JP5454772B2 - Liquid crystal aligning agent, liquid crystal aligning film, method for forming the same, and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a method for forming the same, and a liquid crystal display element.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy is sandwiched between substrates with a transparent electrode having a liquid crystal alignment film, and the major axis of liquid crystal molecules is twisted continuously between the substrates by 0 to 360 ° as necessary. Various liquid crystal cells such as TN (Twisted Nematic) type and STN (Super Twisted Nematic) type, and IPS (In Plane Switching) type in which the long axis of liquid crystal molecules is aligned in the horizontal direction with respect to the substrate. Liquid crystal display elements having the above are known (see Patent Documents 1 to 4).
As a means for aligning the liquid crystal in such a liquid crystal cell, an organic film is formed on the surface of the substrate, and then the surface of the organic film is rubbed in one direction with a cloth material such as rayon. A monomolecular film having a long-chain alkyl group is formed using a method for forming a liquid crystal alignment film (a method for performing a rubbing treatment), a method for obliquely depositing silicon oxide on a substrate surface, or a Langmuir-Blodgett method (LB method). There are ways to do this. Among these, from the viewpoints of substrate size, liquid crystal alignment uniformity, processing time, and processing cost, it is common to provide liquid crystal alignment ability by rubbing.
However, if the alignment of the liquid crystal is performed by rubbing, dust is likely to be generated in the process or static electricity is likely to be generated, so that dust adheres to the alignment film surface and causes display defects. there were. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, there has been a problem that the circuit damage of the TFT element occurs due to the generated static electricity, resulting in a decrease in yield. Furthermore, in liquid crystal display elements that will be further refined in the future, unevenness is inevitably generated on the substrate surface as the density of pixels increases, so that uniform rubbing treatment is gradually becoming difficult.

As another means of imparting liquid crystal alignment ability to the liquid crystal alignment film in the liquid crystal cell, the liquid crystal alignment ability can be improved by irradiating a photosensitive thin film such as polyvinyl cinnamate or polyimide formed on the substrate surface with polarized or non-polarized radiation. The photo-alignment method to provide is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (see Patent Documents 6 to 16 and 19 to 21).
By the way, in a liquid crystal cell of TN (Twisted Nematic) type, STN (Super Twisted Nematic) type or the like, the liquid crystal alignment film needs to tilt the liquid crystal molecules at a predetermined angle (pretilt angle) with respect to the substrate surface. (See Patent Document 2). In the case of forming a liquid crystal alignment film by the photo-alignment method, the pretilt angle is usually given by irradiation with radiation whose incident direction to the substrate surface is inclined from the substrate normal (see Patent Document 6).
On the other hand, a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known as an operation mode of a liquid crystal display element different from the above. 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 molecules must be tilted from the substrate normal direction to one direction in the substrate surface. There is. 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, or using a rubbing alignment film, liquid crystal molecules are slightly directed from the substrate normal direction to one direction in the substrate surface. A method of tilting (pretilting) has been proposed (see Patent Document 5 and Non-Patent Documents 1 to 3).
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 display element (see Patent Documents 15 to 21).
Thus, the liquid crystal alignment film manufactured by the photo-alignment method can be effectively applied to a liquid crystal display element. However, the liquid crystal alignment film manufactured by the conventional photo-alignment method has an unstable pretilt angle, that is, the pretilt property decreases with time even if the pretilt angle characteristic is exhibited immediately after the liquid crystal alignment film is formed. There was a problem to do.

JP-A-4-153622 JP 60-107020 A JP 56-91277 A US Pat. No. 5,928,733 Japanese Patent Laid-Open No. 11-258605 JP-A-9-222605 JP-A-6-287453 JP-A-10-251646 Japanese Patent Laid-Open No. 11-2815 JP-A-11-152475 JP 2000-144136 A JP 2000-319510 A JP 2000-281724 A JP-A-9-297313 JP 2003-307736 A JP 2004-163646 A Japanese Patent Laid-Open No. 9-21468 JP 2003-114437 A JP 2006-171304 A JP 2007-224273 A JP 2007-256484 A JP 2007-191447 A JP-A 63-291922

Liquid crystal, vol. 3, no. 2, p117 (1999) Liquid crystal, vol. 3, no. 4, p272 (1999) Jpn Appl. phys. , Vol. 36, p428 (1997) Chemical Reviews, Volume 95, p1409 (1995) T.A. J. et al. Scheffer et. al. J. et al. Appl. Phys. vol. 19, p2013 (1980)

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal alignment film that can impart a pretilt angle by a photo-alignment method and is excellent in temporal stability of the imparted pretilt angle. It aims at providing a liquid crystal aligning agent.
Another object of the present invention is to provide a method for forming a liquid crystal alignment film from the liquid crystal alignment agent.
Still another object of the present invention is to provide a liquid crystal alignment film and a liquid crystal display element which are excellent in long-term reliability.
Further objects and advantages of the present invention will become apparent from the following description.

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

(In the formula (1), ^{X 1} is a monovalent organic group having an epoxy group, ^{Y 1} represents a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, 6 to 20 alkyl group carbon atoms or from 1 to 20 carbon atoms Of the aryl group.)
At least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the formula:
(A) a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.), - CH = CH ₂ and _-SO 2 group consisting of Cl Cinnamic acid derivatives having at least one group selected from: (B) carboxyl group, hydroxyl group, —SH, —NCO, —NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). ), At least one group selected from the group consisting of —CH═CH ₂ and —SO ₂ Cl, and a compound having a photosensitizing structure;
It is achieved by a liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane obtained by reacting the above.
The above objects and advantages of the present invention are secondly,
This is achieved by a method for forming a liquid crystal alignment film in which a coating film is formed by applying the liquid crystal aligning agent on a substrate, and the coating film is irradiated with polarized or non-polarized radiation.
Third, the above objects and advantages of the present invention are as follows:
Achieved by a liquid crystal alignment film formed from the above liquid crystal alignment agent,
Fourth,
This is achieved by a liquid crystal display element comprising the above liquid crystal alignment film.

  When the liquid crystal aligning agent of this invention is used, the liquid crystal aligning film which is excellent in the temporal stability of a pretilt angle can be formed by the photo-alignment method. The liquid crystal alignment film of the present invention formed from the liquid crystal aligning agent of the present invention can be suitably applied to various liquid crystal display elements. When the liquid crystal display element of the present invention having such a liquid crystal alignment film is used for a long period of time, the display performance does not deteriorate. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, portable information terminals, digital cameras, cellular phones, It can be suitably used for display devices such as various monitors and liquid crystal televisions.

It is a graph which shows the presence distribution in the film thickness direction of the fragment of m / z = 231 observed by ToF-SIMS in Example T-1. It is a graph which shows the integrated value of presence in the film thickness direction of the fragment of m / z = 231 observed by ToF-SIMS in Example T-1.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (1), a hydrolyzate thereof and a condensate of the hydrolyzate (hereinafter referred to as “ "Polyorganosiloxane having an epoxy group"),
(A) a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.), - CH = CH ₂ and _-SO 2 group consisting of Cl A cinnamic acid derivative having at least one group selected from (hereinafter referred to as “cinnamic acid derivative (A)”) and (B) a carboxyl group, a hydroxyl group, —SH, —NCO, —NHR (where R is is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -. CH = CH ₂ and at least one group and compounds having a photosensitizing structure selected from the group consisting of _-SO 2 Cl (hereinafter, " Photosensitizing compound (B) "),
Contains a radiation-sensitive polyorganosiloxane obtained by reacting Here, a part of the cinnamic acid derivative (A) is converted to the following formula (5) within a range not impairing the effects of the present invention.

R ¹⁵ -R ¹⁶ -R ¹⁷ (5)

(In the formula (5), R ¹⁵ is a monovalent or organic group, or an alkyl or alkoxyl group having 4 to 20 carbon atoms having 3 to 40 carbon atoms containing an alicyclic group, provided that the alkyl group Alternatively, some or all of the hydrogen atoms of the alkoxyl group may be substituted with fluorine atoms, R ¹⁶ is a single bond or a phenylene group, provided that when R ¹⁵ is an alkoxyl group, R ¹⁶ is a phenylene group, R ¹⁷ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.), - CH = CH ₂ and _-SO 2 group consisting of Cl At least one group selected from:
It may be used by replacing with a compound represented by

<Radiation sensitive polyorganosiloxane>
[Polyorganosiloxane having epoxy group]
X ¹ in the above formula (1) is the following formula (X ¹ -1) or (X ¹ -2)

(In the above formula, “*” indicates a bond.)
It is preferable that it is group represented by these.
Examples of the alkoxy group having 1 to 10 carbon atoms of Y ¹ include, for example, a methoxyl group and an ethoxyl group; and examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like; As the aryl group having 6 to 20 carbon atoms, for example, phenyl group and the like can be mentioned, respectively. be able to.
The polyorganosiloxane having an epoxy group preferably has a polystyrene-equivalent weight average molecular weight of 500 to 100,000, more preferably 1,000 to 10,000, as measured by gel permeation chromatography (GPC). It is preferably 1,000 to 5,000.
Such polyorganosiloxane having an epoxy group is preferably a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst. It can be synthesized by hydrolysis or hydrolysis / condensation below.

Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxy. Silane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy A silane etc. can be mentioned.
Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, Trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, Fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, Rutriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) ) Ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (tri Fluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltri Methoxy Lan, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane,

2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro- n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro) -N-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri − -Butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (Meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propoxysilane, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxy Propyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i- Lopoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri -I-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, Phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, Methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi- i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane,

(Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i -Propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (Methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercapto Propyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di-n -Butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl ) (Vinyl) di-n-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, Divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n- Lopoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxy Silane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane In addition to silane compounds having one silicon atom such as (ethoxy) (methyl) diphenylsilane,

Product names such as KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X -21-5848, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22 -176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672 , X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-10 3, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (manufactured by Shin-Etsu Chemical Co., Ltd.); glass resin (manufactured by Showa Denko KK); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray Dow Corning Co., Ltd.); FZ3711, FZ3722 (above, manufactured by Nihon Unicar Co., Ltd.); DMS-S1 , DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD -0332, PDS-1615, PDS-9931, XMS-5025 (above, manufactured by Chisso Corporation); Methyl silicate MS51, Methyl silicate MS56 (above, manufactured by Mitsubishi Chemical Corporation); Ethyl silicate 28, Ethyl silicate 40, Examples include partial condensates such as ethyl silicate 48 (manufactured by Colcoat Co., Ltd.); GR100, GR650, GR908, GR950 (manufactured by Showa Denko Co., Ltd.).

Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltri Methoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane is preferred.
The polyorganosiloxane having an epoxy group used in the present invention preferably has an epoxy equivalent of 100 to 10,000 g / mol, more preferably 150 to 1,000 g / mol, and particularly 150 to 300 g / mol. Mole is preferred. Therefore, when synthesizing a polyorganosiloxane having an epoxy group, the ratio of the silane compound having an epoxy group and the other silane compound is adjusted so that the obtained polyorganosiloxane epoxy equivalent is in the above range. It is preferable to set. In synthesizing the polyorganosiloxane having an epoxy group used in the present invention, it is preferable that only the silane compound having an epoxy group is used and no other silane compound is used.

Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane having an epoxy group include hydrocarbons, ketones, esters, ethers, alcohols, and the like.
Examples of the hydrocarbon include toluene and xylene; Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone; Examples of the ester include ethyl acetate, n-butyl acetate, and acetic acid. i-amyl, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; as the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; as the alcohol, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-pro Ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n- propyl ether, can be mentioned, respectively. Of these, water-insoluble ones are preferred.
These organic solvents can be used alone or in admixture of two or more.
The amount of the organic solvent used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total silane compounds.
The amount of water used in producing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 times mol, more preferably 1 to 30 times mol, based on all silane compounds.

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. can be used, for example.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, And tertiary organic amines such as diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide preferable.
As a catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, the desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing side reactions such as ring opening of the epoxy group. This is preferable. In addition, the liquid crystal aligning agent of the present invention containing a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a cinnamic acid derivative is extremely excellent in storage stability, which is advantageous. It is. The reason for this is that, as pointed out in Non-Patent Document 4 (Chemical Reviews, Vol. 95, p1409 (1995)), when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis and condensation reaction, a random structure, It is presumed that a ladder structure or a cage structure is formed and a polyorganosiloxane having a low silanol group content is obtained. That is, since such polyorganosiloxane has a low content of silanol groups, the condensation reaction between silanol groups is suppressed, and when the liquid crystal aligning agent of the present invention contains other polymer described later. Since the condensation reaction between the silanol group and the other polymer is suppressed, it is presumed that the storage stability is excellent.

As the catalyst, an organic base is particularly preferable. The amount of organic base used varies depending on the reaction conditions such as the type of organic base, temperature, and the like, and should be appropriately set. For example, the amount is preferably 0.01 to 3 moles relative to all silane compounds. More preferably, it is 0.05-1 times mole.
The hydrolysis or hydrolysis / condensation reaction in producing an epoxy group-containing polyorganosiloxane is carried out by dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, and dissolving the solution in an organic base. It is preferable to carry out by mixing with water and heating with, for example, an oil bath.
During the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixed solution may be stirred or refluxed.
After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by weight is preferred because the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the target is removed by removing the solvent. A polyorganosiloxane having an epoxy group can be obtained.
In the present invention, a commercially available polyorganosiloxane having an epoxy group may be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (manufactured by Chisso Corporation).

[Cinnamic acid derivative (A)]
The cinnamic acid derivative (A) used in the present invention is a carboxyl group, a hydroxyl group, —SH, —NCO, —NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —CH═. A cinnamic acid derivative having at least one group selected from the group consisting of CH ₂ and —SO ₂ Cl.
As the cinnamic acid derivative (A), the following formula (2)

(In Formula (2), R ¹ is a C3-C40 monovalent organic group or C1-C40 alkyl group containing an alicyclic group, provided that a part of hydrogen atoms of the alkyl group or All may be substituted with fluorine atoms, R ² is a single bond, an oxygen atom, —COO— or —OCO—, R ³ is a divalent aromatic group, a divalent alicyclic group, 2 R ⁴ is a single bond, an oxygen atom, —COO— or —OCO—, and R ⁵ is a single bond, an oxygen atom, a sulfur atom or a methylene group. , An alkylene group having 2 to 10 carbon atoms or a divalent aromatic group, and when R ⁵ is a single bond, t is 1 and R ⁶ is a hydrogen atom, and R ⁵ is a methylene group or an alkylene group. or a divalent t is 0 or 1 is and R ⁶ is a carboxyl group when the aromatic group, a hydroxyl group, SH, -NCO, -NHR, a -CH = CH ₂ or _-SO 2 Cl, provided that said R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, ^{R 7} is a fluorine atom 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 (3)

(In the formula (3), R ⁸ is a monovalent organic group or an alkyl group having 1 to 40 carbon atoms of 3 to 40 carbon atoms containing an alicyclic group, provided that part of the hydrogen atoms of the alkyl group or All may be substituted with a fluorine atom, R ⁹ is an oxygen atom or a divalent aromatic group, R ¹⁰ is an oxygen atom, —COO— or —OCO—, and R ¹¹ is a divalent aromatic group. A group, a divalent heterocyclic group or a divalent condensed cyclic group, and R ¹² is a single bond, —OCO— (CH ₂ ) _e — ^* or —O— (CH ₂ ) _g — ^* . , provided that the e and g are each an integer from 1 to 10, "*", respectively, a bond marked with this is shown to bind with ^{R 13,} a carboxyl group, a hydroxyl group, the ^{R 13} - SH, -NCO, -NHR, a -CH = CH ₂ or _-SO 2 Cl, was The above R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁴ is a fluorine atom or a cyano group, c is an integer of 0 to 3, d is an integer of 0-4.) It is preferable that it is a compound represented by these.

The monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group R ¹ in the formula (2) may include, for example Koresuteniru group, cholestanyl group, an adamantyl group. The alkyl group having 1 to 40 carbon atoms of R ¹ is, for example, an alkyl group having 1 to 20 carbon atoms, provided that part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms. Is preferred. 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-dodecyl group, n -Tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 4,4,4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4,4,5,5,5-heptafluoro group Pentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorooctyl) ethyl group, 2 -(Perf Orodeshiru) ethyl group and the like.
Examples of the divalent aromatic group represented by R ³ and R ⁵ include a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, and 2,3,5. , 6-tetrafluoro-1,4-phenylene group; as the divalent heterocyclic group for R ³ , for example, 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furylene group, etc. Examples of the divalent condensed cyclic group represented by R ³ include a naphthylene group.
Examples of the divalent alicyclic group represented by R ³ include a 1,4-cyclohexylene group.
As the compound represented by the above formula (2), in the above formula (2), R ⁵ is a single bond, t is 1, and R ⁶ is a hydrogen atom, or R ⁵ Is a compound in which is a methylene group, an alkylene group or a divalent aromatic group, t is 0 or 1, and R ⁶ is a carboxyl group.
Preferable examples of the compound represented by the above formula (2) include, for example, the following formulas (2-1) to (2)
-35)

(In the formula, each R ¹ has the same meaning as in the above formula (2), and f is an integer of 1 to 10, respectively.)
The compound represented by each of these can be mentioned.
The monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group R ⁸ in the formula (3) may include, for example Koresuteniru group, cholestanyl group, an adamantyl group. 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 the alkyl group may be substituted with fluorine atoms. Is preferred. Examples of the alkyl group include those exemplified as the alkyl group for R ¹ in the above formula (2).
Examples of the divalent aromatic group, heterocyclic group or condensed cyclic group of R ⁹ and R ¹¹ include a divalent aromatic group, a heterocyclic group of R ³ and R ⁵ in the above formula (2), or What was illustrated as a condensed cyclic group can be mentioned, respectively.
R ¹³ is preferably a carboxyl group.
Preferable examples of the compound represented by the above formula (3) include, for example, the following formulas (3-1) to (3-11)

(In the formula, each R ⁸ has the same meaning as in the above formula (3), and u is an integer of 1 to 10, respectively.)
The compound represented by each of these can be mentioned.
Such a cinnamic acid derivative (A) can be synthesized by appropriately combining information on organic synthesis. The synthetic route and reaction conditions can be easily set by ordinary knowledge of those skilled in the art and a few preliminary experiments.

[Photosensitizing compound (B)]
The photosensitizing compound (B) in the present invention is a carboxyl group, a hydroxyl group, —SH, —NCO, —NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —CH═CH. A compound having at least one group selected from the group consisting of ₂ and —SO ₂ Cl and a photosensitizing structure. The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention is obtained by reacting the polyorganosiloxane having an epoxy group with a mixture of cinnamic acid derivative (A) and photosensitizing compound (B). The photosensitizing structure derived from the cinnamic acid derivative (A) and the photosensitizing structure derived from the photosensitizing compound (B) It has the function of being excited by irradiation and giving this excitation energy to the adjacent photosensitive structure in the polymer. This excited state may be a singlet or a triplet, but is preferably a triplet because of its long lifetime and efficient energy transfer. The radiation absorbed by the photosensitizing structure is preferably ultraviolet rays or visible rays having a wavelength in the range of 150 to 600 nm. Radiation having a shorter wavelength cannot be used in a photo-alignment method because it cannot be handled by a normal optical system. On the other hand, radiation having a wavelength longer than this has low energy and hardly induces an excited state of the photosensitizing structure.

Examples of such photosensitizing structures include acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitroaryl structure, fluorene structure, naphthalene structure, anthracene structure, acridine structure, indole structure, etc. And at least one of them. These structures are composed of groups obtained by removing 1 to 4 hydrogen atoms from acetophenone, benzophenone, anthraquinone, biphenyl, carbazole, nitrobenzene or dinitrobenzene, naphthalene, fluorene, anthracene, acridine or indole, respectively. Say. Here, the acetophenone structure, the carbazole structure and the indole structure are each preferably a structure composed of groups obtained by removing 1 to 4 hydrogen atoms of the benzene ring of acetophenone, carbazole or indole.
Of these, the photosensitizing structure is preferably at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, and a naphthalene structure. Particularly preferred is at least one selected from the group consisting of a benzophenone structure and a nitroaryl structure.
The photosensitizing compound (B) is preferably a compound having a carboxyl group and a photosensitizing structure, and more preferable compounds include, for example, the following formulas (B-1) to (B-42).

(In the above formula, p, q, r and s are each an integer of 1 to 6.)
The compound etc. which are represented by each of these can be mentioned.

The radiation-sensitive polyorganosiloxane used in the present invention comprises a polyorganosiloxane having an epoxy group as described above, a cinnamic acid derivative (A) and a photosensitizing compound (B), preferably in the presence of a catalyst. It can be synthesized by reacting in an organic solvent.
Here, the cinnamic acid derivative (A) is preferably 0.001 to 1 mol, more preferably 0.1 to 1 mol, and still more preferably 0.1 mol to 1 mol of the silicon atom of the polyorganosiloxane having an epoxy group. It is used in the range of 2 to 0.9 mol. The photosensitizing compound (B) is preferably 0.0001 to 0.5 mol, more preferably 0.0005 to 0.2 mol, and still more preferably with respect to 1 mol of the silicon atom of the polyorganosiloxane having an epoxy group. Is used in the range of 0.001 to 0.1 mol.
In the present invention, a part of the cinnamic acid derivative may be replaced with the compound represented by the above formula (5) as long as the effects of the present invention are not impaired. In this case, the synthesis of the radiation-sensitive polyorganosiloxane is carried out by combining a polyorganosiloxane having an epoxy group, a cinnamic acid derivative (A), a compound represented by the above formula (5), and a photosensitizing compound (B). It is performed by reacting.
R ¹⁵ in the above formula (5) is preferably an alkyl group or alkoxyl group having 8 to 20 carbon atoms, a fluoroalkyl group or fluoroalkoxyl group having 4 to 21 carbon atoms, and R ¹⁶ is a single bond, It is preferably a 4-cyclohexylene group or a 1,4-phenylene group, and R ¹⁷ is preferably a carboxyl group.
As preferable examples of the compound represented by the above formula (5), for example, the following formulas (5-1) to (5-4):

(In the above formula, h is an integer of 1 to 3, i is an integer of 3 to 18, j is an integer of 5 to 20, k is an integer of 1 to 3, and m is 0 to 18) And n is an integer of 1 to 18.)
And more preferable examples include the following formulas (5-3-1) to (5-3-3):

The compound represented by each of these can be mentioned.
The compound represented by the above formula (5) reacts with a polyorganosiloxane having an epoxy group together with the cinnamic acid derivative (A) and the photosensitizing compound (B), and exhibits a pretilt angle developability in the obtained liquid crystal alignment film. A compound that introduces a site to be imparted. In the present specification, the compound represented by the formula (5) is hereinafter referred to as “another pretilt angle-expressing compound”.
In the present invention, when a part of the cinnamic acid derivative (A) is replaced with another pretilt angle developing compound, the cinnamic acid derivative (A), the photosensitizing compound (B) and other pretilt angle developing properties are used. The total use ratio of the compound is preferably 0.001 to 1 mol, more preferably 0.1 to 1 mol, and still more preferably with respect to 1 mol of silicon atom of the polyorganosiloxane having an epoxy group. 0.2 to 0.9 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 (A). If the proportion of the other pretilt angle-expressing compound exceeds 50 mol%, there may be a problem that an abnormal domain occurs when the liquid crystal display element is turned on.

As said catalyst, a well-known compound can be used as what is called a hardening accelerator which accelerates | stimulates reaction with an organic base or an epoxy compound, and an acid anhydride.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
A quaternary organic amine such as tetramethylammonium hydroxide can be used. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide preferable.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine;
2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- ( 2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s -Triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2'-methyl] Ruimidazolyl- (1 ′)] ethyl-s-triazine imidazole compounds such as isocyanuric acid adducts; organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium, o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, Tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate Such as over preparative quaternary phosphonium salts;
1,8-diazabicyclo [5.4.0] undecene-7, a diazabicycloalkene such as its organic acid salt;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;
Boron compounds such as boron trifluoride and triphenyl borate;
Metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as amine addition type accelerators such as dicyandiamide or adducts of amine and epoxy resin;
A microcapsule-type latent curing accelerator in which the surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound, or a quaternary phosphonium salt is coated with a polymer; an amine salt-type latent curing accelerator;
Examples include latent curing accelerators such as high-temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.
The catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and further preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane having an epoxy group. .
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
Examples of the organic solvent that can be used in the synthesis of the radiation-sensitive polyorganosiloxane include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Of these, ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products and ease of purification of the products. The amount of the solvent is such that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 50% by weight. used.

  The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention uses a polyorganosiloxane having an epoxy group as a raw material, and a cinnamic acid derivative (A) and a photosensitizing compound (B) by ring-opening addition of the epoxy. A structure derived from is introduced. This manufacturing method is simple. In addition, the method is extremely suitable in that the introduction rate of the cinnamic acid structure derived from the cinnamic acid derivative (A) can be increased. In addition, the photosensitizing structure derived from the photosensitizing compound (B) is chemically bonded to the radiation-sensitive polyorganosiloxane, and the excitation energy generated by the radiation irradiation in the photo-alignment method is converted into the radiation-sensitive poly-siloxane. Since it can be supplied with high efficiency to the cinnamic acid structure derived from the cinnamic acid derivative (A) present in the vicinity of the organosiloxane, sufficient liquid crystal orientation and pretilt angle can be expressed even with a small dose of radiation. Is possible. Furthermore, since the photosensitizing structure is chemically bonded to the base polymer, it is possible to prevent sublimation during post-baking when forming a coating film to be a liquid crystal alignment film.

<Other ingredients>
The liquid crystal aligning agent of this invention contains the above radiation sensitive polyorganosiloxane.
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 polyorganosiloxane (hereinafter referred to as “other polymers”), curing agents, curing catalysts, curing accelerators, and at least one epoxy in the molecule. Examples thereof include a compound having a group (hereinafter referred to as “epoxy compound”), a functional silane compound, a surfactant, and a photosensitizer.
[Other polymers]
Said other polymer can be used in order to improve the solution characteristic of the liquid crystal aligning agent of this invention, and the electrical property of the liquid crystal aligning film obtained. Examples of such other polymers include at least one polymer selected from the group consisting of polyamic acid and polyimide, and the following formula (4):

(In Formula (4), X ² is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y ² is a hydroxyl group or carbon. (It is an alkoxyl group of formula 1 to 10.)
At least one selected from the group consisting of polyorganosiloxanes, hydrolysates thereof and condensates of hydrolysates (hereinafter referred to as “other polyorganosiloxanes”), polyamic acid esters, polyesters, polyamides , Cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like.

[Polyamic acid]
The polyamic acid can be obtained by reacting tetracarboxylic dianhydride with a diamine compound.
Examples of tetracarboxylic dianhydrides that can be used for the synthesis of polyamic acid include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5, 6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydride) -2,5-dioxo-3-furanyl) -8-methyl-naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the following formula (T-1) ~ (T-14)

An aliphatic tetracarboxylic dianhydride such as a tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride represented by each of the following:
Pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide Dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′ , 4 4′-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis ( Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid)- 4,4′-diphenylmethane dianhydride, the following formulas (T-15) to (T-18)

An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of the above.
Among these, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -8-methyl-naphtho [1,2-c] -furan-1 , 3-dione, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2,3,4-Cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic Dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride or the above formula (T-1), (T- Examples thereof include tetracarboxylic dianhydrides represented by 2) and (T-15) to (T-18).
These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  Examples of the diamine compound that can be used for the synthesis of polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 4,4′-diaminodiphenyl sulfide. 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3, , 3-Dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl)- 1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 2,2-bis ( -Aminophenoxy) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis ( 4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) ) Benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) ) Fluorene,

4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino- 5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4 '-Bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 6- (4-chalconyloxy) hexyloxy (2,4-diaminobenzene) 6- (4′-Fluoro-4-calconyloxy) hexyloxy (2,4-diaminobenzene), 8- (4-calconyloxy) octyloxy (2,4-diaminobenzene), 8- (4 ′ -Fluoro-4-calconyloxy) octyloxy (2,4-diaminobenzene), 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy -2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestanyloxy -2,4-diaminobenzene,
Dodecyloxy (3,5-diaminobenzoyl), tetradecyloxy (3,5-diaminobenzoyl), pentadecyloxy (3,5-diaminobenzoyl), hexadecyloxy (3,5-diaminobenzoyl), octadecyloxy ( 3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3,5-diaminobenzoyl), (2,4-diaminophenoxy) palmitate, (2,4-diaminophenoxy) steari Rate, (2,4-diaminophenoxy) -4-trifluoromethylbenzoate, the following formulas (D-1) to (D-5)

An aromatic diamine such as a diamine compound represented by each of
An aromatic diamine having a heteroatom such as diaminotetraphenylthiophene;
Metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopenta Aliphatic amines such as dienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine) Diamines and alicyclic diamines;
Examples include diaminoorganosiloxanes such as diaminohexamethyldisiloxane.
Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 4,4 ′-(p- Phenylene isopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- ( 4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2 -Trifluoromethyl) phenoxy] -octafluorobiphenyl, 1-hexadecyloxy-2,4-di Minobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diaminobenzene, hexadecyloxy (3,5-diaminobenzoyl) , Octadecyloxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3,5-diaminobenzoyl) and the above formulas (D-1) to (D-5) The diamine compound represented by these can be mentioned.
These diamine compounds can be used alone or in combination of two or more.

The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 to 150 ° C., more preferably at a temperature of 0 to 100 ° C., preferably 0.5 to 24 hours, more preferably 2 to 10 Done for 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, Aprotic polar solvents such as N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphoric triamide; and phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol Can do. The amount (a) of the organic solvent used is such that the total amount (b) of tetracarboxylic dianhydride and diamine compound is preferably 0.1 to 50% by weight, more preferably 5 to 5%, based on the total amount (a + b) of the reaction solution. The amount is 30% by weight.
As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction.
The polyamic acid is isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling off the organic solvent in the reaction solution under reduced pressure using an evaporator. Can be performed. Further, the polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the step of distilling under reduced pressure with an evaporator once or several times.

[Polyimide]
The polyimide can be produced by dehydrating and ring-closing and imidizing 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 closed to completely imidize, or only a part of the amic acid structure may be dehydrated and closed to form a partially imidized product in which the amic acid structure and the imide structure coexist. Also good. The imidation ratio of the polyimide in the present invention is preferably 30% or more, and more preferably 40 to 95%.
The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease. 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, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The use ratio of the dehydrating agent is preferably 0.01 to 20 mol with respect to 1 mol of the polyamic acid structural unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The use ratio of the dehydration ring-closing catalyst is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in 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 ring closure reaction is preferably 0 to 180 ° C., more preferably 10 to 150 ° C., and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

  The polyimide obtained by the above method (i) 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 purification. On the other hand, in the method (ii), a reaction solution containing polyimide 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 removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. It may be used for the preparation of a liquid crystal aligning agent or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide. In order to remove the dehydrating agent and the dehydration ring-closing 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 operation as described above as the isolation and purification method of the polyamic acid.

[Other polyorganosiloxanes]
The other polyorganosiloxane in the present invention is at least one selected from the group consisting of the polyorganosiloxane represented by the above formula (4), a hydrolyzate thereof and a condensate of the hydrolyzate. For other polyorganosiloxanes, the polystyrene-equivalent weight average molecular weight measured by GPC is preferably 500 to 100,000, and more preferably 500 to 10,000.
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 solvent. It can be synthesized by hydrolysis or hydrolysis / condensation in the presence of water and a catalyst.
Examples of the raw material silane compound that can be used here include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-. Butoxysilane, tetrachlorosilane, etc .;
Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, Methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyl Trichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, etc .;
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, etc .;
Examples thereof include trimethylmethoxysilane, trimethylethoxysilane, and trimethylchlorosilane.
Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane are preferred.

Examples of organic solvents that can optionally be used in the synthesis of other polyorganosiloxanes include alcohol compounds, ketone compounds, amide compounds, ester compounds, and other aprotic compounds. These can be used alone or in combination of two or more.
Examples of the alcohol compound include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol , Phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, monoalcohol compounds such as diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol compounds such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, partial ethers of a polyhydric alcohol compound and dipropylene glycol monopropyl ether, and the like. 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-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-. Monoketone compounds such as hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fencheon;
Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5 -Methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, etc. The β-diketone compound and the like can be mentioned respectively. These ketone compounds may be used alone or in combination of two or more.
Examples of the amide compound include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-ethyl. Acetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide compounds may be used alone or in combination of two or more.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, acetic acid. i-butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, acetic acid n-nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene acetate monoethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, vinegar Acid diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples include amyl, diethyl malonate, dimethyl phthalate, and diethyl 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 ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N— Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N -Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone and the like can be mentioned.
Of these solvents, polyhydric alcohol compounds or partial ethers or ester compounds of polyhydric alcohol compounds are particularly preferred.

The amount of water used in the synthesis of the other polyorganosiloxane is preferably 0.01 to 100 mol, more preferably 0.1 mol, relative to 1 mol in total of the alkoxyl group and halogen atom of the starting silane compound. It is 1-30 mol, and it is further preferable that it is 1-1.5 mol.
Examples of catalysts that can be used in the synthesis of other polyorganosiloxanes include metal chelate compounds, organic acids, inorganic acids, organic bases, ammonia, alkali metal compounds, and alkaline earth metal compounds.
Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Natto) titanium, di-t-butoxy Su (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n -Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri -S c-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis ( Ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy・ Tris (ethyl aceto Acetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Titanium chelate compounds such as acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;

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

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

[Use ratio of other polymers]
When the liquid crystal aligning agent of the present invention contains another polymer together with the above-mentioned radiation-sensitive polyorganosiloxane, the use ratio of the other polymer is based on 100 parts by weight of the radiation-sensitive polyorganosiloxane. It is preferably 10,000 parts by weight or less. The more preferable usage rate 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 and polyamic acid and polyimide, a more preferable use ratio of both is radiation-sensitive. The total amount of polyamic acid and polyimide with respect to 100 parts by weight of the functional polyorganosiloxane is 100 to 5,000 parts by weight, and this value is preferably 200 to 2,000 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 other than 100 parts by weight of the radiation-sensitive polyorganosiloxane. The amount of 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 one selected from the group consisting of polyamic acid and polyimide. It is preferable that the polymer or other polyorganosiloxane.

[Curing agent, curing catalyst and curing accelerator]
The curing agent and the curing catalyst can be contained in the liquid crystal aligning agent of the present invention for the purpose of further strengthening the crosslinking reaction of the radiation-sensitive polyorganosiloxane, and the curing accelerator is a curing reaction controlled by the curing agent. It can be contained in the liquid crystal aligning agent of the present invention for the purpose of promoting.
As the curing agent, a curable compound having an epoxy group or a curing agent generally used for curing a curable composition containing a compound having an epoxy group can be used. Examples thereof include carboxylic acid anhydrides and polyvalent carboxylic acids.
Examples of the polyvalent carboxylic acid anhydride include cyclohexanetricarboxylic acid anhydride and other polyvalent carboxylic acid anhydrides.
Specific examples of the cyclohexanetricarboxylic acid anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane- 1,2,3-tricarboxylic acid-2,3-acid anhydride, and the like. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic acid anhydride, methylnadic acid anhydride, Dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, formula (6)

(In Formula (6), p is an integer of 1-20.)
Diels-Alder reaction of maleic anhydride with cycloaliphatic compounds having conjugated double bonds such as α-terpinene and allocymene, in addition to tetracarboxylic dianhydrides generally used for the synthesis of compounds and polyamic acids Products and their hydrogenated products can be mentioned.
As the curing catalyst, for example, an antimony hexafluoride compound, a phosphorus hexafluoride compound, aluminum trisacetylacetonate, or the like can be used. These catalysts can catalyze the cationic polymerization of epoxy groups by heating.
Examples of the curing accelerator include imidazole compounds;
Quaternary phosphorus compounds;
Quaternary amine compounds;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as dicyandiamide, amine addition type accelerators such as adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator whose surface is covered with a polymer such as a quaternary phosphonium salt;
An amine salt type latent curing accelerator;
And high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.
The ratio of the curing agent used in the present invention is preferably 100 parts by weight or less with respect to 100 parts by weight of the radiation-sensitive polyorganosiloxane. The use ratio of the curing catalyst is preferably 2 parts by weight or less with respect to 100 parts by weight of the radiation-sensitive polyorganosiloxane. The use ratio of the curing accelerator is preferably 10 parts by weight or less with respect to 100 parts by weight of the radiation-sensitive polyorganosiloxane.

[Epoxy compound]
The said epoxy compound can be contained in the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness with respect to the substrate surface of the liquid crystal aligning film formed.
Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′— Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-dia Bruno diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - may be mentioned as being preferred amino methyl cyclohexane.
When the liquid crystal aligning agent of the present invention contains an epoxy compound, the content is preferably based on 100 parts by weight of the total of the radiation-sensitive polyorganosiloxane and the other polymer optionally used. Is 40 parts by weight or less, more preferably 0.1 to 30 parts by weight.
In addition, when the liquid crystal aligning agent of this invention contains an epoxy compound, you may use together basic catalysts, such as 1-benzyl-2-methylimidazole, in order to raise | generate the crosslinking reaction efficiently. In this case, the use ratio of the base catalyst is preferably 10 parts by weight or less, more preferably 0 to 2 parts by weight with respect to 100 parts by weight of the epoxy compound.

[Functional silane compounds]
The said functional silane compound can be used in order to improve the adhesiveness with the board | substrate of the liquid crystal aligning film obtained. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3. -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltri Methoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7 Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And the patent text 23 such as those described in (JP 63-291922 JP), a reaction product of a silane compound having a tetracarboxylic dianhydride and an amino group, and the like.
When the liquid crystal aligning agent of this invention contains a functional silane compound, as the content rate, it is with respect to a total of 100 weight part of said radiation sensitive polyorganosiloxane and the other polymer arbitrarily used. , Preferably 50 parts by weight or less, more preferably 20 parts by weight or less.

[Surfactant]
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. it can.
When the liquid crystal aligning agent of this invention contains surfactant, as the content rate, Preferably it is 10 weight part or less with respect to 100 weight part of the whole liquid crystal aligning agent, More preferably, it is 1 weight part or less. is there.
[Photosensitizer]
Examples of the photosensitizer include durene, benzonitrile, butyrophenone, propiophenone, acetophenone, xanthone, 4-methoxyacetophenone, 3-methoxyacetophenone, anthrone, benzaldehyde, 4,4′-dimethoxybenzophenone, benzophenone, fluorene, Triphenylene, biphenyl, thioxanthone, anthraquinone, 4,4′-bis (diethylamino) benzophenone, phenanthrene, naphthalene, 4-phenylacetophenone, 4-phenylbenzophenone, 2-iodonaphthalene, acenaphthene, 2-naphthonitrile, 1-iodonaphthalene, 1-naphthonitrile, chrysene, coronene, benzyl, fluoranthene, pyrene, 1,2-benzoanthracene, acridine, anthracene, teto Sen, 2-methoxynaphthalene, 1,4-dicyano naphthalene, 9-cyanoanthracene, 9,10-dicyanoanthracene, mention may be made of 2,6,9,10- tetra cyano anthracene.
When the liquid crystal aligning agent of the present invention contains a photosensitizer, the content is preferably 20 parts by weight or less, more preferably 10 parts by weight with respect to 100 parts by weight of the radiation-sensitive polyorganosiloxane. Or less.

<Liquid crystal aligning 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, but preferably each component is an organic solvent. It is prepared as a dissolved solution composition.
The organic solvent that can be used for preparing the liquid crystal aligning agent of the present invention is preferably one that dissolves the radiation-sensitive polyorganosiloxane and other optional components and does not react with them.
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 and polyamic acid and polyimide, a polyamic acid can be synthesized. The organic solvent illustrated above can be mentioned as what is used. 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 is preferred when it contains a radiation-sensitive polyorganosiloxane and another polyorganosiloxane. Examples of the organic solvent include 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol Propylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Recall monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, Propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, acetic acid Methylpentyl, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate , Amyl acetate, isoamyl acetate, and the like. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate and the like can be mentioned.

A preferred solvent used for the preparation of the liquid crystal aligning agent of the present invention is obtained by combining one or more of the above-described 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 a preferable solid content concentration, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mN / m.
The solid content concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, Preferably it is the range of 1-10 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 of this coating film becomes too small. In some cases, it is difficult to obtain a good liquid crystal alignment film. On the other hand, when 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 aligning agent increases, resulting in insufficient coating characteristics. There is a case. The particularly preferable range of the solid content concentration varies depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by weight is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature when preparing the liquid crystal aligning agent of the present invention is preferably 0 to 200 ° C, more preferably 10 to 60 ° C.

<Method for forming 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.
As a method for forming the liquid crystal alignment film, for example, the liquid crystal alignment film of the present invention is applied to a substrate to form a coating film, and then the coating film is irradiated with polarized or non-polarized radiation to further enhance the liquid crystal alignment ability. The method of giving can be mentioned.
First, the liquid crystal aligning agent of this invention is apply | coated to the transparent conductive film side of the board | substrate with which the pattern-shaped transparent conductive film was provided, for example by appropriate coating methods, such as a roll coater method, a spinner method, a printing method, an inkjet method. . Then, the coated surface is preheated (prebaked) and then baked (postbaked) to form a coating film. The pre-bake conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-bake conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
As the substrate, for example, a glass such as float glass or soda glass, a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used.
As the transparent conductive film, a NESA film made of SnO ₂ , an ITO film made of In ₂ O ₃ —SnO _2, or the like can be used. 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, titanate compound or the like is previously applied on the substrate and the transparent conductive film. May be.

Next, the coating film is given a liquid crystal alignment ability by irradiating linearly polarized light, partially polarized radiation or non-polarized radiation. Here, as radiation, for example, ultraviolet rays and visible light containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation 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 thereof. May be. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction.
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 preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter, a diffraction grating, or the like.
The irradiation dose of radiation, preferably less than 1 J / ^{m 2} or more 10,000 J / ^{m 2,} more preferably from 10~3,000J / ^{m 2.} In addition, when providing the liquid crystal aligning ability by the photo-alignment method to the coating film formed from the conventionally known liquid crystal aligning agent, the irradiation dose of 10,000 J / m < ² > or more was required. However, when the liquid crystal aligning agent of the present invention is used, a good liquid crystal aligning ability is imparted even when the radiation irradiation amount in the photo-alignment method is 3,000 J / m ² or less, and further 1,000 J / m ² or less. This contributes to the reduction of the manufacturing cost of the liquid crystal display element.
The “pretilt angle” in the present invention represents an angle of inclination of liquid crystal molecules from a direction parallel to the substrate surface.

<Liquid crystal alignment film>
The liquid crystal alignment film of the present invention formed from the liquid crystal alignment agent of the present invention is excellent in the temporal stability of the pretilt angle. As a result of detailed studies by the inventors of the present application in order to clarify the reason why such an unexpectedly excellent effect is manifested, the liquid crystal alignment film of the present invention is compared with a conventionally known liquid crystal alignment film. It became clear that it has a special film structure.
That is, when the presence distribution in the film thickness direction of the group derived from the (A) cinnamic acid derivative was examined for the liquid crystal alignment film of the present invention, the liquid crystal alignment film of the present invention was derived from (A) the cinnamic acid derivative. It was surprisingly found that the groups were unevenly distributed in the range of 30% of the thickness from the film surface, even in the range of 25%, in particular in the range of 20%. Moreover, it became clear that the density | concentration of the group derived from (A) cinnamic acid derivative has taken the maximum value in the surface of a liquid crystal aligning film. It is presumed that the uneven distribution of the photosensitive group in the narrow range in the vicinity of the film surface is one factor for giving a pretilt angle having excellent temporal stability with a small exposure amount.
Further, such a special film structure is surely ensured when the liquid crystal aligning agent of the present invention contains the above-mentioned radiation-sensitive polyorganosiloxane and the other polymer in the above-mentioned preferable content ratio. It was also clear that it could be obtained.
The existence distribution in the film thickness direction of the group derived from the (A) cinnamic acid derivative in the liquid crystal alignment film can be known, for example, by ToF-SIMS analysis (time-of-flight secondary ion mass spectrometry).
More specifically, with respect to the liquid crystal alignment film formed on the transparent conductive film of the substrate having the transparent conductive film, using a ToF-SIMS measuring device, Bi ₃ ⁺⁺ cluster ions having an acceleration voltage of 25 kV are used as the primary ion source, Under the conditions of current 0.05 pA, measurement field of view 100 μm, measurement mass range 0 to 1,850 amu, C ₆₀ sputtering and ToF-SIMS analysis are repeated on the liquid crystal alignment film surface, and the atomic species derived from the ITO-derived transparent conductive film Measurement is performed until (for example, indium ions) are detected. Since it is considered that the deepest part of the film was reached when the atomic species derived from the transparent conductive film was detected, the film thickness range of the liquid crystal alignment film was measured from the start of measurement to this point, (A) The distribution in the film thickness direction of the count number of the fragment corresponding to the group derived from the cinnamic acid derivative is examined. In order to eliminate the influence of measurement noise, the distribution is standardized by dividing the count at each film depth (depth from the film surface) by the minimum count (noise level) in the film thickness range. (A) The existence distribution in the film thickness direction of the group derived from the cinnamic acid derivative can be known.
Note that (A) the group derived from the cinnamic acid derivative is unevenly distributed in the range of 30% of the thickness from the film surface, in the above normalized distribution, in the range of 30% from the surface of the liquid crystal alignment film. In (A), the concentration of the group derived from the cinnamic acid derivative is 95% or more of the concentration in the entire film thickness range.

<Method for manufacturing liquid crystal display element>
The liquid crystal display element of this invention comprises the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention. The liquid crystal display element of this invention can be manufactured as follows, for example.
A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.
The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.
In any case, it is desirable to remove the flow alignment at the time of filling the liquid crystal by heating the liquid crystal cell to a temperature at which the liquid crystal used has an isotropic phase and then gradually cooling it to room temperature.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell. Here, when the liquid crystal alignment film is horizontally aligned, the angle formed by the polarization direction of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate are adjusted on the two substrates on which the liquid crystal alignment film is formed. By doing so, a liquid crystal display element having a TN type or STN type liquid crystal cell can be obtained. On the other hand, in the case where the liquid crystal alignment film is vertically aligned, 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, 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 and the like can be preferably used.
In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic type liquid crystal having positive dielectric anisotropy is preferable. For example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, Pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals and the like are used. Cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (Merck); p- A ferroelectric liquid crystal such as decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.
On the other hand, in the case of a vertical alignment type liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane. System liquid crystal or the like is used.
The polarizing plate used outside the liquid crystal cell is composed of a polarizing film called “H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine and sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate etc. can be mentioned.
The liquid crystal display element of the present invention thus produced is excellent in various performances such as display characteristics and long-term reliability.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In the following examples, the weight average molecular weight Mw is a polystyrene equivalent value measured by gel permeation chromatography (GPC) under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
The epoxy equivalent was measured according to the “hydrochloric acid-methyl ethyl ketone method” of JIS C2105.
The solution viscosity of the polymer solution is a value measured at 25 ° C. using an E-type viscometer for the polymer solution indicated in each synthesis example.
In the following, the synthesis of the raw material compound and the polymer was repeated as necessary at the following synthesis scale to secure the necessary amount for subsequent synthesis.

<Synthesis of polyorganosiloxane having epoxy group>
Synthesis Example E-1
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and room temperature. Mixed with. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out and washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure, whereby a polyorgano having an epoxy group is obtained. Siloxane (EPS-1) was obtained as a viscous transparent liquid.
When ¹ H-NMR analysis was performed on the polyorganosiloxane (EPS-1) having this epoxy group, a peak based on the epoxy group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction of the epoxy group occurred.
The weight average molecular weight Mw of this polyorganosiloxane (EPS-1) having an epoxy group was 2,200, and the epoxy equivalent was 186 g / mol.

<Synthesis of cinnamic acid derivative (A)>
Synthesis Example C-1
Scheme 1 below

Then, cinnamic acid derivative (2-4-1) was synthesized.
A 1-L eggplant-shaped flask was charged with 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate, and 320 mL of N-methyl-2-pyrrolidone, stirred at room temperature for 1 hour, and then 99.7 g of 1-bromopentane. And stirred at 100 ° C. for 5 hours. After the reaction is complete
Reprecipitation was performed with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate and refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 102 g of white crystals of the compound (2-4-1-1).
10.41 g of this compound (2-4-1-1) was placed in a reaction vessel, and 100 mL of thionyl chloride and 77 μL of N, N-dimethylformamide were added thereto, followed by stirring at 80 ° C. for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with an aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, concentrated, and then tetrahydrofuran was added to form a solution.
Next, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutylammonium, 50 mL of tetrahydrofuran and 100 mL of water were charged into a 500 mL three-necked flask different from the above. The aqueous solution was ice-cooled, the tetrahydrofuran solution was slowly added dropwise, and the reaction was further performed with stirring for 2 hours. After completion of the reaction, the reaction mixture was neutralized by adding hydrochloric acid, extracted with ethyl acetate, dried over magnesium sulfate, concentrated, and recrystallized with ethanol to obtain cinnamic acid derivative (2-4-1). 9.0 g of white crystals was obtained.
Synthesis Example C-2
The same procedure as in Synthesis Example 4 was performed except that 110.9 g of 1-iodo-4,4,4-trifluorofluorobutane was used instead of 1-bromopentane in Synthesis Example C-1, and the following formula ( 2-4-2)

9.2 g of white crystals of the compound represented by (cinnamate derivative (2-4-2)) was obtained.
Synthesis Example C-3
The same as Synthesis Example C-1, except that 9.91 g of 4-pentyl-transcyclohexylcarboxylic acid was used instead of the compound (2-4-1-1) synthesized and used as an intermediate in Synthesis Example C-1. The following formula (2-23-1)

13 g of a white crystal of the compound represented by (cinnamate derivative (2-23-1)) was obtained.
Synthesis Example C-4
Scheme 2 below

In this manner, a cinnamic acid derivative (23-11-1) was synthesized.
In a 500 mL three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, 31 g of compound (2-231-1-1), 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine, 56 mL of triethylamine, Acrylic acid 8.2mL and N, N- dimethylacetamide 200mL were prepared, and it reacted with stirring at 120 degreeC for 3 hours. After completion of the reaction, 1 L of ethyl acetate was added to the filtrate obtained by filtering the reaction mixture, and the organic layer obtained was washed successively with dilute hydrochloric acid twice and water three times, dried over magnesium sulfate, and then under reduced pressure. The solid obtained by removing the solvent by recrystallization from a mixed solvent of ethyl acetate and tetrahydrofuran gave 15 g of crystals of cinnamic acid derivative (23-11-1).
Synthesis Example C-5
In the synthesis example C-4, the following formula (2-32-1-1) was used instead of the compound (2-31-1-1).

In the same manner as in Synthesis Example C-4 except that the compound 36g represented by the formula:

16 g of a compound represented by the formula (cinnamic acid derivative (23-1)) was obtained.
Synthesis Example C-6
Scheme 3 below

Then, cinnamic acid derivative (2-35-1) was synthesized.
A 300 mL eggplant flask equipped with a reflux tube and a nitrogen introducing tube was charged with 21 g of compound (2-35-1-1), 80 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide, and the mixture was stirred at 80 ° C. for 1 hour. The reaction was performed. After completion of the reaction, thionyl chloride was distilled off from the reaction mixture, and then 150 mL of methylene chloride was added, and the resulting organic layer was washed with water three times. After drying this organic layer with magnesium sulfate, 400 mL of tetrahydrofuran was added to a solid (compound (1-35-1-2)) obtained by removing the solvent under reduced pressure (this is referred to as “solution A”).
Meanwhile, a 1 L three-necked flask equipped with a dropping funnel and a thermometer was charged with 16 g of p-hydroxycinnamic acid, 24 g of potassium carbonate, 0.87 g of tetrabutylammonium bromide, 200 mL of water and 100 mL of tetrahydrofuran, and cooled to 5 ° C. or lower with ice. . The above solution A was added dropwise over 3 hours, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, diluted hydrochloric acid was added to the reaction mixture to adjust the pH to 4 or less, and the organic layer obtained by adding 3 L of toluene and 1 L of tetrahydrofuran was washed with water three times. After drying this organic layer with magnesium sulfate, the solid obtained by removing the solvent under reduced pressure was recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 21 g of cinnamic acid derivative (2-35-1). .

<Synthesis of radiation-sensitive polyorganosiloxane>
Example S-1
In a 200 mL three-necked flask, 5.0 g of the polyorganosiloxane (EPS-1) having an epoxy group obtained in Synthesis Example E-1 above, 46.4 g of methyl isobutyl ketone, and cinnamic acid derivative (A) as in Synthesis Example C- 4.76 g of the compound (2-4-1) obtained in 1 (corresponding to 50 mol% with respect to the silicon atom of EPS-1), the photosensitizing compound (B) represented by the following formula (B-1- 1)

1.08 g of the compound represented by the formula (corresponding to 20 mol% with respect to the silicon atom possessed by EPS-1) and 0.10 g of tetrabutylammonium bromide were charged, and the reaction was carried out at 80 ° C. with stirring for 12 hours. . After completion of the reaction, reprecipitation with methanol was performed, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed with water three times, and then the solvent was distilled off to remove the radiation-sensitive polyorganosiloxane (S- 2.8 g of 1) was obtained as a white powder. The weight average molecular weight Mw of the radiation sensitive polyorganosiloxane (S-1) was 12,500.
Examples S-2 to S-55
Example S-1 was the same as Example S-1, except that the types and amounts of cinnamic acid derivative (A) and photosensitizing compound (B) were as shown in Table 1. Thus, radiation-sensitive polyorganosiloxanes (S-2) to (S-55) were respectively synthesized. The weight average molecular weight of each radiation-sensitive polyorganosiloxane obtained is shown in Table 1.
In Examples S-49 and S-54, two types of compounds were used in combination as the cinnamic acid derivative (A). In Examples S-31, S-48, S-51 and S-52, Each of the cinnamic acid derivatives (A) was used in place of other pretilt angle-expressing compounds.

The abbreviations of cinnamic acid derivative (A), photosensitizing compound (B) and other pretilt angle-expressing compounds in Table 1 have the following meanings, respectively.
<Cinnamic acid derivative (A)>
2-4-1: Cinnamic acid derivative (2-4-1) obtained in Synthesis Example C-1 above
2-4-2: Cinnamic acid derivative (2-4-2) obtained in Synthesis Example C-2 above
2-23-1: Cinnamic acid derivative obtained in Synthesis Example C-3 (2-23-1)
2-31-1: Cinnamic acid derivative obtained in Synthesis Example C-4 (23-11-1)
2-3-1: Cinnamic acid derivative (2-23-1) obtained in Synthesis Example C-5 above
2-35-1: Cinnamic acid derivative obtained in Synthesis Example C-6 (2-35-1)
<Photosensitizing compound (B)>
B-1-1: Compound represented by the above formula (B-1-1) B-2: Compound represented by the above formula (B-2) B-3: Represented by the above formula (B-3) Compound B-5: Compound represented by the above formula (B-5) B-11: Compound represented by the above formula (B-11) B-28-1: In the following formula (B-28-1) Compound represented by B-39-1: Compound represented by the following formula (B-39-1) B-42-1: Compound represented by the following formula (B-42-1) B-42-2: Compound represented by formula (B-42-2) <Other pretilt angle expressing compound>
5-3-1: Compound represented by the above formula (5-3-1)

<Synthesis of other polymers>
[Synthesis of polyamic acid]
Synthesis example PA-1
109 g (0.50 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 98 g (0.50 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4,4 as diamine compound -By dissolving 200 g (1.0 mol) of diaminodiphenyl ether in 2,290 g of N-methyl-2-pyrrolidone, reacting at 40 ° C. for 3 hours, and then adding 1,350 g of N-methyl-2-pyrrolidone About 3,590 g of a solution containing 10% by weight of polyamic acid (PA-1) was obtained. The solution viscosity of this polyamic acid solution was 210 mPa · s.
Synthesis example PA-2
1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) and pyromellitic dianhydride 109 g (0.50 mol) as tetracarboxylic dianhydride and 4,4 as diamine compound 198 g (1.0 mol) of '-diaminodiphenylmethane is dissolved in 2,290 g of N-methyl-2-pyrrolidone, reacted at 40 ° C. for 3 hours, and then 1,350 g of N-methyl-2-pyrrolidone is added. Thus, a solution containing 10% by weight of polyamic acid (PA-2) was obtained. The solution viscosity of this polyamic acid solution was 135 mPa · s.

Synthesis example PA-3
196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 200 g (1.0 mol) of 4,4′-diaminodiphenyl ether as diamine compound are N- After dissolving in 2,246 g of methyl-2-pyrrolidone and reacting at 40 ° C. for 4 hours, by adding 1,321 g of N-methyl-2-pyrrolidone, 10% by weight of polyamic acid (PA-3) is contained. A solution was obtained. The solution viscosity of this polyamic acid solution was 220 mPa · s.
Synthesis example PA-4
196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g (1 of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine compound) 0.0 mol) was dissolved in 3,670 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours to obtain a solution containing 10% by weight of polyamic acid (PA-4). The solution viscosity of this polyamic acid solution was 170 mPa · s.

Synthesis example PA-5
As a tetracarboxylic dianhydride, 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 200 g (1.0 mol) of 4,4′-diaminodiphenyl ether as a diamine compound were added to N-methyl- A solution containing polyamic acid (PA-5) was obtained by dissolving in 2,404 g of 2-pyrrolidone and reacting at 40 ° C. for 4 hours. A small amount of this polyamic acid solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a concentration of 10% by weight was 190 mPa · s.
[Synthesis of polyimide]
Synthesis example PI-1
2,3,5-tricarboxycyclopentyl acetic acid dianhydride 112 g (0.50 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro) as tetracarboxylic dianhydride -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 157 g (0.50 mol) and p-phenylenediamine 95 g (0.88 mol) as the diamine compound 2,2-ditrifluoromethyl-4,4-diaminobiphenyl 32 g (0.10 mol), 6.4 g (0.010 mol) 3,6-bis (4-aminobenzoyloxy) cholestane and octadecanoxy-2, 4.0 g (0.015 mol) of 5-diaminobenzene was dissolved in 960 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 9 hours. A small amount of the resulting polyamic acid solution was taken, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a concentration of 10% by weight was 58 mPa · s.
To the obtained polyamic acid solution, 2,740 g of N-methyl-2-pyrrolidone, 396 g of pyridine and 409 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (by this solvent replacement operation, pyridine and acetic anhydride used in the dehydration cyclization reaction were removed from the system. The same applies hereinafter). As a result, about 2,500 g of a solution containing 15% by weight of polyimide (PI-1) having an imidation ratio of about 95% was obtained.
A small amount of this polyimide solution was collected, the solvent was removed under reduced pressure, and the solution was dissolved in γ-butyrolactone and measured as a solution having a polymer concentration of 8.0% by weight. The solution viscosity was 33 mPa · s.

Synthesis example PI-2
2,3,5-tricarboxycyclopentyl acetic acid dianhydride 112 g (0.50 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro) as tetracarboxylic dianhydride -2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157 g (0.50 mol), p-phenylenediamine 96 g (0.89 mol) as the diamine compound, bis 25 g (0.10 mol) aminopropyltetramethyldisiloxane and 13 g (0.020 mol) 3,6-bis (4-aminobenzoyloxy) cholestane and 8.1 g (0.030 mol) N-octadecylamine as monoamine Was dissolved in 960 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 60 mPa · s.
2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 396 g of pyridine and 409 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 15% by weight of polyimide (PI-2) having an imidation ratio of about 95%. A small amount of this polyimide solution was taken, diluted by adding N-methyl-2-pyrrolidone, and the solution concentration measured as a 6.0 wt% solution was 18 mPa · s.

Synthesis example PI-3
224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 107 g (0.99 mol) of p-phenylenediamine and 3,6-bis (4 as diamine compounds -Aminobenzoyloxy) cholestane 6.43 g (0.010 mol) was dissolved in 3,039 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a polyamic acid solution having a solution viscosity of about 260 mPa · s. Obtained.
2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 396 g of pyridine and 306 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system is replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 9.0% by weight of polyimide (PI-3) having an imidation ratio of about 89%. It was. A small amount of this polyimide solution was taken, diluted by adding N-methyl-2-pyrrolidone, and the solution concentration measured as a solution having a concentration of 5.0% by weight was 74 mPa · s.

Synthesis example PI-4
2,3,5-Tricarboxycyclopentylacetic acid dianhydride 112 g (0.50 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-) as tetracarboxylic dianhydride 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 157 g (0.50 mol) and p-phenylenediamine 89 g (0.82 mol) as a diamine compound, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl 32 g (0.10 mol), 1- (3,5-diaminobenzoyloxy) -4- (4-trifluoromethylbenzoyloxy) -cyclohexane 25 g (0.059 mol) and 4.0 g (0.011 mol) of octadecanoxy-2,5-diaminobenzene were added to N-methyl-2-pyrrole. Was dissolved in Don 2,175G, it was reacted for 6 hours at 60 ° C.. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a concentration of 10% by weight of 110 mPa · s.
1,500 g of the resulting polyamic acid solution was taken, 3,000 g of N-methyl-2-pyrrolidone was added thereto, 221 g of pyridine and 228 g of acetic anhydride were added, and dehydration ring closure reaction was carried out at 110 ° C. for 4 hours. went. After the dehydration ring closure reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 10% by weight of polyimide (PI-4) having an imidization rate of about 92%. A small amount of this polyimide solution was taken, diluted by adding N-methyl-2-pyrrolidone, and the solution concentration measured as a 4.5 wt% solution was 26 mPa · s.

Synthesis example PI-5
2,3,5-tricarboxycyclopentylacetic acid dianhydride 19.9 g (0.089 mol) as tetracarboxylic dianhydride and 6.8 g (0.063 mol) p-phenylenediamine as diamine compound, 4,4 3.6 g (0.018 mol) of '-diaminodiphenylmethane and 4.7 g (0.009 mol) of the compound represented by the above formula (D-4) were dissolved in 140 g of N-methyl-2-pyrrolidone, For 4 hours. A small amount of the resulting polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a solid content concentration of 10% by weight. The solution viscosity was 115 mPa · s.
To the obtained polyamic acid solution, 325 g of N-methyl-2-pyrrolidone was added, 14 g of pyridine and 18 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system is replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 15.4% by weight of polyimide (PI-5) having an imidation ratio of about 77%. It was. A small amount of this polyimide solution was taken, diluted by adding N-methyl-2-pyrrolidone, and the solution concentration measured as a 10 wt% solution was 84 mPa · s.

Synthesis example PI-6
20.9 g (0.093 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 9.2 g (0.085 mol) of p-phenylenediamine as a diamine compound and the above formula ( 4.9 g (0.009 mol) of the compound represented by D-4) was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a concentration of 10% by weight of 126 mPa · s.
To the obtained polyamic acid solution, 325 g of N-methyl-2-pyrrolidone was added, 7.4 g of pyridine and 9.5 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system is replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 16.1% by weight of polyimide (PI-6) having an imidization ratio of about 54%. It was. A small amount of this polyimide solution was taken, diluted by adding N-methyl-2-pyrrolidone, and the solution concentration measured as a solution having a concentration of 10% by weight was 75 mPa · s.

Synthesis example PI-7
As tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 18.8 g (0.084 mol) and diamine compound 7.4 g (0.068 mol) and the above formula ( 8.9 g (0.017 mol) of the compound represented by D-4) was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a concentration of 10% by weight of 126 mPa · s.
To the obtained polyamic acid solution, 325 g of N-methyl-2-pyrrolidone was added, 6.6 g of pyridine and 8.5 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system is replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 15.9% by weight of polyimide (PI-7) having an imidization ratio of about 55%. It was. A small amount of this polyimide solution was taken, diluted by adding N-methyl-2-pyrrolidone, and the solution concentration measured as a solution having a concentration of 10% by weight was 75 mPa · s.
Synthesis example PI-8
2,3,5-tricarboxycyclopentyl acetic acid dianhydride 19.1 g (0.085 mol) as tetracarboxylic dianhydride and 7.4 g (0.069 mol) p-phenylenediamine as diamine compound and the following formula ( D-6)

8.5 g (0.017 mol) represented by the formula was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours. A small amount of the obtained polyamic acid solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a concentration of 10% by weight was 206 mPa · s.
To the obtained polyamic acid solution, 325 g of N-methyl-2-pyrrolidone was added, 6.7 g of pyridine and 8.7 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 15.8% by weight of polyimide (PI-8) having an imidization ratio of about 52%. It was. A small amount of this polyimide solution was collected, diluted by adding N-methyl-2-pyrrolidone, and the solution concentration measured as a 10 wt% solution was 105 mPa · s.
Synthesis example PI-9
As tetracarboxylic dianhydride, 17.3 g (0.077 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 5.9 g (0.054 mol) of p-phenylenediamine as a diamine compound, the above formula 4.1 g (0.008 mol) of the compound represented by (D-4) and 7.7 g (0.016 mol) of the compound represented by the above formula (D-6) were added to 140 g of N-methyl-2-pyrrolidone. And reacted at 60 ° C. for 4 hours. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a concentration of 10% by weight was 117 mPa · s.
To the obtained polyamic acid solution, 325 g of N-methyl-2-pyrrolidone was added, 6.1 g of pyridine and 7.9 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system is replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 15.4% by weight of polyimide (PI-9) having an imidization ratio of about 55%. It was. A small amount of this polyimide solution was taken, diluted by adding N-methyl-2-pyrrolidone, and the solution concentration measured as a 10% by weight solution was 109 mPa · s.

[Synthesis of other polyorganosiloxanes]
Synthesis Example OE-1
A 200 mL three-necked flask equipped with a condenser was charged with 20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol, heated to 60 ° C. and stirred. To this, 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 capacity of 20 mL was added, and the reaction was performed by heating and stirring at 60 ° C. for 4 hours. A polymer solution containing 10% by weight of another polyorganosiloxane (PS-1) is obtained by distilling off the solvent from the obtained reaction solution and then adding 1-ethoxy-2-propanol and concentrating again. Got. It was 5,100 when the weight average molecular weight Mw of other polyorganosiloxane (PS-1) was measured.

<Preparation of liquid crystal aligning agent and evaluation of storage stability>
Example A-1
[Preparation of liquid crystal aligning agent]
Contains 100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in Example S-1 and the polyamic acid (PA-1) obtained in Synthesis Example PA-1 as another polymer. Combined with the amount corresponding to 2,000 parts by weight in terms of polyamic acid (PA-1) in the solution, N-methyl-2-pyrrolidone and butyl cellosolve were added thereto, and the solvent composition was N-methyl-2-pyrrolidone. : Butyl cellosolve = 50: 50 (weight ratio), solid content concentration of 3.0% by weight. The liquid crystal aligning agent (A-1) was prepared by filtering this solution with a filter having a pore diameter of 1 μm.
[Evaluation of storage stability]
This liquid crystal aligning agent (A-1) was stored at −15 ° C. for 6 months. Before and after storage, the viscosity was measured at 25 ° C. with an E-type viscometer. When the change rate of the viscosity of the solution before and after storage was less than 10%, the storage stability was evaluated as “good”, and when it was 10% or more, the storage stability was evaluated as “bad”. ) Storage stability was “good”.

Examples A-2 to A-16, A-18 to A-68, A-70 to A-89 and A-91 to A-109
The liquid crystal aligning agent (A-2) to (A-2) were prepared in the same manner as in Example A-1, except that the type of radiation-sensitive polyorganosiloxane and the type and amount of other polymers were as described in Table 2. (A-16), (A-18) to (A-68), (A-70) to (A-89) and (A-91) to (A-109) were prepared, respectively.
With respect to these liquid crystal aligning agents, the storage stability was evaluated in the same manner as in Example A-1. The evaluation results are shown in Table 2.

Example A-17
It corresponds to 2,000 parts by weight in terms of another polyorganosiloxane (PS-1) in a solution containing the other polyorganosiloxane (PS-1) obtained in Synthesis Example OE-1 as another polymer. To this, 100 parts by weight of the radiation-sensitive polyorganosiloxane (S-3) obtained in Example S-3 was added, and 1-ethoxy-2-propanol was further added to obtain a solid content concentration of 4. The solution was 0% by weight. The solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent (A-17).
With respect to this liquid crystal aligning agent (A-17), the storage stability was evaluated in the same manner as in Example A-1. The evaluation results are shown in Table 2.
Examples A-69 and A-90
Liquid crystal aligning agents (A-69) and (A-90) were prepared in the same manner as in Example A-17 except that the type of radiation-sensitive polyorganosiloxane used was as shown in Table 2. .
With respect to these liquid crystal aligning agents, the storage stability was evaluated in the same manner as in Example A-1. The evaluation results are shown in Table 2.

<Manufacture and evaluation of liquid crystal display elements>
Example D-1
[Formation of liquid crystal alignment film and production of liquid crystal display element]
The liquid crystal aligning agent (A-1) prepared in Example A-1 is applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film by a spinner, and prebaked for 1 minute on an 80 ° C. hot plate. Then, it was heated at 200 ° C. for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen to form a coating film having a thickness of 0.1 μm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays 200 J / m ² containing a 313 nm emission line from a direction inclined by 40 ° from the normal to the liquid crystal alignment film using a Hg—Xe lamp and a Grand Taylor prism. The same operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface of the substrate having the liquid crystal alignment film by screen printing, and the liquid crystal alignment film surfaces of the pair of substrates are made to face each other. The adhesive was pressure-bonded so that the projection direction of the optical axis of the ultraviolet ray of each substrate onto the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, after filling the gap between the substrates from the liquid crystal injection port with negative type liquid crystal (MLC-6608, manufactured by Merck), the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 150 ° C. and then gradually cooled to room temperature. Next, the polarizing plates are bonded to both the outer surfaces of the substrate so that the polarization directions thereof 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. A liquid crystal display device was manufactured.
This liquid crystal display element was evaluated by the following method. The evaluation results are shown in Table 3.

(1) Evaluation of liquid crystal orientation The liquid crystal display element manufactured above was observed with an optical microscope for the presence or absence of abnormal domains in the change in brightness when a voltage of 5 V was turned ON / OFF (applied / released) at room temperature. The case where there was no abnormal domain was defined as “good”.
(2) Evaluation of pretilt angle The liquid crystal display device manufactured above is subjected to the method described in Non-Patent Document 5 (TJ Scheffer et. Al. J. Appl. Phys. Vol. 19, p2013 (1980)). In conformity, the pretilt angle was measured by a crystal rotation method using He—Ne laser light.
(3) Evaluation of voltage holding ratio For the liquid crystal display device manufactured as described above, a voltage of 5 V was applied at an environmental temperature of 60 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and then 167 milliseconds from the release of application. The subsequent voltage holding ratio was measured. As a measuring device, model “VHR-1” manufactured by Toyo Corporation was used.
(4) Evaluation of pretilt angle stability The liquid crystal display device produced above was stored at 23 ° C for 30 days, and then the pretilt angle was measured again. When the amount of change from the initial value was less than 1 °, the pretilt angle stability was determined to be “good”.

Examples D-2 to D-109
A liquid crystal alignment film was formed in the same manner as in Example D-1 except that the type of liquid crystal alignment agent used was as described in Table 3, and a liquid crystal display element was produced and evaluated.
The results are shown in Table 3.

Example T-1
The liquid crystal aligning agent (A-46) prepared in Example A-46 is applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film by a spinner, and prebaked on a hot plate at 80 ° C. for 1 minute. Then, heating was performed at 210 ° C. for 20 minutes in an oven in which the inside of the chamber was replaced with nitrogen to form a coating film having a thickness of 80 nm.
Using a ToF-SIMS measurement apparatus manufactured by ULVAC-PHI, using Bi ₃ ⁺⁺ cluster ions with an acceleration voltage of 25 kV as a primary ion source, an ion current of 0.05 pA, a measurement field of view of 100 μm, and a measurement mass range of 0 to 1,850 amu Then, C ₆₀ sputtering and ToF-SIMS analysis are repeated for the coating surface formed as described above, and measurement is performed until indium ions derived from ITO are detected, and from the coating surface when indium ions are detected. The composition distribution in the film thickness direction of the coating film was examined as having reached a depth of 80 nm. The graphs showing the distribution of the fragment of m / z = 231 at this time are shown in FIG. 1 (existence distribution) and FIG. 2 (integrated value). The graphs shown in these figures are normalized by assigning the count number of the fragment at each depth by the noise level.
The fragment of m / z = 231 is the following formula derived from cinnamic acid derivative (2-4-2)

It is thought that it corresponds to the fragment represented by Therefore, from the results of FIG. 1, in the coating film formed in this example, (A) the group derived from the cinnamic acid derivative is present at the highest concentration on the coating film surface, and 20% of the thickness from the surface. It is strongly inferred that it is unevenly distributed within a range of the extent (at most 30%).

Claims (11)

Following formula (1)

(In the formula (1), ^{X 1} is a monovalent organic group having an epoxy group, ^{Y 1} represents a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, 6 to 20 alkyl group carbon atoms or from 1 to 20 carbon atoms Of the aryl group.)
At least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the formula:
(A) a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.), - CH = CH ₂ and _-SO 2 group consisting of Cl Cinnamic acid derivatives having at least one group selected from: (B) carboxyl group, hydroxyl group, —SH, —NCO, —NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). ), At least one group selected from the group consisting of —CH═CH ₂ and —SO ₂ Cl, and a compound having a photosensitizing structure;
A liquid crystal aligning agent characterized by containing a radiation-sensitive polyorganosiloxane obtained by reacting. The (A) cinnamic acid derivative is represented by the following formula (2):

(In Formula (2), R ¹ is a C3-C40 monovalent organic group or C1-C40 alkyl group containing an alicyclic group, provided that a part of hydrogen atoms of the alkyl group or All may be substituted with fluorine atoms, R ² is a single bond, an oxygen atom, —COO— or —OCO—, R ³ is a divalent aromatic group, a divalent alicyclic group, 2 R ⁴ is a single bond, an oxygen atom, —COO— or —OCO—, and R ⁵ is a single bond, an oxygen atom, a sulfur atom or a methylene group. , An alkylene group having 2 to 10 carbon atoms or a divalent aromatic group, and when R ⁵ is a single bond, t is 1 and R ⁶ is a hydrogen atom, and R ⁵ is a methylene group or an alkylene group. or a divalent t is 0 or 1 is and R ⁶ is a carboxyl group when the aromatic group, a hydroxyl group, SH, -NCO, -NHR, a -CH = CH ₂ or _-SO 2 Cl, provided that said R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, ^{R 7} is a fluorine atom 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 (3)

(In the formula (3), R ⁸ is a monovalent organic group or an alkyl group having 1 to 40 carbon atoms of 3 to 40 carbon atoms containing an alicyclic group, provided that part of the hydrogen atoms of the alkyl group or All may be substituted with a fluorine atom, R ⁹ is an oxygen atom or a divalent aromatic group, R ¹⁰ is an oxygen atom, —COO— or —OCO—, and R ¹¹ is a divalent aromatic group. A group, a divalent heterocyclic group or a divalent condensed cyclic group, and R ¹² is a single bond, —OCO— (CH ₂ ) _e — ^* or —O— (CH ₂ ) _g — ^* . , provided that the e and g are each an integer from 1 to 10, "*", respectively, a bond marked with this is shown to bind with ^{R 13,} a carboxyl group, a hydroxyl group, the ^{R 13} - SH, -NCO, -NHR, a -CH = CH ₂ or _-SO 2 Cl, was The above R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁴ is a fluorine atom or a cyano group, c is an integer of 0 to 3, d is an integer of 0-4.) The liquid crystal aligning agent of Claim 1 which is a compound represented by these. The group X ¹ in the above formula (1) is represented by the following formula (X ¹ -1) or (X ¹ -2)

(In the above formula, “*” indicates a bond.)
The liquid crystal aligning agent of Claim 1 or 2 which is group represented by these.   (B) The photosensitizing structure in the compound having a photosensitizing structure has an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, a fluorene structure, a naphthalene structure, an anthracene structure, an acridine structure, and an indole structure. The liquid crystal aligning agent as described in any one of Claims 1-3 which is at least 1 sort (s) selected from the group which consists of.   Furthermore, the liquid crystal aligning agent as described in any one of Claims 1-4 containing the at least 1 sort (s) of polymer selected from the group which consists of a polyamic acid and a polyimide. Further, the following formula (4)

(In Formula (4), X ² is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y ² is a hydroxyl group or carbon. (It is an alkoxyl group of formula 1 to 10.)
The liquid crystal aligning agent as described in any one of Claims 1-4 containing at least 1 sort (s) selected from the group which consists of polyorganosiloxane represented by these, its hydrolyzate, and the condensate of a hydrolyzate.   A method for forming a liquid crystal alignment film, comprising: coating a liquid crystal aligning agent according to any one of claims 1 to 6 on a substrate to form a coating film; and irradiating the coating film with radiation. .   A liquid crystal alignment film formed from the liquid crystal alignment agent according to claim 1.   A liquid crystal alignment film, wherein the group derived from the (A) cinnamic acid derivative is unevenly distributed in a range of 30% of the thickness from the surface of the liquid crystal alignment film.   A liquid crystal display device comprising a liquid crystal alignment film formed from the liquid crystal alignment agent according to claim 1. At least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (1), a hydrolyzate thereof, and a hydrolyzate condensate;
(A) a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.), - CH = CH ₂ and _-SO 2 group consisting of Cl Cinnamic acid derivatives having at least one group selected from: (B) carboxyl group, hydroxyl group, —SH, —NCO, —NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). ), At least one group selected from the group consisting of —CH═CH ₂ and —SO ₂ Cl, and a compound having a photosensitizing structure;
A radiation-sensitive polyorganosiloxane obtained by reacting

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