JP5041599B2 - Liquid crystal aligning agent, liquid crystal aligning film, formation method thereof, liquid crystal display element and optical member - Google Patents

Description

  The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a method for forming the same, a liquid crystal display element, and an optical member. More specifically, a liquid crystal aligning agent capable of forming a liquid crystal alignment film with a small amount of polarized or non-polarized radiation without rubbing, a liquid crystal alignment film and a method for forming the same, and a liquid crystal alignment film having such a liquid crystal alignment film are provided. The present invention relates to a liquid crystal display element and an optical member.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy is sandwiched with a substrate with a transparent electrode having a liquid crystal alignment film, and the major axis of the liquid crystal molecules is continuously twisted between 0 and 360 ° between the substrates as necessary. Liquid crystal display elements having liquid crystal cells such as TN (twisted nematic), STN (super twisted nematic), and IPS (in-plane switching) are known (see Patent Documents 1 and 2). .
As a means for aligning liquid crystals in such a liquid crystal cell, an organic film (liquid crystal alignment 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 method of applying a rubbing treatment), a method of obliquely depositing silicon oxide on the surface of a substrate, a method of forming a monomolecular film having a long chain alkyl group using the Langmuir-Blodgett method (LB method), etc. There is. 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. Further, in liquid crystal display elements that will be further refined in the future, unevenness occurs on the surface of the substrate as the density of pixels increases, so that uniform rubbing is a problem.
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 is obtained 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 3 to 12 and 19).

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.
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. That is, it is known that the tilt direction of liquid crystal molecules at the time of voltage application can be uniformly controlled by using a vertical alignment film imparted with an alignment regulating force by a photo-alignment method (see Patent Documents 11 to 14 and 17 to 19). ).
Conventionally, in the display, optoelectronics, and optical fields, optical members such as polarizing plates, phase difference plates, and optically rotatory optical films have been used. These optical members have various uses. For example, in addition to being widely used as a member such as a polarizing plate, a compensation plate, and a viewing angle improving film in a liquid crystal display device, they are also used as a phase difference plate for an optical pickup element in an optical disk device. It has been.
As a method for producing such an optical member, many methods such as a method using a stretched and oriented resin film have been conventionally known. However, the optical member manufactured by such a method has the same optical characteristics over the entire surface, and it has not been possible to obtain an optical member having different optical characteristics in different regions within the surface.
As described above, the liquid crystal alignment film manufactured by the photo-alignment method can be effectively applied to a liquid crystal display element and an optical member. However, the conventional photo-alignment method using polyvinyl cinnamate, polyimide, or the like has a problem that a large amount of radiation is necessary to obtain liquid crystal alignment ability.
JP 56-91277 A JP-A-1-120528 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-A-6-289374 JP 2004-20658 A JP 2006-171304 A JP 2007-224273 A JP 2007-256484 A T.A. J. et al. Scheffer et. al. J. et al. Appl. Phys. vo. 19, p2013 (1980)

An object of the present invention is to provide a liquid crystal aligning agent that can form a liquid crystal alignment film with a small amount of polarized or non-polarized radiation without rubbing, and a small amount of polarized light or The object is to provide a method of forming a liquid crystal alignment film by non-polarized radiation, and a liquid crystal display element and an optical member comprising the liquid crystal alignment film formed by such a method.
Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the object of the present invention is firstly,
The following formulas (a-1) and (a-2)

(In the above formula, X ¹ and X ² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and Y ¹ and Y ² are each independently a halogen atom or a monovalent organic group. And W ¹ and W ² are each independently a single bond or a divalent linking group, provided that when Y ¹ is a halogen atom, W ¹ is a single bond, and when Y ² is a halogen atom, W 1 ² is a single bond, ^{Z 1} is Tan'yui case, n1 and n2 are each independently an integer of 0-4.)
It is achieved by a liquid crystal aligning agent containing a polymer or compound having at least one group selected from the groups represented by
The object of the present invention is secondly,
It is achieved by a method for forming a liquid crystal alignment film, wherein a coating film is formed by applying the above liquid crystal aligning agent on a substrate, and the coating film is irradiated with polarized or non-polarized radiation to impart liquid crystal alignment ability. .
The object of the present invention is thirdly achieved by the liquid crystal alignment film formed by the above method, and fourthly by a liquid crystal display element or an optical member having such a liquid crystal alignment film.

The liquid crystal aligning agent of this invention can obtain a liquid crystal aligning film with a small amount of radiation irradiation compared with the case of the conventional photo-alignment method. Therefore, when this liquid crystal alignment film is applied to a liquid crystal display element, a liquid crystal display element having excellent display characteristics can be manufactured at a lower cost than before. When the liquid crystal alignment film of the present invention is applied to the production of an optical member, an optical member having excellent in-plane uniformity can be produced at a lower cost than before.
Therefore, these liquid crystal display elements or optical members can be effectively applied to various devices, for example, suitably used for devices such as desk calculators, watches, table clocks, counting display boards, word processors, personal computers, liquid crystal televisions, and optical disk devices. Can do.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of this invention contains the polymer or compound which has at least 1 sort (s) of group selected from the group represented by each of said formula (a-1) and (a-2).
X ¹ and X ² in the above formulas (a-1) and (a-2) are each independently a hydrogen atom, a halogen atom or a monovalent organic group, preferably a hydrogen atom or a C 1-6 carbon atom. An alkyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. Y ¹ and Y ² are each independently a halogen atom or a monovalent organic group, preferably a fluorine atom or a monovalent organic group having 1 to 30 carbon atoms, more preferably substituted with fluorine. It is a C1-C20 alkyl group or C3-C30 monovalent organic group having an alicyclic structure. Specific examples of the monovalent organic group include amyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, trifluoromethyl group, 2,2,2-trifluoro. Ethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, perfluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 3,3,4 , 4,4-pentafluorobutyl group, 4,4,5,5,5-pentafluoroamyl group, perfluoropropyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4- Propylcyclohexyl group, 4-butylcyclohexyl group, 4-amylcyclohexyl group, cyclohexylmethyl group, 4-methylcyclyl Hexylmethyl group, 4-ethylcyclohexylmethyl group, 4-propylcyclohexylmethyl group, 4-butylcyclohexylmethyl group, 4-amylcyclohexylmethyl group, 4 (4-amylcyclohexyl) cyclohexylmethyl group, 4 (4-methylcyclohexyl) Phenyl group, 4 (4-ethylcyclohexyl) phenyl group, 4 (4-propylcyclohexyl) phenyl group, 4 (4-butylcyclohexyl) phenyl group, 4 (4-amylcyclohexyl) phenyl group, cholesteryl group, cholestanyl group, etc. Can be mentioned.
W ¹ and W ² are each independently a single bond or a divalent linking group, preferably a single bond, an ether bond, an ester bond, a urethane bond or a urea bond. However, W ¹ is a single bond when Y ¹ is a halogen atom, and W ² is a single bond when Y ² is a halogen atom.
Z ¹ is a Tan'yui case. n1 and n2 are each independently an integer of 0 to 4, preferably 1.

  Specific examples of the group represented by the above formula (a-1) include, for example, the following formula (a-1-1)

A group represented by:
Specific examples of the group represented by the above formula (a-2) include, for example, the following formulas (a-2-1) to (a-2-3):

The groups represented by each of the above can be mentioned.
The polymer having at least one group selected from the groups represented by formulas (a-1) and (a-2) used in the present invention (hereinafter also referred to as “specific group”) is as follows. For example, it can be a polymer having a specific group as a side chain. Examples of such polymers include polyorganosiloxane having a specific group, styrene (co) polymer, phenylmaleimide (co) polymer, (meth) acrylic acid ester (co) polymer, polyamic acid, polyimide, polyamic acid. Examples thereof include esters, polyesters, polyamides, celluloses, and polyacetals. Of these, polyorganosiloxane having a specific group is preferred.
The polyorganosiloxane having a specific group is, for example, a polyorganosiloxane having an epoxy group and the following formulas (b-1) to (b-3):

(In the above formula, X ¹ , X ² , Y ¹ , Y ² , W ¹ , W ² , Z ¹ and the definitions of n1 and n2 are as defined in the above formula (a-1) or (a-2), respectively. And n3 is an integer of 1 to 4.)
It can obtain by making it react with at least 1 sort (s) selected from the group which consists of the compound represented by each (carboxylic acid which has a specific group).
The polyorganosiloxane having an epoxy group is obtained by hydrolyzing, for example, 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. Alternatively, it can be synthesized by hydrolysis and condensation. Moreover, you may use the commercial item of the polyorganosiloxane which has an epoxy group like the brand names DMS-10, DMS-12, DMS-21, DMS-32 by Chisso Corporation as it is.
Examples of the silane compound having an epoxy group used for the synthesis of the polyorganosiloxane having the epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropyl. Methyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like 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- (perfluorosilane Fluoro-n-octyl) ethyltri-i-propoxysilane, 2- (Perful Olo-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri N-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-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) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltri Chlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane , -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- (perfluoroon-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoroon-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoroon-n- (Cutyl) ethyl] di-i-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di- sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane,

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

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

Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltri Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercapto Mention may be made of methyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane.
The polyorganosiloxane having the above epoxy group preferably has an epoxy equivalent of 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol. Therefore, in synthesizing a polyorganosiloxane having an epoxy group, the use ratio of the silane compound having an epoxy group and another silane compound is adjusted so that the obtained polyorganosiloxane epoxy equivalent is in the above range. It is preferable to set.

The polyorganosiloxane having a specific group is at least one selected from the group consisting of a polyorganosiloxane having an epoxy group as described above and a compound represented by each of the above formulas (b-1) to (b-3). The seed can be obtained by reacting, preferably in the presence of a catalyst. Here, at least one selected from the group consisting of the compounds represented by each of the above formulas (b-1) to (b-3) is preferably 0 with respect to 1 mol of the epoxy group of the polyorganosiloxane. 0.001 to 1.5 mol, more preferably 0.01 to 1 mol, and still more preferably 0.05 to 0.9 mol.
When synthesizing a polyorganosiloxane having a specific group, other carboxylic acids are used in combination with at least one selected from the group consisting of the compounds represented by formulas (b-1) to (b-3). May be. Examples of such other carboxylic acids include hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, cyclohexanecarboxylic acid, benzoic acid, and the following formulas (c-1) to (c-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.)
The compound represented by each of these can be mentioned.
Among these, preferable examples include compounds represented by any of the above formulas (c-1) to (c-4), and more preferable examples are represented by the above formula (c-3). 4- (Trifluoromethoxy) benzoic acid, 4- (4,4,4-trifluorobutoxy) benzoic acid and 4- (4,4,5,5,5-pentafluoroamyloxy) benzoic acid among the compounds Can be mentioned.
The use ratio of the other carboxylic acid is preferably 0.001 to 0.9 mol, more preferably 0.01 to 0.5 mol, with respect to 1 mol of the epoxy group of the polyorganosiloxane. More preferably, it is 0.05-0.25 mol.

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; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, Examples thereof include tertiary organic amines such as diazabicycloundecene (except for those corresponding to curing accelerators described later); 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.
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] An imidazole compound such as an isocyanuric acid adduct of loumidazolyl- (1 ′)] ethyl-s-triazine;
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 bets quaternary phosphonium salts;
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;
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 accelerators such as dicyandiamide and adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator in which the surface of a curing accelerator such as the imidazole compound, organophosphorus compound or quaternary phosphonium salt is coated with a polymer;
An amine salt type latent curing agent 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, preferred are quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

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 still more 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.
The synthesis reaction of the polyorganosiloxane having a specific group can be performed in the presence of an organic solvent, if necessary. Examples of such organic solvents include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like. 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 solvent is used in such an amount that the solid content concentration (the ratio of the weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 50% by weight. Is done.

As the compound having a specific group that can be used in the present invention, a low molecular weight compound can be preferably used, and examples thereof include an epoxy compound having a specific group. Such an epoxy compound reacts, for example, a carboxylic acid represented by any one of the above formulas (b-1) to (b-3) with a compound having two or more epoxy groups in a molar ratio of 1: 1. Can be obtained.
Of the polymers and compounds having a specific group as described above, polymers having a specific group are preferred.

Although the liquid crystal aligning agent of this invention contains the polymer or compound which has the above specific groups as an essential component, it can contain another component as needed. Examples of such other components include other polymers and compounds having at least one epoxy group in the molecule (excluding epoxy compounds having a specific group. Compounds having at least one epoxy group in the molecule, Hereinafter, it is referred to as “epoxy compound”), a sensitive silane compound, and the like.
The other polymer is a polymer having no specific group, and can be contained in the liquid crystal aligning agent of the present invention in order to improve the varnish properties, electrical properties, etc. of the liquid crystal aligning agent of the present invention. .
Examples of such other polymers include polyorganosiloxane, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, and poly (meth) acrylate. Can be mentioned. Of these, polyorganosiloxane, polyamic acid, or imidized polymer is preferable from the viewpoint that the varnish properties and electrical characteristics of the liquid crystal aligning agent containing the same are more excellent.
The polyorganosiloxane that is another polymer is represented by, for example, the above-described polyorganosiloxane having an epoxy group, the polyorganosiloxane having the epoxy group, and the above formulas (c-1) to (c-4). Examples include polyorganosiloxanes obtained by reacting at least one selected from compounds according to the above method, and polyorganosiloxanes obtained by hydrolysis and condensation of one or more of the other silane compounds. .
The polyamic acid which is another polymer can be obtained by reacting tetracarboxylic dianhydride and diamine. Polyimide which is another polymer can be obtained by dehydrating and ring-closing the polyamic acid.

Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxyl Lopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b -Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -7-methyl-5- (tetrahydro-2 , 5-Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl- 5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, -C] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran -2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tri Carboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone The following formula (T-1) or (T-II)

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

An aromatic tetracarboxylic dianhydride such as a compound represented by each of the above can be exemplified. These may be used alone or in combination of two or more.
Among the above, tetracarboxylic dianhydrides used for synthesizing polyamic acid are butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3 , 3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b- Xahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy- 2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyro Mellitic dianhydride 3,3 ', 4,4'-benzofu Non-tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 1,4,5 , 8-Naphthalenetetracarboxylic dianhydride, among the compounds represented by the above formula (TI), the following formulas (T-5) to (T-7)

Of the compounds represented by each of the above and the compounds represented by the above formula (T-II), the following formula (T-8)

It is preferable from the viewpoint that it can exhibit good liquid crystal alignment properties including at least one selected from the group consisting of the compounds represented by (hereinafter referred to as “specific tetracarboxylic dianhydride”). . Particularly preferred among the specific tetracarboxylic dianhydrides are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a , 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5 , 9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2. 1] Octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3 -Cyclohexene-1,2 Dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6} It is at least one selected from the group consisting of undecane-3,5,8,10-tetraone, pyromellitic dianhydride and the compound represented by the above formula (T-5).
The tetracarboxylic dianhydride used for synthesizing the polyamic acid preferably contains 50 mol% or more of the specific tetracarboxylic dianhydride as described above with respect to the total tetracarboxylic dianhydride, It is more preferable to contain more than mol%, and it is particularly preferable to contain more than 90 mol%.

  Examples of the diamine used for synthesizing the polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2, 2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'- Ditrifluoromethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-amino Enyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis 4-Aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-methylene -Bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxy Biphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 1,4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2 '-Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (tri Aromatic diamines such as fluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl;

1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 , 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4 Aliphatic or cycloaliphatic diamines such as 1,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane;
2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4 -Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3 , 5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl -S-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6 Phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl -3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N '-Dimethyl-benzidine, the following formula (DI)

(In the formula (DI), R ⁵ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ¹ represents a divalent organic group. .)
A compound represented by formula (D-II):

(In Formula (D-II), R ⁶ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ² represents a divalent organic group, respectively. A plurality of X ² may be the same or different from each other.)
A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in a molecule such as a compound represented by:
The following formula (D-III)

(In the formula (D-III), R ⁷ represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R ⁸ represents a steroid. (A monovalent organic group having a group selected from a skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, or an alkyl group having 6 to 30 carbon atoms.)
Monosubstituted phenylenediamines such as compounds represented by:
The following formula (D-IV)

(In the formula (D-IV), R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁹ may be the same or different, and p represents 1 to 3 respectively. And q is an integer of 1 to 20.)
Diaminoorganosiloxane represented by:
The following formulas (D-1) to (D-5)

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5.)
And the like, and the like. These diamines can be used alone or in combination of two or more.
Among these, diamines used for synthesizing polyamic acid include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, and 2,2′-. Dimethyl-4,4′-diaminobiphenyl, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4 -Aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 1,4-diaminocyclohexane, 4 , 4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, compounds represented by the above formulas (D-1) to (D-5), 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl -3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophen Le) -N, N'-dimethyl - benzidine, formula among the compounds represented by the above formula (D-I) (D-6)

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

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

And at least one selected from the group consisting of 1,3-bis (3-aminopropyl) -tetramethyldisiloxane among the compounds represented by the formula (D-IV) Hereinafter, it is preferable to include [specific diamine].
The diamine used for synthesizing the polyamic acid preferably contains the specific diamine as described above in an amount of 50 mol% or more, more preferably 80 mol% or more, particularly 90 mol% or more. It is preferable that it is included.

The proportion of tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is such that the acid anhydride group of tetracarboxylic dianhydride is 0.5 to 1 equivalent to 1 equivalent of amino group contained in the diamine. A ratio of 2 equivalents is preferable, and a ratio of 0.7 to 1.2 equivalents is more preferable.
The polyamic acid synthesis reaction is preferably performed in an organic solvent under a temperature condition of preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably 0.5 to 120 hours, more preferably 2 to 10 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide And aprotic polar solvents such as γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of organic solvent used (α: the total of the organic solvent and the poor solvent when the organic solvent and the poor solvent described later are used in combination) is the total amount of tetracarboxylic dianhydride and diamine compound ( It is preferable that β) is 0.1 to 30% by weight based on the total amount of the reaction solution (α + β).

For the organic solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like, which are poor solvents for polyamic acid, can be used in combination as long as the polyamic acid to be produced does not precipitate. Specific examples of the poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene Glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n- Chill ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1 , 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoamylisobutyrate, diisopentyl ether and the like.
When the organic solvent and the poor solvent are used in combination, the proportion of the poor solvent used is preferably 50% by weight or less, more preferably 20% by weight or less, based on the total of the organic solvent and the poor solvent.
As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. Polyamic acid can be isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. it can. Further, the polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the step of distilling under reduced pressure with an evaporator once or several times.

Another polymer, polyimide, can be synthesized by dehydrating and ring-closing the polyamic acid obtained as described above. This polyimide may be a completely imidized product obtained by dehydrating and ring-closing all of the amic acid structure of the polyamic acid as a raw material, and only a part of the amic acid structure is dehydrated and ring-closed. It may be a partially imidized product having a structure. The polyimide that is another polymer preferably has an imidization ratio of 40% or more, and more preferably 80% or more.
The said imidation rate represents the ratio which the number of the imide ring structure accounts with respect to the sum total of the number of the amic acid structures of polyimide, and the number of imide ring structures in percentage. At this time, a part of the imide ring may be an isoimide ring. The imidation rate is calculated by the following formula (i) based on the result of ¹ H-NMR measured at room temperature using tetramethylsilane as a reference substance by dissolving polyimide in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide). Can be sought.

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

(In Formula (i), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a polyimide precursor (polyamic acid). The number ratio of other protons to one proton of NH group in

Dehydration and ring closure of polyamic acid to synthesize such polyimide can be performed by (i) heating the polyamic acid or (ii) dissolving polyamic acid in an organic solvent and adding a dehydrating agent and a dehydrating ring closure catalyst to this solution. And it is performed by the method of heating as needed.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease. The reaction time is preferably 1 to 120 hours, more preferably 2 to 30 hours.
On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol relative to 1 mol of the polyamic acid repeating 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 amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. The reaction time is preferably 0.5 to 30 hours, more preferably 2 to 10 hours.
The polyimide obtained in 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 purifying the obtained polyimide. On the other hand, in the above 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 dehydrating 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.

The polyamic acid and polyimide which are other polymers may be of a terminal modified type having a controlled molecular weight. Such a terminal-modified type can be synthesized by adding an appropriate molecular weight regulator such as acid monoanhydride, monoamine compound, monoisocyanate compound to the reaction system when synthesizing the polyamic acid. Here, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride , N-hexadecyl succinic anhydride and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecyl. Amine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. be able to. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
As a use ratio of the molecular weight regulator, with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid having a group represented by the above formula (a), Preferably it is 20 weight part or less, More preferably, it is 10 weight part or less.

  When the liquid crystal aligning agent of the present invention contains another polymer, the use ratio of the other polymer is specified when the liquid crystal aligning agent contains a polymer having a specific group. It is preferably 50 to 99% by weight, more preferably 75 to 95% by weight, and particularly preferably 80 to 90% by weight based on the total of the polymer having a group and another polymer. . On the other hand, when the liquid crystal aligning agent contains a compound having a specific group, the use ratio of the other polymer is preferably 5,000 parts by weight or less with respect to 100 parts by weight of the compound having the specific group. More preferably, it is 100-4,000 weight part, More preferably, it is 200-3,000 weight part, It is especially preferable that it is 500-2,000 weight part.

The epoxy compound can be contained in the liquid crystal aligning agent of the present invention from the viewpoint of further improving the adhesion of the liquid crystal alignment film to be formed to the substrate surface. Examples of the epoxy compound include ethylene glycol diglycidyl ether, Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2 -Dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N',-tetraglycidyl- Xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N-diglycidyl-benzylamine N, N-diglycidyl-aminomethylcyclohexane and the like can be mentioned as preferable ones. The blending ratio of these epoxy compounds is preferably 40 parts by weight with respect to 100 parts by weight of the total of the polymers (referring to the total of the polymer represented by the above formula (a) and other polymers. The same shall apply hereinafter). It is below, More preferably, it is 0.1-30 weight part.
Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N- Benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis ( Examples thereof include oxyethylene) -3-aminopropyltrimethoxysilane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane. The blending ratio of these functional silane compounds is preferably 2 parts by weight or less, more preferably 0.2 parts by weight or less, with respect to 100 parts by weight of the total polymer.

The liquid crystal aligning agent of the present invention is constituted by the polymer or compound having the specific group as described above and other components optionally added, preferably dissolved in an organic solvent.
Examples of the organic solvent that can be used in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4- Hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n- Propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Examples thereof include dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, and diisopentyl ether. These can be used alone or in admixture of two or more. A particularly preferable solvent composition is a composition obtained by combining the above-mentioned solvents, wherein no polymer is precipitated in the aligning agent, and the surface tension of the aligning agent is in the range of 25 to 40 mN / m. It is.

The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is selected in consideration of viscosity, volatility, Preferably it is the range of 1-10 weight%. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface to remove the solvent to form a coating film that becomes a liquid crystal aligning film, but the solid content concentration of the liquid crystal aligning agent is less than 1% by weight. In this case, it is difficult to obtain a good liquid crystal alignment film because the film thickness is too small, and when the solid content concentration exceeds 10% by weight, the film thickness is too large to be equally good. A liquid crystal alignment film is difficult to obtain, and the viscosity of the liquid crystal aligning agent may increase, resulting in poor coating characteristics. The particularly preferable range of the solid content concentration varies depending on the method used 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 inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature at which the liquid crystal aligning agent of the present invention is prepared is preferably 0 ° C to 200 ° C, more preferably 20 ° C to 60 ° C.

The liquid crystal alignment film of the present invention is formed by applying the liquid crystal aligning agent of the present invention as described above to form a coating film, and irradiating the coating film with polarized or non-polarized radiation to impart liquid crystal alignment ability. can do. Specifically, for example, the following method can be used.
When the liquid crystal alignment film of the present invention is used for a liquid crystal display element, the liquid crystal aligning agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film to form a coating film, After the coating film is irradiated with polarized or non-polarized radiation to give liquid crystal alignment ability to provide liquid crystal alignment ability, it can be used as it is as a substrate with a liquid crystal alignment film of a liquid crystal display element. Here, as the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, alicyclic polyolefin, or the like can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. In order to obtain these patterned transparent conductive films, for example, a method of forming a pattern by a photo-etching method after forming a transparent conductive film without a pattern, and having a desired pattern shape in advance when forming the transparent conductive film A method of directly forming a patterned transparent conductive film using a mask can be used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound or the like is applied in advance to the surface of the substrate. It may be left.
On the transparent conductive film of the substrate, the liquid crystal aligning agent of the present invention is applied by an appropriate application method such as a roll coater method, a spinner method, a printing method, an ink jet method, etc., and then the coated surface is heated. Form.
After the application of the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Thereafter, a baking (post-baking) step is performed for the purpose of completely removing the solvent and heat imidizing the polyamic acid. The post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
Thus, the liquid crystal aligning agent of this invention forms the coating film used as a liquid crystal aligning film by removing an organic solvent after application | coating in this way. In addition, when the liquid crystal aligning agent of the present invention contains a polyamic acid or a polyimide in which an amic acid structure remains as another polymer, the dehydration ring closure of the amic acid structure further proceeds by further heating after the coating film is formed. Further, a liquid crystal alignment film that is more imidized may be used.
The film thickness of the liquid crystal alignment film to be formed is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm.

Next, the coating film is irradiated with polarized or non-polarized radiation, and in some cases, further subjected to heat treatment at a temperature of 150 to 250 ° C. to give a liquid crystal alignment ability, whereby a liquid crystal alignment film can be obtained.
Examples of polarized radiation include linearly polarized radiation and partially polarized radiation. As the radiation, ultraviolet rays or visible rays having a wavelength of 150 nm to 800 nm can be used. Among these, ultraviolet rays having a wavelength of 150 nm to 450 nm are preferable, and ultraviolet rays having a wavelength of 250 nm to 350 nm are more preferable. As the radiation, non-polarized light is preferable because it is more easily obtained than linearly polarized light or partially polarized light. When the used radiation is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an oblique direction in order to give a pretilt angle. You may carry out in combination. When irradiating non-polarized radiation, the direction of irradiation needs to be oblique to the substrate surface. In order to improve the liquid crystal alignment ability, irradiation may be performed while heating the substrate to 50 to 250 ° C. Dose of the radiation is preferably is preferably less than 10,000 J / ^{m 2,} more preferably in the range of 10~5,000J / ^{m 2,} the range of 50~3,000J / ^{m 2} More preferably, it is particularly preferably in the range of 100 to 1,000 J / m ² .
Upon irradiation with radiation, for the purpose of forming liquid crystal alignment films having different alignment orientations in different regions within the plane, radiation having at least one of the polarization state, the direction of the optical axis, and the energy is different within the plane. Each region can be irradiated. As a method of changing the polarization state, optical axis direction or energy of the irradiated radiation in a plane, for example, a method of irradiating through a photomask, coating while changing the light intensity, incident angle, etc. as necessary. Examples thereof include a method of sweeping the film with radiation. These methods can be used alone or in combination. Further, one or both of these methods may be combined with batch irradiation on the entire surface of the substrate.
As a light source for radiation irradiation, 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, or an excimer laser can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using a filter or a diffraction grating in combination with the light source.
The heating time optionally performed after radiation irradiation is preferably 10 to 100 minutes, and more preferably 30 to 60 minutes.

The liquid crystal display element of the present invention comprises the liquid crystal alignment film formed as described above. The liquid crystal display element of the present invention is produced by manufacturing a pair (two sheets) of substrates on which the liquid crystal alignment films are formed as described above, so that the rubbing directions in the respective liquid crystal alignment films are orthogonal or antiparallel. The two substrates are placed facing each other with a gap (cell gap) between them, and the peripheral parts of the two substrates are bonded together using a sealing agent, and liquid crystal is injected and filled into the substrate gap and the cell gap defined by the sealing agent. After the injection hole is sealed to form a liquid crystal cell, it can be manufactured by disposing a polarizing plate on the outer surface of the liquid crystal cell.
Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl. Cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck & Co., Inc.). Etc. may be added and used.
As a polarizing plate bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of itself can be mentioned.

  The optical member of the present invention is a known manufacturing method for each optical member, except that a liquid crystal alignment film formed by the method described above or by a method obvious to those skilled in the art is added to the above method. It can be manufactured similarly.

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 synthesis examples, the weight average molecular weight and epoxy equivalent of the polyorganosiloxane, the solution viscosity of the polymer solution, and the imidization ratio of the polyimide were evaluated by the following methods, respectively.
[Weight average molecular weight Mw of polyorganosiloxane]
The polystyrene conversion value measured by gel permeation chromatography under the following conditions was used.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Epoxy equivalent]
Measured according to JIS C2105 “hydrochloric acid-methyl ethyl ketone method”.
[Solution viscosity of polymer]
About a predetermined polymer solution, it measured at 25 degreeC using the E-type rotational viscometer.
[Imidation rate of polyimide]
The polyimide was sufficiently dried at room temperature under reduced pressure, dissolved in deuterated dimethyl sulfoxide, measured at room temperature using tetramethylsilane as a reference substance, and determined from ¹ H-NMR by the above formula (i).

<Synthesis of polyorganosiloxane having epoxy group>
Synthesis example 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 at room temperature. Mixed. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then reacted at 80 ° C. under reflux for 6 hours. After completion of the reaction, the organic layer is taken out and washed with a 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure, whereby a polyorgano having an 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 an epoxy group, a peak based on the epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction of the epoxy group occurred.
Table 1 shows the viscosity, weight average molecular weight Mw, and epoxy equivalent of the polyorganosiloxane (EPS-1) having this epoxy group.
Synthesis Examples 2-3
Polyorganosiloxanes (EPS-2) and (EPS-3) having an epoxy group were obtained as viscous transparent liquids in the same manner as in Synthesis Example 1 except that the raw materials were as shown in Table 1. .
Table 1 shows the weight average molecular weight Mw and epoxy equivalent of the polyorganosiloxane having these epoxy groups.
In Table 1, the abbreviations of the raw material silane compounds have the following meanings.
ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane MTMS: methyltrimethoxysilane PTMS: phenyltrimethoxysilane

<Synthesis of polyorganosiloxane having specific group>
Synthesis example 4
In a 200 mL three-necked flask, 5.0 g of the polyorganosiloxane (EPS-1) having an epoxy group obtained in Synthesis Example 1 above, 16.9 g of N, N-dimethylacetamide, and a carboxylic acid having a specific group represented by the following formula (b -I-1)

Was charged with 2.7 g of a compound represented by the formula (II) and 0.25 g of tetrabutylammonium bromide, and the reaction was performed at 110 ° C. with stirring for 8 hours. After completion of the reaction, reprecipitation is performed with methanol, and the precipitate is dissolved in ethyl acetate to obtain a solution. The solution is washed with water five times, and then the solvent is distilled off to obtain a polyorganosiloxane having a specific group (H 2.5 g of -1) was obtained as a white powder. The weight average molecular weight Mw of the polyorganosiloxane (H-1) having a specific group was 7,000.
Synthesis Examples 5-11
In Synthesis Example 4, the type of polyorganosiloxane having an epoxy group and the type and amount of a carboxylic acid having a specific group were as shown in Table 2, and the same as in Synthesis Example 4 and having a specific group Polyorganosiloxanes (H-2) to (H-8) were respectively prepared. Table 2 shows the weight average molecular weight Mw of the polyorganosiloxane having these specific groups.
The abbreviations of carboxylic acids having specific groups in Table 2 each represent a compound represented by the following chemical formula.

<Synthesis of other polymers>
Synthesis Example 12
110 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 200 g (1.0 mol) of diaminodiphenyl ether was dissolved in a mixed solvent consisting of 230 g of N-methyl-2-pyrrolidone (NMP) and 2,100 g of γ-butyrolactone, reacted at 40 ° C. for 3 hours, and then γ-butyrolactone 1 , 350 g was added to obtain about 4,050 g of a solution containing 10% by weight of polyamic acid (A-1). The solution viscosity of this polyamic solution was 200 mPa · s.
Synthesis Example 13
1,2,3,4-Cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) and pyromellitic dianhydride 110 g (0.50 mol) as tetracarboxylic dianhydride and 4,4 ′ as diamine -200 g (1.0 mol) of diaminodiphenylmethane was dissolved in a mixed solvent consisting of 230 g of NMP and 2,100 g of γ-butyrolactone, reacted at 40 ° C. for 3 hours, and then 1,350 g of γ-butyrolactone was added to add polyamic About 4,050 g of a solution containing 10% by weight of acid (A-2) was obtained. The solution viscosity of this polyamic solution was 125 mPa · s.

Synthesis Example 14
200 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 were added to 230 g of NMP and γ -A solution containing 10% by weight of polyamic acid (A-3) was obtained by dissolving in a mixed solvent consisting of 2,050 g of butyrolactone, reacting at 40 ° C for 3 hours, and then adding 1,300 g of γ-butyrolactone. 3,950 g was obtained. The solution viscosity of this polyamic solution was 210 mPa · s.
Synthesis Example 15
200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 210 g of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine (1. 0 mol) is dissolved in a mixed solvent consisting of 370 g of NMP and 3,300 g of γ-butyrolactone and reacted at 40 ° C. for 3 hours to obtain about 4,050 g of a solution containing 10% by weight of polyamic acid (A-4). It was. The solution viscosity of this polyamic solution was 160 mPa · s.

Synthesis Example 16
240 g of NMP and γ-butyrolactone were obtained by adding 220 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 200 g (1.0 mol) of 4,4′-diaminodiphenyl ether as diamine. It melt | dissolved in the mixed solvent which consists of 3,500g, and it was made to react at 40 degreeC for 4 hours, and about 4,150g of solutions containing 10 weight% of polyamic acids (A-5) were obtained. The solution viscosity of this polyamic solution was 38 mPa · s.
Synthesis Example 17
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 49 g (0.45 mol) and 3 (3,5-diaminobenzoyl) of p-phenylenediamine as diamine 26 g (0.05 mol) of oxy) cholestane was dissolved in 750 g of NMP and reacted at 60 ° C. for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 58 mPa · s.
Next, 1,800 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 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 NMP (in this operation, pyridine and acetic anhydride used in the dehydration cyclization reaction were removed from the system), and the imidation rate was about 50%. About 1,100 g of a solution containing 15% by weight of polyimide (B-1) was obtained.

Example 1
<Preparation of liquid crystal aligning agent>
Of a solution containing 100 parts by weight of the polyorganosiloxane (H-1) having a specific group obtained in Synthesis Example 4 and the polyamic acid (A-1) obtained in Synthesis Example 12 as another polymer. Combined with the amount corresponding to 1,000 parts by weight in terms of polyamic acid (A-1), γ-butyrolactone, NMP and butyl cellosolve are added thereto, and the solvent composition is γ-butyrolactone: NMP: butyl cellosolve = 71: 17. : 12 (weight ratio) and a solid content concentration of 2.5% by weight. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.
Using this liquid crystal aligning agent, a liquid crystal cell was produced and evaluated as follows.
<Manufacture of liquid crystal cells>
An oven in which the liquid crystal aligning agent prepared above was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by spin coating, prebaked on an 80 ° C. hot plate for 1 minute, and the inside of the chamber was replaced with nitrogen. The film was post-baked at 200 ° C. for 1 hour to form a film having a thickness of 600 nm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays of 1,000 J / m ² containing a 313 nm emission line from a direction inclined by 40 ° from the normal line of the liquid crystal using a Hg—Xe lamp and a Grand Taylor prism. It was. The same operation was repeated to prepare a pair (two) of substrates having a liquid crystal alignment film.
After applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing, the liquid crystal alignment film surfaces of the pair of substrates are opposed to each other, The adhesive was heat-cured at 150 ° C. for 1 hour so that the projection direction of the optical axis of each substrate onto the substrate surface was antiparallel. Next, a positive liquid crystal (MLC-6221 manufactured by Merck & Co., Inc.) was filled into the gap between the substrates from the liquid crystal injection port, and then 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 120 ° C. and then gradually cooled to room temperature to produce a liquid crystal cell.
<Evaluation of liquid crystal cell>
(1) Evaluation of liquid crystal alignment The presence or absence of an abnormal domain when a voltage of 5 V is turned ON / OFF (applied / released) at 25 ° C. is observed with a polarizing microscope for a liquid crystal cell. The quality was evaluated as “good”. The liquid crystal alignment of the liquid crystal cell produced above was good.
(2) Evaluation of pretilt angle In accordance with the method described in Non-Patent Document 1 (T. J. Scheffer et. Al. J. Appl. Phys. Vo. 19, p2013 (1980)), He-Ne laser light is used. It was measured by the crystal rotation method used. The pretilt angle of the liquid crystal cell produced above was 0.1 °.

Examples 2-13
In Example 1 above, a liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the types and amounts of the polyorganothioxan having a specific group and other polymers used were as shown in Table 3. A cell called “Kokusho” was manufactured and evaluated. The evaluation results are shown in Table 3.
In addition, all the other polymers are used for the preparation of the liquid crystal aligning agent as the polymer solution synthesized in the above synthesis example, and the amount of the other polymer in Table 3 is the amount of the polymer contained in the corresponding polymer solution. It is a value converted into a quantity.

Examples 14-22
In Example 1 above, the types and amounts of the polyorganosioxane having the specific group and other polymers used are as shown in Table 4, and the negative type liquid crystal (MLC-6221, manufactured by Merck & Co.) was used instead of the negative type liquid crystal. A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that type liquid crystal (MLC-6608 manufactured by Merck & Co., Inc.) was used. The evaluation results are shown in Table 4.
In addition, all the other polymers are used for the preparation of the liquid crystal aligning agent as the polymer solution synthesized in the above synthesis example, and the amount of the other polymer in Table 4 is the amount of the polymer contained in the corresponding polymer solution. It is a value converted into a quantity.

Claims (6)

The following formulas (a-1) and (a-2)

(In the above formula, X ¹ and X ² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and Y ¹ and Y ² are each independently a halogen atom or a monovalent organic group. And W ¹ and W ² are each independently a single bond or a divalent linking group, provided that when Y ¹ is a halogen atom, W ¹ is a single bond, and when Y ² is a halogen atom, W 1 ² is a single bond, ^{Z 1} is Tan'yui case, n1 and n2 are each independently an integer of 0-4.)
A liquid crystal aligning agent comprising a polymer or a compound having at least one group selected from the groups represented by each of the above:
  The liquid crystal according to claim 1, wherein the polymer is a polyorganosiloxane having at least one group selected from the groups represented by the formulas (a-1) and (a-2). Alignment agent.   A liquid crystal aligning agent according to claim 1 or 2 is applied onto a substrate to form a coating film, and the coating film is irradiated with polarized or non-polarized radiation to impart liquid crystal alignment ability. And a method for forming a liquid crystal alignment film.   A liquid crystal alignment film formed by the method according to claim 3.   A liquid crystal display element comprising the liquid crystal alignment film according to claim 4.   An optical member comprising the liquid crystal alignment film according to claim 4.