KR101765504B1 - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

(Problems to be Solved) A liquid crystal aligning agent capable of forming a liquid crystal alignment film excellent in electrical characteristics and having good storage stability and having a low voltage-holding ratio even when subjected to light irradiation with high intensity, .
The liquid crystal aligning agent is at least one selected from the group consisting of an acetal ester structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkyl cycloalkyl ester structure of a carboxylic acid, and a tertiary alkyl ester structure of a carboxylic acid And a polyorganosiloxane having one kind of structure.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent and a liquid crystal display element,

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element.

At present, as a liquid crystal display element, a liquid crystal alignment film made of an organic resin or the like is formed on a surface of a substrate on which a transparent conductive film is formed to form a substrate for a liquid crystal display element. Two liquid crystal alignment films are disposed opposite to each other, Called Twisted Nematic liquid crystal cell in which a nematic liquid crystal layer having anisotropic properties is formed into a cell having a sandwich structure and the long axis of the liquid crystal molecules is continuously twisted by 90 DEG C from one substrate toward the other substrate A TN type liquid crystal display element is known. In addition, a liquid crystal display device such as an STN (super twisted nematic) type liquid crystal display device or an IPS (In-Plane Switching) type liquid crystal display device which can realize a high contrast ratio as compared with a TN type liquid crystal display device, (Vertical Alignment) type liquid crystal display device using a nematic liquid crystal having a light emitting layer (see Patent Documents 1 to 5).

The operation principle of such various liquid crystal display elements is largely classified into a transmission type and a reflection type. The transmissive liquid crystal display element performs display using the change in the intensity of light transmitted through the back light source from the back surface of the element at the time of device driving. The reflection type liquid crystal display device uses display light using a change in the intensity of light reflected from the outside such as sunlight at the time of device driving without using a backlight source and consumes less power than the transmission type, Which is particularly advantageous for use.

In the transmissive liquid crystal display element, the liquid crystal alignment film provided in the transmissive liquid crystal display element is exposed to light from the backlight source for a long time. Particularly, in addition to business applications, a light source having a very high irradiation intensity, such as a metal halide lamp, is used for a liquid crystal projector in which demand for a home theater is increasing. It is also conceivable that the temperature of the system itself of the liquid crystal display element increases at the time of driving with the light irradiation with high intensity.

In a reflection type liquid crystal display device, there is a high possibility of being used outdoors. In this case, sunlight including strong ultraviolet light becomes a light source. Also, in the reflection type, the distance through which light passes through the device is longer than the transmission type.

In addition, both transmission type liquid crystal display elements and reflection type liquid crystal display elements tend to be installed in, for example, automobiles, and the like. In comparison with the case conventionally considered as a use state of liquid crystal display elements, The use and installation environment has become reality.

However, liquid crystal dropping method, that is, ODF (One Drop Fill) method, is beginning to be used in view of process shortening and improvement of yield in the process of manufacturing liquid crystal display elements. The ODF method differs from the conventional method in which liquid crystal is injected into a vacant liquid crystal cell assembled by using a thermosetting sealant in advance. After applying a sealant of ultraviolet light curing property to a necessary portion of a one-side substrate coated with a liquid crystal alignment film The liquid crystal cell is manufactured by dropping a liquid crystal to a necessary portion and bonding the other substrate to the entire surface, and then irradiating ultraviolet light to the entire surface to cure the sealant. The ultraviolet light irradiated at this time is usually stronger than a few joules per square centimeter. That is, in the liquid crystal display element manufacturing process, the liquid crystal alignment layer is exposed to the strong ultraviolet light together with the liquid crystal.

As described above, the liquid crystal display element is exposed to a harsh environment such as high-intensity light irradiation, high-temperature environment, and long-time driving that conventionally could not be expected, accompanied with improvement in performance, versatility, and manufacturing process. It is required to further improve the electric characteristics such as the liquid crystal alignment property and the voltage holding ratio, or the display characteristics of the liquid crystal display device. Further, the liquid crystal display device is required to have a longer life.

Conventionally, organic resins such as polyimide, polyamic acid, polyamide and polyester have been known as a material of the liquid crystal alignment film constituting the liquid crystal display element. In particular, polyimide has been used in many liquid crystal display elements because it exhibits excellent physical properties such as heat resistance, affinity with liquid crystals, and mechanical strength among organic resins (Patent Documents 6 to 8).

However, in recent liquid crystal display devices, there is a strong demand for a new manufacturing environment and a use environment that are becoming severe. As a result, there is still insufficient heat resistance and light resistance to such an extent that an organic resin, It became one.

Thus, a liquid crystal alignment film excellent in heat resistance and light resistance has been studied. For example, Patent Document 9 discloses a vertical alignment type liquid crystal alignment film formed of a polysiloxane solution obtained from a silicon compound having four alkoxyl groups and a silicon compound having three alkoxyl groups, and has a vertical alignment property, a heat resistance, And the stability as a coating liquid is excellent. However, the liquid crystal alignment film according to this technique does not satisfy the required performance accompanying the current production environment and use environment, and the storage stability of the coating liquid is still insufficient. Therefore, There is a problem with the convenience of.

Further, as a liquid crystal display element, there is still a strong demand for development of a liquid crystal aligning agent which does not cause a problem of afterimage, that is, an electric characteristic is excellent.

On the other hand, when the formation of the liquid crystal alignment film is performed by rubbing treatment, dust or static electricity easily occurs in the process, dust adheres to the surface of the alignment film to cause display defects. A photo alignment method of imparting liquid crystal aligning ability by irradiating a photosensitive thin film such as polyvinyl cinnamate, polyimide or azobenzene derivative with radiation of polarized light or non-polarized light is known (Patent Documents 10 to 12). According to these methods, uniform liquid crystal alignment can be realized without generating static electricity or dust. However, even if the liquid crystal alignment film formed by these techniques exhibits a good pretilt angle at the beginning of the formation, there is a phenomenon that the pretilt angularity is lost with the lapse of time, and the stability of the pretilt angle over time is insufficient .

As described above, it is possible to provide a liquid crystal alignment film which can give a liquid crystal alignment film having a very harsh current manufacturing environment, sufficient heat resistance and light resistance in a use environment, and is excellent in storage stability and exhibits excellent electric characteristics when used as a liquid crystal display device It is not yet known. In addition, a liquid crystal aligning agent which exhibits stability over time at a sufficient pretilt angle when formed by the photo alignment method is not yet known.

In order to solve these problems, the present inventors have recently reported on a liquid crystal aligning agent containing a liquid crystal aligning polyorganosiloxane obtained by introducing a structure having liquid crystal aligning ability by utilizing the reactivity of a polyorganosiloxane having an epoxy group (Patent Documents 13 to 16).

However, the severity of the above-mentioned use environment tends to be intensified, and further improvement in the heat resistance of the liquid crystal alignment film is required.

Japanese Patent Application Laid-Open No. 4-153622 Japanese Patent Application Laid-Open No. 60-107020 Japanese Laid-Open Patent Publication No. 56-91277 U.S. Patent No. 5,928,733 Japanese Patent Application Laid-Open No. 11-258605 Japanese Patent Application Laid-Open No. 9-197411 Japanese Patent Application Laid-Open No. 2003-149648 Japanese Patent Application Laid-Open No. 2003-107486 Japanese Patent Application Laid-Open No. 9-281502 Japanese Patent Application Laid-Open No. 6-287453 Japanese Patent Application Laid-Open No. 2003-307736 Japanese Laid-Open Patent Publication No. 2004-163646 Japanese Patent Application No. 2008-19346 International Publication No. 09/25385 pamphlet International Publication No. 09/25386 pamphlet International Publication No. 09/25388 pamphlet Japanese Patent Application Laid-Open No. 63-291922 Japanese Unexamined Patent Application Publication No. 6-222366 Japanese Patent Application Laid-Open No. 6-281937 Japanese Unexamined Patent Publication No. 5-107544

 &Quot; Science of Sol-Gel Method ", Agnes Shofusha, Kabushiki Kaisha, 1988, pp. 155-161  T. J. Scheffer et al., J. Appl. Phys. vol. 48, p. 1783 (1977)  F. Nakano et al., JPN. J. Appl. Phys. vol.19, p2013 (1980)

SUMMARY OF THE INVENTION 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 having excellent liquid crystal alignability and high light resistance, particularly a low voltage- And a liquid crystal aligning agent which is excellent in storage stability.

Another object of the present invention is to provide a liquid crystal alignment film which is excellent in light resistance and electric characteristics and can be used in a case where the photo alignment method is employed in forming the liquid crystal alignment film, And to provide a liquid crystal display element excellent in stability with the passage of time.

Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are achieved by firstly,

A polyorganosiloxane having at least one structure selected from the group consisting of an acetal ester structure of carbonic acid, a ketal ester structure of carbonic acid, a 1-alkyl cycloalkyl ester structure of carbonic acid, and a tertiary alkyl ester structure of carbonic acid (Hereinafter referred to as " polyorganosiloxane (A) ").

The above objects and advantages of the present invention are secondly,

And a liquid crystal alignment layer formed of the liquid crystal aligning agent.

The liquid crystal aligning agent of the present invention is capable of forming a liquid crystal alignment film excellent in electrical characteristics and having a low storage stability even when irradiated with light with high light intensity, Do.

The liquid crystal display element of the present invention having the liquid crystal alignment layer formed of the liquid crystal alignment agent of the present invention is excellent in light resistance and electrical characteristics, and even when the photo alignment method is employed in the formation of the liquid crystal alignment layer, Which is superior in stability.

(Mode for carrying out the invention)

The liquid crystal aligning agent of the present invention contains at least the above-mentioned polyorganosiloxane (A).

≪ Polyorganosiloxane (A) >

The polyorganosiloxane (A) in the present invention is a polyorganosiloxane having a structure comprising an acetal ester structure of a carboxylic acid, a ketal ester structure of a carbonic acid, a 1-alkyl cycloalkyl ester structure of a carboxylic acid, and a tertiary alkyl ester structure of a carboxylic acid And at least one kind of structure selected from the above.

The polyorganosiloxane (A) is a mixture of a polyorganosiloxane having an epoxy group (hereinafter referred to as " polyorganosiloxane (a) having an epoxy group "),

A carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, at least one member selected from (where, R is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom), the group consisting of -CH = CH ₂ and -SO ₂ Cl And a compound having at least one member selected from the group consisting of an acetal ester structure of carbonic acid, a ketal ester structure of carbonic acid, a 1-alkyl cycloalkyl ester structure of carbonic acid, and a tertiary alkyl ester structure of carbonic acid (hereinafter, Quot; compound b "), preferably in the presence of an organic solvent, if necessary in the presence of a catalyst.

The polyorganosiloxane (A) preferably has an epoxy structure. The polyorganosiloxane (A) preferably has an epoxy equivalent of 100 to 10,000 g / mole, more preferably 150 to 1,000 g / mole.

<Polyorganosiloxane Having an Epoxy Group (a)>

The polyorganosiloxane (a) having an epoxy group is obtained by introducing an acetal ester structure of a carboxylic acid, a ketal ester structure of a carbonic acid, a 1-alkyl cycloalkyl ester structure of a carboxylic acid, and a tertiary alkyl ester structure of a carboxylic acid , And the epoxy group is introduced as the side chain in the polyorganosiloxane (A). The polyorganosiloxane (a) having an epoxy group is preferably at least one member selected from the group consisting of a polyorganosiloxane having a structural unit represented by the following formula (1), a hydrolyzate thereof and a condensate of a hydrolyzate .

(1) wherein X ¹ is a monovalent organic group having an epoxy group; Y ¹ is a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

The hydrolyzed condensate of the polyorganosiloxane having the structural unit represented by the above formula (1) can be obtained not only by hydrolysis and condensation between the polyorganosiloxanes but also by hydrolysis of the structural unit represented by the formula (1) A concept including a hydrolyzed condensate in the case where the polyorganosiloxane obtained by branching or crosslinking of the main chain in the process of producing the polyorganosiloxane by the condensate has the structural unit represented by the formula (1) to be.

X ¹ in the formula (1) is not particularly limited as long as it is a monovalent organic group having an epoxy group, and examples thereof include a group containing a glycidyl group, a glycidyloxy group, and an epoxycyclohexyl group . X ¹ is preferably represented by the following formula (X ¹ -1) or (X ¹ -2).

(Formula (X ¹ -1) of, A is an oxygen atom or a single bond; h is an integer of 1~3, i is an integer from zero to six; however, if i is 0, A is a single bond and ;

In the formula (X ¹ -2), j is an integer of 1 to 6;

In the formulas (X ¹ -1) and (X ¹ -2), * indicates that each is a bonding hand).

Among the epoxy groups represented by the above formula (X ¹ -1) or (X ¹ -2), groups represented by the following formula (X ¹ -1-1) or (X ¹ -2-1) are preferred.

(In the formula (X ¹ -1-1) or the formula (X ¹ -2-1), * indicates a bonding hand).

In Y ¹ in the formula (3)

Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, ethoxy group and the like;

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-hexadecyl group, Practical group, n-eicosyl group, etc .;

As the aryl group having 6 to 20 carbon atoms, for example, a phenyl group and the like can be given.

The weight average molecular weight (Mw) of the polyorganosiloxane (a) having an epoxy group in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 500 to 100,000, more preferably 1,000 to 10,000, 5,000 is particularly preferred.

In the present specification, Mw is a polystyrene conversion value measured by GPC under the following specifications.

Column: TSKgelGRCXLII, manufactured by Toso Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 6.8 MPa

The polyorganosiloxane (a) having such an epoxy group is preferably prepared by reacting 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 an appropriate organic solvent, water and a catalyst Can be synthesized by hydrolysis or hydrolysis / condensation.

Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra- -Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri- , Fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec -Methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltri- Tri-sec-butoxy silane, 2- (trifluoromethyl) ethyl trichlorosilane, 2- (Trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyl tri-n-butoxysilane, 2- (trifluoromethyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- N-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro- (Perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri- Octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- (Perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (Perfluoro-n-octyl) ethyl tri-n-octyl) ethyl tri-i-propoxysilane, 2- (perfluoro- Tri-sec-butoxysilane, hydroxymethyl trichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propyl (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri- (Meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltriethoxysilane, Mercaptopropyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, N-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxy Silane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyl Triethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri- butoxysilane, methyldi-n-butoxysilane, methyldi-n-butoxysilane, methyldi-n-butoxysilane, methyldimethoxysilane, methyldiethoxysilane, butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyldimethoxy silane, dimethyl diethoxy silane, dimethyl di- (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro- n-octyl) ethyl] dichlorosilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (Perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (methyl) (3- mercaptopropyl) dichlorosilane, (methyl) (Methyl) (3-mercaptopropyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (Methyl) (vinyl) dichlorosilane, (methyl) (3-mercaptopropyl) di-n-butoxysilane, (methyl) (Methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl) (vinyl) di-n-propoxysilane, (Vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propyl Butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiethoxysilane, diphenyldiethoxysilane, N-propoxy silane, diphenyl di-i-propoxy silane, diphenyl di-n-butoxy silane, diphenyl Di-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxy Propoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, Silane having one silicon atom such as (methoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane and (ethoxy) Compounds and the like.

As a product name, for example,

KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X- X-22-170B, X-22-170B, X-22-170D, X-22-170DX, X-22-176B, X-22-170B, -22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, -9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056 , X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR-212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206 , KR5230, KR5235, KR9218, KR9706 (all, Shin-Etsu Chemical Co., Ltd.);

GlassResin (manufactured by Showa Denko K.K.);

SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (Toray, Dow Corning);

FZ3711 and FZ3722 (manufactured by Nippon Unicar Co., Ltd.);

DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, Chisso Corporation);

Methyl silicate MS51, methyl silicate MS56 (all available from Mitsubishi Chemical Corporation);

Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, Colcoat);

GR100, GR650, GR908, and GR950 (all trade names, manufactured by Showa Denko K.K.).

Of these other silane compounds, from the viewpoints of orientation and chemical stability of the obtained liquid crystal alignment film, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane (Meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane is preferable .

The polyorganosiloxane (a) having an epoxy group to be used in the present invention can be obtained by introducing a compound b and a side chain having a photo-orientable property in a sufficient amount, if necessary, while introducing an excessive amount of an epoxy group, The epoxy equivalent is preferably 100 g / mol to 10,000 g / mol, more preferably 150 g / mol to 1,000 g / mol. Therefore, in the synthesis of the polyorganosiloxane (a) having an epoxy group, it is preferable to prepare such that the ratio of the epoxy group-containing silane compound to the other silane compound is such that the epoxy equivalent of the resulting polyorganosiloxane is within the above range Do.

Specifically, such other silane compounds are preferably used in an amount of 0% by weight to 50% by weight, and more preferably 5% by weight to 30% by weight, based on the total amount of the silane compound having an epoxy group and the other silane compounds.

Examples of the organic solvent which can be used in the synthesis of the polyorganosiloxane (a) having an epoxy group include hydrocarbon compounds, ketone compounds, ester compounds, ether compounds and alcohol compounds.

Examples of the hydrocarbon compound include toluene, xylene, and the like; Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and the like; Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; As the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; Examples of the alcohols 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- , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Of these, non-water-soluble ones are preferable. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is preferably 10 parts by weight to 10,000 parts by weight, more preferably 50 parts by weight to 1,000 parts by weight, based on 100 parts by weight of the total silane compound. The amount of water used when preparing the polyorganosiloxane (a) having an epoxy group is preferably from 0.5 to 1 mole, more preferably from 1 mole to 30 times, based on the total amount of the silane compound.

As the catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound and the like can be used.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.

As the organic base, for example,

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 and diazabicyclo-undecene;

And quaternary organic ammonium salts such as tetramethylammonium hydroxide. In view of the fact that the reaction proceeds mildly among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; And a quaternary organic ammonium salt such as tetramethylammonium hydroxide.

As the catalyst for preparing 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, it is possible to obtain a desired polyorganosiloxane at a high hydrolysis / condensation rate without causing a side reaction such as ring-opening of an epoxy group and the like, . Further, the composition for organic semiconductor alignment of the present invention, which contains 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 a specific cinnamic acid derivative, It is appropriate because it is very good.

This is because, as indicated in 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, a ladder- Structure is formed and a polyorganosiloxane having a small content of silanol groups is obtained. In the case where the condensation reaction between the silanol groups is suppressed because the content of the silanol groups is small and the composition for orienting the organic semiconductor of the present invention contains the other polymer described below, the condensation reaction between the silanol groups and other polymers It is deduced that the reaction is inhibited and therefore, the storage stability is excellent.

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used differs depending on the kind of the organic base, reaction conditions such as temperature, and the like, and can be appropriately set. The specific amount of the organic base to be used is, for example, 0.01 to 3 moles per mole of the total silane compound, more preferably 0.05 to 1 mole per mole of the total silane compound.

The hydrolysis or hydrolytic condensation reaction in the production of the polyorganosiloxane (a) having an epoxy group can be carried out by dissolving the silane compound (a) having an epoxy group and, if necessary, other silane compounds in an organic solvent, It is preferably carried out by mixing with an organic base and water, and heating it by, for example, an oil bath.

In the hydrolysis and condensation reaction, the heating temperature of the oil bath is preferably 130 ° C. or lower, more preferably 40 ° C. to 100 ° C., preferably 0.5 to 12 hours, more preferably 1 to 8 hours . During the heating, the mixed solution may be stirred or refluxed.

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of this washing, it is preferable to wash with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 wt% or the like in that the washing operation becomes easy. The washing is carried out until the water layer after the washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain a polyorganosiloxane having a desired epoxy group Siloxane (a) can be obtained.

In the present invention, a commercially available polyorganosiloxane (a) having an epoxy group may be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21 and EMS-32 (manufactured by Chisso Corporation).

The polyorganosiloxane (a) having an epoxy group is a moiety derived from a hydrolyzate produced by hydrolysis of the polyorganosiloxane (a) itself having an epoxy group, or a polyorganosiloxane (a) having an epoxy group, And may contain a moiety derived from the hydrolyzed condensate obtained by the decomposition and condensation. These hydrolysates and hydrolyzed condensates, which are the constituent materials of the above-mentioned parts, can also be prepared in the same manner as the hydrolysis or condensation conditions of the polyorganosiloxane (a) having an epoxy group.

<Compound b>

The compound b is selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH ₂ and -SO ₂ Cl At least one group selected from the group consisting of an acetal ester structure of a carbonic acid, a ketal ester structure of a carbonic acid, a 1-alkyl cycloalkyl ester structure of a carbonic acid, and a tertiary alkyl ester structure of a carboxylic acid / RTI &gt;

Examples of the group forming the acetal ester structure of the carbonic acid include groups represented by the following formulas (B-1) and (B-2):

(In the formula (B-1), R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aliphatic group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms,

In the formula (B-2), n1 is an integer of 2 to 10)

And the like. Here, examples of the alkyl group represented by R &^lt; 1 &gt; in the formula (B-1) include a methyl group;

As the alicyclic group, there is a cyclohexyl group;

As the aryl group, there can be mentioned a phenyl group;

As the aralkyl group, a benzyl group is preferable,

The alkyl group represented by R &lt; ² &gt; is an alkyl group having 1 to 6 carbon atoms;

The alicyclic group includes an alicyclic group having 6 to 10 carbon atoms;

As the aryl group, there can be mentioned a phenyl group;

The aralkyl group is preferably a benzyl group or a 2-phenylethyl group,

The n1 in the formula (B-2) is preferably 3 or 4.

Examples of the group represented by the formula (B-1) include 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1- Butoxyethoxycarbonyl group, 1-t-butoxyethoxycarbonyl group, 1-n-butoxyethoxycarbonyl group, 1-n-butoxyethoxycarbonyl group, 1-n-butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 1-norbornyloxyethoxycarbonyl group, 1-boronyloxyethoxycarbonyl group, 1-phenoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, (1-naphthyloxy) ethoxycarbonyl, 1-benzyloxyethoxycarbonyl, 1-phenethyloxyethoxycarbonyl, (cyclohexyl) (methoxy) methoxycarbonyl, (cyclohexyl) (Cyclohexyl) methoxycarbonyl group, (cyclohexyl) (n-propoxy) methoxycarbonyl group, (cyclohexyl) (i-propoxy) methoxycarbonyl group, Carbonyl group, (cyclo (Phenyl) (methoxy) methoxycarbonyl, (phenyl) (ethoxy) methoxycarbonyl, (phenyl) (methoxy) methoxycarbonyl, (phenyl) (phenoxy) methoxycarbonyl, (phenyl) (phenoxy) methoxycarbonyl, (phenyl) (cyclohexyloxy) methoxycarbonyl, (Benzyl) (n-propoxy) methoxycarbonyl, (benzyl) (methoxycarbonyl) methoxycarbonyl, (Benzyl) (phenoxy) methoxycarbonyl group, (benzyl) (benzyl) methoxycarbonyl group, benzyl (methoxy) carbonyl group, Ethoxycarbonyl group and the like;

Examples of the group represented by the formula (B-2) include a 2-tetrahydrofuranyloxycarbonyl group, a 2-tetrahydropyranyloxycarbonyl group and the like. Of these, preferred are 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, 2-tetrahydropyranyloxy Carbonyl group and the like are preferable.

Examples of the group forming the ketal ester structure of the carbonic acid include groups represented by the following formulas (B-3) to (B-5):

(In the formula (B-3), R ³ represents an alkyl group having 1 to 12 carbon atoms, and R ⁴ and R ⁵ each represent an alkyl group having 1 to 12 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, Or an aralkyl group having 7 to 20 carbon atoms,

In the formula (B-4), R ⁶ is an alkyl group having 1 to 12 carbon atoms, n 2 is an integer of 2 to 8,

In the formula (B-5), R ⁷ is an alkyl group having 1 to 12 carbon atoms and n 3 is an integer of 2 to 8)

And the like. Here, the alkyl group of R ^{3 in} the above formula (B-3) is preferably a methyl group,

The alkyl group for R ⁴ is preferably a methyl group;

As the alicyclic group, a cyclohexyl group

As the aryl group, there can be mentioned a phenyl group;

As the aralkyl group, a benzyl group is preferable,

The alkyl group of R &lt; ⁵ &gt; is an alkyl group having 1 to 6 carbon atoms;

The alicyclic group includes an alicyclic group having 6 to 10 carbon atoms;

As the aryl group, there can be mentioned a phenyl group;

The aralkyl group is preferably a benzyl group or a 2-phenylethyl group,

The alkyl group represented by R ^{6 in} the formula (B-4) is preferably a methyl group;

n2 is preferably 3 or 4,

The alkyl group represented by R ^{7 in} the formula (B-5) is preferably a methyl group;

and n3 is preferably 3 or 4, respectively.

Examples of the group represented by the above formula (B-3) include 1-methyl-1-methoxyethoxycarbonyl group, 1-methyl-1-ethoxyethoxycarbonyl group, Propoxyethoxycarbonyl group, 1-methyl-1-n-butoxyethoxycarbonyl group, 1-methyl-1-i-butoxyethoxycarbonyl group Methyl-1-sec-butoxyethoxycarbonyl group, 1-methyl-1-t-butoxyethoxycarbonyl group, 1-methyl-1-cyclopentyloxyethoxycarbonyl group, -Cyclohexyloxyethoxycarbonyl group, 1-methyl-1-norbornyloxyethoxycarbonyl group, 1-methyl-1-borenyloxyethoxycarbonyl group, 1-methyl-1-phenoxyethoxycarbonyl group , 1-methyl-1- (1-naphthyloxy) ethoxycarbonyl group, 1-methyl-1-benzyloxyethoxycarbonyl group, 1-cyclohexyl-1-ethoxyethoxycarbonyl group, 1-cyclohexyl-1-n-propoxyethoxycarbonyl group, Cyclohexyl-1-phenoxyethoxycarbonyl group, 1-cyclohexyl-1-phenoxyethoxycarbonyl group, 1-cyclohexyl-1-cyclohexyloxyethoxycarbonyl group, 1-phenyl-1-ethoxyethoxycarbonyl group, 1-phenyl-1-n-propoxyethoxycarbonyl group, 1-phenyl-1-ethoxyethoxycarbonyl group, Phenyl-1-i-propoxyethoxycarbonyl group, 1-phenyl-1-cyclohexyloxyethoxycarbonyl group, 1-phenyl-1-phenoxyethoxycarbonyl group, Benzyl-1-ethoxyethoxycarbonyl group, 1-benzyl-1-n-propoxyethoxycarbonyl group, 1-benzyl-1-methoxyethoxycarbonyl group, Benzyl-1-phenoxyethoxycarbonyl group, 1-benzyl-1-cyclohexyloxyethoxycarbonyl group, 1-benzyl-1-phenoxyethoxycarbonyl group, 1-benzyl-1-benzyloxyethoxy Carbonyl group and the like;

Examples of the group represented by the formula (B-4) include a 2- (2-methyltetrahydrofuranyl) oxycarbonyl group, a 2- (2-methyltetrahydropyranyl) oxycarbonyl group and the like;

Examples of the group represented by the above formula (B-5) include a 1-methoxycyclopentyloxycarbonyl group, a 1-methoxycyclohexyloxycarbonyl group and the like. Of these, 1-methyl-1-methoxyethoxycarbonyl group and 1-methyl-1-cyclohexyloxyethoxycarbonyl group are preferable.

Examples of the group forming the 1-alkylcycloalkyl ester structure of the carbonic acid include a group represented by the following formula (B-6):

(In the formula (B-6), R ⁸ is an alkyl group having 1 to 12 carbon atoms and n 4 is an integer of 1 to 8)

And the like. Here, the alkyl group of R &lt; ⁸ &gt; in the above formula (B-6) is preferably an alkyl group of 1 to 10 carbon atoms.

Examples of the group represented by the above formula (B-6) include 1-methylcyclopropoxycarbonyl group, 1-methylcyclobutoxycarbonyl group, 1-methylcyclopentoxycarbonyl group, 1-methylcyclohexyloxycarbonyl group , 1-methylcycloheptyloxycarbonyl group, 1-methylcyclooctyloxycarbonyl group, 1-methylcyclonyloxycarbonyl group, 1-methylcyclodecyloxycarbonyl group, 1-ethylcyclopropoxycarbonyl group, 1- Ethylcyclohexyloxycarbonyl group, 1-ethylcyclooctyloxycarbonyl group, 1-ethylcyclooctyloxycarbonyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, (Isopropyl) cyclopropoxycarbonyl group, 1- (iso) propylcyclopropoxycarbonyl group, 1- (isopropyl) cyclopentyloxycarbonyl group, 1- Propylcyclohexyloxycar Propylcyclohexyloxycarbonyl group, a 1- (isopropyl) cyclohexyloxycarbonyl group, a 1- (isopropyl) cyclohexyloxycarbonyl group, a 1- Butyl cyclohexyloxycarbonyl group, a 1- (iso) butylcyclopropoxycarbonyl group, a 1- (iso) butylcyclobutoxycarbonyl group, a 1- Butyl cycloheptyloxycarbonyl group, 1- (iso) butylcyclohexyloxycarbonyl group, 1- (iso) butylcyclohexyloxycarbonyl group, 1- Pentylcyclohexyloxycarbonyl group, 1- (iso) pentylcarbonyl group, 1- (iso) pentylcyclohexyloxycarbonyl group, Cycloheptyloxycarbonyl group, 1- (iso) pentylcyclooctyloxycarbonyl group, 1- (iso) pentyloxy An iso-pentylcyclohexyloxycarbonyl group, a 1- (iso) pentylcyclohexyloxycarbonyl group,

Hexylcyclohexyloxycarbonyl group, 1- (iso) hexylcyclohexyloxycarbonyl group, 1- (iso) hexylcyclopropoxycarbonyl group, 1- (Iso) hexylcyclohexyloxycarbonyl group, 1- (iso) hexylcyclohexyloxycarbonyl group, 1- (iso) hexylcyclohexyloxycarbonyl group, 1- Heptylcyclohexyloxycarbonyl group, 1- (iso) heptylcyclohexyloxycarbonyl group, 1- (benzyloxycarbonyloxycarbonyl) group, 1- Heptylcyclohexyloxycarbonyl group, 1- (iso) heptylcyclohexyloxycarbonyl group, 1- (iso) heptylcyclohexyloxycarbonyl group, 1- A 1- (iso) octylcyclobutoxycarbonyl group, a 1- (iso) octylcyclopentoxycarbo (Iso) octylcyclohexyloxycarbonyl group, 1- (iso) octylcyclohexyloxycarbonyl group, 1- (iso) octylcyclohexyloxycarbonyl group, 1- (iso) octyl cyclodecyloxycarbonyl group, and the like.

Examples of the group having a tertiary alkyl ester structure of the above-mentioned carbonic acid include a tertiary alkoxycarbonyl group and the like. Examples of the tertiary alkoxycarbonyl group include a t-butoxycarbonyl group, a t-amyloxycarbonyl group, a 2-methyl-2-amyloxycarbonyl group, a 3-methyl-3-amyloxycarbonyl group and a texyloxycarbonyl group have. Among them, t-butoxycarbonyl group and t-amyloxycarbonyl group are preferable, and t-butoxycarbonyl group is particularly preferable.

As the compound b in the present invention, a compound represented by the following formula (B):

B _n RC (B)

(In the formula (B), B is preferably a group represented by any of the formulas (B-1) to (B-6) or a tertiary alkoxycarbonyl group, n is an integer of 1 to 10, A group obtained by removing (n + 1) hydrogens from a heterocyclic compound having 1 to 10 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms (n + 1);

C is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH ₂ and -SO ₂ Cl,

, And a carboxyl group is preferable.

The n in the formula (B) is preferably 1 or 2.

Specific examples of R in the formula (B) include a case where n is 1, and examples thereof include a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, a 1,2-phenylene group, A 4-phenylene group, a 2,6-naphthalenyl group, a 5-sodium sulfo-1,3-phenylene group, a 5-tetrabutylphosphonium sulfo-1,3-phenylene group and the like;

When n is 2, the following formula:

A benzene-1,3,5-triyl group, and the like. The alkylene group is preferably a linear chain.

The compound b represented by the formula (B) can be synthesized by a conventional method of organic chemistry or by appropriately combining the methods of organic chemistry.

For example, a compound in which the group B in the formula (B) is a group represented by the formula (B-1) (except when R ¹ is a phenyl group) is preferably a compound CR - (COOH) _n (stage, C, R and n are each the same as defined as in the formula (B)) and a compound ^{R 2 -O-CH = R 1} '( However, R ² is the formula ( B-1), and R ^{1 '} is a group obtained by removing a hydrogen atom from the 1-position carbon of the group R ¹ in the formula (B-1)).

In the polyorganosiloxane (A) of the present invention, side chains having photo-alignment properties can be introduced as necessary. With the introduction of the photo-alignable group, it can be oriented by light irradiation without rubbing.

As the photo-aligning group, various groups derived from compounds showing photo-alignment properties can be adopted. For example, azobenzene-containing groups containing azobenzene or a derivative thereof as a basic skeleton, Shin A coumarin-containing group having as a basic skeleton, a chalcone-containing group containing a chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, coumarin or a derivative thereof as a basic skeleton, And a polyimide-containing structure containing a polyimide or a derivative thereof as a basic skeleton. Among these photo-orientable groups, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton is preferable in view of high alignability and easiness of introduction.

The structure of the group having a cinnamic acid structure is not particularly limited as long as it contains cinnamic acid or a derivative thereof as a basic skeleton, but a group derived from a specific cinnamic acid derivative shown below is preferable.

(2): &lt; EMI ID =

(In the formula (2), R ⁹ is a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms or an alkyl group having 1 to 40 carbon atoms and containing an alicyclic group, with the proviso that some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms may optionally, R ¹⁰ represents a single bond, an oxygen atom, -COO- or -OCO-, R ¹¹ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, R ¹² R ¹³ is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms or a divalent aromatic group, t is 0 when R ¹³ is a single bond, and R ¹⁴ is a hydroxyl group or -SH, t is 0 or 1 when R ¹³ is a methylene group, an alkylene group or a bivalent aromatic group and R ¹⁴ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH = a CH ₂ or -SO ₂ Cl, wherein R has only a hydrogen atom or an alkyl group having a carbon number of 1~6, R ¹⁵ is a fluorine atom or a cyano nogiyi , A is an integer of 0~3, b is an integer of 0 to 4)

Or a compound represented by the following formula (3):

(In the formula (3), R ¹⁶ is a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group or an alkyl group having 1 to 40 carbon atoms, provided that a part or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom , R ¹⁷ is an oxygen atom, a divalent aromatic group, or a single bond, R ¹⁸ is an oxygen atom, -COO- or -OCO-, R ¹⁹ is a divalent aromatic group, a divalent heterocyclic group or a divalent condensed ring group And R ²⁰ is a single bond, -OCO- (CH ₂ ) _e - ^* or -O- (CH ₂ ) _g - ^* with the proviso that e and g are each an integer of 1 to 10, are, respectively, indicates that the bonding hand is combined with R ²¹ attached do this, R ²¹ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH = CH 2 or -SO ₂ Cl, wherein R is hydrogen only An alkyl group having 1 to 6 carbon atoms, R ²² is a fluorine atom or a cyano group, c is an integer of 0 to 3, and d is an integer of 0 to 4).

Examples of the monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group represented by R ⁹ in the formula (2) include a cholesteryl group, a cholestanyl group and an adamantyl group. As the alkyl group having 1 to 40 carbon atoms for R ⁹ , for example, an alkyl group having 1 to 20 carbon atoms (provided that part or all of the hydrogen atoms of the alkyl group may be substituted by a fluorine atom) is preferable. Examples of such alkyl groups include n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, N-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, A 4,4,5,5,5-pentafluoropentyl group, a 4,4,5,5,6,6,6-heptafluorohexyl group, a 3,3,4,4-tetrafluorobutyl group, Heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group , A 2- (perfluorooctyl) ethyl group, a 2- (perfluorodecyl) ethyl group, and the like.

Examples of the divalent aromatic group represented by R ¹¹ and R ¹³ include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro- Tetrafluoro-1,4-phenylene group and the like; Examples of the divalent heterocyclic group represented by R ¹¹ include a 1,4-pyridylene group, a 2,5-pyridylene group, a 1,4-furanylene group and the like; Examples of the divalent condensed ring group of R ¹¹ include a naphthylene group and the like.

Examples of the bivalent alicyclic group represented by R ¹¹ include a 1,4-cyclohexylene group and the like.

The compound represented by the formula (2) is preferably a compound wherein R ¹³ is a single bond and t is 0 and R ¹⁴ is a hydroxyl group, or R ¹³ is a methylene group, an alkylene group or a divalent It is preferred that the aromatic group is a compound wherein t is 0 or 1 and R &lt; ¹⁴ &gt; is a carboxyl group.

Preferable examples of the compound represented by the formula (2) include, for example, compounds represented by the following formulas (2-1) to (2-34):

(Wherein R ¹ has the same meaning as R ⁹ in the formula (2) and f is an integer of 1 to 10, respectively)

&Lt; / RTI &gt;

Examples of the monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group represented by R ¹⁶ in the formula (3) include a cholesteryl group, a cholestanyl group and an adamantyl group. As the alkyl group having 1 to 40 carbon atoms for R ¹⁶ , for example, an alkyl group having 1 to 20 carbon atoms (provided that part or all of the hydrogen atoms of the alkyl group may be substituted by a fluorine atom) is preferable. Examples of such an alkyl group include those exemplified as the alkyl group of R ⁹ in the formula (2). Examples of the bivalent aromatic group, heterocyclic group or condensed ring group of R ¹⁷ and R ^{19 include} a bivalent aromatic group represented by R ¹¹ and R ¹³ in the formula (2), a heterocyclic group or a condensed ring group Respectively.

As R ²¹ , a carboxyl group is preferable.

Preferable examples of the compound represented by the formula (3) include, for example, compounds represented by the following formulas (3-1) to (3-11):

(Wherein R ⁸ has the same meaning as R ¹⁶ in the formula (3) and u is an integer of 1 to 10, respectively)

&Lt; / RTI &gt;

These compounds can be synthesized by appropriately combining information of organic synthesis. The synthesis route and the reaction conditions can be easily set by the general knowledge of the person skilled in the art and a few preliminary experiments.

In the present invention, the compound represented by the following formula (4) can be further reacted with the polyorganosiloxane (a) having an epoxy group within the range not to impair the effect of the present invention. In this case, the synthesis of the polyorganosiloxane (A) is carried out by reacting a mixture of the polyorganosiloxane (a) having an epoxy group with the compound b, a cinnamic acid derivative, if necessary, and a compound represented by the following formula (4) Is done.

In the above formula (4)

A ¹ is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 20 carbon atoms or alkoxyl group, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton . Provided that some or all of the hydrogen atoms of the alkyl group and the alkoxy group may be substituted with substituents such as a cyano group, a fluorine atom, and a trifluoromethyl group.

L ⁰ is a single bond, * -O-, * -COO- or * -OCO-. A combined hand with "*" joins A ¹ .

L ¹ represents a single bond, an alkylene group having 1 to 20 carbon atoms, a phenylene group, a biphenylene group, a cyclohexylene group, a bicyclohexylene group or a group represented by the formula (L ¹ -1) or (L ¹ -2) to be.

Z is a monovalent organic group capable of forming a bonding group by reacting with an epoxy group in the polyorganosiloxane (A).

However, when L ¹ is a single bond, L ⁰ is a single bond.

The combined hands having &quot; * &quot; in the above-mentioned expressions (L ¹ -1) and (L ¹ -2) join with Z, respectively.

Z is preferably a carboxyl group.

Examples of the linear or branched alkyl group having 1 to 30 carbon atoms represented by A ¹ in the formula (4) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, , n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2- Dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1, 3-dimethylbutyl group, Dimethylbutyl group, 1,1-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group , 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl, 2,4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl, 2,3 Dimethylpentyl, 1,3-dimethylpentyl, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3 , 3-trimethylbutyl group, 1,2,3-tri Methylheptyl group, a 2-methylheptyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 3-methylheptyl group, a 2-methylheptyl group, , n-nonanyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-heptadecyl, , n-octadecyl group, and n-nonadecyl group.

Examples of the cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group or alkoxy group having 1 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononanyl group, Dodecyl group and the like.

Examples of the hydrocarbon group having a steroid skeleton and having from 17 to 51 carbon atoms include groups represented by the following formulas (A-1) to (A-3).

As A ¹ in the formula (4), an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and a group selected from the above formula (A-1) or (A-3) are preferable.

The compound represented by the formula (4) is preferably a compound represented by any of the following formulas (4-1) to (4 to 6).

In the formulas (4-1) to (4-6), u is an integer of 1 to 5. v is an integer of 1 to 18; w is an integer of 1 to 20; k is an integer of 1 to 5; p is 0 or 1; q is an integer of 0 to 18; r is an integer of 0 to 18; s and t are each independently an integer of 0 to 2;

Among these compounds, compounds represented by the following formulas (5-1) to (5-7) are more preferable.

The compound represented by the above formula (4) is a compound which reacts with a polyorganosiloxane (a) having an epoxy group together with a specific carbonic acid to become a site that gives pretilt angularity to the resulting liquid crystal alignment film. In the present specification, the compound represented by the formula (4) is hereinafter sometimes referred to as "other pretilt angle-expressing compound".

The ratio of the compound (b) used in the synthesis of the polyorganosiloxane (A) in the present invention is preferably 0.01 to 0.5 mol based on 1 mol of the epoxy group of the polyorganosiloxane (a) having an epoxy group , More preferably 0.03 to 0.4 mol, and still more preferably 0.05 to 0.30.

When a compound having a photo-aligning group is used, the use ratio thereof is preferably 0.1 to 0.5 mol, more preferably 0.15 to 0.4 mol, per mol of the epoxy group of the epoxy group-having polyorganosiloxane (a) , And more preferably 0.2 to 0.3 mol.

When other pretilt angle-expressing compounds are used, the use ratio thereof is preferably 0.01 to 0.4 mol, more preferably 0.03 to 0.3 mol, per 1 mol of the epoxy group of the polyorganosiloxane (a) having an epoxy group And more preferably 0.05 to 0.2 mol.

As the catalyst, known compounds can be used as so-called curing accelerators for accelerating the reaction of an organic base or an epoxy compound with an acid anhydride.

The organic base includes, for example, 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 and diazabicycloundecene;

And quaternary organic amines such as tetramethylammonium hydroxide. Of 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 are preferred.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine and triethanolamine;

2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) 1- (2-cyanoethyl) -2-n-octylimidazole, 1- (2-cyanoethyl) 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- (2-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate (2- cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- Diamino-6- (2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- -Triazine, 2,4-di Methyl-imidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adducts of 2-methylimidazole, 2-phenylimidazole Imidazole compounds such as the isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine; Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenylphosphate;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphor N-butylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium, O, O-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, Quaternary phosphonium salts such as tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate; Diazabicyclo [5.4.0] undecene-7, a diazabicyclicalkene such as an organic acid salt thereof;

Organometallic compounds such as zinc octylate, tin octylate, and aluminum acetyl acetone complex;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride;

Boron compounds such as boron trifluoride, triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

A high melting point dispersed latent curing accelerator such as dicyandiamide or an amine addition type accelerator such as an adduct of an amine and an epoxy resin;

A microcapsulated latent curing accelerator wherein 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; Amine salt type latent curing accelerator;

And latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride are preferable.

The catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyorganosiloxane (a) having an epoxy group.

The reaction temperature is preferably 0 to 200 캜, more preferably 50 to 150 캜.

The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane (A) include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, and an alcohol compound. Of these, ether compounds, ester compounds, and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of products. The solvent is used in such an amount that the solid concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5 to 50% .

<Other components>

The liquid crystal aligning agent of the present invention contains the above-described polyorganosiloxane (A).

The liquid crystal aligning agent of the present invention may further contain other components in addition to the above-described polyorganosiloxane (A), so long as the effect of the present invention is not impaired. Examples of such other components include a polymer other than the radiation-sensitive polyorganosiloxane (hereinafter referred to as "other polymer (C)"), a curing agent, a curing catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule (Hereinafter referred to as &quot; epoxy compound &quot;), a functional silane compound, a surfactant, and a photosensitizer.

[Other polymer (C)]

The other polymer (C) can be used for further improving the solution characteristics of the liquid crystal aligning agent of the present invention and the electrical characteristics of the resulting liquid crystal alignment film. Examples of the other polymer (C) include at least one kind of polymer (C1) selected from the group consisting of polyamic acid and polyimide,

A polyorganosiloxane which does not have an acetal ester structure of carbonic acid, a ketal ester structure of carbonic acid, a 1-alkyl cycloalkyl ester structure of carbonic acid, and a tertiary alkyl ester structure of carbonic acid (hereinafter referred to as &quot; other polyorganosiloxanes C2) "), polyamic acid esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives and poly (meth) acrylates.

[Polyamic acid]

The polyamic acid can be obtained by reacting a tetracarboxylic acid dianhydride with a diamine.

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid in the present invention include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane 2: 3,5: 6-2 anhydride, 2 , 4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- 5,8,10-tetralone, and the like;

As aromatic tetracarboxylic acid dianhydrides, for example, pyromellitic dianhydride and the like can be used, and tetracarboxylic dianhydrides described in JP-A-2010-97188 can be used.

Among the tetracarboxylic acid dianhydrides used for synthesizing the polyamic acid, those containing an alicyclic tetracarboxylic dianhydride are preferable, and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, and particularly preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. Do.

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid may be selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride. Is contained preferably in an amount of 10 mol% or more, more preferably 20 mol% or more, and more preferably in the range of 2, 3, 5-tricarboxycyclopentyl acetic acid dianhydride and / And most preferably at least one selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride.

Examples of diamines used for synthesizing polyamic acid include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;

As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

As aromatic diamines, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9- 4,4'- (m-tert-butylphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 - diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl- , 6-diaminocarbazole, N- (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-diaminocyclohexane, N, N'- Bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy- 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecanoxy- Diaminobenzene,

Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, Stearyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 , 5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis , 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate , 1, 1 -bis (4 - ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1, , 1-bis (4 - ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1- ) Phenyl) -4- (4-heptyl cyclohexyl) cyclohexane, N- (2,4- diamino-phenyl) -piperidine and the following formula (D-1):

(Formula (D-1) of, X ^I are also combined with the alkyl group having a carbon number of 1~3, ^* -O-, ^* -COO- or ^* -OCO- (However, the combined hand-diamino phenyl group attached to "*" ), X is 0 or 1, y is an integer of 0 to 2, and z is an integer of 1 to 20)

And the like;

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and diamines described in JP-A-2010-97188 can be used .

X ^I in the above formula (D-1) is preferably an alkyl group having 1 to 3 carbon atoms, ^* -O- or ^* -COO- (provided that the bond with "*" is bonded to a diaminophenyl group) Do. Specific examples of the group C _z H _{2z + 1} - include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, N-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-octadecyl group, n-octadecyl group, Nonadecyl group, and n-eicosyl group. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or the 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-4)

And the like.

In the above formula (D-1), it is preferable that x and y do not become 0 at the same time.

These diamines may be used alone or in combination of two or more.

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used for the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic acid dianhydride is 0.2 to 2 equivalents based on 1 equivalent of the amino group contained in the diamine compound , More preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under a temperature condition of preferably -20 to 150 占 폚, more preferably 0 to 100 占 폚, preferably 0.5 to 24 hours, 2 to 10 hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, , Aprotic polar solvents such as N, N-dimethylimidazolidinone, dimethylsulfoxide,? -Butyrolactone, tetramethylurea and hexamethylphosphotriamide;

phenol-based solvents such as m-cresol, xylenol, phenol, halogenated phenol and the like. The amount (a) of the organic solvent to be used is preferably 0.1 to 50% by weight, more preferably 5 to 30% by weight, based on the total amount (a + b) of the tetracarboxylic acid dianhydride and the diamine compound %.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or after the isolated polyamic acid is purified, .

When the polyamic acid is subjected to dehydration ring closure to form a polyimide, the reaction solution may be directly supplied to the dehydration ring-closing reaction. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration ring- May be purified and then subjected to a dehydration ring-closing reaction.

The polyamic acid may be isolated by a method in which the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate and the precipitate is dried under reduced pressure or a method in which an organic solvent in the reaction solution is distilled off under reduced pressure . Alternatively, the polyamic acid may be dissolved again in an organic solvent and then precipitated with a poor solvent, or a method in which after the solution after the redissolution is washed with water, a step of distilling off the organic solvent in the solution by vacuum distillation is carried out once Or the polyamic acid can be purified by a method of several times or the like.

[Polyimide]

The polyimide can be produced by dehydrating and ring closure of the acid structure of the polyamic acid obtained as described above. At this time, the whole of the arboric acid structure may be fully imidized by dehydration ring closure, or only a part of the arboric acid structure may be dehydrated and ring-closed to be a partial imide cargo wherein the arid acid structure and the imide structure coexist.

The dehydration ring-closure of the polyamic acid can be carried out by a method of (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring- Lt; / RTI &gt;

The reaction temperature in the method of heating the polyamic acid of (i) is preferably 50 to 200 캜, more preferably 60 to 170 캜. If the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the resulting imidized polymer may be lowered. The reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.

On the other hand, in the method of adding the dehydrating agent and the dehydrating ring-closing catalyst to the polyamic acid solution of the above (ii), an acid anhydride such as acetic anhydride, anhydrous propionic acid or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the polyamic acid structural unit. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, the present invention is not limited to these. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration cyclization reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

The polyimide obtained in the method (i) may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided in the preparation of the liquid crystal aligning agent after the obtained polyimide is purified. On the other hand, in the method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent or may be provided in the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated, Or may be provided to the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent substitution can be applied. Isolation and purification of polyimide can be carried out by performing the same operation as described above as a method for isolating and purifying polyamic acid.

[Other polyorganosiloxane (C2)]

The other polyorganosiloxane (C2) can be produced, for example, by mixing at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter also referred to as a &quot; raw silane compound &quot;), Can be synthesized by hydrolysis or hydrolysis / condensation in an organic solvent in the presence of water and a catalyst.

Examples of the raw material silane compounds usable herein include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra- -Butoxysilane, tetra-tert-butoxysilane, tetrachlorosilane; Butoxysilane, methyltri-sec-butoxysilane, methyltri-sec-butoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri- propyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopropoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri- butoxy silane, ethyl tri-tert-butoxy silane, ethyl trichlorosilane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl trichlorosilane, dimethyl dimethoxy silane, Silane, dimethyldiethoxysilane, dimethyldichlorosilane; Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and the like. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane Or trimethylethoxysilane is preferable.

Examples of the organic solvent that can optionally be used in the synthesis of the other polyorganosiloxane (C2) include an alcohol compound, a ketone compound, an amide compound or an ester compound or other aprotic compound. These may be used alone or in combination of two or more.

Examples of the alcohol compound include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, sec-pentanol, sec-heptanol, 3-heptanol, n-hexanol, sec-pentanol, Octanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol , sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4- Polyhydric alcohol compounds such as 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;

Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene And partial ethers of polyhydric alcohol compounds such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether. These alcohol compounds may be used singly or in combination of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, Butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethyl nonane, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, Monoketone compounds;

Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, Dione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4 -Diketone compounds such as heptanedione, and the like. These ketone compounds may be used singly or in combination of two or more kinds.

Examples of the amide compound include N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N -Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. These amide compounds may be used singly or in combination of two or more.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate,? -Butyrolactone,? -Valerolactone, n-propyl acetate, Butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate , Acyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol mono Ethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol acetate Propyleneglycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, acetic acid methoxy triglycol Butyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid, methyl phthalate, ethyl phthalate, ethyl lactate, isopropyl myristate, isopropyl myristate, Diethyl and the like. These ester compounds may be used singly or in combination of two or more kinds.

Examples of the other aprotic compounds include acetonitrile, dimethylsulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, , N-methylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl- Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1 H) - Pyrimidone, and the like.

Of these solvents, polyhydric alcohol compounds and partial ethers or ester compounds of polyhydric alcohol compounds are particularly preferred.

The ratio of the water used in the synthesis of the other polyorganosiloxane (C2) is preferably 0.5 to 100 moles per mole of the total amount of the alkoxyl group and the halogen atom contained in the raw material silane compound, more preferably 0.5 to 100 moles, More preferably 1 to 30 moles, and still more preferably 1 to 1.5 moles.

Examples of the catalyst that can be used in the synthesis of the other polyorganosiloxane (C2) include a metal chelate compound, an organic acid, an inorganic acid, an organic base, ammonia, and an alkali metal compound.

Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium (Acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis (Acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di- (Acetyl acetonate) titanium, di-sec-butoxy bis (acetylacetonate) titanium, di-t-butoxy bis (acetylacetonate) titanium, monoethoxy tris · Tris (acetylacetonate) titanium, mono-i-propoxy · tris (acetylacetonate ) Titanium, mono-t-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, (Acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri- (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (Ethyl acetoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-n-butoxy bis (ethylacetoacetate) titanium, Di-sec-butoxy bis (ethylacetoacetate) titanium, di-t-butoxy (Ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris Butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethylacetoacetate) titanium, tetrakis (Ethyl acetoacetate) titanium, bis (acetylacetonate) titanium, tris (acetylacetonate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis ;

Tri-n-butoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri- (Acetylacetonate) zirconium, diethoxy bis (acetylacetonate) zirconium, di-tert-butoxy mono (acetylacetonate) zirconium, n-butoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di- (Acetylacetonate) zirconium, di-t-butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris Mono-i-propoxy tris (Acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium (Ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (ethylacetoacetate) (Ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, tri-t-butoxy mono (ethylacetoacetate) zirconium, diethoxy Bis (ethylacetoacetate) zirconium, di-n-propoxy bis (ethylacetoacetate) zirconium, di-i-propoxy bis Acetate) zirconium, di-sec-butoxy bis (ethylacetoacetate) zirconium, di-t-butoxy bis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, Propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-sec-butoxy tris Ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis Zirconium chelate compounds such as bis (ethylacetoacetate) zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium;

Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethyl acetoacetate) aluminum, and the like.

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, Dihydroxy benzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, Acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanol Amine, triethanolamine, diazabicycloundane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, and the like.

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

These catalysts may be used alone or in combination of two or more.

Among these catalysts, a metal chelate compound, an organic acid or an inorganic acid is preferable, and a titanium chelate compound or an organic acid is more preferable.

The amount of the catalyst to be used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the raw material silane compound.

The water to be added in the synthesis of the other polyorganosiloxane (C2) can be added intermittently or continuously in a silane compound as a raw material or in a solution in which a silane compound is dissolved in an organic solvent.

The catalyst may be added in advance in a silane compound as a raw material or in a solution in which a silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.

The reaction temperature in the synthesis of the other polyorganosiloxane (C2) is preferably 0 to 100 占 폚, more preferably 15 to 80 占 폚. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

[Use ratio of other polymer (C)] [

When the liquid crystal aligning agent of the present invention contains other polymer (C) in addition to the above-mentioned polyorganosiloxane (A), the content of the other polymer (C) is preferably 100 parts by weight of the polyorganosiloxane (A) To 10,000 parts by weight or less. A more preferable content of the other polymer (C) differs depending on the kind of the other polymer (C).

In the case where the liquid crystal aligning agent of the present invention contains at least one kind of polymer (C1) selected from the group consisting of polyorganosiloxane (A) and polyamic acid and polyimide, , And the total amount of polyamic acid and polyimide relative to 100 parts by weight of the polyorganosiloxane (A) is 200 to 5,000 parts by weight, particularly preferably 500 to 2,500 parts by weight.

On the other hand, in the case where the liquid crystal aligning agent of the present invention contains the polyorganosiloxane (A) and the other polyorganosiloxane (C2), a more preferable ratio of the both is 100% Is 100 to 2,000 parts by weight as the amount of other polyorganosiloxane (C2) relative to parts by weight.

When the liquid crystal aligning agent of the present invention contains other polymer (C) together with the polyorganosiloxane (A), the kind of the other polymer (C) is preferably at least one selected from the group consisting of polyamic acid and polyimide It is preferable that the polymer (C1) of the species, or the other polyorganosiloxane (C2). The other polymer (C) is particularly preferably at least one polymer (C1) selected from the group consisting of polyamic acid and polyimide.

[Epoxy Compound]

The epoxy compound may be contained in the liquid crystal aligning agent of the present invention from the viewpoint of further improving the adhesion to the substrate surface of the liquid crystal alignment film to be 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, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- Di-aminomethylcyclohexane, and the like.

The mixing ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 40 parts by weight or less based on 100 parts by weight of the sum of the polymers (the sum of the polyorganosiloxane (A) and the other polymer (C) Is 0.1 to 30 parts by weight. When the liquid crystal aligning agent of the present invention contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of efficiently causing a cross-linking reaction of an epoxy group.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the adhesion of the obtained liquid crystal alignment film to the substrate. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3- , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silane triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N- 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like can be given. , And a reaction product of a tetracarboxylic acid dianhydride and a silane compound having an amino group, which are described in Patent Document 17 (Japanese Unexamined Patent Publication (Kokai) No. 63-291922).

When the liquid crystal aligning agent of the present invention contains a functional silane compound, the content thereof is preferably 50 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the total amount of the polymer.

[Curing agent, curing catalyst]

The curing agent and the curing catalyst may be contained in the liquid crystal aligning agent of the present invention for the purpose of strengthening the crosslinking of the polyorganosiloxane (A) and further increasing the strength of the liquid crystal alignment film. When the liquid crystal aligning agent of the present invention contains a curing agent, a curing accelerator may be further used in combination.

As the curing agent, a curing agent generally used for curing an epoxy group can be used. As such a curing agent, for example, a polyvalent amine, a polyvalent carboxylic acid, and a polyvalent carboxylic acid anhydride can be used. Specific examples include benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, cyclohexane- Acid, cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid- -Tetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, terpinene, dodecanedicarboxylic anhydride, and the like, in addition to anhydride, cyclohexane-1,2,3-tricarboxylic acid- Alicyclic compounds having a conjugated double bond such as alococene and anhydrides and maleic anhydride, or addition products of these aliphatic dicarboxylic acids with aliphatic dicarboxylic acids such as aliphatic aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, Examples of the tetracarboxylic acid dianhydride used in the synthesis include the compounds exemplified above.

Examples of the curing accelerator include imidazole compounds, quaternary compounds, quaternary amine compounds, diazacycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and its organic acid salts;

Organometallic compounds such as zinc octylate, tin octylate, and aluminum acetyl acetone complex;

Boron compounds such as boron trifluoride, triphenyl borate; Metal halide compounds such as zinc chloride, zinc stannate,

A high melting point dispersed latent curing accelerator such as an amine addition type accelerator such as dicyandiamide or an adduct of an amine with an epoxy resin;

A microcapsulated latent curing accelerator wherein the surface of the curing accelerator such as the quaternary phosphonium salt is coated with a polymer; Amine salt type latent curing accelerator; And latent curing accelerators such as high temperature dissociation type thermal cationic polymerization latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

As the curing catalyst, for example, an antimony hexafluoride compound, a hexafluorophosphate compound, and aluminum trisacetylacetonate can be used.

[Surfactants]

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants.

When the liquid crystal aligning agent of the present invention contains a surfactant, the content thereof is preferably 10 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the total amount of the liquid crystal aligning agent.

<Liquid Crystal Aligner>

As described above, the liquid crystal aligning agent of the present invention contains the polyorganosiloxane compound (A) as an essential component and, if necessary, other components, but preferably each component is dissolved in an organic solvent Based on the total weight of the composition.

As the organic solvent that can be used for preparing the liquid crystal aligning agent of the present invention, it is preferable that the polyorganosiloxane (A) and other optional components are not dissolved and reacted with them.

The preferable organic solvent which can be preferably used in the liquid crystal aligning agent of the present invention differs depending on the kind of the other polymer (C) optionally added.

When the liquid crystal aligning agent of the present invention contains at least one kind of polymer (C1) selected from the group consisting of polyorganosiloxane (A), polyamic acid and polyimide, preferable organic solvents include polyamic acid Organic solvents exemplified above can be used for the synthesis. These organic solvents may be used alone or in combination of two or more.

On the other hand, in the case where the liquid crystal aligning agent of the present invention contains only the polyorganosiloxane (A) as the polymer, or contains the polyorganosiloxane (A) and the other polyorganosiloxane (C2) Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether (ethylene glycol monoethyl ether), ethylene glycol monomethyl ether , Ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetone Butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate Butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n- Hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate and isoamyl acetate. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-

The preferred solvent used in the preparation of the liquid crystal aligning agent of the present invention is one obtained by combining one or more of the above organic solvents depending on whether or not other polymer (C) is used and the kind thereof, In which the respective components contained in the liquid crystal aligning agent are not precipitated in the solid concentration and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mN / m.

The solid concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., By weight. The liquid crystal aligning agent of the present invention is applied to the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. When the solid concentration is less than 1% by weight, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film have. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large, which makes it difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased and coating properties are sometimes insufficient. A particularly preferable range of the solid concentration is different depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the range of 1.5 to 4.5 wt% is particularly preferable. In the case of the printing method, it is particularly preferable to set the solid concentration in the range of 3 to 9% by weight and the solution viscosity in the range of 12 to 50 mPa · s accordingly. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and the solution viscosity is in the range of 3 to 15 mPa · s accordingly.

The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 0 ° C to 200 ° C, and more preferably 10 ° C to 60 ° C.

<Liquid crystal display element>

The liquid crystal display element of the present invention comprises the liquid crystal alignment layer formed of the liquid crystal aligning agent of the present invention as described above.

The method of forming a liquid crystal alignment film using the liquid crystal aligning agent of the present invention is a method in which the liquid crystal aligning agent of the present invention is applied onto a substrate when the polyorganosiloxane (A) in the present invention does not have a photo aligning group A coating film is formed, and rubbing treatment is performed as necessary, whereby a liquid crystal alignment film can be formed.

On the other hand, when the polyorganosiloxane (A) has a photo-aligning group, a liquid crystal aligning film can be formed by applying a liquid crystal aligning agent of the present invention on a substrate to form a coating film and then irradiating the coating film with radiation .

[When the polyorganosiloxane (A) does not have a photo-orientable group]

First, the liquid crystal aligning agent of the present invention is coated on a substrate, and then a coated film is formed on the substrate by heating the coated surface. The liquid crystal aligning agent of the present invention is preferably applied to a surface of each of the two transparent substrates having the patterned transparent conductive film formed thereon by a roll coater method, a spinner method, a printing method, an inkjet method Respectively. Then, the coated surface is preheated (prebaked) and then baked (post baked) to form a coated film. The prebaking condition is, for example, 0.1 to 5 minutes at 40 to 120 占 폚, and the postbaking condition is preferably 120 to 300 占 폚, more preferably 150 to 250 占 폚, preferably 5 to 200 minutes, Preferably 10 to 100 minutes. The film thickness of the coated film after post baking is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

Examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and alicyclic polyolefin can be used.

As the transparent conductive film to be formed on one surface of the substrate, an ITO film made of NESA film (a registered trademark of PPG Corporation of the US) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) . In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photoetching after forming a pattern-free transparent conductive film, a method of using a mask having a desired pattern for forming a transparent conductive film, and the like . When applying the liquid crystal aligning agent, a functional silane compound, a functional titanium compound or the like is preferably added to the surface of the substrate on which the coating film should be formed in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film The pre-treatment for pre-coating may be carried out.

When the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film for a vertically aligned liquid crystal display element, the thus formed film can be used as it is as a liquid crystal alignment film for a vertically aligned liquid crystal display element. Surface may be arbitrarily subjected to rubbing treatment. On the other hand, when the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film for a horizontal alignment type liquid crystal display device, a coating film formed as described above may be rubbed to form a liquid crystal alignment film.

The rubbing treatment can be carried out by rubbing the fabric in a predetermined direction with a roll formed of fibers such as nylon, rayon, and cotton. In this case, as shown in, for example, Patent Document 18 (Japanese Unexamined Patent Application Publication No. 6-222366) and Patent Document 19 (Japanese Unexamined Patent Application Publication No. 6-281937), a liquid crystal alignment layer The pretilt angle may be changed by irradiating a part of the ultraviolet ray. Alternatively, as shown in Patent Document 20 (Japanese Patent Application Laid-Open No. 5-107544), a resist film may be formed on a part of the surface of the formed liquid crystal alignment layer The rubbing treatment is performed in a direction different from that of the rubbing treatment, and then the resist film is removed and the liquid crystal alignment film has a different liquid crystal aligning ability for each region, thereby improving the visual characteristics of the obtained horizontal liquid crystal display element It is also good.

Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is arranged between the two substrates to manufacture a liquid crystal cell. To produce a liquid crystal cell, for example, the following two methods can be used.

The first method is a conventionally known method. First, two substrates are opposed to each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other. The peripheral portions of the two substrates are bonded together using a sealant, After the liquid crystal is injected and filled in the cell gap, the injection hole is sealed to manufacture the liquid crystal cell.

The second method is a so-called ODF (One Drop Fill) method. For example, an ultraviolet curable sealant is applied to a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, the liquid crystal is further dropped on the liquid crystal alignment film surface, A liquid crystal cell can be manufactured by bonding one of the substrates and then curing the sealing agent by irradiating ultraviolet light to the entire surface of the substrate.

In either case, it is preferable to remove the flow orientation at the time of injection by heating the liquid crystal cell to a temperature at which the liquid crystal using the liquid crystal takes an isotropic phase (isotropic phase), and gradually cooling to room temperature.

The liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell.

As the sealing agent, for example, an aluminum oxide spheres 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 producing a liquid crystal display element having a TN type liquid crystal cell or an STN type liquid crystal cell, it is preferable to use a nematic type liquid crystal having positive dielectric anisotropy (positive type liquid crystal), for example, biphenyl type liquid crystal, phenyl cyclohexane Based liquid crystal, ester liquid, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, quaternary liquid crystal and the like. Examples of the liquid crystal include cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate; Chiral agents such as those sold under the trade names C-15 and CB-15 (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate and the like may be further added and used.

On the other hand, in the case of a vertically aligned liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy (negative liquid crystal) is preferable, and for example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, Biphenyl-based liquid crystal, phenylcyclohexane-based liquid crystal, and the like are used.

As the polarizing plate used for the outside of the liquid crystal cell, a polarizing plate in which a polarizing film called &quot; H film &quot; in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched orientation is sandwiched by a cellulose acetate protective film or a polarizing plate made of H film itself have.

[When the polyorganosiloxane (A) has a photo-orientable group]

In this case, in the method for producing a liquid crystal alignment film in the case where the polyorganosiloxane (A) does not have a photo-aligning group, a liquid crystal display element can be manufactured by performing irradiation treatment with radiation instead of rubbing treatment.

As the radiation used for the radiation irradiation treatment, linearly polarized or partially polarized radiation or non-polarized radiation can be used. For example, ultraviolet rays or visible rays including light having a wavelength of 150 to 800 nm can be used, Ultraviolet rays containing light having a wavelength of 400 nm are preferred. When the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed in a direction perpendicular to the substrate surface, or may be performed in an oblique direction to give a pre-tilt angle, or in combination. In the case of irradiating non-polarized radiation, the irradiation direction needs to be an oblique direction.

As the 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 and an excimer laser can be used. The ultraviolet ray of the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with a filter, a diffraction grating, or the like.

The irradiation dose of the radiation is preferably 1 J / m 2 or more and less than 10,000 J / m 2, and more preferably 10 to 3,000 J / m 2. Further, in the case of imparting the liquid crystal aligning ability to the coating film formed by the conventionally known liquid crystal aligning agent by the photo alignment method, a radiation dose of 10,000 J / m 2 or more was required. However, by using the liquid crystal aligning agent of the present invention, it is possible to impart good liquid crystal alignability even when the irradiation dose in the photo alignment method is 3,000 J / m2 or less, more preferably 1,000 J / m2 or less, particularly 500 J / m2 or less, Thereby contributing to a reduction in the manufacturing cost of the battery.

The liquid crystal display element of the present invention is preferably a vertically aligned liquid crystal display element.

The liquid crystal display element of the present invention thus produced is excellent in heat resistance, light resistance, and electrical characteristics, and is excellent in stability over time of the pretilt angle even when a liquid crystal alignment film is formed by a radiation irradiation treatment.

(Example)

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

In the following examples, the weight average molecular weight is a polystyrene-reduced value measured by gel permeation chromatography under the following conditions.

Column: TSKgelGRCXLII, manufactured by Toso Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

The epoxy equivalent was measured in accordance with JIS C2105 &quot; hydrochloric acid-methyl ethyl ketone method &quot;.

The following synthesis examples were repeated with the following synthesis scales as necessary to ensure the required amount of product used in the following synthesis examples and examples.

<Synthesis of polyorganosiloxane (a) having an epoxy group>

Synthesis Example 1

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, And mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out, washed with a 0.2 wt% aqueous ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane EPS- As a transparent liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane EPS-1, a peak based on the oxiranyl group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm as the theoretical intensity, and a side reaction of the epoxy group occurred during the reaction It was confirmed that there was not.

The polyorganosiloxane EPS-1 had an Mw of 2,200 and an epoxy equivalent of 186.

&Lt; Synthesis of compound b >

Compound b (B-1-1) was synthesized according to the following reaction formula.

                                                        (B-1-1)

Synthesis Example 2

1.80 g of monomethyl terephthalate, 3.27 g of di-tert-butyl dicarbonate and 25 ml of THF were mixed and stirred at room temperature for 10 minutes. After adding 0.37 g of 4-dimethylaminopyridine, the mixture was reacted at 25 DEG C for 6 hours with stirring. After mixing with ethyl acetate, the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution and distilled water. Concentrated and dried to obtain 1.54 g of the objective intermediate. 1.16 g of the intermediate, 0.42 g of lithium hydroxide hydrate, 6 ml of methanol and 2 ml of distilled water were mixed and reacted at 25 ° C for 1 hour with stirring. After mixing with 50 ml of ethyl acetate, the mixture was washed with diluted hydrochloric acid and distilled water, and concentrated. The obtained powder was mixed with chloroform, and insoluble matter was removed by filtration. The filtrate was concentrated and dried to obtain 0.80 g of compound b (B-1-1) as a white powder.

Synthesis Example 3

45 g of a compound represented by the compound b (B-1-2) was obtained according to the following reaction formula.

5.0 g of 1,3-benzenecarboxylic acid (1,1-dimethylethyl) methyl, 16.35 g of di-tert-butyl dicarbonate and 50 ml of THF were mixed and stirred at room temperature for 10 minutes. After adding 1.85 g of 4-dimethylaminopyridine, the mixture was reacted at 25 DEG C for 6 hours with stirring. After mixing with ethyl acetate, the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution and distilled water. Concentrated and dried to obtain 7.70 g of the objective intermediate. 5.80 g of the above intermediate, 2.10 g of lithium hydroxide hydrate, 20 ml of methanol and 4 ml of distilled water were mixed and reacted by stirring at 25 DEG C for 1 hour.

After mixing with 50 ml of ethyl acetate, the mixture was washed with diluted hydrochloric acid and distilled water, and concentrated. The obtained powder was mixed with chloroform, and insoluble matter was removed by filtration. The filtrate was concentrated and dried to obtain 3.0 g of compound b (B-1-2) as a white powder.

Synthesis Example 4

According to the following reaction formula, 7.2 g of a compound represented by the compound b (B-1-3) was obtained.

0.15 mol (15.0 g) of succinic anhydride, 0.045 mol (5.0 g) of N-hydroxysuccinimide, 0.015 mol (1.75 g) of 4-dimethylaminopyridine and 75 ml of toluene were mixed and stirred.

17.5 ml of tert-butanol and 6.25 ml of triethylamine, and the mixture was reacted by heating under reflux for 24 hours.

The mixture was mixed with 75 ml of ethyl acetate, washed with 10% citric acid water and saturated brine, and dehydrated with sodium sulfate. The mixture was concentrated using a rotary evaporator to obtain a viscous liquid. Recrystallization in acetone afforded 0.04 mol (7.2 g) of compound b (B-1-3).

&Lt; Synthesis of specific cinnamic acid derivatives >

All synthesis reactions of specific cinnamic acid derivatives were carried out in an inert atmosphere.

Synthesis Example 5

The following scheme:

, The cinnamic acid derivative (A-1) was synthesized.

31 g of the compound (A-1-1), 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine, 56 ml of triethylamine, 56 g of acrylic acid And 200 ml of N, N-dimethylacetamide were placed, and the reaction was carried out at 120 deg. C for 3 hours with stirring. After completion of the reaction, the reaction mixture was filtered, and 1 liter of ethyl acetate was added to the filtrate. The resulting organic layer was washed twice with diluted hydrochloric acid and three times with water, dried over magnesium sulfate, and then the solvent was removed under reduced pressure. Was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain 15 g of crystals of the cinnamic acid derivative (A-1).

Synthesis Example 6

The following scheme:

, The cinnamic acid derivative (A-2) was synthesized.

91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 ml of N-methyl-2-pyrrolidone were placed in a 1 L eggplant-shaped flask and stirred at room temperature for 1 hour. Then, 99.7 g of 1-bromopentane And the reaction was carried out with stirring at 100 DEG C for 5 hours. After completion of the reaction, re-precipitation was performed with water. Next, to this precipitation, 48 g of sodium hydroxide and 400 ml of water were added and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 104 g of white crystals of intermediate (A-2A).

104 g of this intermediate (A-2A) was placed in a reaction vessel, to which 1 L of thionyl chloride and 770 uL of N, N-dimethylformamide were added, followed by stirring at 80 DEG C for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, and methylene chloride was added thereto, followed by washing with an aqueous solution of sodium hydrogencarbonate, drying with magnesium sulfate, concentration and then adding tetrahydrofuran to obtain a solution.

Next, 74 g of 4-hydroxycinnamic acid, 138 g of potassium carbonate, 4.8 g of tetrabutylammonium, 500 ml of tetrahydrofuran, and 1 L of water were put into a 5 L three-necked flask different from the above. This aqueous solution was ice-cooled, and a tetrahydrofuran solution containing a reaction product of the above intermediate (A-2A) and thionyl chloride was slowly added dropwise, and the reaction was further carried out for 2 hours with stirring. After completion of the reaction, hydrochloric acid was added to the reaction mixture to neutralize and extracted with ethyl acetate. The extract was dried with magnesium sulfate, concentrated and recrystallized with ethanol to obtain 90 g of a white crystal of the cinnamic acid derivative (A-2) .

Synthesis Example 7

The following scheme:

, The cinnamic acid derivative (A-3) was synthesized.

82 g of methyl 4-hydroxybenzoate, 166 g of potassium carbonate and 400 ml of N, N-dimethylacetamide were placed in a 1 L eggplant-shaped flask and stirred at room temperature for 1 hour. Then, 4,4,4-trifluoro- 95 g of iodobutane was added and the reaction was carried out at room temperature for 5 hours with stirring. After completion of the reaction, re-precipitation was performed with water. Next, 32 g of sodium hydroxide and 400 ml of water were added to this precipitation, and the mixture was refluxed for 4 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 80 g of white crystals of intermediate (A-3A).

46.4 g of this intermediate (A-3A) was placed in a reaction vessel, to which 200 ml of thionyl chloride and 0.2 ml of N, N-dimethylformamide were added and the mixture was stirred at 80 ° C for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, and methylene chloride was added thereto, followed by washing with an aqueous solution of sodium hydrogencarbonate, drying with magnesium sulfate, concentration and then adding tetrahydrofuran to obtain a solution.

Next, 36 g of 4-hydroxycinnamic acid, 55 g of potassium carbonate, 2.4 g of tetrabutylammonium, 200 ml of tetrahydrofuran, and 400 ml of water were placed in a 2 L three-necked flask different from the above. This aqueous solution was ice-cooled, and a tetrahydrofuran solution containing a reaction product of the above intermediate (A-3A) and thionyl chloride was slowly added dropwise and the reaction was further carried out for 2 hours with stirring. After completion of the reaction, hydrochloric acid was added to the reaction mixture to neutralize and extracted with ethyl acetate. The extract was dried with magnesium sulfate, concentrated and recrystallized with ethanol to obtain 39 g of white crystals of the cinnamic acid derivative (A-3) .

Synthesis Example 8

The following scheme:

, The cinnamic acid derivative (A-4) was synthesized.

Namely, the synthesis was carried out in the same manner as in the synthesis of the cinnamic acid derivative (A-2) in Synthesis Example 6 except that 14 g of 4-pentyltrans bicyclohexylcarbonic acid was used instead of the intermediate (A-2A) 15 g of a white crystal of the cinnamic acid derivative (A-4) was obtained.

Synthesis Example 9

The following scheme:

, A cinnamic acid derivative (A-5) was synthesized.

82 g of p-hydroxycinnamic acid, 304 g of potassium carbonate and 400 ml of N-methyl-2-pyrrolidone were placed in a 1 L eggplant-shaped flask and stirred at room temperature for 1 hour. Then 166 g of 1-bromopentane was added, C &lt; / RTI &gt; for 5 hours. Thereafter, the solvent was distilled off under reduced pressure. 48 g of sodium hydroxide and 400 ml of water were added thereto and refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was recovered and recrystallized from ethanol to obtain 80 g of a white crystal of the cinnamic acid derivative (A-5).

&Lt; Synthesis of other pretilt angle-expressing compound >

Synthesis Example 10

The following scheme:

, Compound (T-1) was synthesized.

39 g of? -Cholestanol, 20 g of succinic anhydride, 1.5 g of N, N-dimethylaminopyridine, 200 ml of ethyl acetate and 17 ml of triethylamine were placed in a 500 ml three-necked flask equipped with a stirrer, The reaction was carried out under reflux. After completion of the reaction, 200 ml of tetrahydrofuran was added to the reaction mixture, and the organic layer was washed successively with 2N aqueous hydrochloric acid and three times with water, dried over magnesium sulfate and the solvent was removed under reduced pressure. The resulting solid was dissolved in acetic acid Ethyl to obtain 38 g of white crystals of the compound (T-1).

&Lt; Synthesis of polyorganosiloxane (A) >

Synthesis Example 11

10.0 g of the polyorganosiloxane EPS-1 having the epoxy group synthesized in Synthesis Example 1, 30.28 g of methyl isobutyl ketone, and the compound b (B-1-1) obtained in the above Synthesis Example 2 were added to a 200 ml three- 1.59 g of the specific cinnamic acid derivative (A-1) obtained in Synthesis Example 5 (corresponding to 10% by mole of the polyorganosiloxane ESP-1) (Corresponding to 10 mol% with respect to the epoxy group of the polyorganosiloxane ESP-1) and UCAT 18X (corresponding to 10 mol% with respect to the epoxy group of the polyorganosiloxane ESP-1) represented by the following specific cinnamic acid derivative (A- , A curing accelerator of an epoxy compound, manufactured by San A Pro Co., Ltd.), and the reaction was carried out at 100 ° C for 48 hours with stirring. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate, and the resulting solution was dissolved in ethyl acetate, and the resulting solution was washed three times. The organic layer was dried with magnesium sulfate and the solvent was distilled off, 8.1 g of white powder of siloxane (A) POS-1 was obtained. POS-1 had a weight average molecular weight of 10,700.

Synthesis Examples 12 to 34, Comparative Synthesis Examples 1 to 6

The procedure of Synthesis Example 11 was repeated except that the compound shown in Table 1 was used instead of the compound b (B-1-1) and the specific cinnamic acid derivative (A-1) to prepare a polyorganosiloxane (A) POS-2 To 23, and POSA-1 to 6 were obtained.

However, the specific cinnamic acid derivative (A-7) has the following structure.

The ratio of the compound b, the specific cinnamic acid derivative, and other pretilt angle-expressing compounds in Table 1 is the mole% relative to the epoxy group of the polyorganosiloxane EPS-1.

In the table, T-2 is stearic acid.

&Lt; Synthesis of other polymer (C) >

[Synthesis of polyamic acid]

Synthesis Example PA-1

(1.0 mole) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride as a tetracarboxylic dianhydride and 212 g (1.0 mole) of 2,2'-dimethyl-4,4'-diaminobiphenyl as a diamine, Was dissolved in 4,050 g of N-methyl-2-pyrrolidone and reacted at 40 占 폚 for 3 hours to obtain 4,400 g of a solution containing 10% by weight of polyamic acid (PA-1). The solution viscosity of this polyamic acid solution was 170 mPa · s.

Synthesis Example PA-2

41 g of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 46 g of pyromellitic dianhydride, and 114 g of BAPC as diamine were dissolved in 800 g of N-methyl-2-pyrrolidone as a tetracarboxylic acid dianhydride, Deg.] C for 3 hours, 1,000 g of N-methyl-2-pyrrolidone was added to obtain about 1,900 g of a solution containing 10% by weight of polyamic acid (PA-2). The solution viscosity of this polyamic acid solution was 115 mPa · s.

Synthesis Example PA-3

82 g of 2,3,5-tricarboxy dicyclopentyl acetic acid dihydrate as tetracarboxylic dianhydride, 20 g of paraphenylenediamine as diamine and 97 g of 3ξ-cholestan-3-yl-3, 5-diaminobenzoate were dissolved in N -Methyl-2-pyrrolidone and reacted at 60 占 폚 for 5 hours. Then, 3 g of maleic anhydride was added as a polymerization terminator to prepare a solution solution containing 20% by weight of polyamic acid (PA-3) 1,000 g was obtained. The solution viscosity of this polyamic acid was 110 mPa s.

Synthesis Example PA-4

38 g of 2,3,5-tricarboxy dicyclopentyl acetic acid dihydrate as a tetracarboxylic acid dianhydride, 17 g of 4,4'-diaminodiphenyl ether as a diamine and 17 g of 3ξ-cholestan-3-yl- (PA-4) was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 占 폚 for 5 hours, followed by addition of 2 g of maleic anhydride as a polymerization terminator. To obtain about 500 g of a solution containing 0.1% by weight. The solution viscosity of this polyamic acid was 80 mPa · s.

Synthesis Example PA-5

512 g of 2,3,5-tricarboxy dicyclopentyl acetic acid dihydrate as a tetracarboxylic acid dianhydride, 324 g of 4,4'-diaminodiphenyl ether as a diamine and 324 g of 3ξ-cholestan-3-yl- (PA-5) was dissolved in 4800 g of N-methyl-2-pyrrolidone and reacted at 60 占 폚 for 5 hours. Thereafter, 22 g of maleic anhydride was added as a polymerization terminator to obtain 20 To obtain about 6000 g of a solution containing the solution. The solution viscosity of this polyamic acid was 80 mPa · s.

[Synthesis of polyimide]

Synthesis Example PI-1

(0.093 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride and 9.2 g (0.085 mole) of p-phenylenediamine as diamine and the following formula (D-2):

Was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing polyamic acid.

A small amount of the obtained polyamic acid solution was collected and added with N-methyl-2-pyrrolidone to measure the solution viscosity as a solution having a polymer concentration of 10% by weight. As a result, the solution viscosity was 126 mPa · s.

Subsequently, 325 g of N-methyl-2-pyrrolidone was added to the resulting polyamic acid solution, and 7.4 g of pyridine and 9.5 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain about 210 g of a solution containing 16.1 wt% of polyimide (PI-1) having an imidization rate of about 54%.

A small amount of this polyimide solution was collected and N-methyl-2-pyrrolidone was added thereto to measure the solution viscosity as a solution having a polymer concentration of 10% by weight, and the solution viscosity was 75 mPa · s.

[Synthesis of curing agent]

Synthesis Example S-1

The following scheme:

, The compound (S-1) was synthesized.

21 g of trimesic acid, 60 g of n-butyl vinyl ether and 0.09 g of phosphoric acid were placed in a 500 ml three-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, and the reaction was carried out at 50 DEG C for 30 hours with stirring. After completion of the reaction, 500 ml of hexane was added to the reaction mixture, and the resulting organic layer was washed twice with 1 M aqueous sodium hydroxide solution and three times with water. Thereafter, the solvent was distilled off from the organic layer to obtain 50 g of the compound (S-1) as a colorless transparent liquid.

<Preparation of liquid crystal aligning agent and evaluation of storage stability>

Example 1

2,000 parts by weight of the solution containing the polyamic acid PA-1 synthesized in Synthesis Example PA-1 as PA-1 was taken as the other polymer (C), and the amount of the polyorganosiloxane (A) , 100 parts by weight of the polyorganosiloxane (A) POS-1 synthesized in Synthesis Example 11 was added, and further N-methyl-2-pyrrolidone and butyl cellosolve were added to obtain a solution having a solvent composition of N-methyl- - pyrrolidone: butyl cellosolve = 50: 50 (weight ratio), and a solid content concentration of 3.6% by weight. This solution was filtered with a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent C-1. The storage stability of the liquid crystal aligning agent C-1 was evaluated by the following methods and criteria. As a result, the storage stability of the liquid crystal aligning agent C-1 was found to be &quot; good &quot;.

[Evaluation method of storage stability]

The liquid crystal aligning agent was stored at -15 캜 for 6 months. Before and after storage, the viscosity was measured by an E-type clay system at 25 ° C. When the change rate of the solution viscosity before and after storage was less than 10%, the storage stability was evaluated as &quot; good &quot;, and when it was 10% or more, the storage stability was evaluated as &quot; defective &quot;.

Examples 2 to 23 and Comparative Examples 1 to 11

The liquid crystal aligning agents C-2 to C-23 and CA-1 to 11 were prepared in the same manner as in Example 1 except that kinds and amounts of the polyorganosiloxane were changed as shown in Table 2, I appreciated. The evaluation results are shown in Table 2.

In the table, S-2 is 1,2,4-benzenetricarboxylic acid.

Example 24

&Lt; Production and Evaluation of Liquid Crystal Display Device >

[Production of liquid crystal display device]

The liquid crystal aligning agent C-1 prepared in Example 1 was coated on the transparent electrode surface of the glass substrate with the transparent electrode made of ITO film using a spinner and prebaked on a hot plate at 80 DEG C for 1 minute, Was heated at 200 캜 for 1 hour in an oven substituted with nitrogen to form a coating film having a thickness of 0.1 탆. Subsequently, polarizing ultraviolet rays (200 J / m 2) including a bright line of 313 nm were irradiated onto the surface of the coating film from a direction inclined 40 ° from the normal to the substrate using a Hg-Xe lamp and a Glane Taylor prism to form a liquid crystal alignment film. The same operation was repeated to prepare a pair of substrates (two pieces) having a liquid crystal alignment film.

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied to the periphery of the surface having one liquid crystal alignment film in the above substrate by screen printing and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, So that the projection direction of the optical axis of the optical axis to the substrate surface was anti-parallel, and the adhesive was heat-cured at 150 DEG C for 1 hour. Subsequently, a negative type liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 150 占 폚 and slowly cooled to room temperature. Next, a polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions thereof were orthogonal to each other, and the optical axis of the ultraviolet ray of the liquid crystal alignment film was angled at an angle of 45 degrees with respect to the substrate surface.

[Evaluation of liquid crystal display element]

(3) evaluation of light resistance, and (4) evaluation of stability of the pretilt angle were carried out on the liquid crystal display device manufactured as described above, in addition to (1) evaluation of liquid crystal orientation and (2) . The evaluation results are shown in Table 3.

(1) Evaluation of liquid crystal alignment property

The presence or absence of an abnormal domain in the change of light and dark when a voltage of 5 V was turned ON / OFF (applied / released) to the liquid crystal display device manufactured above was visually observed.

A case where no light leakage is observed from the cell at the time of voltage OFF and a cell drive region is white display at the time of voltage application and no light leakage from the other region is referred to as &quot; good &quot;, and when the voltage is OFF, When light leakage was observed, or when light leakage was observed from an area other than the cell driving area when the voltage was turned on, the liquid crystal alignment property was evaluated as &quot; poor &quot;, and as a result, the liquid crystal alignment property of this liquid crystal display device was found to be &quot; good &quot;.

(2) Evaluation of Voltage Conservation Rate

A voltage of 5 V was applied to the liquid crystal display device manufactured at 60 캜 for an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the release voltage was measured. VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

(3) Evaluation of light resistance

The initial voltage holding ratio was measured on the liquid crystal display device manufactured as described above under the same conditions as the evaluation of the voltage holding ratio. Thereafter, the sample was placed at a distance of 5 cm under a 100-watt white fluorescent lamp, irradiated with light for 500 hours, and then the voltage maintenance rate was measured again under the same conditions as above. Quot; A &quot; when the rate of decrease of the voltage holding ratio was 1% or less as compared with the initial value, and &quot; B &quot;

(4) Evaluation of stability of pre-tilt angle

Non-Patent Document 2 (TJ Scheffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)), Non-Patent Document 3 (F. Nakano, et al., JPN. The pretilt angle was measured (initial pretilt angle) by a crystal rotation method using He-Ne laser light in accordance with the method described in J. Appl. Phys. Vol. 19, p2013 (1980).

Subsequently, the liquid crystal display element after the initial pretilt angle measurement was allowed to stand at 23 DEG C for 30 days, and the pretilt angle was again measured (pretilt angle after storage) by the same method as described above.

At this time, the amount of change of the pretilt angle after storage with respect to the initial pretilt angle was examined. When this value was less than 0.1, stability was evaluated as "good" with respect to the elapsed time of the pretilt angle, "possible" when it was less than 0.3 and less than 0.3, and "impossible" when it was more than 0.3.

Examples 25 to 39, 42 to 45, and Comparative Examples 12 to 17

Liquid crystal display devices were prepared and evaluated in the same manner as in Example 24 except that the kind of the liquid crystal aligning agent used was changed as shown in Table 3. [ The results are shown in Table 3.

Examples 40 and 41 and Comparative Examples 18 to 21

The polarizing plate was irradiated with polarized ultraviolet rays from the direction of the normal line of the substrate and the polarizing plate was polarized perpendicular to the polarizing direction using a nematic liquid crystal (ZLI-1565, manufactured by Merck Co., Ltd.) Liquid crystal display elements were produced and evaluated in the same manner as in Example 24 except that the liquid crystal display elements were bonded so as to be orthogonal to the projection direction. The results are shown in Table 3.

Example 46, Comparative Example 22

Liquid crystal display elements were each produced and evaluated in the same manner as in Example 24 except that the kind of the liquid crystal aligning agent used was as shown in Table 3 and the polarized ultraviolet ray irradiation step was not performed. The results are shown in Table 3.

Claims (7)

A polyorganosiloxane having at least one structure selected from the group consisting of a 1-alkyl cycloalkyl ester structure of a carboxylic acid and a tertiary alkyl ester structure of a carboxylic acid. The method according to claim 1,
Wherein the polyorganosiloxane has an epoxy structure. The method according to claim 1,
Wherein the polyorganosiloxane is a polyorganosiloxane having an epoxy group,
A carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, at least one member selected from (where, R is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom), the group consisting of -CH = CH ₂ and -SO ₂ Cl And a compound having at least one member selected from the group consisting of a 1-alkyl cycloalkyl ester structure of carbonic acid and a tertiary alkyl ester structure of carbonic acid
Wherein the liquid crystal aligning agent is a polyorganosiloxane. 4. The method according to any one of claims 1 to 3,
Wherein the polyorganosiloxane has a photo-orientable group. 4. The method according to any one of claims 1 to 3,
And further at least one polymer selected from the group consisting of polyamic acid and polyimide. 4. The method according to any one of claims 1 to 3,
A liquid crystal aligning agent characterized by further comprising a 1-alkyl cycloalkyl ester structure of a carboxylic acid and a polyorganosiloxane having no tertiary alkyl ester structure of a carboxylic acid. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal aligning agent according to any one of claims 1 to 3.