ketone, methyl-i monobutyl ketone, methyl n-pentyl ketone, ethyl n-ptyl ketone, methyl n- Hexyl ketone, G-I-butyl ketone, Limethylnonanone, Siku Monoketone compounds such as oral hexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, etc .;

Acetylacetone, 2,4 monohexanedione, 2,4 one heptanedione, 3,5 one heptanedione, 2,4 one octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione And j6-diketone compounds such as 5-methyl-2,4-monohexanedione and 2,2,6,6-tetramethyl-3,5-heptanedione. 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-jetylformamide, acetoamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-jetylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetyl Examples include morpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. These amide compounds may be used alone or in combination of two or more.

Examples of the ester compound include jetyl carbonate, ethylene carbonate, propylene carbonate, jetyl carbonate, methyl acetate, ethyl acetate, aptyrolactone, valerolactone, n-propyl acetate, i-propyl acetate, and n-butyl acetate. I-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxyptyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cycloacetate Hexyl, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl acetate, methyl ethylene glycol monoacetate Yetil Ether, acetic acid diethylene glycol mono-over n- Petit ether, acetic profile propylene glycol monomethyl E one ether, acetic acid propylene glycol monomethyl E Chill Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene darlicol monomethyl ether, dipropylene glycol monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, propion N-Ptyl acid, i-amyl propionate, Jetyl oxalate, Di-n-butyl oxalate, Methyl lactate, Ethyl lactate, N-Ptyl lactate, N-amyl lactate, Jetyl malonate, Dimethyl fumarate Examples include chill and jetyl phthalate. These ester compounds may be used alone or in combination of two or more.

 Examples of the other aprotic compounds include: acetonitrile, dimethyl sulfoxide, N, N,, ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, Ν-methylmorpholone, Ν-methylpyrrole, Ν- Ethylpyrrole, Ν-methyl-Δ 3-pyrroline, Ν-methylbiperidine, Ν-ethylpiperidine, Ν, Ν-dimethylpiperazine, Ν-methylimidazole, Ν-methyl-4-piperidone, 一 -methyl-2-piperidone, Ν-methyl- Examples include 2-pyrrolidone, 1,3-dimethyl-1,2-imidazolidinone, 1,3-dimethyltetrahydro-2- (1Η) -pyrimidinone, and the like.

 Of these solvents, polyhydric alcohol compounds, partial ethers of polyhydric alcohol compounds, or ester compound strength (preferred for #).

 The amount of water used in the synthesis of the other polyorganosiloxane is preferably 0.5 to 100 moles with respect to 1 mole of the total amount of alkoxyl groups and halogen atoms of the starting silane compound. The amount is preferably 1 to 30 mol, and more preferably 1 to 1.5 mol.

 Examples of the catalyst that can be used in the synthesis of other polyorganosiloxanes include metal vicinal compounds, organic acids, inorganic acids, organic bases, ammonia, and alkali metal compounds.

Examples of the metal chelate compound include triethoxy mono (acetylene toner) titanium, tri-n-propoxy 'mono (acetylacetonate) titanium, trie i monopropoxy' mono (acetylacetonate) titanium, tri-n — Butoxy Mono (Acetylacetonate) Titanium, Tree sec-Butoxy Mono (Acetylasetoner) Titanium, Tri-Topoxy Mono (Acetylase Toner) Titanium, Diethoxy Bis (Acetylacetate) NATO) Titanium, GE n Propoxy bis (Acetyl acetonate) Titanium, DI i Propoxy bis (Acetyl acetonate) Titanium, GE n-butoxy bis (Acetyl acetonate) Titanium, GE sec— Butoxy bis (acetylacetonate) Titanium, di-tapoxy bis (acetylacetate) Titanium, monoethoxy tris (acetylacetate) Titanium, mononoxypropoxy (Acetyl Acetate) Titanium, Mono I Propoxy Tris (Acetyl Acetate) Titanium, Mono n— Toxi-Tris (Acetylacetonate) Titanium, Mono sec—Butoxy. Tris (Acetylasetonate) Titanium, Monotube Toxy-Tris (Acetylasetonate) Titanium, Tetrakis (Acetylacetonate) Titanium, triethoxy mono (ethylacetoacetate) Titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, Tori i mono-propoxy mono (ethylacetoacetate) titanium, tri-n-butoxy · Mono (ethyl acetate) Titanium, Tree sec-Butoxy · Mono (ethyl acetate) Titanium, Tri-Boxy · Mono (ethyl acetate) Titanium, Jexi Bis Tilacetoacetate) Titanium, G-N-propoxy bis (Ethylacetoacetate) Chita I-propoxy bis (ethylacetoacetate) titanium, di-n-butoxy-bis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetoacetate) titanium, di-t1 Butoxy'bis (ethyl ^ / acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i-propoxy tris (Ethylacetocetate) Titanium, Mono-n-Butoxy 'Tris (Ethylacetoacetate) Titanium, Mono-sec-Butoxy-Tris (Ethylacetoacetate) Titanium, Mono-Butoxy * Tris (Ethylacetate) Acetate) Titanium, Tetrakis (ethylacetoacetate) Titanium, Mono (Aceti) Asetonato) tris (Echiru Acetatoacetate) Titanium, Bis (Acety ^ / Acetoner) Bis (Ethylacetoacetate) Titanium, Tris (Acetylacetate) Mono (Ethylacetate Tate)

Triethoxy Mono (Acetylacetonate) Zirconium, Tree n-Propoxy Mono (Acetylasetonate) Zirconium, Tree i One Propoxy Mono (Acetylacetonate) Zirconium, Tree n-Butoxy 'mono (Acetyl acetonate) Zirconium, Tree sec-Butoxy mono (Acetyl acetonate) Zirconium, Tri-t-Butoxy 'mono (Acetyl acetonate) Zirconium, Diethoxy, bis (Acetyl acetonate) Zirconium, Di- n-propoxy bis (acetyl acetylene) zirconium, zi i-propoxy bis (acetyl cetner) zirconium, zi n-butoxy bis

(Acetylacetonate) Zirconium, Di-sec-Butoxy bis (Acetyl lucacetonate) Zirconium, G-Butoxy bis (Acetyl acetonate) Zirconium, monoethoxy tris (Acetyl acetonate) Zirconium , Mono-propoxy tris (acetyl acetate) zirconium, mono-propoxy tris (acetyl acetate) zirconium, mono-n-butoxy tris (acetyl acetate) zirconium, mono—sec— Butoxy * Tris (Acetylacetonate) Zirconium, Monot t-Butoxy · Lis (Acetylasetonate) Zirconium, Tetrakis (Acetylacetonate) Zirconium, Triethoxy mono (Ethylacetate Acetate) Gyrileconium Tree n-propoxy mono (ethyl acetate acetate) zirconium, tree i propoxy mono (ethyl acetate acetate) zirconium, tree n butoxy mono (ethyl acetate acetate) zirconium, tree sec- Dioxy / monoacetate Di ^ / conium, tri-t-butoxy * mono (ethylacetoacetate) zirconium, jetoxy'bis (ethylacetoacetate) zirconium, di-n-propoxy 'Bis (ethylacetoacetate) zirconium, di-i-propoxy.Bis (ethylacetoacetate) zirconium, di-n-butoxy' Bis (ethylacetoacetate) zirco Nium, G-sec-Butoxy bis (Ethylacetate) Zirconium, Di-t-Butoxy bis (Ethylacetate Acetate) Zirconium, Monoethoxy 卜 Lith (Ethylacetate Acetate) Zirconium, Mono n-propoxy tris (ethylacetoacetate) zirconium, monoi i —propoxy tris (ethylacetoacetate) zirconium, monon n-butoxy tris (ethylacetoacetate) zirconium, monono sec— Butoxy 卜 ris (ethyl acetoacetate) Zirconium, mono-t-butoxy, tris (ethyl acetoacetate) Zirconium, tetrakis (ethyl acetoacetate) Zirconium, mono (acetyl cetatoate) Tris ( Ethylacetoacetate) Jill Two © beam, bis (§ cetyl § Seth diisocyanate) bis (E chill § Seth acetate) zirconium two © beam, Bok squirrel (§ cetyl § Seth diisocyanate) mono (E chill § Seth acetate) zirconium chelate compounds such as Gilles Koniumu;

Examples thereof include aluminum chelate compounds such as tris (acetylacetate) aluminum and tris (ethylsylacetate) 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, Gallic acid, Butyric acid, Mellitic acid, Arachidonic acid, Shikimic acid, 2-Ethylhexanoic acid, Oleic acid, Stearic acid, Linoleic acid, Linolenic acid, Salicylic acid, Benzoic acid, P-Aminobenzoic acid, P-Toluenesulfonic acid, Examples thereof include benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, fumaric acid, fumaric acid, citrate, 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, and monomethylethanolamine. , Triethanolamine, diazabicycloochrane, diazabi 4 hours

Examples include chrononane, diazabicycloundecene, and tetramethylammonium hydroxide.

 Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

 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 0.01 to 1 part by weight, based on 100 parts by weight of the raw material silane compound.

 The water added in the synthesis of other polyorganosiloxanes can be added intermittently or continuously in the raw 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 added water.

 The reaction temperature in the synthesis of other polyorganosiloxane is preferably 0 to 100 ° C., more preferably 15 to 8 O. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

 When the liquid crystal aligning agent of the present invention contains other polymer together with the above-mentioned radiation-sensitive polyorganosiloxane, the content of the other polymer is as follows: Radiation-sensitive polyorganosiloxane 100 parts by weight The amount is preferably 10 0,000 parts by weight or less. The more preferable content of the other polymer varies depending on the type of the other polymer.

In the case where the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation-sensitive polyorganosiloxane, polyamic acid and polyimide, a more preferable use ratio of both is The total amount of polyamic acid and polyimide with respect to 100 parts by weight of the radiation-sensitive polyorganosiloxane is 10 0 to 5 and 0 0 0 parts by weight, and this value is further 2 0 to 2 and 0 0 It is preferably 0 parts by weight.

 On the other hand, in the case where the liquid crystal aligning agent of the present invention contains a radiation-sensitive polyorganosiloxane and another polyorganosiloxane, the more preferable use ratio of both is relative to 100 parts by weight of the radiation-sensitive polyorganosiloxane. The amount of other polyorganosiloxane is 100 to 2,000 parts by weight.

 When the liquid crystal aligning agent of the present invention contains another polymer together with the radiation-sensitive polyorganosiloxane, the type of the other polymer is at least selected from the group consisting of polyamic acid and polyimide. One polymer or other polyorganosiloxane is preferred. The heat-sensitive crosslinking agent can be used for stabilizing the pretilt angle and improving the coating film strength. For example, a polyfunctional epoxy compound is effective as the heat-sensitive cross-linking agent. Bisphenol A type epoxy resin, phenolic nopolac type epoxy resin, cresol nopolac type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy Resins, glycidyldiamin epoxy resins, heterocyclic epoxy resins, acrylic resins having an epoxy group, and the like can be used. Examples of these commercially available products include Ebolait 400 0 E, 3 00 2 (manufactured by Kyoeisha Chemical Co., Ltd.), Epicoat 8 2 8, 1 52, and Epoxy Nopolac 1 80 S (Japan) Epoxy resin (manufactured by Co., Ltd.). When a polyfunctional epoxy compound is used as the heat-sensitive crosslinking agent, a base catalyst such as 1-benzyl-1-2-methylimidazole may be used in combination for the purpose of efficiently causing a crosslinking reaction.

When the liquid crystal aligning agent of the present invention contains a heat-sensitive cross-linking agent, the content ratio thereof is about 100 parts by weight in total of the above-mentioned radiation-sensitive polyorganosiloxane and other polymers optionally used. On the other hand, it is preferably 100 parts by weight or less, more preferably 50 parts by weight or less. The functional silane compound can be used for the purpose of improving the adhesion of the obtained liquid crystal alignment film to the substrate. Examples of functional silane compounds include 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-a

-(2-Aminoethyl) 1-3-aminomino trimethoxysilane, N- (2-aminoethyl) 1-aminopropylmethyldimethoxysilane, 3-ureido-propyl trimethoxysilane, 3-ureidopropyltri Ethoxysilane, N-ethoxycarbonyl 3-aminominotrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylene Reamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,9,7-triazadecane, 9-trimethoxysilyl-3: 6-diazanonyl acetate, 9 Triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-ami Propyltrimethoxysilane, N-benzil 3-3-aminopropyltriethoxysilane, N-phenol 3-triaminosilane, N-phenylene 3-ethoxysilane, N-bis (Oxyethylene) 1 3-Aminopropyl trimethoxysilane, N 1 Bis (oxyethylene) 1 3-Aminoprovir triethoxysilane, 3-Dalisidyloxypropyl trimethoxysilane, 2- (3, 4 1 epoxy Cyclohexyl) dimethyltrimethoxysilane and the like, and further described in Japanese Patent Application Laid-Open No. 6 3-2 9 1 9 2 2 are silanes having a tetracarboxylic dianhydride and an amino group. A reaction product with a compound can be exemplified.

When the liquid crystal aligning agent of the present invention contains a functional silane compound, the content ratio is a total of 100 parts by weight of the above radiation-sensitive polyorganosiloxane and other polymers optionally used. On the other hand, it is preferably 50 parts by weight or less, and more preferably 20 parts by weight or less. 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 the present invention contains a surfactant, the content is preferably 10 parts by weight or less, more preferably 1 part by weight with respect to 100 parts by weight of the entire liquid crystal aligning agent. Less than parts by weight. Liquid crystal alignment agent>

 As described above, the liquid crystal aligning agent of the present invention contains a radiation-sensitive polyorganosiloxane as an essential component, and additionally contains other components as necessary. Preferably, each component is an organic solvent. It is prepared as a solution-like composition dissolved in The organic solvent that can be used for preparing the liquid crystal aligning agent of the present invention is preferably one that dissolves the radiation-sensitive polyorganosiloxane and other optional components and does not react with these.

 The organic solvent that can be preferably used in the liquid crystal aligning agent of the present invention varies depending on the type of other polymer that is optionally added.

 As a preferable 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 radiation-sensitive polyorganosiloxane, polyamic acid and polyimide, synthesis of polyamic acid The organic solvent illustrated above can be mentioned as what is used for. At this time, the poor solvent exemplified as used in the synthesis of the polyamic acid of the present invention may be used in combination. These organic solvents can be used alone or in combination of two or more.

On the other hand, when the liquid crystal aligning agent of the present invention contains only a radiation-sensitive polyorganosiloxane as a polymer, or contains a radiation-sensitive polyorganosiloxane and another polyorganosiloxane. Preferred organic solvents in this case include, for example, 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene brickol monopropyl ether, propylene glycol monopropyl ether, propylene glycol monoacetate, propylene glycol methyl ether. , Dipropylene glycol ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether Tert-ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (Petylcetosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl Cellosolve acetate, ethyl acetate sorb acetate, propyl cellosolvate acetate, butyl cellosolve acetate, methylcarb) ^ 1, ethylcarb! ^ 1, propylcarbyl, ptylcarbitol, n-propyl acetate, acetic acid i— Propyl, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyryl acetate, methylpentyl acetate, acetic acid 2 Echirupuchiru, hexyl acetate 2-Echiru acetate benzyl acetate n- to key sill, cyclohexyl acetate cycloalkyl, acetic Okuchiru acetate Amiru, such as acetic Isoamiru thereof. 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.

 A preferred solvent used in the preparation of the liquid crystal aligning agent of the present invention is obtained by combining one or more of the above organic solvents according to the presence or absence of other polymers and their types, Each component contained in the liquid crystal aligning agent does not precipitate at the following preferable solid content concentration, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mNZm.

The solid content concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the total 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 selected in consideration of viscosity, volatility, etc. Preferably, it is in the range of 1 to 10% by weight. 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, the film thickness force S of the coating film is too small. Thus, it may be difficult to obtain a good liquid crystal alignment film. On the other hand, if the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal alignment agent increases, resulting in insufficient coating characteristics. There is a case. The particularly preferable solid content concentration range varies depending on the method employed when applying the liquid crystal aligning agent to the substrate. For example, by the spinner method In this case, the range of 1.5 to 4.5% by weight is particularly preferred. In the case of the printing method, it is particularly preferred that the solid content concentration is in the range of 3 to 9% by weight, whereby the solution viscosity is in the range of 12 to 5 O mPa · s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thus 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 10 ° C. to 40 ° C. Forming method of liquid crystal alignment film>

 The liquid crystal aligning agent of this invention can be used conveniently in order to form a liquid crystal aligning film by the photo-alignment method.

 Examples of the method for forming the liquid crystal alignment film include a method in which a liquid crystal alignment film of the present invention is formed on a substrate and then the liquid crystal alignment ability is imparted to the coating film by a photo-alignment method.

 First, on the transparent conductive film side of a substrate provided with a patterned transparent conductive film, the liquid crystal aligning agent of the present invention is appropriately applied by, for example, a roll coater method, a spinner method, a printing method, an ink jet method, or the like. For example, the coating film is formed by heating at a temperature of 40 to 25 50 for 0.1 to 12 minutes. The thickness of the coating film is preferably from 0.001 to 1111, more preferably from 0.05 to 0.5 m as the thickness after removal of the solvent.

 As the substrate, for example, a glass such as flow glass or soda glass, a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used.

Examples of the transparent conductive film, S n 0 ₂ consisting NE SA films, I n ₂ 0 ₃ - or the like can be used consisting of S N_〇 ₂ I TO film. For patterning these transparent conductive films, a photo-etching method or a method using a mask when forming the transparent conductive film is used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate or the transparent conductive film and the coating film, a functional silane compound, a titanate compound or the like is previously applied on the substrate and the transparent conductive film. It may be applied.

 Next, the coating film is irradiated with linearly polarized light or partially polarized radiation or non-polarized radiation, and in some cases, the coating is further heated at a temperature of 150 to 250 ° C, preferably for 1 to 120 minutes. By performing, it imparts liquid crystal alignment ability. Here, as the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 80 nm can be used, but light having a wavelength of 300 nm to 400 nm is used. Including UV power S is preferred. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination of these. You may go. When irradiating unpolarized radiation, the direction of irradiation must be oblique.

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

The radiation dose is preferably 1 J Zm ² or more and less than 10 0, 0 00 J / m ² , more preferably 10 to 3 0,000 J / m ² . In addition, when a liquid crystal alignment ability was imparted to a coating film formed from a conventionally known liquid crystal alignment agent by a photo-alignment method, a radiation dose of 10 0, 0 00 J Zm ² or more was required. However, when the liquid crystal aligning agent of the present invention is used, good liquid crystal alignment is imparted even when the irradiation dose in the photo-alignment method is 3, OOOJ Zm ² or less, and further 1, 00 0 J / m ² or less. This contributes to reducing the manufacturing cost of liquid crystal display elements.

 The “pretilt angle” in the present invention represents the angle of inclination of liquid crystal molecules from a direction parallel to the substrate surface.

<Liquid crystal display device manufacturing method> The liquid crystal display element formed using the liquid crystal aligning agent of this invention can be manufactured as follows, for example.

 Prepare a pair (two) of substrates on which the liquid crystal alignment film is formed as described above, and make these liquid crystal alignment films face each other so that the polarization direction of the irradiated linearly polarized radiation becomes a predetermined angle. The peripheral part between the substrates is sealed with a sealing agent, liquid crystal is injected and filled, and the liquid crystal injection port is sealed to form a liquid crystal cell. Next, it is desirable to heat the liquid crystal cell to a temperature at which the liquid crystal used takes an isotropic phase, and then cool it to room temperature to remove the flow alignment at the time of injection.

 Then, a polarizing plate is bonded to both surfaces so that the polarization direction forms a predetermined angle with the orientation axis of the liquid crystal alignment film of the substrate, thereby obtaining a liquid crystal display element. If the liquid crystal alignment plane is horizontal, adjust the angle between the polarization directions of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate on the two substrates on which the liquid crystal alignment film is formed. Thus, a liquid crystal display element having a TN type or S TN type liquid crystal cell can be obtained. On the other hand, in the case of the liquid crystal alignment film force vertical alignment, the cell is configured so that the directions of easy alignment axes of the two substrates on which the liquid crystal alignment film is formed are parallel, and a polarizing plate A liquid crystal display element having a vertical alignment type liquid crystal cell can be obtained by bonding so that the polarization direction forms an angle of 45 ° with the easy alignment axis.

 As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.

As the liquid crystal, for example, nematic liquid crystal, smectic liquid crystal, or the like can be used. In the case of a TN type liquid crystal cell or S TN type liquid crystal cell, it has a positive dielectric anisotropy to form a nematic type liquid crystal S, for example, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, Terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like are used. For example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate; trade names C 1 15 and CB-15 (made by Merck & Co., Inc.) Chiral agents such as those available on the market; P-decyloxybenzylidene, P-amino-2-methylbutyl cinnamate, and other ferroelectric liquid crystals can also be added and used.

 On the other hand, in the case of a vertical alignment type liquid crystal cell, those having negative dielectric anisotropy to form a nematic type liquid crystal are preferable. For example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, an azoxy liquid crystal, For example, fluorinated liquid crystal and phenylcyclohexane liquid crystal are used.

 As a polarizing plate used outside the liquid crystal cell, a polarizing film called an “H film” in which polyvinyl alcohol is stretched and absorbed while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself. For example, a polarizing plate made of

 The liquid crystal display element of the present invention manufactured by force is excellent in various properties such as display characteristics and reliability. Example

 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

 The weight average molecular weight of the polyorganosiloxane in the following is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.

 The solution viscosity of the polyamic acid solution is a value measured at 25 using an E-type viscometer. Column: Tosohichi Co., Ltd., T S Kge 1 GR C XL I I

 Solvent: Tetrahydrofuran

 Temperature: 40 ° C

Pressure: 6 8 kgf / cm ² Synthesis of cinnamate derivatives>

 [Synthesis of a compound represented by the above formula (A-1)]

Synthesis example 1

 The following scheme

C3F ₇ G ₃ H ₆ -OH

 (A-1-C4-1A)

K ₂ CO, HO- ^ /) — COOCH ₃

NaOH / H ₂ 0

 (A-1-C4-1B)

SOCI ₂

K ₂ C0 ₃ HO ^ -CH = CH— COOH

C ₃ F ₇ C ₃ H ₆ -0- ^ COO-<^ CH = CH— COOH

 (A-1-C4-1)

According to this, the compound (A-1—C4-1) was synthesized.

In a 50 OmL eggplant-shaped flask, 53 g of 4, 4, 5, 5, 6, 6, 6-hepteven fluorohexanol and 10 OmL of pyridine were charged and ice-cooled. P- A solution prepared by dissolving 63 g of toluenesulfonic acid chloride in 10 mL of pyridine was added dropwise over 30 minutes, and the reaction was further performed by stirring at room temperature for 5 hours. After completion of the reaction, 12 OmL of concentrated hydrochloric acid and 500 g of ice were added to the reaction mixture. Ethyl acetate was further added, and the organic layer was washed successively with water and saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, then concentrated and dried to obtain 96 g of the compound (A-1-C4-1A).

 Next, in a 50 OmL three-necked flask equipped with a thermometer, 96 g of the above compound (A-1-C 4-1 A), 55 g of methyl 4-hydroxybenzoate, 124 g of potassium carbonate, and N, N-dimethyla Cetamide 30 OmL was charged and the reaction was allowed to stir at 80 ° C for 8 hours. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the organic layer was washed with water. The organic layer was then dried over magnesium sulfate, concentrated and dried to obtain a white powder. To this white powder, 60 g of sodium hydroxide, 30 OmL of water and 300 mL of tetrahydrofuran were added and reacted under reflux for 24 hours. After completion of the reaction, filtration was performed, and subsequently concentrated hydrochloric acid was added to the filtrate to neutralize it to form a white precipitate. The precipitate was collected by filtration and recrystallized from ethanol to obtain 34 g of white crystals of compound (A-1-C4-1 B).

 Next, 10 OmL of thionyl chloride and 0.2 mL of N, N-dimethylformamide were added to 34 g of this compound (A-1 1 C4 1 1B) and stirred at 80 ° C for 1 hour to carry out the reaction. Thereafter, thionyl chloride was distilled off under reduced pressure, and methylene chloride was added. The organic layer was washed with an aqueous sodium hydrogen carbonate solution, then dried over magnesium sulfate, concentrated, and then tetrahydrofuran was added.

Separately, a 2 L three-necked flask was charged with 14 g of 4-hydroxycinnamic acid, 22 g of potassium carbonate, 0.96 g of tetrabuty / ammonium, 8 OmL of tetrahydrofuran and 16 OmL of water. While this solution was ice-cooled, a tetrahydrofuran solution containing a reaction product of the above compound (A-1-C4-1B) and thionyl chloride was slowly added dropwise thereto, and the mixture was further stirred for 2 hours after the completion of the addition. Reaction was performed. After completion of the reaction, the reaction mixture is neutralized by adding hydrochloric acid, extracted with ethyl acetate, the extract is dried over magnesium sulfate, concentrated, and recrystallized with ethanol. Gave 19 g of white crystals of the compound (A-1—C4 1),

[Synthesis of a compound represented by the above formula (A-2)]

Synthesis example 2

 The following scheme

CH ₂ 2 CH—COO

Pd (PPh ₃ ) ₄

HO ^ CH = CH-COO-C ₆ H ₁₃

 (A-2-C1-1A)

HOCO-C ₂ H ₄ -COO—NO V ~ CH 2 CH—COO-C ₆ H ₁₃

 (A-2-C1-1)

According to the above, compound (A-2-C1-1) was synthesized.

Thermometer, 2 L three-necked flask equipped with a nitrogen inlet tube 4 iodophenol 22 g, hexyl acrylate 16 g, triethylamine 14 mL, tetrakistriphenylphosphine palladium 2.3 g and N, N-dimethylformamide 1 L The inside of the system was thoroughly dried. Subsequently, the mixture was heated to 90 ° C. and stirred for 2 hours under a nitrogen stream to carry out the reaction. After completion of the reaction, dilute hydrochloric acid was added and extracted with ethyl acetate. The organic layer is washed with water, dried over magnesium sulfate, concentrated, and purified by column purification with a mixed solvent consisting of hexane and ethyl acetate, and then concentrated and dried to give compound (A-2-CI — 12 g of 1A) was obtained. Next, in a 20 OmL three-necked flask equipped with a thermometer, nitrogen inlet tube, and reflux tube, 12 g of the above compound (A-2-CI-1A), succinic anhydride 5.5 g, 4-dimethylaminopyridine 0. 6 g was charged and the system was thoroughly dried. Next, 5.6 g of triethylamine and 10 OmL of tetrahydrofuran were added to this mixture, and the reaction was performed under reflux for 5 hours. After completion of the reaction, dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain 8.7 g of compound (A-2-CI-1).

<Preparation of radiation-sensitive polyorganosiloxane>

Synthesis example 3

 XO-SQ (trade name, manufactured by Toagosei Co., Ltd.) as a polyorganosiloxane having an oxetane ring in a 20 OmL three-necked flask. (A-1 1 C4 -1) 11 g and ^ W- 200- N alumina (trade name, manufactured by ICN Pharmac eutica 1 s, Inc.) were prepared and stirred at room temperature for 48 hours. A reaction was performed. After completion of the reaction, reprecipitation with methanol was performed, and then the solution obtained by re-dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was distilled off to remove the radiation-sensitive polyorganosiloxane (S-CO — 3.6 g of white powder of 1) was obtained. The weight average molecular weight of the radiation sensitive polyorganosiloxane (S—CO-1) was 14,500. Synthesis example 4

As in Synthesis Example 3, except that 8 g of the compound (A-2-C1-1) synthesized in Synthesis Example 2 was used instead of Compound (A-1-C4-1) in Synthesis Example 3 above. As a result, 3. O g of a white powder of radiation-sensitive polyorganosiloxane (S—CO—2) was obtained. The weight-average molecular weight of the radiation-sensitive polyorganosiloxane (S—CO—2) was 14,200. Synthesis of other polymers>

 [Synthesis of polyamic acid]

Synthesis example 5

 1,2,3,4-Cyclobutanetetraforce dianhydride 196 g (1.0 mol) as tetracarboxylic dianhydride and 2,2'-dimethyl-1,4,4, didiamino as diammine compound Dissolve 212 g (1.0 mol) of biphenyl in 4,050 g of N-methyl-2-pyrrolidone and react for 3 hours at 40 ° C to contain 10% by weight of polyamic acid (PA-1) A solution of 3,700 g was obtained. The solution viscosity of this polyamic acid solution was 17 OmPa · s.

[Synthesis of other polyorganosiloxanes]

Synthesis example 6

 A 20 OmL three-necked flask equipped with a condenser was charged with 20.08 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol, and heated to 60 ° C and stirred. To this was added a maleic anhydride aqueous solution prepared by dissolving 0.26 g of maleic anhydride in 10.8 g of water, prepared in another flask with a volume of 2 OmL, and heated and stirred at 60 ° C for another 4 hours. Went. The solvent was distilled off from the resulting reaction mixture, 1 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>

Example 1

Converted to PA-1 of the solution containing 100 parts by weight of the radiation-sensitive polyorganosiloxane S—CO-1 obtained in Synthesis Example 3 and the polyamic acid (PA-1) obtained in Synthesis Example 5 1 , 000 parts by weight, and add N-methyl-2-pyrrolidone and ptylcetosolve to this, and the solvent composition is N-methyl-2-pyrrolidone: ptylcetesolve = 50:50 (weight ratio), solid Partial concentration 3.0 A liquid crystal aligning agent A-CO-1 was prepared by making an amount% solution and filtering this through a filter with a pore size of 1 m. Example 2

 Example 1 In the same manner as in Example 1 except that the radiation-sensitive polyorganosiloxane S—CO—2 obtained in Synthesis Example 4 was used in place of the radiation-sensitive polyorganosiloxane S—CO—1. A liquid crystal aligning agent A—CO—2 was prepared. Example 3

 The solution containing the other polyorganosiloxane (PS-1) obtained in Synthesis Example 6 above was converted to PS-1 in an amount corresponding to 500 parts by weight (solid content). 100 parts by weight of the radiation-sensitive polyorganosiloxane S—CO-1 obtained in Example 3 was added, and 1 ethoxy-2-propanol was further added to obtain a solid content concentration of 4.0% by weight. Then, this solution was filtered with a filter having a pore size of 1 / xm to prepare a liquid crystal aligning agent A—C—O—3.

<Manufacture and evaluation of vertically aligned liquid crystal display elements>

Example 4

The liquid crystal aligning agent A—CO-1 obtained in Example 1 above was applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of an IT ○ film using a spinner, and 1 on a 80 hot plate. After pre-baking for 1 minute, it was heated at 200 ° C. for 1 hour in an oven purged with nitrogen to form a coating film having a thickness of 0.1 m. Next, on the surface of this coating film, polarized ultraviolet light 1, 00 0 J / m ² including a 3 13 nm emission line is tilted 40 ° from the substrate normal line using a H g—X e lamp and a Grand Taylor prism. The liquid crystal alignment film was given by irradiating from the opposite direction to give liquid crystal alignment ability. By repeating the same operation, two substrates (one pair) having a liquid crystal alignment film were prepared.

For the pair of substrates having the above liquid crystal alignment film, an epoxy resin adhesive containing 5.5 m diameter aluminum spheres is screen-printed on the outer periphery of the surface on which the liquid crystal alignment film is formed. After coating by printing, the substrates were stacked and pressure-bonded so that the projection direction of the UV optical axis onto the substrate surface was antiparallel, and the adhesive was heat-cured at 150 ° C for 1 hour. Next, a negative liquid crystal (MLC-6608 manufactured by Merck & Co., Inc.) was filled in the gap between the substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment during liquid crystal injection, this was heated to 150 ° C. and then slowly cooled to room temperature. Next, the polarizing plates are bonded to both sides of the substrate so that the polarization directions are orthogonal to each other and form an angle of 45 ° with the projection direction of the optical axis of the liquid crystal alignment film onto the substrate surface. Thus, a vertically aligned liquid crystal display element was manufactured.

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

(1) Evaluation of liquid crystal alignment

 The liquid crystal display device manufactured above was observed with an optical microscope for the presence of abnormal domains in the change in brightness when a 5 V voltage was turned ON / OFF (applied / released). "

 (2) Pretilt angle evaluation

 For the liquid crystal display device manufactured as described above, T. J. S che ff er t. A 1. J. Ap p 1. Phy s. Vo l. 19, p 2013 (19

80), the pretilt depression angle was measured by the crystal rotation method using He—Ne laser light.

 (3) Evaluation of voltage holding ratio

 After applying a voltage of 5 V to the liquid crystal display device manufactured above at 60 ° C for a 60-microphone-second application time with a 167-millisecond span, the voltage holding ratio 167 milliseconds after the application was released Was measured. The measuring device used was VHR-1 manufactured by Toyo Corporation.

 (4) Burn-in

After applying a 30 Hz, 3 V rectangular wave with 5 V DC superimposed on the liquid crystal display device manufactured above for 2 hours at an ambient temperature of 60, the DC voltage was turned off and left at room temperature for 15 minutes. The DC voltage remaining in the liquid crystal display element is obtained by the flicker elimination method. It was. Example 5

 In the above Example 4, a vertical alignment type liquid crystal was prepared in the same manner as in Example 4 except that the liquid crystal alignment agent A-CO-3 prepared in Example 3 was used instead of the liquid crystal alignment agent A—C〇-1. Display elements were manufactured and evaluated. The evaluation results are shown in Table 1. Comparative Example 1

 [Synthesis of polyamic acid]

 2,3,5-tri-stroxyl-poxycyclopentylacetic acid dianhydride 22.4 g (0.1 mol) and the following formula (d-1) synthesized according to JP 2003-520878

(d-1)

48.46 g (0.1 mol) of the compound represented by the formula (1) was dissolved in N-methyl-2-pyrrolidone 283.4 g and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C under reduced pressure for 15 hours to obtain 67 g of polyamic acid (RPA-CO-1).

 <Preparation of liquid crystal alignment agent>

The polyamic acid RPA-CO-1 obtained above is dissolved in a mixed solvent (mixing ratio = 50: 50 (weight ratio)) consisting of N-methyl-2-pyrrolidone and butylceguchi sorb. A comparative liquid crystal aligning agent R—C 0-1 was prepared by preparing a 0 wt% solution and filtering this through a filter having a pore size of 1 m. Preparation and evaluation of vertical alignment liquid crystal display elements>

 A vertical alignment type liquid crystal display device was produced in the same manner as in Example 4 except that the liquid crystal alignment agent R-CO-1 prepared above was used instead of the liquid crystal alignment agent A-CO-1 in Example 4. And evaluated. The evaluation results are shown in Table 1. Example 6

<Preparation and Evaluation of TN Oriented Liquid Crystal Display Device>

The liquid crystal aligning agent A—CO-2 prepared in Example 2 above was applied to the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film by using a spinner, and was applied on a hot plate at 80 ° C. After pre-baking for 1 minute, the film was heated at 200 ° C. for 1 hour to form a coating film having a thickness of 0.1 m. Using a H g— X e lamp and a Grand Taylor prism on the surface of this coating film, polarized ultraviolet light 1, 00 0 J / m ² containing a 3 13 nm emission line was tilted 40 ° from the substrate normal. By irradiating from the direction, a liquid crystal alignment film was formed by imparting liquid crystal alignment ability. The same operation was repeated to produce a pair (two) of glass substrates having a liquid crystal alignment film on the transparent conductive film surface.

After applying an epoxy resin adhesive containing aluminum oxide spheres with a diameter of 5.5 m on the periphery of each surface of the pair of substrates on which the liquid crystal alignment film is formed, The substrates were stacked and pressure-bonded so that the irradiation directions were orthogonal to each other, and heated at 1550 ° C. for 1 hour to heat the adhesive. Next, a positive nematic liquid crystal (Merck, ML C-6 2 2 1, with chiral agent) is injected into the gap between the substrates through the liquid crystal injection port, and then filled with an epoxy adhesive. Sealed. Further, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 15 50 ^ for 10 minutes and then gradually cooled to room temperature. Further, by attaching polarizing plates on both outer sides of the substrate, the polarizing directions of the polarizing plates are perpendicular to each other, and are aligned so that the optical axis of the ultraviolet light irradiated to the liquid crystal alignment film is parallel to the direction of projection onto the substrate surface. An alignment type liquid crystal display device was manufactured. The liquid crystal display element was evaluated in the same manner as in Example 4 for liquid crystal orientation, voltage holding ratio, and image sticking characteristics (residual voltage). The results are shown in Table 1. Table 1

<Evaluation of storage stability of liquid crystal alignment agent>

Example 7

 On the glass substrate, the coating film of the liquid crystal aligning agent A—CO—1 prepared in Example 1 above was formed by changing the number of rotations by the spin coat method, and the film thickness after removing the solvent was 1, The number of revolutions at 000 A was examined.

 Next, a part of the liquid crystal aligning agent A—CO—1 was taken and stored at 15 for 5 weeks. The liquid crystal alignment agent after storage was visually observed, and when insoluble precipitates were observed, the storage stability was judged as “poor”.

 If no insoluble matter was observed after storage for 5 weeks, a coating film was formed on the glass substrate by spin coating with a rotational speed of 1.00 OA before storage, and the solvent was removed. The subsequent film thickness was measured. If this film thickness is more than 10% off from 1,00 OA, the storage stability is judged as “bad”, and if the film thickness deviation is less than 10%, the storage stability is judged as “good”. Judged.

 The evaluation results are shown in Table 2.

 The film thickness of the coating film was measured using a knitted needle type step thickness gauge manufactured by KLA-Tencor. Examples 8 and 9

 In Example 7 above, the storage stability of the liquid crystal aligning agent was evaluated in the same manner as in Example 7 except that the liquid crystal aligning agent described in Table 2 was used instead of the liquid crystal aligning agent A—CO-1. It was.

The evaluation results are shown in Table 2. Table 2

As is clear from the above examples, the liquid crystal aligning agent containing the radiation-sensitive polyorganosiloxane of the present invention has excellent liquid crystal alignment by a photo-alignment method with a small radiation dose without performing a rubbing treatment. A liquid crystal alignment film exhibiting excellent properties, a good pretilt angle and excellent electrical properties can be obtained. The liquid crystal display element comprising the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has a particularly improved image sticking property compared to a polyimide having a known cinnamic acid derivative in the side chain.

 Therefore, when the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention is applied to a liquid crystal display element, the liquid crystal display element can be manufactured at a lower cost than the conventional one, and has excellent performance such as display characteristics and reliability. It becomes. Therefore, these liquid crystal display elements can be effectively applied to various devices, and can be suitably used for devices such as desk calculators, wrist watches, table clocks, counting display boards, word processors, personal computers, and liquid crystal televisions.

Claims

The scope of the claims

1. Strong lpoxyl group, 7 acid group, 1 SH, 1 NCO, -NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), — CH = CH ₂ and 1 S0 ₂ C 1 A cinnamic acid derivative having at least one group selected from the group, a polyorganosiloxane having an oxetane ring;

A liquid crystal aligning agent characterized by containing a radiation-sensitive polyorganosiloxane obtained by reacting. 2. Cinnamic acid derivative is represented by the following formula (A-1)

(A-1)

(In the formula (A-1), R ¹ is a monovalent organic group having 3 to 40 carbon atoms including an alkyl group having 1 to 40 carbon atoms or an alicyclic group, provided that one of hydrogen atoms of the alkyl group is Part or all may be substituted with a fluorine atom, R ² is a single bond, an oxygen atom, one C 1001 or one OCO—, R ³ is a divalent aromatic group, a divalent aromatic group, An alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, provided that part or all of the hydrogen atoms of the divalent aromatic group may be substituted with fluorine atoms, R ⁴ is a single bond, an oxygen atom, —COO— or one OCO—, R ⁵ is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms or a divalent aromatic group, and R ⁵ is When it is a single bond, R ⁶ is a hydrogen atom, and when R ⁵ is a methylene group, an alkylene group or a divalent aromatic group, R ⁶ is a carboxyl group, a hydroxyl group, —SH, —NCO , —NHR, —CH═CH ₂ or one S0 ₂ C 1, wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁷ is a fluorine atom, a methyl group or a cyan group, a is an integer from 0 to 3, and b is an integer from 0 to 4.) Or a compound represented by the following formula (A-2)

(A-2)

(In the formula (A-2), RS is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group or an aromatic group, provided that hydrogen of the alkyl group is Some or all of the atoms may be substituted with fluorine atoms, R ⁹ is a single bond, an oxygen atom, one COO— or —OCO—, R ^1Q is a methylene group, or an alkylene group having 2 to 10 carbon atoms. A divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group, provided that a part of the hydrogen atoms of the divalent aromatic group Alternatively, all of them may be substituted with fluorine atoms, and R ¹¹ is a single bond, 10 CO— (CH ₂ ) — _e —, —COO— (CH ₂ ) _g —, or 1 O— (CH ₂ ) i. —, Where e, g and i are each an integer from 1 to 10, R ¹² is a force lpoxyl group, a hydroxyl group, —SH, —NC〇, — NHR, one CH = CH ₂ or — S〇 is a ₂ C 1, it was And wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹³ is a fluorine atom, a methyl group or Shiano group, c is an integer of 0 to 3, d is 0 to 4 integer .)

The liquid crystal aligning agent of Claim 1 which is a compound represented by these. 3. The polyorganosiloxane has the following formula (S-1)

(In the formula (S-1), X is the following formula (X-1)

(In the formula (X-1), R ¹⁴ is an alkyl group having 1 to 6 carbon atoms, and “*” indicates a bond.)

Y ¹ is a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. )

The liquid crystal aligning agent according to claim 1 or 2, which is at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the formula: a hydrolyzate thereof and a condensate of the hydrolyzate.

4. The liquid crystal aligning agent according to claim 1 or 2, further comprising at least one polymer selected from the group consisting of polyamic acid and polyimide. Furthermore, the following formula (S-2)

(In the formula (S-2), R ¹⁷ is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, Y ² is a hydroxyl group, a halogen atom, 1 carbon atom. A polyorganosiloxane having a repeating unit represented by: a hydrolyzate thereof and a condensate of the hydrolyzate. 3. The liquid crystal aligning agent according to claim 1 or 2, comprising at least one selected from the group consisting of:

6. A method for forming a liquid crystal alignment film, comprising: applying a liquid crystal aligning agent according to claim 1 on a substrate to form a coating film; and irradiating the coating film with radiation. 7. A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1.