JP2010217867A - Liquid crystal aligning agent, process for forming liquid crystal alignment layer and process for producing liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent providing a liquid crystal alignment layer which can be given a pretilt angle by an optical alignment method and includes superior temporal stability in given pretilt angle. <P>SOLUTION: The liquid crystal aligning agent includes radiation-sensitive polyorganosiloxane having a structure expressed by formula (1). The radiation-sensitive polyorganosiloxane is a reaction product of, preferably, (a) polyorganosiloxane having an epoxy group and (b) a compound having the structure expressed by formula (1) and a carboxyl group or a compound having a group expressed by formula (2). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

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. There are known liquid crystal display elements having liquid crystal cells such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS (In Plane Switching) type (see Patent Documents 1 and 2). .
In such a liquid crystal cell, it is necessary to provide a liquid crystal alignment film on the substrate surface in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon. However, when the liquid crystal alignment film is formed by a rubbing process, dust and static electricity are likely to be generated in the process, so that there is a problem that dust adheres to the alignment film surface and causes display defects. In particular, in the case of a substrate having 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 generated on the substrate surface as the density of pixels increases, and it is becoming difficult to perform rubbing treatment uniformly.
As another means of aligning the liquid crystal in the liquid crystal cell, light that imparts liquid crystal alignment ability by irradiating a photosensitive thin film such as polyvinyl cinnamate, polyimide, or azobenzene derivative formed on the substrate surface with polarized or non-polarized radiation. Orientation methods are known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (see Patent Documents 3 to 13). Here, in a liquid crystal cell of TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, etc., the liquid crystal alignment film has a pretilt angle characteristic in which liquid crystal molecules are tilted and aligned at a predetermined angle with respect to the substrate surface. There is a need. In the case of forming a liquid crystal alignment film by the photo-alignment method, the pretilt angle is usually given by tilting the incident direction of the irradiated radiation to the substrate surface from the substrate normal.

On the other hand, as an operation mode of a liquid crystal display element different from the above, a VA (Vertical Alignment) type liquid crystal cell in a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also available. Are known. In this operation mode, when a voltage is applied between the substrates and the liquid crystal molecules are tilted in the direction parallel to the substrate, the liquid crystal 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 cell. That is, it is known that the tilt direction of liquid crystal molecules during voltage application can be uniformly controlled by using a vertical alignment liquid crystal alignment film imparted with alignment regulating ability and pretilt angle expression by a photo alignment method (patent) Reference 11-12 and 14-16).
Thus, the liquid crystal alignment film manufactured by the photo-alignment method can be effectively applied to various liquid crystal display elements. However, even if the liquid crystal alignment film formed by these techniques exhibits a good pretilt angle at the beginning of formation, a phenomenon in which the pretilt angle develops over time occurs and the temporal stability of the pretilt angle is lacking. It has been pointed out.

By the way, in order to increase the viewing angle in a vertical alignment mode liquid crystal panel, there is known an MVA (Multi-Domain Vertical Alignment) type panel in which protrusions are formed in the liquid crystal panel, thereby restricting the tilting direction of liquid crystal molecules. ing. However, according to this method, the lack of transmittance and contrast due to the protrusions is unavoidable, and there is a problem that the response speed of the liquid crystal molecules is slow.
Recently, a PSA (Polymer Sustained Alignment) mode has been proposed in order to solve such problems of the MVA type panel. The PSA mode is a polymerizable compound in a gap between a pair of substrates composed of a substrate with a patterned conductive film and a substrate with a conductive film having no pattern, or between a pair of substrates composed of two substrates with a patterned conductive film. An attempt is made to control the alignment direction of the liquid crystal by expressing a pretilt angle characteristic by irradiating ultraviolet rays in a state where a voltage is applied between the conductive films while sandwiching the liquid crystal composition containing the liquid crystal and polymerizing the polymerizable compound. Technology. According to this technology, it is possible to increase the viewing angle and speed up the liquid crystal molecule response by making the conductive film into a specific configuration, and also solve the problem of lack of transmittance and contrast that was inevitable in the MVA type panel. Is done. However, in order to polymerize the polymerizable compound, it is necessary to irradiate a large amount of ultraviolet light, for example, 100,000 J / m ^2. It becomes clear that the reactive compounds remain in the liquid crystal layer, which together cause display unevenness, adversely affect the voltage holding characteristics, or cause problems in the long-term reliability of the panel. Has not reached.

  On the other hand, Non-Patent Document 3 proposes a method using a liquid crystal alignment film formed from a polyimide liquid crystal aligning agent containing a reactive mesogen. According to Non-Patent Document 3, a liquid crystal display element including a liquid crystal alignment film formed by such a method is said to respond quickly to liquid crystal molecules. However, Non-Patent Document 3 does not provide any guidance on what kind of reactive mesogen should be used, and the amount of necessary UV irradiation is still large, and there are concerns regarding display characteristics, particularly voltage holding characteristics. Not wiped out.

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 JP 2002-250924 A JP 2004-83810 A Japanese Patent Laid-Open No. 9-21468 JP 2003-114437 A JP-A-5-107544

Chemical Reviews, Volume 95, p1409 (1995) T.A. J. et al. Scheffer et. al. J. et al. Appl. Phys. vo. 19, p2013 (1980) Y. -J. Lee et. al. , SID 09 DIGEST, p666 (2009)

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 applied 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 method for manufacturing a liquid crystal display device having excellent electrical characteristics and long-term reliability.
Further objects and advantages of the present invention will become apparent from the following description.

In accordance with the present invention, the above objects and advantages of the present invention are primarily as follows:
Following formula (1)

It is achieved by a liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane having a structure represented by:
The above liquid crystal aligning agent is preferably used for forming a liquid crystal alignment film of a liquid crystal display element having a known structure such as TN type, STN type, IPS type, VA type, etc. by a photo-alignment method with a small exposure amount. In addition, it can be used to manufacture a novel liquid crystal display element in which the problems of the MVA panel are solved.
Therefore, the above objects and advantages of the present invention are secondly,
The liquid crystal aligning agent is applied to form a coating film, which is achieved by a method of forming a liquid crystal alignment film through a step of irradiating the coating film with radiation,
On the conductive film of a pair of substrates having a conductive film, respectively, the liquid crystal aligning agent is applied to form a coating film,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to each other through a layer of liquid crystal molecules,
This is achieved by a method for manufacturing a liquid crystal display element, which includes a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between conductive films of the pair of substrates.

ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal aligning agent which can provide a pretilt angle by the photo-alignment method of a small exposure amount, and provides the liquid crystal aligning film excellent in the temporal stability of the provided pretilt angle is provided.
Since the liquid crystal display element provided with the liquid crystal aligning film formed from the liquid crystal aligning agent of the said invention is excellent in long-term reliability, it can be applied suitably for various display apparatuses.
In addition, the liquid crystal display element manufactured by the above-described method for manufacturing a liquid crystal display element of the present invention has a wide viewing angle, a high response speed of liquid crystal molecules, good electrical characteristics, sufficient transmittance and contrast, and display. In addition to being excellent in particular, the display characteristics are not impaired even when driven continuously for a long time.
Furthermore, according to the method of the present invention, the amount of light required for irradiation can be reduced, which contributes to a reduction in manufacturing costs of the liquid crystal alignment film and the liquid crystal display element.

It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell which has the patterned transparent conductive film manufactured in Example 42.

The liquid crystal aligning agent of this invention contains the radiation sensitive polyorganosiloxane which has a structure represented by the said Formula (1).
<Radiation sensitive polyorganosiloxane>
The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention has a structure represented by the above formula (1).
The content ratio of the structure represented by the above formula (1) in the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention is preferably 0.2 to 6 mmol / g-polymer. More preferably, it is 3-5 mmol / g-polymer.
The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention preferably further has an epoxy group in addition to the structure represented by the above formula (1). In this case, the epoxy equivalent of the radiation-sensitive polyorganosiloxane is preferably 150 g / mol or more, more preferably 200 to 10,000 g / mol, and further preferably 200 to 2,000 g / mol. By using an epoxy equivalent radiation-sensitive polyorganosiloxane at such a ratio, the liquid crystal aligning agent of the present invention is superior in liquid crystal aligning property without deteriorating the storage stability of the liquid crystal aligning agent, and the pretilt angle over time. A liquid crystal alignment film having excellent stability can be formed, which is preferable.
Regarding the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is preferably 500 to 1,000,000, and 1,000. More preferably, it is ˜100,000, and particularly preferably 2,000 to 50,000.

<Synthesis of radiation-sensitive polyorganosiloxane>
The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention may be synthesized by any method as long as it is as described above. Examples of the method for synthesizing the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention include a hydrolyzable silane compound having a structure represented by the above formula (1), or the hydrolyzable silane compound and others. Hydrolyzing and condensing a mixture of a hydrolyzable silane compound with
(A) a polyorganosiloxane having an epoxy group (hereinafter referred to as “polyorganosiloxane having an epoxy group (a)”);
(B) A compound having a structure and a carboxyl group represented by the above formula (1) or the following formula (2)

Or the like (hereinafter referred to as “compound (b)”).
Of these, the latter method is preferred from the viewpoints of ease of synthesis of the raw material compound, ease of reaction, and the like.
Hereinafter, the reaction method of the polyorganosiloxane (a) having an epoxy group and the compound (b), which is a preferred method for synthesizing the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, will be described. To do.
[Polyorganosiloxane having epoxy group (a)]
The epoxy group in the polyorganosiloxane (a) having an epoxy group is an ethylene oxide skeleton or a 1,2-epoxycycloalkane skeleton directly or via an alkylene which may be interrupted by an oxygen atom. It is preferably present in the polyorganosiloxane as contained in a group bonded to an atom (group having an epoxy group). Examples of the group having such an epoxy group include the following formula (X ¹ -1) or (X ¹ -2)

(In formulas (X ¹ -1) and (X ¹ -2), “*” indicates a bond, respectively.)
It is preferable that it is group represented by these.
The epoxy equivalent of the polyorganosiloxane (a) having an epoxy group is preferably 100 to 10,000 g / mol, more preferably 150 to 1,000 g / mol, and further 150 to 300 g / mol. preferable.
Regarding the polyorganosiloxane (a) having an epoxy group, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably 500 to 100,000, and preferably 1,000 to 10,000. More preferably, it is preferably 1,000 to 5,000.
Such polyorganosiloxane having an epoxy group is, 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. Can be synthesized by hydrolysis and condensation. Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 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 Corporation); 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) acryloxypropyltriethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltri Methoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane is preferred.
In synthesizing the polyorganosiloxane (a) having an epoxy group in the present invention, the proportion of the silane compound having an epoxy group and the other silane compound is used, and the epoxy equivalent of the obtained polyorganosiloxane (a) is as described above. It is preferable to prepare and set so as to be within a preferable range.

Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane (a) 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, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate;
Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;
Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl. Examples include ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like. Of these, water-insoluble ones are preferred.
These organic solvents can be used alone or in admixture of two or more.
The amount of the organic solvent used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total silane compounds.
The amount of water used in producing the polyorganosiloxane (a) having an epoxy group is preferably 0.5 to 100 times mol, more preferably 1 to 30 times mol, based on the total silane compound. .

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. can be used, for example.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; 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 the polyorganosiloxane (a) 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 (a) can be obtained at a high hydrolysis / condensation rate without causing side reactions such as ring opening of an epoxy group. It is preferable because it is excellent in production stability. The liquid crystal aligning agent of the present invention containing a reaction product of a polyorganosiloxane (a) having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and the compound (b) has storage stability. It is convenient because it is extremely excellent. The reason for this is that, as pointed out in Non-Patent Document 1 (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 the polyorganosiloxane has a small content of silanol groups, the liquid crystal aligning agent of the present invention containing the radiation-sensitive polyorganosiloxane obtained from the polyorganosiloxane (a) having such an epoxy group is In the case where the condensation reaction between silanol groups between the radiation-sensitive polyorganosiloxanes is suppressed, and the liquid crystal aligning agent of the present invention contains other polymers described later, the silanol groups of the radiation-sensitive polyorganosiloxanes It is surmised that the condensation reaction between the polymer and other polymers is suppressed, resulting in excellent storage stability.
As the catalyst, an organic base is particularly preferable. The amount of the organic base used varies depending on the reaction conditions such as the type of organic base, temperature, and the like, and should be set as appropriate. More preferably, it is 0.05-1 times mole.

In the hydrolysis and condensation reaction in producing the polyorganosiloxane (a) having an epoxy group, a silane compound having an epoxy group and, if necessary, another silane compound are dissolved in an organic solvent, and this solution is dissolved 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 preferable because the washing operation becomes easy. 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 (a) 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, EMS-32 (manufactured by Chisso Corporation).

<Compound (b)>
The compound (b) used in the present invention is a compound having a structure and a carboxyl group represented by the above formula (1) or a compound having a group represented by the above formula (2). When the compound (b) is a compound having a structure represented by the above formula (1) and a carboxyl group, the carboxyl group possessed by the compound (b) is on the left or right side with respect to the structure represented by the above formula (1) May be.
As the compound (b) used in the present invention, the following formula (3) or (4)

(R ¹ in Formula (3) is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a monovalent group having 3 to 40 carbon atoms including an alicyclic group. R ² is a single bond, an oxygen atom, a sulfur atom, ^* —COO—, ^* —COS—, ^* —SCO— or ^* —OCO— (in the above, a bond marked with “*”) There binds to R ^1.) a and, if R ³ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group properly divalent condensed cyclic group, or A divalent group having a structure in which a heterocycle and an aromatic ring are condensed or a divalent group having a structure in which a heterocycle and an alicyclic ring are condensed, and R ⁴ is a single bond, an oxygen atom, a sulfur atom, ^* − COO-, ^* -COS-, ^* -SCO- or ^* -OCO- (in the above, the bonding hand marked with "*" A bind ^{R 3.),} R ⁵ is a fluorine atom or a cyano group, a is an integer of 0 to 3, b is an integer from 0 to 4,
R ⁶ in Formula (4) is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a monovalent monovalent having 3 to 40 carbon atoms including an alicyclic group. An organic group, R ⁷ is an oxygen atom or a divalent aromatic group, and R ⁸ is an oxygen atom, —COO— ^* or —OCO— ^* (in the above, the bond marked with “*” is R binds ^9.), and, R ⁹ is a divalent aromatic group, a divalent alicyclic group, a divalent or heterocyclic group is properly divalent condensed cyclic group, or a heterocyclic Is a divalent group having a structure in which an aromatic ring is condensed or a divalent group having a structure in which a heterocyclic ring and an alicyclic ring are condensed, and R ¹⁰ is a single bond, —OCO— (CH ₂ ) _e — ^*. or ^{_{-O- (CH 2) f - *}} ( except at least a bond marked with "*" is bonded to the carboxyl group. And with the proviso e and f represents an integer of 1 to 10, ^{respectively, R 11} 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.

Examples of the alkyl group having 1 to 40 carbon atoms of ^{R 1} in the formula (3) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 4 to 20 carbon atoms. Examples of such preferable 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, and 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.
The fluoroalkyl group of 1 to 40 carbon atoms in R ^1, preferably a fluoroalkyl group having 1 to 20 carbon atoms, more preferably a fluoroalkyl group having 4 to 20 carbon atoms. Examples of such preferred fluoroalkyl groups include 4,4,4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl group, 4,4,5,5,6,6, for example. , 6-heptafluorohexyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoro A propyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorooctyl) ethyl group, 2- (perfluorodecyl) ethyl group and the like can be mentioned.
The monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group R ^1, may include, for example Koresuteniru group, cholestanyl group, an adamantyl group.
R ² is a single bond, an oxygen atom, or ^* —COO— (where a bond marked with “*” is bonded to R ¹ );
R ⁴ is preferably a single bond, an oxygen atom or ^* —COO— (wherein a bond marked with “*” is bonded to R ³ ).
Examples of the divalent aromatic group for R ³ include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6- A tetrafluoro-1,4-phenylene group or the like;
Examples of the divalent alicyclic group for R ³ include a 1,4-cyclohexylene group;
Examples of the divalent heterocyclic group represented by R ³ include 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furylene group,

(In the above formula, a bond marked with “*” is bonded to R ^4. )
A group represented by:
Examples of the divalent condensed cyclic group represented by R ³ include a naphthylene group.
Examples of the divalent group having a structure in which a heterocycle of R ³ and an aromatic ring are condensed include the following formulas:

(In the above formula, a bond marked with “*” is bonded to R ^4. )
A group represented by:
Examples of the divalent group having a structure in which the heterocyclic ring of R ³ and the alicyclic ring are condensed include the following formulas:

(In the above formula, a bond marked with “*” is bonded to R ^4. )
The group etc. which are represented by each can be mentioned.
A in formula (3) is 0 or 1;
b is preferably 0.
More specific examples of the compound represented by the above formula (3) include, for example, the following formulas (3-1) to (3-19):

(In the above formula, each R ¹ has the same meaning as in the above formula (3).)
The compound etc. which are represented by each of these can be mentioned.
The compound represented by the above formula (3) can be synthesized by appropriately combining organic chemistry methods. For example, the compound represented by the above formula (3-2) is represented by the following scheme 1.

(In the above formula, R ¹ has the same meaning as in the above formula (3), and X is a halogen atom.)
As shown in the above, it can be synthesized by reacting a halogenated aryl compound having a desired group R ¹ and propionic acid in the presence of a palladium catalyst, cuprous chloride and an amine compound. This reaction is what is referred to by those skilled in the art as “Sonogashira coupling”.
In the above formula (4), the monovalent organic group having 3 to 40 carbon atoms including the alkyl group having 1 to 40 carbon atoms, the fluoroalkyl group having 1 to 40 carbon atoms, and the alicyclic group represented by R ⁶ , respectively, The same as described above for R ¹ in the above formula (3).
R ⁷ is a single bond;
c must be 0;
R ¹⁰ is preferably —OCO— (CH ₂ ) _e − ^* (where e is an integer of 1 to 10, and a bond marked with “*” is bonded to a carboxyl group).
As a more specific example of the compound represented by the above formula (4), for example, the following formula (4-1)

(In the above formula, R ⁶ has the same meaning as in the above formula (4), and e is an integer of 1 to 10.)
The compound etc. which are represented by these can be mentioned. This e is preferably 2 or 3.
The compound represented by the above formula (4) can be synthesized by appropriately combining organic chemistry methods. For example, in the above formula (4-1), in the case where e is 2 or 3, ring-opening addition of succinic anhydride (when e = 2) or glutaric anhydride (when e = 3) to 4-bromophenol This intermediate can be synthesized, and a propiolic acid ester having the desired group R ⁶ can be obtained by Sonogashira coupling.

[Synthesis of radiation-sensitive polyorganosiloxane]
The radiation-sensitive polyorganosiloxane used in the present invention can be synthesized by reacting the polyorganosiloxane (a) having an epoxy group as described above with the compound (b), preferably in the presence of a catalyst. it can.
Here, the compound (b) is preferably used in an amount of 0.001 to 10 mol, more preferably 0.01 to 5 mol, still more preferably 0.05 to 2 mol based on 1 mol of the epoxy group of the polyorganosiloxane. The
In the present invention, a part of the compound (b) is represented by the following formula (5) as long as the effects of the present invention are not impaired.
R ¹² -R ¹³ -COOH (5)
(In formula (5), is R ¹² an alkyl group having 4 to 20 carbon atoms, an alkoxyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, or a fluoroalkoxyl group having 4 to 20 carbon atoms? Or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, R ¹³ is a single bond or a phenylene group, provided that when R ¹² is an alkoxyl group, R ¹³ is a phenylene group. )
It may be used by replacing with a compound represented by In this case, the radiation-sensitive polyorganosiloxane is synthesized by reacting the polyorganosiloxane (a) having an epoxy group with the compound (b) and a mixture of the compounds represented by the above formula (5). .
R ¹² 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 ¹³ is a single bond, A 4-cyclohexylene group or a 1,4-phenylene group is preferred.
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.)
The compound represented by either of these can be mentioned, Among these, following formula (5-3-1)-(5-3-3)

The compound represented by either is preferable.
The compound represented by the above formula (5) is a compound that reacts with the polyorganosiloxane (a) having an epoxy group together with the compound (b) and becomes a site that imparts pretilt angle expression to the obtained liquid crystal alignment film. is there. In the present specification, the compound represented by the formula (5) is hereinafter referred to as “another pretilt angle developing compound”.
In the present invention, when another pretilt angle-expressing compound is used together with the compound (b), the total use ratio of the compound (b) and the other pretilt angle-expressing compound is the polyorganosiloxane having an epoxy group (a ) Is preferably 0.001 to 1.5 mol, more preferably 0.01 to 1 mol, and still more preferably 0.05 to 0.9 mol, relative to 1 mol of the epoxy group possessed by). In this case, another 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 compound (b). If the proportion of other pretilt angle-expressing compounds exceeds 50 mol%, there may be a problem that abnormal domains occur 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 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 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 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 (a) having an epoxy group. used.
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 radiation-sensitive polyorganosiloxane can be carried out 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.
In the radiation-sensitive polyorganosiloxane of the present invention, a structure derived from the compound (b) is introduced into the polyorganosiloxane (a) having an epoxy group by ring-opening addition of epoxy. This production method is simple and is a very suitable method in that the introduction rate of the structure derived from the compound (b) can be increased.

<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, and a surfactant.
[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 polyorganosiloxanes other than the radiation-sensitive polyorganosiloxane (hereinafter referred to as “other polyorganosiloxanes”). .), Polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, 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 and the above formulas (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 diamines that can be used for the synthesis of 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, 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 (4-a Nophenoxy) 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'-diaminobipheny 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-Calconyloxy) hexyloxy (2,4-diaminobenzene), 6- (4′-fluoro-4-chalconyloxy) hexyloxy (2,4-diaminobenzene), 8- (4- Calconyloxy) octyloxy (2,4-diaminobenzene), 8- (4′-fluoro-4-calconyloxy) octyloxy (2,4-diaminobenzene), 1-dodecyloxy-2,4-diamino Benzene, 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, Decyloxy (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) stearylate , (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 diaminoorganosiloxane 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) Can be mentioned.
These diamines can be used alone or in combination of two or more.

The ratio of the tetracarboxylic dianhydride and the diamine compound used in the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.001 with respect 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 carried out in an organic solvent, preferably at a temperature of −20 to 150 ° C., more preferably at 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, etc. 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 to form polyimide, the reaction solution may be subjected to dehydration and cyclization reaction as it is, 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.
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. In addition, a method of dissolving this polyamic acid in an organic solvent again and then precipitating with a poor solvent, or a step in which a polyamic acid is again dissolved in an organic solvent, and the solution is washed and then distilled off under reduced pressure with an evaporator. The polyamic acid can be purified by a method performed once or several times.

{Polyimide}
The polyimide can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid obtained as described above. At this time, all of the amic acid structure may be dehydrated and 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 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. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of a 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. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents 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 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 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 closure catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. The isolation and purification of the polyimide can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

{Other polyorganosiloxanes}
The other polyorganosiloxane in the present invention is a polyorganosiloxane other than the above-mentioned radiation-sensitive polyorganosiloxane. 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. In which it can be synthesized by hydrolysis and condensation in the presence of water and a catalyst. Examples of the raw material silane compound that can be used here include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert- Butoxysilane, tetrachlorosilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane , Methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxy Lan, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; dimethyldimethoxysilane, dimethyldiethoxysilane, Dimethyldichlorosilane;
Examples thereof include trimethylmethoxysilane, trimethylethoxysilane, and trimethylchlorosilane. Among these, preferable raw material silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane and Mention may be made of trimethylethoxysilane.

Other polyorganosiloxanes in the present invention can be synthesized in the same manner as described above as a method for synthesizing the polyorganosiloxane (a) having an epoxy group, except that the raw material silane compound as described above is used.
For other polyorganosiloxanes, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably 100 to 100,000, and more preferably 500 to 20,000.

{Use ratio of other polymers}
When the liquid crystal aligning agent of the present invention contains another polymer together with the aforementioned radiation-sensitive polyorganosiloxane, the content 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 content of the other polymer varies depending on the type of the other polymer.
In the case where the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation-sensitive polyorganosiloxane 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 this invention contains another polymer with radiation sensitive polyorganosiloxane, as a kind of other polymer, at least 1 sort (s) selected from the group which consists of a polyamic acid and a polyimide. It is preferable that the polymer or other polyorganosiloxane.

[Curing agent and curing catalyst]
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 accelerates the curing reaction controlled by the curing agent. Therefore, it can be contained in the liquid crystal aligning agent of the present invention.
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. An acid anhydride and polyhydric carboxylic acid can be illustrated.
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 (7)

(In Formula (7), 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.

[Epoxy compound]
The said epoxy compound can be contained in the liquid crystal aligning agent of this invention from a viewpoint which improves 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 100 parts by weight with respect to the total of 100 parts by weight of the above-mentioned radiation-sensitive polyorganosiloxane and other polymers 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.

[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 In addition, JP-A Is described in 3-291922 JP include a reaction product of a silane compound having a tetracarboxylic dianhydride and an amino group.
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.

<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. 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, the synthesis of polyamic acid is preferable. 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 preferable 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 organic solvents according to the presence or absence of other polymers and their types, The components contained in the liquid crystal aligning agent do not precipitate at the preferred 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 alignment 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 alignment 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 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 for preparing the liquid crystal aligning agent of the present invention is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 40 ° C.

The liquid crystal aligning agent of the present invention obtained as described above forms a liquid crystal alignment film of a liquid crystal display element having a known structure such as a TN type, STN type, IPS type, VA type, etc. by a photo-alignment method with a small exposure amount. In addition to being able to be used suitably, it can be used for manufacturing a novel liquid crystal display element in which the problems of the MVA panel are solved.
Hereinafter, a method for forming a liquid crystal alignment film performed using the liquid crystal alignment agent of the present invention, a method for manufacturing a liquid crystal display element including the liquid crystal alignment film, and a novel liquid crystal display element performed using the liquid crystal alignment agent of the present invention A manufacturing method is demonstrated in order.

<Method for forming liquid crystal alignment film>
Examples of the method for forming the liquid crystal alignment film include a method of forming a coating film of the liquid crystal alignment film of the present invention on a substrate and then irradiating the coating film with radiation.
When the liquid crystal aligning agent of the present invention is applied to a TN type, STN type, or VA type, two substrates provided with a patterned transparent conductive film are used as a pair. On the other hand, when the liquid crystal aligning agent of the present invention is applied to the IPS type, a pair of a substrate provided with a transparent conductive film having a comb-like pattern and a substrate not having a conductive film are used.
First, the liquid crystal aligning agent of the present invention is applied to one side of a transparent conductive film side of a substrate provided with a transparent conductive film or a substrate having no conductive film, for example, a roll coater method, a spinner method, a printing method, an inkjet method, etc. Application is performed by an appropriate application 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. In order to obtain a patterned transparent conductive film, 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 or the like is previously applied on the substrate and the transparent conductive film. Also good.
Next, the coating film is irradiated with linearly polarized light, partially polarized radiation, or non-polarized radiation to impart liquid crystal alignment ability. 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.

<Method for Producing Liquid Crystal Display Device Comprising the Liquid Crystal Alignment Film>
A liquid crystal display device comprising a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention can be produced, for example, as follows.
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 injection by heating the liquid crystal cell to a temperature at which the liquid crystal used has an isotropic phase and then slowly 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, STN type or IPS 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 VA 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, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. In the case of a TN type liquid crystal cell, STN type liquid crystal cell or IPS type liquid crystal cell, those having positive dielectric anisotropy forming a nematic type liquid crystal are preferable. For example, biphenyl type liquid crystal, phenyl cyclohexane type liquid crystal, ester type liquid crystal, Phenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like are used. Further, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate; chiral agents such as those commercially available as trade names “C-15” and “CB-15” (manufactured by 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 VA type liquid crystal cell, those having negative dielectric anisotropy forming a nematic type liquid crystal are preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal Phenylcyclohexane-based liquid crystal 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 properties such as display characteristics and reliability.

<Method for manufacturing novel liquid crystal display element>
A method for producing a novel liquid crystal display element performed using the liquid crystal aligning agent of the present invention,
A coating film is formed by applying the liquid crystal aligning agent of the present invention as described above on the conductive film of the pair of substrates having the conductive film,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to each other through a layer of liquid crystal molecules,
A step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates is characterized.
Here, the substrate used is the same as that of the liquid crystal display device including the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention as described above.
As the conductive film, a transparent conductive film is preferably used. For example, a NESA film made of SnO ₂ or an ITO film made of In ₂ O ₃ —SnO ₂ can be used. Each of the conductive films is preferably a patterned conductive film partitioned into a plurality of regions. With such a conductive film configuration, when a voltage is applied between the conductive films (described later), the direction of the pretilt angle of the liquid crystal molecules can be changed for each region by applying a different voltage for each region. This makes it possible to further widen the viewing angle characteristics.
Regarding the method of applying a liquid crystal aligning agent on the conductive film of the substrate, pre-baking and post-baking after coating, and the film thickness of the coating film after post-baking, the liquid crystal aligning film formed from the liquid crystal aligning agent of the present invention described above It is the same as that of the case of the liquid crystal display element which comprises.

The coating film thus formed may be used as it is for the production of a liquid crystal cell in the next step, or may be subjected to a rubbing treatment on the coating surface as necessary prior to the production of the liquid crystal cell. This rubbing treatment can be performed by rubbing the coating surface with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton. Here, as described in Patent Document 17 (Japanese Patent Application Laid-Open No. 5-107544), a resist film is formed on a part of the coating surface after once rubbing, and is different from the previous rubbing. By performing a process of removing the resist film after performing the rubbing process in the direction and setting the rubbing direction to be different for each region, it is possible to further improve the visual field characteristics of the obtained liquid crystal display element.
Next, a liquid crystal cell having a configuration in which the coating film of the pair of substrates on which the coating film is formed is disposed to face each other through a layer of liquid crystal molecules is formed.
The liquid crystal molecules used here are preferably nematic liquid crystals having negative dielectric anisotropy, such as dicyanobenzene liquid crystals, pyridazine liquid crystals, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals. Etc. can be used. The thickness of the liquid crystal molecule layer is preferably 1 to 5 μm.
A method for forming a liquid crystal cell using such a liquid crystal is the same as in the case of a liquid crystal display element having a liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention.

Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.
The voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
As light to irradiate, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light having a wavelength of 300 to 400 nm is preferable. As a light source of irradiation light, 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 amount of light irradiation is preferably 1,000 J / m ² or more and less than 100,000 J / m ² , more preferably 1,000 to 50,000 J / m ² . In the manufacture of a conventionally known PSA mode liquid crystal display element, it was necessary to irradiate light of about 100,000 J / m ^{2. In} the method of the present invention, the amount of light irradiation was set to 50,000 J / M ² or less, and even if it is 10,000 J / m ² or less, a desired liquid crystal display element can be obtained, which contributes to a reduction in manufacturing cost of the liquid crystal display element and is caused by irradiation with strong light. It is possible to avoid deterioration of electrical characteristics and long-term reliability.
And a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after performing the above-mentioned treatment. Examples of the polarizing plate used here include a polarizing plate in which an H film is sandwiched between cellulose acetate protective films, or a polarizing plate made of the H film itself.
The liquid crystal display device manufactured as described above has a wide viewing angle, an extremely fast response speed of liquid crystal molecules, excellent both in display characteristics and long-term reliability, and at a low cost with reduced manufacturing costs. Therefore, it can be suitably applied to various uses.

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 is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Corporation, 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.
In the following examples, the necessary amounts in the examples were ensured by repeating the synthesis of the raw material compound and the polymer as necessary on the following synthesis scale.
<Synthesis of Compound (b)>
Example 1 (Synthesis of Compound (3-2-1))
Scheme 2 below

Thus, compound (3-2-1) was synthesized.
[Synthesis of Compound (3-2-1-1)]
In a 1 L eggplant flask, 99 g of 4-iodophenol, 124 g of potassium carbonate and 585 mL of N, N-dimethylacetamide were charged and stirred at room temperature for 30 minutes, and then 96 g of 4,4,4-trifluoro-iodobutane was added thereto. The reaction was further carried out at room temperature with stirring for 6 hours. After completion of the reaction, 1.8 L of hexane was added to the reaction mixture, and then washed with water, once with 1 mol / L sodium hydroxide aqueous solution, and once with water, and then concentrated, The crude product obtained by drying was recrystallized from ethanol to obtain 81 g of a light brown compound (3-2-1-1).
[Synthesis of Compound (3-2-1)]
In a 1 L three-necked flask equipped with a nitrogen introduction tube and a thermometer, 66 g of the compound (3-2-1-1) obtained above, 12.2 mL of propiolic acid, 70 mL of diisopropylamine, 2.8 g of bistriphenylphosphine palladium diacetate Then, 1.54 g of copper (I) iodide and 200 mL of N, N-dimethylformamide were charged, and the reaction was performed at room temperature for 1 hour. After completion of the reaction, the organic layer obtained by adding 1 L of ethyl acetate to the reaction mixture was washed with dilute hydrochloric acid and water, dried over magnesium sulfate, and concentrated to dryness. By purifying the obtained solid with a silica column using ethyl acetate and hexane as a developing solvent, the solvent was distilled off to obtain 18 g of a brown powder of the compound (3-2-1).

<Synthesis of polyorganosiloxane (a) having an 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 with. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and then the reaction was performed 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% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to give a polyorgano having an epoxy group. 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 the chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction of the epoxy group occurred.
Mw of this polyorganosiloxane EPS-1 having an epoxy group was 2,200, and the epoxy equivalent was 186.

<Synthesis of radiation-sensitive polyorganosiloxane>
Example 2
In a 200 mL three-necked flask, 6.3 g of polyorganosiloxane EPS-1 having an epoxy group obtained in Synthesis Example 1 above, 60 g of methyl isobutyl ketone, 18 g of Compound (3-2-1) obtained in Example 1 above, and Tetrabutylammonium bromide (0.6 g) was charged and reacted at 80 ° C. with stirring for 12 hours. After completion of the reaction, reprecipitation is performed with hexane, and the precipitate is dissolved in ethyl acetate to obtain a solution. The solution is washed with water three times, and then the solvent is distilled off to remove the radiation-sensitive polyorganosiloxane S-1. Was obtained as a brown powder. The weight average molecular weight Mw of the radiation sensitive polyorganosiloxane S-1 was 9,900.
Example 3
In a 200 mL three-necked flask, 6.3 g of polyorganosiloxane EPS-1 having an epoxy group obtained in Synthesis Example 1 above, 60 g of methyl isobutyl ketone, 18 g of Compound (3-2-1) obtained in Example 1 above, 2.0 g of stearic acid and 0.6 g of tetrabutylammonium bromide were charged, and the reaction was performed at 80 ° C. with stirring for 12 hours. After completion of the reaction, reprecipitation is performed with hexane, and the precipitate is dissolved in ethyl acetate to obtain a solution. The solution is washed with water three times, and then the solvent is distilled off to remove the radiation-sensitive polyorganosiloxane S-2. Was obtained as a brown powder. The weight average molecular weight Mw of the radiation sensitive polyorganosiloxane S-2 was 10,200.

<Synthesis of other polymers>
[Synthesis of polyamic acid]
Synthesis example PA-1
Pyromellitic dianhydride 109 g (0.50 mol) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) as tetracarboxylic dianhydride and 4,4- as diamine By dissolving 200 g (1.0 mol) of diaminodiphenyl ether in 2,290 g of N-methyl-2-pyrrolidone and reacting at 40 ° C. for 3 hours, 1,350 g of N-methyl-2-pyrrolidone was added. About 4,000 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 -Dissolve 198 g (1.0 mol) of diaminodiphenylmethane in 2,290 g of N-methyl-2-pyrrolidone, react at 40 ° C. for 3 hours, and then add 1,350 g of N-methyl-2-pyrrolidone. As a result, about 4,000 g of 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 were added to N-methyl. After dissolving in 2,246 g of 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. About 3,950 g of 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, .2) of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine. 0 mol) was dissolved in 4,050 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours to obtain 3,700 g of a solution containing 10% by weight of polyamic acid (PA-4). The solution viscosity of this polyamic acid solution was 170 mPa · s.

Synthesis example PA-5
224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 200 g (1.0 mol) of 4,4′-diaminodiphenyl ether as diamine were added to N-methyl-2 -Dissolved in 2,404 g of pyrrolidone and reacted at 40 ° C. for 4 hours to obtain about 2,800 g of a solution containing 15% by weight of polyamic acid (PA-5).
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 polymer concentration of 10% by weight was 190 mPa · s.
Synthesis example PA-6
22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 14.23 g (0.1 mol) of cyclohexanebis (methylamine) were added to 299.3 g of N-methyl-2-pyrrolidone. And reacted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 32 g of polyamic acid PA-6.
Synthesis example PA-7
Cyclobutanetetracarboxylic dianhydride 19.61 g (0.1 mol) and 4,4′-diamino-2,2′-dimethylbiphenyl 21.23 g (0.1 mol) were combined with N-methyl-2-pyrrolidone 367. Then, the reaction was carried out at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 35 g of polyamic acid PA-7.

[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 95 g (0.88 mol) of p-phenylenediamine as diamine, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl 32 g (0.10 mol), 3,6-bis (4-aminobenzoyloxy) cholestane 6.4 g (0.010 mol) and 4.0 g (0.015 mol) of octadecanoxy-2,5-diaminobenzene was dissolved in 960 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 9 hours. . A small amount of the obtained polyamic acid solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer 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 is replaced with new N-methyl-2-pyrrolidone (by this operation, pyridine and acetic anhydride used in the dehydration cyclization reaction are removed from the system. The same shall apply 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, and after removing the solvent under reduced pressure, the solution viscosity measured as a solution having a polymer concentration of 8.0% by weight dissolved in N-methyl-2-pyrrolidone was 33 mPa · s. .

Synthesis example PI-2
112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro -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 diamine, bisamino 25 g (0.10 mol) of propyltetramethyldisiloxane and 13 g (0.020 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane and 8.1 g (0.030 mol) of N-octadecylamine as monoamine The product 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 taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 60 mPa · s.
Next, 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-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain about 2,400 g of a solution containing 15% by weight of polyimide (PI-2) having an imidation ratio of about 95%. Got.
A small amount of this polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 6.0% by weight 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- 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 solution containing 10% by weight of polyamic acid. Obtained. The solution viscosity of this polyamic acid was 260 mPa · s.
Next, 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 was replaced with new N-methyl-2-pyrrolidone, whereby about 3% of a solution containing 9.0% by weight of polyimide (PI-3) having an imidization ratio of about 89% , 500 g was obtained.
A small amount of this polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 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 diamine, 4 , 4′-Diamino-2,2′-bis (trifluoromethyl) biphenyl 32 g (0.10 mol), 1- (3,5-diaminobenzoyloxy) -4- (4-trifluoromethylbenzoyloxy)- 25 g (0.059 mol) of cyclohexane and 4.0 g (0.011 mol) of octadecanoxy-2,5-diaminobenzene were added to N-methyl-2-pyrrole. It was dissolved in Don 2,175G, by carrying out the reaction for 6 hours at 60 ° C., to obtain a solution containing a polyamic acid. 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 polymer concentration of 10% by weight. The solution viscosity was 110 mPa · s.
To 1,500 g of the obtained polyamic acid solution, 3,000 g of N-methyl-2-pyrrolidone was added, 221 g of pyridine and 228 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, whereby about 4,000 g of a solution containing 10% by weight of polyimide (PI-4) having an imidization ratio of about 92%. Got.
A small amount of this polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 4.5% by weight was 28 mPa · s.

Synthesis example PI-5
1,9.9 g (0.089 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 6.8 g (0.063 mol) of p-phenylenediamine as diamine, 4,4 ′ -3.6 g (0.018 mol) of diaminodiphenylmethane and the following formula (D-6)

4.7 g (0.009 mol) of the compound 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 resulting polyamic acid solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 115 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 14 g of pyridine and 18 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, whereby about 220 g of a solution containing 15.4% by weight of polyimide (PI-5) having an imidation ratio of about 77% Got.
A small amount of this polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 84 mPa · s.

Synthesis example PI-6
As tetracarboxylic dianhydride, 20.9 g (0.093 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 9.2 g (0.085 mol) of p-phenylenediamine as diamine and the above formula ( A solution containing polyamic acid is obtained by dissolving 4.9 g (0.009 mol) of the compound represented by D-6) in 140 g of N-methyl-2-pyrrolidone and reacting at 60 ° C. for 4 hours. It was. 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 polymer concentration of 10% by weight. As a result, it was 126 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 7.4 g of pyridine and 9.5 g of acetic anhydride were added, and dehydration ring closure 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, whereby about 220 g of a solution containing 16.1% by weight of polyimide (PI-6) having an imidation ratio of about 54% Got.
A small amount of this polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 75 mPa · s.

Synthesis example PI-7
1,8.8 g (0.084 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 7.4 g (0.068 mol) of p-phenylenediamine as diamine and the above formula (D The compound represented by -6) is dissolved in 140 g of N-methyl-2-pyrrolidone in 8.9 g (0.017 mol) and reacted at 60 ° C. for 4 hours to obtain a solution containing polyacic acid. It was. 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 polymer concentration of 10% by weight. As a result, it was 126 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 6.6 g of pyridine and 8.5 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, whereby about 210 g of a solution containing about 15.9% by weight of polyimide (PI-7) having an imidation ratio of about 55% Got.
A small amount of this polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 75 mPa · s.

Synthesis example PI-8
2,3,5-tricarboxycyclopentylacetic acid dianhydride 19.1 g (0.085 mol) as tetracarboxylic dianhydride and 7.4 g (0.069 mol) p-phenylenediamine as diamine and the following formula (D -7)

A compound containing polyamic acid was obtained by dissolving 8.5 g (0.017 mol) of the compound represented by formula (I) in 140 g of N-methyl-2-pyrrolidone and reacting 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 was measured as a solution having a polymer concentration of 10% by weight. As a result, it was 206 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 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. About 200 g of a solution containing about 15.8% by weight of polyimide (PI-8) having an imidation ratio of about 52% is obtained by replacing the solvent in the system with new N-methyl-2-pyrrolidone after the dehydration ring-closing reaction. Got.
A small amount of this polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight was 105 mPa · s.

Synthesis example PI-9
As tetracarboxylic dianhydride, 17.3 g (0.077 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 5.9 g (0.054 mol) of p-phenylenediamine as diamine, the above formula ( 4.1 g (0.008 mol) of the compound represented by D-6) and 7.7 g (0.016 mol) of the compound represented by the above formula (D-7) were converted 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 taken, N-methyl-2-pyrrolidone was added, and the solution viscosity was measured as a solution having a polymer concentration of 10% by weight. As a result, it was 117 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 6.1 g of pyridine and 7.9 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, whereby about 210 g of a solution containing 15.4% by weight of polyimide (PI-9) having an imidation ratio of about 55% Got.
A small amount of this polyimide solution was taken, and N-methyl-2-pyrrolidone was added to measure the viscosity of the solution as a solution having a polymer concentration of 10% by weight of 109 mPa · s.

[Synthesis of other polysiloxanes]
Synthesis example PS-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. A maleic anhydride aqueous solution prepared by dissolving 0.26 g of maleic anhydride in 10.8 g of water prepared in another flask having a capacity of 20 mL was added thereto, and the reaction was performed by heating and stirring at 60 ° C. for further 4 hours. The solvent was distilled off from the resulting reaction mixture, 1-ethoxy-2-propanol was added, and the mixture was concentrated again to obtain a polymer solution containing 10% by weight of polyorganosiloxane PS-1. The weight average molecular weight Mw of PS-1 was 5,100.

<Preparation of liquid crystal aligning agent>
Example 4
As another polymer, an amount corresponding to 1,000 parts by weight in terms of polyamic acid PA-1 in a solution containing polyamic acid PA-1 obtained in Synthesis Example PA-1 was taken. 100 parts by weight of the radiation-sensitive polyorganosiloxane S-1 obtained in Step 2 was added, and N-methyl-2-pyrrolidone and butyl cellosolve were further added. The solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50. (Weight ratio) and a solid content concentration of 3.0% by weight.
Liquid crystal aligning agent A-1 was prepared by filtering this solution with a filter having a pore diameter of 1 μm.
This liquid crystal aligning agent A-1 was stored at -15 degreeC for 6 months. The viscosity was measured with an E-type viscometer at 25 ° C. before and after storage. When the change rate of the viscosity of the solution before and after storage was less than 10%, the storage stability was “good” and when it was 10% or more was evaluated as the storage stability “bad”. The storage stability was “good”.
Examples 5-8, 10-14 and 17-21
Liquid crystal aligning agents A-2 to A-5, A- are the same as in Example 4 except that the type of radiation-sensitive polyorganosiloxane and the type and amount of other polymers are as shown in Table 1. 7-A-11 and A-14-A-18 were prepared respectively.
With respect to these liquid crystal aligning agents, the storage stability was evaluated in the same manner as in Example 4. The evaluation results are shown in Table 1.

Example 9
In a mixed solvent consisting of N-methyl-2-pyrrolidone and butyl cellosolve, 100 parts by weight of the radiation-sensitive polyorganosiloxane S-1 obtained in Example 2 above, and the above Synthesis Example PA-6 as another polymer A solution having 1,000 parts by weight of the obtained polyamic acid PA-6 dissolved therein, a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio), and a solid content concentration of 3.0% by weight It was.
This solution was filtered with a filter having a pore diameter of 1 μm to prepare a liquid crystal aligning agent A-6.
The storage stability of this liquid crystal aligning agent was evaluated in the same manner as in Example 4. The evaluation results are shown in Table 1.
Examples 15 and 16
Liquid crystal aligning agents A-12 and A-13 were respectively prepared in the same manner as in Example 9 except that the types and amounts of other polymers were as shown in Table 1.
With respect to these liquid crystal aligning agents, the storage stability was evaluated in the same manner as in Example 4. The evaluation results are shown in Table 1.
Example 22
As another polymer, an amount corresponding to 2,000 parts by weight in terms of PS-1 of a solution containing the other polyorganosiloxane PS-1 obtained in Synthesis Example PS-1 was taken. 100 parts by weight of the radiation-sensitive polyorganosiloxane S-1 obtained in Example 2 was added, and 1-ethoxy-2-propanol was further added to obtain a solution having a solid content concentration of 4.0% by weight.
Liquid crystal aligning agent A-19 was prepared by filtering this solution with a filter with a pore diameter of 1 μm.
The storage stability of this liquid crystal aligning agent was evaluated in the same manner as in Example 4. The evaluation results are shown in Table 1.

<Formation of liquid crystal alignment film and production and evaluation of liquid crystal display element>
Example 23
On the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film, the liquid crystal aligning agent A-1 prepared in Example 4 was applied using a spinner, and prebaked on an 80 ° C. hot plate for 1 minute. Then, it heated at 200 degreeC for 1 hour in the oven which substituted the inside with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. 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 ultraviolet optical axis 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 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 2.
(1) Evaluation of liquid crystal orientation For the liquid crystal display device manufactured above, the presence or absence of an abnormal domain in the change in brightness when a voltage of 5 V is turned ON / OFF (applied / released) is observed with an optical microscope. The case where there was no “good”.
(2) Evaluation of pretilt angle The liquid crystal display device manufactured above is subjected to the method described in Non-Patent Document 2 (T. J. 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 After applying a voltage of 5 V to the liquid crystal display element manufactured above with an application time of 60 microseconds and a span of 167 milliseconds, the voltage holding ratio after 167 milliseconds from the release of application is obtained. It was measured. As a measuring device, “VHR-1” manufactured by Toyo Corporation was used.
(4) Evaluation of burn-in The liquid crystal display element manufactured above was applied with a 30 Hz, 3 V rectangular wave superimposed with a direct current of 5 V at an ambient temperature of 70 ° C. for 2 hours, and remained in the liquid crystal cell immediately after the DC voltage was turned off. The residual DC voltage was determined by the flicker elimination method.
(5) 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 stage was less than 1 ° C., the pretilt angle stability was determined to be “good”.
Examples 24-41
As the liquid crystal aligning agent, a liquid crystal aligning film was formed in the same manner as in Example 23 except that liquid crystal aligning agents of the type shown in Table 2 were used. The results are shown in Table 2.

Example 42
<Manufacture of liquid crystal cells>
Using the liquid crystal aligning agent A-1 prepared in Example 4 above, the pattern of the transparent electrode (2 types) and the amount of ultraviolet irradiation (3 levels) were changed as follows to obtain a total of 6 liquid crystal display elements. Manufactured and evaluated.
[Manufacture of liquid crystal cell having transparent electrode without pattern]
The liquid crystal aligning agent A-1 prepared above was applied onto a transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.), and 80 ° C. After heating (pre-baking) on the hot plate for 1 minute to remove the solvent, it was heated (post-baking) on a hot plate at 150 ° C. for 10 minutes to form a coating film having an average film thickness of 600 mm.
The coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.1 mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, followed by drying in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a rubbed coating film. This operation was repeated to obtain a pair (two) of substrates having a rubbed coating film.
Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to each outer edge of the pair of substrates having a rubbing-treated film, and then superimposed so that the coating film faces each other. Crimped and cured the adhesive. Next, a liquid crystal cell is manufactured by filling a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port and then sealing the liquid crystal injection port with an acrylic photo-curing adhesive. did.

The above operation was repeated to produce three liquid crystal cells having unpatterned transparent electrodes. One of them was used for the evaluation of the pretilt angle described later. The remaining two liquid crystal cells were irradiated with light in a state where a voltage was applied between the conductive films by the following method, and then subjected to evaluation of a pretilt angle and a voltage holding ratio.
For two of the liquid crystal cells obtained above, an alternating current of 10 Hz is applied between the electrodes, and the liquid crystal is driven, using an ultraviolet gland irradiation device using a metal halide lamp as the light source, UV was irradiated at dose of 10,000 J / ^{m 2} or 100,000J / ^{m 2.} This irradiation amount is a value measured using a light meter that is measured on the basis of a wavelength of 365 nm.

[Evaluation of pretilt angle]
As a result of measuring the pretilt angle of each of the liquid crystal cells manufactured as described above in the same manner as in Example 23, the pretilt angle of the liquid crystal cell not irradiated with light was 89 °, and the irradiation amount was 10,000 J / m ^2. The pretilt angle of the liquid crystal cell was 88 °, and the pretilt angle of the liquid crystal cell with an irradiation amount of 100,000 J / m ² was 84 °.
[Evaluation of voltage holding ratio]
About each liquid crystal cell manufactured above, the voltage holding ratio was measured in the same manner as in Example 23. As a result, the voltage holding ratio of the liquid crystal cell with an irradiation amount of 10,000 J / m ² was 99%, and The voltage holding ratio of the liquid crystal cell with the irradiation amount of 100,000 J / m ² was 84 °.

[Manufacture of Liquid Crystal Cell Having Patterned Transparent Electrode]
The liquid crystal aligning agent A-1 prepared as described above is patterned into a slit shape as shown in FIG. It is applied using a film printer (Nissha Printing Co., Ltd.), heated on a hot plate at 80 ° C. for 1 minute (prebaked) to remove the solvent, and then heated on a hot plate at 150 ° C. for 10 minutes ( The film was post-baked to form a coating film having an average film thickness of 600 mm. The coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a coating film. This operation was repeated to obtain a pair (two) of substrates having a coating film.
Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to each outer edge having the coating film on the pair of substrates. Cured. Next, a liquid crystal cell is manufactured by filling a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port and then sealing the liquid crystal injection port with an acrylic photo-curing adhesive. did.
The above operation was repeated to produce three liquid crystal cells having patterned transparent electrodes. One of them was used for evaluation of response speed as described later. For the remaining two liquid crystal cells, 10,000 J / m ² or 100,000 J / m with a voltage applied between the conductive films in the same manner as in the production of the liquid crystal cell having the transparent electrode without pattern. After irradiating with light at an irradiation amount of m ² , the response speed was evaluated.
The electrode pattern used here is the same type as the electrode pattern in the PSA mode.

[Evaluation of response speed]
For each liquid crystal cell produced above, first, the luminance of the light transmitted through the liquid crystal cell by irradiating a visible light lamp without applying a voltage was measured with a photomultimeter, and this value was defined as a relative transmittance of 0%. . Next, the transmittance when 60 V AC was applied between the electrodes of the liquid crystal cell for 5 seconds was measured in the same manner as described above, and this value was defined as a relative transmittance of 100%.
At this time, when 60 V AC was applied to each liquid crystal cell, the time until the relative transmittance shifted from 10% to 90% was measured, and this time was defined as the response speed and evaluated.
As a result, the response speed of the liquid crystal cell not irradiated with light is 52 msec, the response speed of the liquid crystal cell with the irradiation amount of 10,000 J / m ² is 48 msec, and the response speed of the liquid crystal cell with the irradiation amount of 100,000 J / m ^2. The speed was 29 msec.
From the results of Example 42, in the method of the present invention, when the ultraviolet irradiation amount is 100,000 J / m ² (which is a value usually employed in the PSA mode), the degree of the pretilt angle obtained becomes excessive, It can be seen that an appropriate pretilt angle is obtained at an irradiation dose of 10,000 J / m ² or less. Moreover, even when the irradiation amount is small, a sufficiently fast response speed is obtained, and the voltage holding ratio is also excellent. Therefore, according to the method of the present invention, the merits of the PSA mode can be realized with a small amount of light irradiation. Therefore, the occurrence of display unevenness due to the high amount of light irradiation, the decrease in voltage holding characteristics, and the lack of long-term reliability. Without concern, a liquid crystal display element having a wide viewing angle, a high response speed of liquid crystal molecules, a high transmittance, and a high contrast can be manufactured.

Claims (11)

Following formula (1)
The liquid crystal aligning agent characterized by including the radiation sensitive polyorganosiloxane which has a structure represented by these. The radiation sensitive polyorganosiloxane is
(A) a polyorganosiloxane having an epoxy group;
(B) A compound having a structure and a carboxyl group represented by the above formula (1) or the following formula (2)
The liquid crystal aligning agent of Claim 1 which is a reaction product with the compound which has group represented by these. The compound (b) is represented by the following formula (3) or (4)
(R ¹ in Formula (3) is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a monovalent group having 3 to 40 carbon atoms including an alicyclic group. R ² is a single bond, an oxygen atom, a sulfur atom, ^* —COO—, ^* —COS—, ^* —SCO— or ^* —OCO— (in the above, a bond marked with “*”) There binds to R ^1.) a and, if R ³ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group properly divalent condensed cyclic group, or A divalent group having a structure in which a heterocycle and an aromatic ring are condensed or a divalent group having a structure in which a heterocycle and an alicyclic ring are condensed, and R ⁴ is a single bond, an oxygen atom, a sulfur atom, ^* − COO-, ^* -COS-, ^* -SCO- or ^* -OCO- (in the above, the bonding hand marked with "*" A bind ^{R 3.),} R ⁵ is a fluorine atom or a cyano group, a is an integer of 0 to 3, b is an integer from 0 to 4,
R ⁶ in Formula (4) is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a monovalent monovalent having 3 to 40 carbon atoms including an alicyclic group. An organic group, R ⁷ is an oxygen atom or a divalent aromatic group, and R ⁸ is an oxygen atom, —COO— ^* or —OCO— ^* (in the above, the bond marked with “*” is R binds ^9.), and, R ⁹ is a divalent aromatic group, a divalent alicyclic group, a divalent or heterocyclic group is properly divalent condensed cyclic group, or a heterocyclic Is a divalent group having a structure in which an aromatic ring is condensed or a divalent group having a structure in which a heterocyclic ring and an alicyclic ring are condensed, and R ¹⁰ is a single bond, —OCO— (CH ₂ ) _e — ^*. or ^{_{-O- (CH 2) f - *}} ( except at least a bond marked with "*" is bonded to the carboxyl group. And with the proviso e and f represents an integer of 1 to 10, ^{respectively, R 11} 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 2 which is a compound represented by these.   Furthermore, the liquid crystal aligning agent as described in any one of Claims 1-3 containing the at least 1 sort (s) of polymer selected from the group which consists of a polyamic acid and a polyimide.   Furthermore, the liquid crystal aligning agent as described in any one of Claims 1-3 containing polyorganosiloxane other than the said radiation sensitive polyorganosiloxane.   A liquid crystal alignment film comprising a step of applying a liquid crystal aligning agent according to any one of claims 1 to 5 on a substrate to form a coating film and irradiating the coating film with radiation. Forming method.   A liquid crystal display device comprising a liquid crystal alignment film formed by the method for forming a liquid crystal alignment film according to claim 6. A coating film is formed by applying the liquid crystal aligning agent according to any one of claims 1 to 5 on the conductive film of a pair of substrates having a conductive film,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to each other through a layer of liquid crystal molecules,
A method for producing a liquid crystal display element, comprising a step of irradiating the liquid crystal cell with light while applying a voltage between conductive films of the pair of substrates.   The method for manufacturing a liquid crystal display element according to claim 8, wherein each of the conductive films is a patterned conductive film partitioned into a plurality of regions.   A liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element according to claim 8.   A radiation-sensitive polyorganosiloxane having a structure represented by the above formula (1).