KR101642788B1 - Liquid crystal aligning agent, liquid crystal display device and polyorganosiloxane compounds - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent capable of forming a liquid crystal display element having excellent performance such as a voltage holding ratio and a residual image characteristic while realizing a high-speed response of the liquid crystal element, a liquid crystal display comprising a liquid crystal alignment film formed of the liquid crystal aligning agent It is an object of the present invention to provide a polyorganosiloxane compound which is suitably used for a device and a liquid crystal aligning agent.
(A) a polyorganosiloxane compound, wherein the polyorganosiloxane compound [A] comprises a part derived from a polyorganosiloxane having an epoxy group and a part derived from a polyorganosiloxane having a carboxyl group represented by the following formula (1) Is a liquid crystal aligning agent having a moiety derived from a compound.
[Chemical Formula 1]

Description

LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL DISPLAY DEVICE AND POLYORGANOSILOXANE COMPOUNDS <br> <br> <br> Patents - stay tuned to the technology LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL DISPLAY DEVICE AND POLYORGANOSILOXANE COMPOUNDS

The present invention relates to a liquid crystal aligning agent which is very suitable as a material for forming an alignment film of a liquid crystal display element (LCD), a liquid crystal display element having a liquid crystal alignment film formed of the liquid crystal aligning agent and a polyorganosiloxane compound .

In recent years, liquid crystal display devices have advantages such as small power consumption, small size, and ease of flattening. Therefore, the liquid crystal display devices can be widely used for applications ranging from small liquid crystal display devices such as cellular phones to large screen liquid crystal display devices such as liquid crystal televisions .

Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), VA (Vertical Alignment), and the like are used as driving modes of the liquid crystal display in accordance with changes in the orientation It is known. In addition, in the VA mode, a multi-domain vertical alignment (MVA) method or a PVA (patterned vertical alignment) method is adopted to increase the viewing angle by the orientation division. Further, A tilt angle is given to thereby adopt a photo-vertical alignment method, a PSA (Polymer Sustained Alignment) method, or the like. In any of the driving modes, the alignment state of the liquid crystal molecules is directly controlled by the liquid crystal alignment film, and the liquid crystal alignment film takes a considerable proportion of the expression and control of the functional characteristics of the liquid crystal display device.

Such a liquid crystal display device is expected to be used as a moving picture display device such as a cellular phone or a liquid crystal television. As a characteristic required for a liquid crystal display device, in order to smoothly display a moving picture and to suppress the afterimage as much as possible, A higher speed is required. With respect to this demand, there has been reported a technique for improving the performance by providing a structure for imparting dielectric anisotropy to the polymer side chain used in the liquid crystal alignment film (see Japanese Patent Publication No. 2007-521361 and Japanese Patent Publication No. 2007-521506) . However, this patent document does not disclose electrical characteristics such as orientation, voltage holding ratio, and afterimage characteristic which are important in practical use in addition to speeding up the electrooptical response time.

Under such circumstances, it has been desired to develop a liquid crystal aligning agent capable of forming a liquid crystal aligning element having a short electro-optical response time while satisfying electrical characteristics such as orientation and voltage holding ratio generally required as a liquid crystal aligning element.

Japanese Patent Publication No. 2007-521361 Japanese Patent Publication No. 2007-521506

SUMMARY OF THE INVENTION The present invention has been made based on the above-described circumstances, and an object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal display element having excellent performance such as voltage holding ratio and afterimage characteristics while continuously realizing high- A liquid crystal display element such as a vertical type having a liquid crystal alignment film formed of an alignment agent, and a polyorganosiloxane compound suitably used for a liquid crystal aligning agent.

According to an aspect of the present invention,

[A] A composition containing a polyorganosiloxane compound,

The polyorganosiloxane compound [A]

A part derived from a polyorganosiloxane having an epoxy group,

Is a liquid crystal aligning agent having a moiety derived from a compound having a carboxyl group represented by the following formula (1) (hereinafter occasionally referred to as "specific carbonic acid").

[In the formula (1), R ¹ is a methylene group or an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group; These groups may have a substituent; R ² is a linking group comprising a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom; R ³ is a group having at least two monocyclic structures; a is an integer of 0 to 1].

Since the liquid crystal aligning agent contains a polyorganosiloxane compound, the liquid crystal display device comprising the liquid crystal alignment film formed using the liquid crystal aligning agent has good orientation, high voltage holding characteristics, It is possible to shorten the response time (start time) together with the excellentness. Further, by having an epoxy group, the liquid crystal aligning agent improves electrical characteristics such as orientation and voltage holding ratio. Further, since the liquid crystal aligning agent has a specific structural unit, a structure having dielectric anisotropy is introduced into the side chain, and the liquid crystal display device having the liquid crystal alignment film formed using the liquid crystal aligning agent has further improved electrical characteristics and afterimage characteristics And the response time is further shortened. Further, by using the reactivity between the epoxy group and the carboxyl group, it is possible to easily introduce a structure having the dielectric anisotropy represented by the above formula (1) as a side chain in the polyorganosiloxane as a main chain.

R ³ in the formula (1) is preferably a group represented by the following formula (2).

[Wherein R ⁴ and R ⁶ are each a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle, May have; R ⁵ is a linking group containing any of an alkylene group, a double bond, a triple bond, an ether bond, an ester bond and a heterocycle having 1 to 10 carbon atoms which may have a substituent; R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group or an alkoxy group, and when R ⁶ has plural substituents, they may be the same or different; b is an integer from 0 to 1; and c is an integer of 1 to 9.

By introducing the structure represented by the formula (2) into the side chain of the polyorganosiloxane compound of the liquid crystal aligning agent, the electro-optical responsiveness of the obtained liquid crystal aligning element can be further increased.

It is preferable that the epoxy group is a group represented by the following formula (X ¹ -1) or (X ¹ -2).

[Wherein, in the formula (X ¹ -1), A is an oxygen atom or a single bond; h is an integer from 1 to 3; i is an integer from 0 to 6; Provided that when i is 0, A is a single bond; "*" Indicates a combined hand).

A side chain group derived from a compound having a specific structure represented by the formula (1) is introduced into the polyorganosiloxane compound of the liquid crystal aligning agent by including a group represented by the formula (X ¹ -1) or (X ¹ -2) It becomes easier to do.

The liquid crystal aligning agent preferably further comprises at least one polymer selected from the group consisting of [B] polyamic acid and polyimide (hereinafter sometimes referred to as &quot; [B] polymer &quot;). When a liquid crystal alignment film is produced using such a polymer, a liquid crystal display device having improved electric characteristics is obtained.

The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed of the liquid crystal aligning agent. Thereby, a liquid crystal display element having excellent electric characteristics such as orientation, voltage conservation, and afterimage characteristics and having high electro-optical response can be obtained.

A liquid crystal display element having a transparent electrode and the liquid crystal alignment film stacked on the transparent electrode, and having two or more regions in which the liquid crystal alignment mode is vertical and the alignment direction is different are also suitably included in the present invention. As means having two or more regions having different orientation orientations, it is preferable to use a means using a transparent electrode patterned as the transparent electrode or a means for imparting an alignment division function to the liquid crystal alignment film. Such a liquid crystal display element can be suitably applied also in a driving mode such as TN, STN, IPS, and VA (including VA-MVA system and VA-PVA system) and further improves the contrast, Speed response.

The present invention provides a liquid crystal display element having a transparent electrode and a liquid crystal alignment film laminated on the transparent electrode, wherein the liquid crystal alignment mode is vertical, and the liquid crystal alignment film has two or more regions having different orientation orientations, As a liquid crystal aligning agent, a liquid crystal alignment system characterized by containing a compound having a group represented by the following formula (3) is suitably included. As a means having two or more regions having different orientation orientations, it is preferable to use a patterned transparent electrode or a liquid crystal alignment film having an alignment division function.

[In the formula (3), R ² is a linking group comprising a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom; R ³ is a group having at least two monocyclic structures; a is an integer of 0 to 1; "*" Indicates a combined hand).

The liquid crystal display device of the present invention is a liquid crystal display device having two or more regions in which the liquid crystal alignment mode is vertical and the alignment direction is different, wherein the liquid crystal alignment agent (liquid crystal alignment characterized by containing a compound having a group represented by the formula (3) And a liquid crystal alignment film formed from a liquid crystal alignment film formed on the substrate.

The polyorganosiloxane compound of the present invention is a compound having a part derived from a polyorganosiloxane having an epoxy group and a compound having a carboxyl group represented by the following formula (1), or a compound in which R ³ in the formula (1) Having a moiety derived from a compound having a group.

[Chemical Formula 1]

[In the formula (1), R ¹ is a methylene group or an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group; These groups may have a substituent; R ² is a linking group comprising a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom; R ³ is a group having at least two monocyclic structures; a is an integer of 0 to 1;

(2)

[Wherein R ⁴ and R ⁶ are each a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle, May have; R ⁵ is a linking group containing any of an alkylene group, a double bond, a triple bond, an ether bond, an ester bond and a heterocycle having 1 to 10 carbon atoms which may have a substituent; R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group or an alkoxy group, and when R ⁶ has plural substituents, they may be the same or different; b is an integer from 0 to 1; and c is an integer of 1 to 9.

Such a polyorganosiloxane compound can be suitably used for a liquid crystal aligning agent for constituting a liquid crystal display element having a performance such as an orientation property, a high-speed responsiveness, a voltage characteristic and a residual image characteristic.

According to the present invention, it is possible to provide a liquid crystal aligning agent capable of forming a liquid crystal display element excellent in orientation, capable of high-speed response, and excellent in performances such as voltage characteristics and afterimage characteristics. Therefore, the liquid crystal display element can be suitably applied also in a driving mode such as TN, STN, IPS, VA (VA-MVA system, VA-PVA system, etc.) and the like.

1 (a) is a plan view showing one form of a patterned transparent electrode used in the present invention. 1 (b) is an enlarged sectional view taken along the line X-X 'in the plan view.
2 is a plan view showing another form of the patterned transparent electrode used in the present invention.
3 is a plan view showing another embodiment of the patterned transparent electrode used in the present invention.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention contains a [A] polyorganosiloxane compound. Since the liquid crystal aligning agent contains the [A] polyorganosiloxane compound, the liquid crystal display device comprising the liquid crystal alignment film formed using the liquid crystal aligning agent has good orientation properties and high voltage retention characteristics, Further, the afterimage characteristic is excellent and the response time can be shortened. Further, it may contain the "other polymer" described later such as the [B] polymer. Other optional components may be contained within the range not impairing the effects of the present invention. Each component will be described in detail below.

<[A] polyorganosiloxane compound>

[A] The polyorganosiloxane compound has a part derived from a polyorganosiloxane having an epoxy group and a part derived from a specific carbonic acid represented by the formula (1). Since the liquid crystal aligning agent has a specific structural unit, a structure having dielectric anisotropy is introduced into the side chain, and the liquid crystal display device including the liquid crystal alignment film formed using the liquid crystal aligning agent has further improved electrical characteristics and afterimage characteristics , The response time is shortened. Further, by utilizing the reactivity between the epoxy group and the carboxyl group, it is possible to easily introduce the structure having the dielectric anisotropy represented by the above formula (1) as the side chain in the polyorganosiloxane as the main chain.

It is considered that the polyorganosiloxane compound [A] is mainly obtained as a reaction product of the epoxy group of the polyorganosiloxane and the carboxyl group of the specific carbonic acid. However, in order to facilitate the following description, the polyorganosiloxane compound having an epoxy group A derivative thereof) and a part derived from a specific carbonic acid, and then the [A] polyorganosiloxane compound contained in the liquid crystal aligning agent will be described.

[Portion derived from polyorganosiloxane having an epoxy group]

This part is a concept including a polyorganosiloxane skeleton as a polymer main chain and an epoxy group-containing skeleton as a side chain extending from the main chain of the polyorganosiloxane in the structure of the [A] polyorganosiloxane compound. As described above, in the polyorganosiloxane compound [A], it is considered that most epoxy groups do not have an initial structure due to reaction with a specific carbon acid, but there may be a case where a specific carbon acid is bonded to a portion other than an epoxy group. Thus, in the present invention, the term &quot; part derived from a polyorganosiloxane having an epoxy group &quot;

When the [A] polyorganosiloxane compound has an epoxy group such as a glycidyl group, a glycidyloxy group, or an epoxycyclohexyl group, the liquid crystal aligning agent has improved electrical properties such as orientation and voltage holding ratio. The epoxy group is preferably a group represented by the formula (X ¹ -1) or (X ¹ -2). (X ¹ -1) or (X ¹ -2) in the polyorganosiloxane having the structural unit represented by the above-mentioned formula (1), the polyorganosiloxane compound of the liquid crystal aligning agent is added to the polyorganosiloxane having the formula 1), it is easy to introduce a side chain group derived from a compound having a specific structure.

Among the above-mentioned formula (X ¹ -1) or (X ¹ -2), groups represented by the following formulas are preferable.

[In the formulas (X ¹ -1 -1) and (X ¹ -2 -1), "*" indicates a combined hand).

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyorganosiloxane having an epoxy group is preferably 500 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 1,000 to 20,000 .

[Method for synthesizing polyorganosiloxane having epoxy group]

The polyorganosiloxane having such an epoxy group is preferably obtained by hydrolyzing a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and other silane compounds, preferably in the presence of an appropriate organic solvent, water and a catalyst, Can be synthesized by decomposition and condensation.

Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidylsilane, 3-glycidyloxypropyldimethylethoxysilane, 2- 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyl Glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldi 4-glycidyloxybutyldimethylmethoxysilane, 4-glycidyloxybutyldimethylethoxy (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) Ethoxy silane, 3- (3,4-epoxycyclohexyl) propyl triethoxy silane and the like. These may be used alone or in combination of two or more.

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- Acryloxypropyltrimethoxysilane, acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3- Mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltriethoxysilane, 3- Silane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane N-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyl tri Ethoxy silane, phenyl tri-n-propoxy silane, phenyl tri-i-propoxy silane, phenyl tri-n-butoxy silane, phenyl tri- Methyldiethoxy silane, methyl di-n-butoxy silane, methyl di-sec-butoxy silane, dimethyl di-n-propoxy silane, methyl di- Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyl di-n-butoxysilane, dimethyl di-sec- Ethyl) dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro- n-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] (Methyl) [2- (perfluoro-n-octyl) ethyl] di-i-propoxysilane, ) Ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3- Methoxy silane, (methyl) (3-mercaptopropyl) diethoxy silane, (methyl) (3-mercaptopropyl) di- Propoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (3-mercaptopropyl) di-n-butoxysilane, (Methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl) (vinyl) di- (Vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi- Silane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, di Phenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyl di-n-butoxysilane, diphenyl di-sec- Propyltrimethylsilane, n-propoxytrimethylsilane, i-propyltrimethylsilane, i-propyltrimethylsilane, n-propyltrimethylsilane, n-propyltrimethylsilane, i-propyltrimethylsilane, Butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) ) Silane compounds having one silicon atom such as dimethylsilane, dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane and (ethoxy) (methyl) diphenylsilane.

Examples of commercially available products include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-22-170BX, X-22-170D, X-22-170DX, X-22-170B, X-21-5846, X- X-22-176D, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X- 2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X- KR-200, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR- KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (all, Shin-Etsu Chemical Co., Ltd.);

Glass resin (manufactured by Showa Denko K.K.);

SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, 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, Kolkot K.K.);

And partial condensates of GR100, gR650, gR908 and gR950 (manufactured by Showa Denko K.K.).

Of these other silane compounds, tetraethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltri (meth) acrylate, (Meth) acrylates such as methoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane are preferable Do.

The polyorganosiloxane having an epoxy group preferably used in the present invention preferably has an epoxy equivalent of 100 to 10,000 g / mol, more preferably 150 to 1,000 g / mol, for introducing a side chain having dielectric anisotropy in a sufficient amount And particularly preferably 150 to 300 g / mole. Therefore, when synthesizing a precursor of a polyorganosiloxane having an epoxy group, it is preferable to prepare and set such that the ratio of the silane compound to the other silane compound is such that the epoxy equivalent of the polyorganosiloxane having the epoxy group obtained is within the above range . In synthesizing the polyorganosiloxane having an epoxy group used in the present invention, it is more preferable to use only the silane compound and not use any other silane compound.

Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane having an epoxy group include a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, and an alcohol compound.

Examples of the hydrocarbons 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 to be used is preferably 10 to 10,000 parts by mass, more preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of the total silane compound. The amount of water used when preparing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 moles, and more preferably 1 to 30 moles per mole of the total 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.

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. 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; Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

As the catalyst for preparing the polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing a side reaction such as ring opening of an epoxy group, . The liquid crystal aligning agent containing a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a specific carboxylic acid is very suitable because of its excellent storage stability. 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 can be 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 liquid crystal aligning agent contains other polymers as described later, the condensation reaction between the silanol groups and other polymers is suppressed , Resulting in excellent storage stability.

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

The hydrolysis or hydrolytic condensation reaction in the production of the polyorganosiloxane having an epoxy group can be carried out by dissolving an epoxy group-containing silane compound and, if necessary, other silane compounds in an organic solvent, mixing the solution with an organic base and water For example, an oil bath or the like.

In the hydrolysis and condensation reaction, the heating temperature of the oil bath is preferably 130 DEG C or lower, more preferably 40 to 100 DEG C, preferably 0.5 to 12 hours, more preferably 1 to 8 hours desirable. 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 cleaning, it is preferable that the cleaning is performed by washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 mass% or the like. The washing is carried out until the water layer after 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 desired polyorganosiloxane having an epoxy group Can be obtained.

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

The [A] polyorganosiloxane compound is a compound derived from a hydrolyzate generated by hydrolysis of an epoxy group-containing polyorganosiloxane per se or a hydrolyzed condensate obtained by hydrolysis and condensation of polyorganosiloxanes having an epoxy group May be included. These hydrolyzate and hydrolyzed condensate which are constituent materials of the part can also be prepared in the same manner as the hydrolysis and condensation conditions of the polyorganosiloxane having an epoxy group.

[Part derived from a specific carbon acid]

This part represented by the above formula (1) is a part of the structure of the polyorganosiloxane compound of the component [A] contained in the liquid crystal aligning agent, and the carboxyl group bonded to the structure derived from the epoxy group mainly extending from the main chain of the polyorganosiloxane Chain structure having a structure derived from a group as a starting point. However, in the present invention, the term &quot; a part derived from a specific carbon acid &quot; is also referred to as &quot; a part derived from a specific carbon acid, &quot; including a case where a specific carbon acid bonds with a part other than an epoxy group.

R ¹ in the formula (1) is a methylene group or an alkylene group, a phenylene group or a cyclohexylene group having 2 to 30 carbon atoms, which may further have a substituent.

Examples of the alkylene group having 2 to 30 carbon atoms include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, And examples thereof include a silane group, a silane group, an octadecylene group, a nonadecylene group, an eicosylene group, a heneicosylene group, a docosylene group, a tricosylene group, a tetracosylene group, A heptacosylene group, an octacosylene group, a nonacosylene group, and a triacontylene group. Of these, in order to stably express the liquid crystal alignment, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, an octadecylene group, An alkylene group having 8 to 20 carbon atoms such as a silylene group is preferable.

R ² is a linking group containing any of a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom. In addition, R ² may contain any of the above-mentioned bonds, but these may be combined. When R &lt; ¹ &gt; is a phenylene group or a cyclohexylene group, it is preferable that R &lt; ² &gt; contains an alkylene group having 1 to 30 carbon atoms, from the viewpoint of the orientation of the formed alignment film and the solubility in solvents. Also, a is an integer of 0 to 1.

R ³ is a group having at least two monocyclic structures and preferably exhibits positive or negative dielectric anisotropy. The monocyclic structure is a structure having no so-called condensed ring structure in which one cyclic structure exists independently from other cyclic structures, and one cyclic structure is shared with another cyclic structure. As the monocyclic structure, any of an alicyclic structure, an aromatic cyclic structure and a heterocyclic structure may be used, or a combination thereof may be used.

R ³ is not particularly limited as long as it is a group having at least two monocyclic structures, and typically, R ³ is a group represented by the formula (2). By introducing the structure represented by the formula (2) into the side chain of the polyorganosiloxane compound of the liquid crystal aligning agent, the electro-optical responsiveness of the obtained liquid crystal aligning element can be further increased. In the formula (2), R ⁴ and R ⁶ each independently represent a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle. Examples of the heterocyclic ring include a pyridine ring, a pyridazine ring, and a pyrimidine ring.

In the above formula (2), R ⁵ is preferably an alkylene group having 1 to 10 carbon atoms, which may have a substituent, R ⁴ and / or R ⁵ , which may contain an alkylene group, a double bond, a triple bond, an ether bond, R ⁶ , and can be appropriately selected in accordance with the orientation and dielectric anisotropy required for the polyorganosiloxane compound. In addition, since b is an integer of 0 or 1, R ⁵ may or may not be included in the design of the side chain structure.

In the formula (2), R ⁷ is any of a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group and an alkoxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group and a propoxycarbonyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group and an isobutyl group, Examples of the alkoxy group such as a straight chain or branched chain alkyl group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group and a propoxy group.

In the above formula (2), when R ⁶ has a plurality of substituents (R ⁷ ), different ones may be used in combination. As a combination when R ⁶ has a plurality of substituents, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, and a combination of a cyano group and an alkyl group are preferable in order to stably express the desired dielectric anisotropy. Also, c is an integer of 0 to 9.

Examples of the compound having a carboxyl group represented by the formula (1) include compounds represented by the following formulas (D-1) to (D-25).

[In the formulas (D-1) to (D-25), R ³ has the same meaning as in the formula (1); m is an integer of 1 to 30;

Examples of the group represented by the formula (2) include groups represented by the following formulas (E-1) to (E-58).

In the formulas (E-1) to (E-58), R represents an alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, n- butyl group, isobutyl group, n- ) Or an alkoxy group (methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, etc.)].

[Method for synthesizing a specific carbon acid]

The synthesis procedure of the specific carbonic acid is not particularly limited, and can be carried out by combining conventional known methods. As a typical synthetic procedure, for example, (1) a method of reacting a compound having a phenol skeleton with a compound in which an alkyl chain portion of a higher fatty acid ester is substituted with a halogen under basic conditions to obtain a (2) reacting a compound having a phenol skeleton with ethylene carbonate to produce a terminal alcohol compound, reacting the hydroxyl group with a halogenated benzene sulfonyl chloride to form a terminal alcohol compound, and And then reacting the activated portion with methyl benzoate containing a hydroxyl group to produce a bond with the hydroxyl group of the terminal alcohol compound and the hydroxyl group of the methyl benzoate including a hydroxyl group as a substituent with the elimination of the sulfonyl moiety, Is reduced to give a specific carbonic acid. However, the synthesis procedure of the specific carbonic acid is not limited to these.

&Lt; Synthesis method of [A] polyorganosiloxane compound >

The method for synthesizing the [A] polyorganosiloxane compound is not particularly limited, and can be synthesized by a generally known method. As a method for synthesizing the [A] polyorganosiloxane compound having an epoxy group, a polyorganosiloxane having an epoxy group and a specific carbon acid can be synthesized preferably by reacting in the presence of a catalyst.

Here, the specific carbonic acid is preferably selected from the group consisting of

Preferably 0.001 to 10 moles, more preferably 0.01 to 5 moles, and still more preferably 0.05 to 2 moles.

In the present invention, a part of the specific carbonic acid may be substituted by a compound represented by the following formula (5) within the range not to impair the effect of the present invention. In this case, the synthesis of the [A] polyorganosiloxane compound is carried out by reacting a polyorganosiloxane having an epoxy group with a mixture of a specific carbon acid and a compound represented by the following formula (4).

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 [A] polyorganosiloxane compound.

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, Methylbutyl group, a 1-methylbutyl group, a 2,2-dimethylpropyl group, a n-hexyl group, a 4-methylpentyl group, a 3-methylbutyl group, a 3-methylbutyl group, Dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 1-methylbutyl group, a 1-methylbutyl group, a 1-methylbutyl group, Methylbutyl, 2-methylbutyl, 2-methylbutyl, 1,1-dimethylbutyl, Dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group, Dimethylpentyl group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,3,3-trimethylbutyl group, 1,2,3-trimethylbutyl methylheptyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a n-hexyl group, a n-hexyl group, N-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-hexadecyl, 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 an alkoxy group having 1 to 20 carbon atoms represented by A ¹ in the formula (4) include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, A t-butyl group, a cyclononanyl group, a cyclodecyl group, and a cyclododecyl group.

Examples of the hydrocarbon group having 17 to 51 carbon atoms and having a steroid skeleton represented by A ¹ in the formula (4) 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 having an epoxy group together with a specific carbonic acid to become a site giving 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".

In the present invention, when other pretilt angle-expressing compounds are used together with specific carbonic acid, the total use ratio of the specific carbonic acid and other pretilt angle-expressing compounds is preferably in the range of 1 mole to 1 mole of the epoxy group of the polyorganosiloxane Is preferably 0.001 to 1.5 moles, more preferably 0.01 to 1 mole, and still more preferably 0.05 to 0.9 mole. In this case, the other pretilt angle-expressing compound is used in an amount of preferably not more than 75 mol%, more preferably not more than 50 mol% with respect to the total amount with the specific carbonic acid. When the proportion of the other pretilt angle-expressing compound is more than 75 mol%, there is a case where the high-speed responsiveness of the liquid crystal is adversely affected.

Examples of the catalyst used in the reaction of the epoxy group in the polyorganosiloxane with the carboxylic acid group-containing compound represented by the formula (4) and other pretilt angle-expressing compounds include organic bases or so-called catalysts which promote the reaction between the epoxy compound and the acid anhydride Known compounds can be used as the curing accelerator.

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, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and 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- (2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s - triazine, 2 , 4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, Imidazole compounds such as isocyanuric acid adduct of imidazole and adduct of isocyanuric acid of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s- ;

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenphosphate; Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium Iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O-diethylphosphorodithioonate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoro Quaternary phosphonium salts such as roboate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts 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 trichloride and triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

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 in which the surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;

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.

Among these catalysts, 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 mass or less, more preferably 0.01 to 100 parts by mass, and still more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polyorganosiloxane 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.

The synthesis reaction of the polyorganosiloxane compound [A] can be carried out in the presence of an organic solvent if necessary. Examples of such an organic solvent 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 preferably has a solid content concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) of preferably 0.1 mass% or more and 70 mass% or less, more preferably 5 mass% or more and 50 mass% As shown in FIG.

The weight average molecular weight of the polyorganosiloxane compound thus obtained by gel permeation chromatography in terms of styrene by the gel permeation chromatography is not particularly limited, but is preferably 1,000 to 200,000, more preferably 2,000 to 20,000. Within this molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

The polyorganosiloxane compound [A] of the present invention introduces into the polyorganosiloxane having an epoxy group a structure derived from a specific carbonic acid by ring-opening addition to the epoxy group of the carboxylate portion of the specific carbonic acid. This production method is very convenient in that it is simple, and further, the introduction ratio of the structure derived from a specific carbon acid can be increased.

<Optional ingredients>

The liquid crystal aligning agent may contain, in addition to the [A] polyorganosiloxane compound, a polymer other than the [A] polyorganosiloxane compound (hereinafter referred to as &quot; other polymer &quot; (Hereinafter may be referred to as &quot; epoxy compound &quot;), a functional silane compound, a surfactant, and the like may be added to the composition of the present invention in the presence of a curing catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule .

[Other Polymers]

Other polymers can be used to further improve the solution properties of the liquid crystal aligning agent and the electrical characteristics of the obtained liquid crystal aligning element. As the other polymer, for example,

At least one polymer selected from the group consisting of polyamic acid and polyimide ([B] polymer);

At least one selected from the group consisting of a polyorganosiloxane represented by the following formula (5), a hydrolyzate thereof and a condensate of the hydrolyzate thereof (hereinafter sometimes referred to as "other polyorganosiloxane");

Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like can be given as examples of the polyamide acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative,

[In the formula (5), X ¹ is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms; Y ¹ is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms].

<[B] Polymer>

[B] The polymer is at least one polymer selected from the group consisting of polyamic acid and polyimide. Hereinafter, polyamic acid and polyimide will be described in detail.

[Polyamic acid]

The polyamic acid is obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound. Examples of tetracarboxylic acid dianhydrides which can be used for the synthesis of polyamic acid include 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetra Carbonic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 3,5,6-tri Carboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- , 5-dioxo-3-furanyl) -naphtho, 2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- , 5-dioxo-3-furanyl) -8-methyl-naphtho [1,2-c] -Cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, ) To (F-14) Aliphatic or alicyclic tetracarboxylic dianhydrides such as carbonic acid dianhydride;

Pyromellitic dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene tetra 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3 ', 4,4'- , 4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride , 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,4'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) dianhydride, m-phenylene- Acid) and the like can be mentioned 4,4'-diphenylmethane dianhydride, the following formula (F-15) ~ (aromatic tetracarboxylic acid dianhydride such as tetracarboxylic dianhydride represented by the F-18).

Among these, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] , 3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) c] -furan-1,3-dione, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarbon Acid anhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5 Naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, and the formula (F-1 ), (F-2), and (F-15) to (F-18). These tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

Examples of diamine compounds usable for the synthesis of polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4 , 4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4 , 4'-diaminodiphenyl ether, 4,4'-diamino-2,2'-dimethylbiphenyl, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl Amino-1- (4'-aminophenyl) -1,3,3-trimethylindene, 3-amino- , 4'-diaminodiphenyl ether, 2,2-bis (4-aminophenoxy) propane, 2,2-bis [4- Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (aminophenoxy) phenyl] hexafluoropropane, 2,2- 1,4-bis (4-aminophenoxy) benzene, 1,3-bis Bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2 -Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4 '- (p- Isopropylidene) bisaniline, 4,4 '- (m-phenylene isopropylidene) bisaniline, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoro 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octa, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, Fluorobiphenyl, 6- (4-chalconyloxy) hexyloxy (2,4-diaminobenzene), 6- (4'- 4-diaminobenzene), 8- (4-chalconyloxy) octyloxy (2,4-diaminobenzene), 8- 2,4-diaminobenzene, 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy Diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholestearyloxy- Diaminobenzene, 1-cholestanyloxy-2,4-diaminobenzene, dodecyloxy (3,5-diaminobenzoyl), tetradecyloxy (3,5-diaminobenzoyl), pentadecyloxy (3,5-diaminobenzoyl), hexadecyloxy (3,5-diaminobenzoyl), octadecyloxy (3,5-diaminobenzoyl), cholestearyloxy (3,5-diaminobenzoyl ), Cholestanyloxy (3,5-diaminobenzoyl), (2,4-diaminophenoxy) palmitate, (2,4-diaminophenoxy) stearate, (2,4- Phenoxy) -4-trifluoromethylbenzoate, and diamine compounds represented by the following formulas (G-1) to (G-7);

Aromatic diamines having a hetero atom such as diaminotetraphenylthiophene;

1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4- Tetramethyldicyclopentadienylenediamine, hexahydro-4,7-methanoindenyldimethylenediamine, tricyclo [6.2.1.0 &lt; ^2,7 &gt; Aliphatic or alicyclic diamines such as undecylenedimethyldiamine and 4,4'-methylenebis (cyclohexylamine);

And diamino organosiloxanes such as diaminohexamethyldisiloxane and the like.

Of these, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2'-dimethylbiphenyl, cyclohexanebis (methylamine) 4,4'-diaminodiphenyl ether, 4,4 '- (p-phenylene isopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2- Phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [

2-trifluoromethylphenoxy] -octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1- Cholestanoloxy-2,4-diaminobenzene, hexadecyloxy (3,5-diaminobenzoyl), octadecyloxy (3,5 Diaminobenzoyl), cholestearyloxy (3,5-diaminobenzoyl), cholestanyloxy (3,5-diaminobenzoyl), diamines represented by the above formulas (G-1) to . These diamines may be used singly or in combination of two or more.

The ratio of the tetracarboxylic dianhydride and the diamine compound to be used in the synthesis reaction of the polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid dianhydride relative to 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, more preferably 2 10 hours. Here, 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, tetramethyl urea, and hexamethylphosphotriamide; phenol-based solvents such as m-cresol, xylenol, phenol, and halogenated phenol. The amount (a) of the organic solvent to be used is preferably 0.1 to 50% by mass, more preferably 5 to 30% by mass, based on the total amount (a + b) of the tetracarboxylic acid dianhydride and the diamine compound Mass%.

The organic solvent may be used in combination with alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbons, etc., which are poor solvents of polyamic acid, within a range in which polyamic acid to be produced is not precipitated. Examples of such poor solvents include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, ethylene glycol monomethyl ether, , Butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, propylene carbonate, diethyl oxalate, Diethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether (ethylene glycol monoethyl ether), ethylene glycol diethyl ether, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, , Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4- Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene and xylene. These poor solvents may be used alone or in combination of two or more.

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, . The polyamic acid can be isolated by pouring the reaction solution into a large amount of a poor solvent to obtain a precipitate, drying the precipitate under reduced pressure, or a method of distilling off the reaction solution by distillation under reduced pressure. The polyamic acid can be purified by a method in which the polyamic acid is dissolved again in an organic solvent, followed by precipitation with a poor solvent, or a step of distillation under reduced pressure using a diverter, once or several times.

[Polyimide]

The polyimide can be produced by subjecting the acid structure of the polyamic acid obtained as described above to dehydration ring closure. At this time, the entire acid structure may be completely imidized by dehydrating and ring closure, or only a part of the acid structure may be dehydrated and cyclized to form a partial imide, in which the 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. When the reaction temperature is 50 ° C or higher, the dehydration ring-closure reaction can be sufficiently promoted. By setting the reaction temperature to 200 ° C or lower, it is possible to suppress the decrease in the molecular weight of the resulting imidized polymer. 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 dehydrating ring-closing catalyst to the polyamic acid solution of (ii), an acid anhydride such as acetic anhydride, propionic anhydride 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 ring closure reaction is preferably 0 to 180 DEG C, more preferably 10 to 150 DEG C, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

In the method (ii), a reaction solution containing polyimide is obtained as described above. 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]

The liquid crystal aligning agent may contain other polyorganosiloxane besides the [A] polyorganosiloxane compound. The other polyorganosiloxane is preferably at least one selected from the group consisting of a polyorganosiloxane represented by the formula (5), a hydrolyzate thereof and a condensate of the hydrolyzate thereof. When the liquid crystal aligning agent contains other polyorganosiloxane, most of the other polyorganosiloxanes are present independently of the [A] polyorganosiloxane compound, and some of them are [A] a polyorganosiloxane compound and May be present as a condensate.

In X ¹ and Y ¹ in the formula (5)

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, a n-hexyl group, n-heptadecyl group, n-heptadecyl group, n-octadecyl group, n-hexadecyl group, n-hexadecyl group, N-nonadecyl, n-eicosyl and the like;

Examples of the alkoxy group having 1 to 16 carbon atoms include a methoxy group and ethoxy group;

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

The other polyorganosiloxane is preferably at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter sometimes referred to as a &quot; raw silane compound &quot;), preferably in an appropriate organic solvent Can be synthesized by hydrolysis or hydrolysis / condensation 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-sec-butoxy silane, ethyl tri-tert-butoxy silane, ethyl trichlorosilane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl trichlorosilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane; Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and the like. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane, and trimethylethoxysilane are preferable.

Examples of the organic solvent that can optionally be used in the synthesis of other polyorganosiloxanes 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-octanol, sec-hexanol, sec-pentanol, Octyl alcohol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, secundecyl alcohol, trimethylnonyl alcohol, monoalcohol compounds such as 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 alone or in combination of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, Ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-petanthion, acetonyl acetone, acetophenone, Of 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- 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, sec-butyl acetate, sec-butyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, Acetic acid methyl ester, acetic acid ethylene glycol monomethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid ethyleneglycol monomethyl ether, Ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monoacetate T-butyl ether, acetic acid propylene glycol monoethyl ether, acetic acid propylene glycol monopropyl ether, acetic acid propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, Ethyl lactate, n-butyl lactate, diethyl malonate, dimethyl phthalate, di-n-butyl lactate, di-n-butyl lactate, di-n-propyl lactate, Ethyl and the like. These ester compounds may be used alone or in combination of two or more.

Examples of other aprotic compounds include acetonitrile, dimethylsulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4- Piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl- 2- imidazolidinone, 1,3-dimethyltetrahydro- Rice paddies, and the like. Of these solvents, polyhydric alcohol compounds, partial ethers of polyhydric alcohol compounds, and ester compounds are particularly preferable.

The amount of water used in the synthesis of the other polyorganosiloxane is preferably 0.01 to 100 moles, more preferably 0.1 to 30 moles, per 1 mole of the total amount of the alkoxy group and the halogen atom contained in the raw material silane compound , Further preferably 1 to 1.5 mols.

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

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, but are not limited to, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linolic acid, linoleic acid, salicylic acid, benzoic acid, p- aminobenzoic acid, Monochloroacetic acid, dichloroacetic 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, picolin, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, Diethanolamine, methyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicyclo-undecene, 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.

Of these catalysts, metal chelate compounds, organic acids and inorganic acids are preferable. As the metal chelate compound, a titanium chelate compound is more preferable.

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

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.

Water to be added in the synthesis of other polyorganosiloxanes may 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 reaction temperature in the synthesis of other polyorganosiloxanes is preferably 0 to 100 占 폚, and more preferably 15 to 80 占 폚. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

When the liquid crystal aligning agent contains other polymer in addition to the [A] polyorganosiloxane compound, the content of the other polymer is preferably 10,000 parts by mass or less based on 100 parts by mass of the [A] polyorganosiloxane compound. The more preferable content of the other polymer differs depending on the kind of the other polymer.

A preferable ratio of the liquid crystal aligning agent to the liquid crystal aligning agent in the case of containing the [A] polyorganosiloxane compound and the [B] polymer is from 100 to 100 parts by mass of the [A] polyorganosiloxane compound, To 5,000 parts by mass, and more preferably 200 to 3,000 parts by mass.

On the other hand, in the case where the liquid crystal aligning agent contains [A] a polyorganosiloxane compound and other polyorganosiloxane, the preferred ratio of both of them is [A] 100 parts by weight of the polyorganosiloxane compound, And the amount of the siloxane is 100 to 2,000 parts by mass.

When the liquid crystal aligning agent contains other polymer in addition to the [A] polyorganosiloxane compound, the [B] polymer or other polyorganosiloxane is preferable as the other polymer.

[Curing agent, curing catalyst and curing accelerator]

The curing agent and the curing catalyst may be included in the liquid crystal aligning agent for the purpose of strengthening the crosslinking reaction of the [A] polyorganosiloxane compound. The curing accelerator may be included in the liquid crystal aligning agent for the purpose of accelerating the curing reaction which is carried out by the curing agent.

As the curing agent, a curing agent generally used for curing a curable compound having an epoxy group or a compound containing an epoxy group can be used. Examples of such a curing agent include a polyvalent amine, a polyvalent carboxylic anhydride, and a polyvalent carboxylic acid.

Examples of the polyvalent carboxylic acid anhydride include anhydrides of cyclohexanetricarboxylic acid and other polyvalent carboxylic acid anhydrides.

Examples of the cyclohexanetricarboxylic acid anhydrides include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic-3,5- Hexane-1,2,3-tricarboxylic acid-2,3-anhydride and the like. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, Compounds appearing thereon, tetracarboxylic acid dianhydrides generally used for the synthesis of polyamic acids, alicyclic compounds having conjugated double bonds such as? -Terpinene, alloocimene and the like, Aldehyde reaction products and hydrogenated products thereof.

[In the formula (6), x is an integer of 1 to 20].

As the curing catalyst, for example, antimony hexafluoride compound, hexafluorophosphate compound, aluminum trisacetylacetonate and the like can be used. These catalysts can catalyze the cationic polymerization of an epoxy group by heating.

As the curing accelerator, for example, an imidazole compound; A quaternary compound; Quaternary amine compounds; diazabicyclic alkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and its organic acid salts; An organometallic compound such as zinc octylate, tin octylate and an aluminum acetyl acetone complex, a boron compound such as boron trifluoride and triphenyl borate, a metal halide compound such as zinc chloride and stannic chloride, dicyandiamide, an amine and an epoxy A high melting point dispersed latent curing accelerator such as an amine addition type accelerator such as an adduct with a resin, a microcapsule type latent curing accelerator in which a surface of a quaternary phosphonium salt or the like is coated with a polymer, an amine type latent curing accelerator, High temperature dissociation type thermal cationic polymerization latent curing accelerators such as acid salts and Bronsted acid salts.

[Epoxy Compound]

The epoxy compound can be included in the liquid crystal aligning agent from the viewpoint of improving the adhesion to the substrate surface of the liquid crystal alignment layer to be formed.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglyl N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane , N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- Methyl cyclohexane is preferred.

When the liquid crystal aligning agent contains an epoxy compound, the content thereof is preferably 0.01 to 40 parts by mass or less based on 100 parts by mass of the total amount of the above-mentioned [A] polyorganosiloxane compound and other polymer optionally used , And more preferably 0.1 to 30 parts by mass.

When the liquid crystal aligning agent contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of efficiently causing the crosslinking reaction.

[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-ureidopropyltriethoxysilane , 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- Bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. And reaction products of the tetracarboxylic acid dianhydride described in JP-A-63-291922 with a silane compound having an amino group.

When the liquid crystal aligning agent contains a functional silane compound, the content thereof is preferably 50 parts by mass or less based on 100 parts by mass of the total amount of the above-mentioned [A] polyorganosiloxane compound and other polymer optionally used And more preferably 20 parts by mass or less.

[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 contains a surfactant, the content thereof is preferably 10 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the liquid crystal aligning agent.

&Lt; Preparation method of liquid crystal aligning agent >

As described above, the liquid crystal aligning agent may contain [A] a polyorganosiloxane compound as an essential component and may contain other arbitrary components as required. Preferably, the liquid crystal aligning agent is a solution in which each component is dissolved in an organic solvent Shaped composition.

As the organic solvent that can be used for preparing the liquid crystal aligning agent, it is preferable that the specific polyorganosiloxane and other optional components are dissolved and not reacted with them. The organic solvent which can be preferably used for the liquid crystal aligning agent depends on the kind of the other polymer optionally added.

Preferred examples of the organic solvent when the liquid crystal aligning agent contains the [A] polyorganosiloxane compound and the [B] polymer include the organic solvents exemplified above, which are used for the synthesis of polyamic acid. At this time, the poor solvent exemplified for use in the synthesis of the polyamic acid of the present invention may be used in combination. These organic solvents may be used alone or in combination of two or more.

On the other hand, as the preferred organic solvent when the liquid crystal aligning agent contains the [A] polyorganosiloxane compound alone as the polymer or the [A] polyorganosiloxane compound and other polyorganosiloxane, for example, 1 Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, di Propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol , Methyl cellosolve acetate, ethyl Propylcarbitol, butylcarbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, acetic acid i-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, Hexyl acetate, octyl acetate, amyl acetate, isoamyl acetate and the like. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-

The preferred solvent used for preparing the liquid crystal aligning agent may be one or more of the above-mentioned organic solvents depending on whether or not other polymers are used and the kind thereof. In such a solvent, the components contained in the liquid crystal aligning agent are not precipitated at the following preferable 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, that is, the proportion of the total weight of the liquid crystal aligning agent 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., but preferably 1 to 10% . The liquid crystal aligning agent is applied to the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. However, when the solid concentration is 1% by mass or more, the film thickness of the coating film is less likely to be unduly low, and a good liquid crystal alignment film can be obtained. On the other hand, when the solid concentration is 10% by mass or less, it is possible to prevent an excessive film thickness of the coating film from being obtained and to obtain a good liquid crystal alignment film and prevent the viscosity of the liquid crystal aligning agent from increasing, have. A particularly preferable range of the solid concentration varies 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 mass% is particularly preferable. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9 mass% and the solution viscosity is in the range of 12 to 50 mPa 占 퐏. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 mass%, and the solution viscosity is accordingly in the range of 3 to 15 mPa · s. The temperature at which the liquid crystal aligning agent is prepared is preferably 0 ° C to 200 ° C, and more preferably 0 ° C to 40 ° C.

<Liquid crystal display element>

The driving method of the liquid crystal display element of the present invention is not particularly limited and the present invention is applied to various known methods such as TN, STN, IPS, and VA (including VA-MVA method and VA-PVA method) And the liquid crystal alignment layer formed of the liquid crystal aligning agent. In general, a liquid crystal display device has a pair of substrates on which a transparent electrode and a liquid crystal alignment film are laminated in this order, and the pair of substrates are disposed inside to face each other, and liquid crystal is charged And the peripheral portion is sealed with a sealant.

<Manufacturing Method of Liquid Crystal Display Element>

The liquid crystal display element formed using the liquid crystal aligning agent can be produced, for example, in the following manner. The liquid crystal alignment film used in the present invention is formed on a substrate by applying the liquid crystal aligning agent on the substrate and then heating the applied surface. As the substrate, for example, a transparent substrate made of a glass such as glass of float glass or soda glass, or plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and alicyclic polyolefin can be used. 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. For example, the following two methods can be used for manufacturing the liquid crystal cell.

The first method is a conventionally known method. First, two substrates are opposed to each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded to each other using a sealant. The liquid crystal is injected and filled in the gap, and then the injection hole is sealed, whereby the liquid crystal cell can be manufactured.

The second method is a so-called ODF (One Drop Fill) method. For example, an ultraviolet curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and furthermore liquid crystal is dropped on the liquid crystal alignment film surface, The liquid crystal cell can be manufactured by bonding the substrate and then curing the sealant 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 using the liquid crystal cell to a temperature at which 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 sealant, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal or the like can be used. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, it is preferable to have a positive dielectric anisotropy for forming a nematic liquid crystal. Examples of such liquid crystals include biphenyl-based liquid crystal, phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine- Quartz liquid crystal or the like is used. Further, it is also possible to add a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonanoate or cholesteryl carbonate to the liquid crystal; A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, etc., which is commercially available under the trade names of C-15 and CB-15 (Merck) May also be used.

On the other hand, in the case of the vertical alignment type liquid crystal cell, it is preferable to have a negative dielectric anisotropy for forming a nematic liquid crystal. As such a liquid crystal, for example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a cypher base-based liquid crystal, an agglutinative liquid crystal, a biphenyl-based liquid crystal, a phenylcyclohexane-based liquid crystal and the like are used.

The polarizing plate used for the outside of the liquid crystal cell is not particularly limited, but a polarizing plate in which a polarizing film called &quot; H film &quot;, in which a polyvinyl alcohol film is oriented by stretching while iodine is absorbed is sandwiched by a cellulose acetate protective film or a polarizing plate And the like.

The liquid crystal display element of the present invention manufactured in this way is superior in response performance and display characteristics of the liquid crystal, and excellent in performances such as orientation, voltage holding ratio, and residual image characteristics.

&Lt; Liquid crystal display element having two or more regions having different orientation directions &

The liquid crystal display element has two or more regions in which the liquid crystal alignment mode is vertical and the orientation is different, and the basic structure is the same as that of the liquid crystal display element. The means having two or more regions different in this alignment method is not particularly limited, and for example, a means using a patterned transparent electrode or an orientation dividing means such as a rubbing treatment of a liquid crystal alignment film can be used. Such a liquid crystal display element can be suitably applied also in a driving mode such as TN, STN, IPS, and VA (including VA-MVA system and VA-PVA system) and further improves the contrast, Speed response.

As a method for producing the patterned transparent electrode, the liquid crystal aligning agent is preferably applied by an offset printing method, a spin coating method, or an inkjet printing method, and then the coated surface is formed by heating each coated surface. 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 ) . Next, a pattern is formed by, for example, a method of forming a pattern by photo-etching after forming a pattern-free transparent conductive film, a method of using a mask having a desired pattern in forming a transparent conductive film, and the like.

Specific examples of the patterned transparent electrode include those shown in Figs. 1 to 3. The patterned transparent electrode will be described with reference to FIG. Referring to Fig. 1 (b), the transparent substrate 3 has an ITO film 1 partitioned into a plurality of regions, and a plurality of slits 2 are formed and patterned. The width w1 of the slit 2 is, for example, about 10 mu m, and the distance w2 between the slits 2 is about 35 mu m, for example. In this case, the ITO line W1 shown in Fig. 1 (a) is about 9 mm (about 200 in 35 m width). As the material of the transparent substrate, for example, glass and the like can be mentioned. In the case of manufacturing a liquid crystal display element using the patterned transparent electrode shown in Fig. 1, two substrates having such patterned transparent electrodes are prepared, and when the two substrates are opposed to each other, (The slits 2 are shifted from each other and are in contact with the ITO film 1).

As a means for dividing the alignment of the liquid crystal alignment film, for example, a pair of substrates having a liquid crystal alignment film is formed by operating in the same manner as the above-mentioned &quot; method for manufacturing a liquid crystal display element &quot;, and two or more orientations And rubbing treatment through a mask so that the orientation has different areas. As a form of the mask, there is a mask in which one pixel having a hole corresponding to the size of one region is divided into four (a matrix having a quarter of the pixel size, holes are formed at an interval and the holes are arranged diagonally A mask that appears to be present).

The liquid crystal aligning agent used in the production of a liquid crystal display element having two or more regions having different orientation orientations of the present invention preferably contains a compound having a group represented by the formula (3).

In the formula (3), R ² is a linking group comprising a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom. R ³ is a group having at least two monocyclic structures. and a is an integer of 0 to 1. A detailed description of these conformations is made in the description of the [A] polyorganosiloxane compound, and therefore is omitted here.

&Lt; Polyanosiloxane compound >

The polyorganosiloxane compound of the present invention is a compound having a part derived from a polyorganosiloxane having an epoxy group and a compound having a carboxyl group represented by the following formula (1), or a compound in which R ³ in the formula (1) Having a moiety derived from a compound having a group. A detailed description of the polyorganosiloxane compound is given in the description of the [A] polyorganosiloxane compound contained in the liquid crystal aligning agent, and therefore will not be described here. Such a polyorganosiloxane compound can be suitably used for a liquid crystal aligning agent for constituting a liquid crystal display element having a performance such as an orientation property, a high-speed response property, a voltage characteristic and an afterimage characteristic.

(Example)

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

The weight average molecular weight (Mw) of the obtained polyorganosiloxane and [A] polyorganosiloxane compound obtained in the following Examples is the polystyrene equivalent measured by GPC in the following specification.

Column: TSKgelGRCXLII, Toso K.K.

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

The necessary amounts of the starting compounds and polymers used in the following examples were ensured by repeating the synthesis of the starting compounds and the polymers in the synthesis scale shown in the following synthesis examples as necessary.

&Lt; Synthesis of polyorganosiloxane having epoxy group >

[Synthesis Example 1]

100 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 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 tube And the mixture was mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise to the flask over 30 minutes with a dropping funnel, and the flask was reacted at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a transparent Liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane having the epoxy group, it was found that a peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm in accordance with the theoretical intensity and no side reaction of the epoxy group occurred during the reaction .

[Synthesis Examples 2 to 3]

A polyorganosiloxane having an epoxy group was obtained as a viscous transparent liquid by operating in the same manner as in Synthesis Example 1, except that the starting materials for the injection were as shown in Table 1 below. The Mw and the epoxy equivalent of the polyorganosiloxane having epoxy groups obtained in Synthesis Examples 1 to 3 are shown in Table 1. The abbreviations of the raw material silane compounds in Table 1 have the following meanings.

ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

MTMS: methyltrimethoxysilane

PTMS: phenyltrimethoxysilane

&Lt; Synthesis of Specific Carbonic Acid >

A specific carbonic acid 1 was synthesized according to the following reaction formula.

[Synthesis Example 4]

6.3 g of 4-cyano-4'-hydroxybiphenyl, 10 g of methyl 11-bromododecanoate, 14.2 g of potassium carbonate and 200 mL of N, N-dimethylformamide were added to a 500 mL three-necked flask equipped with a cooling tube , And the mixture was heated and stirred at 160 DEG C for 5 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, followed by mixing and stirring. The precipitated white solid was filtered off and further washed with water. The resulting solid was vacuum-dried at 80 占 폚 to obtain 11 g of Compound 1.

[Synthesis Example 5]

Next, 10 g of Compound 1, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 DEG C for 4 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, diluted hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered and washed with water and ethanol in this order. The resulting solid was vacuum-dried at 80 占 폚 to obtain 8 g of a specific carboxylic acid 1.

A specific carbonic acid 2 was synthesized according to the following reaction formula.

[Synthesis Example 6]

15 g of 4-cyano-4'-hydroxybiphenyl, 13.5 g of ethylene carbonate, 2.5 g of tetrabutylammonium bromide (TBAB) and 300 mL of N, N-dimethylformamide were added to a 500 mL three- , And the mixture was heated and stirred at 150 占 폚 for 9 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was separated and washed with a mixed solution of 300 mL of ethyl acetate and 100 mL of 1N-aqueous sodium hydroxide solution. The organic layer was extracted, and further, 100 mL of 1N aqueous sodium hydroxide solution and 100 mL of water were sequentially washed. The organic layer was dried over magnesium sulfate, and then the organic solvent was distilled off. The obtained solid was vacuum-dried and then recrystallized from 100 mL of ethanol / 250 mL of hexane to obtain 13.1 g of Compound 2.

[Synthesis Example 7]

12 g of Compound 2, 12.7 g of 4-chlorobenzenesulfonyl chloride and 60 mL of dehydrated methylene chloride were added to a 200 mL three-necked flask equipped with a stirrer, a condenser, and a dropping funnel. While cooling the reaction solution with an ice bath, a solution of 6.6 g of triethylamine in 10 mL of dehydrated methylene chloride was added dropwise over 10 minutes. The mixture was stirred for 30 minutes while remaining in an ice bath state, and then returned to room temperature and further stirred for 6 hours. To the reaction solution was added 150 mL of chloroform, and the solution was washed 4 times with 100 mL of water. The extracted organic layer was dried with magnesium sulfate, and the organic solvent was distilled off. The resulting solid was washed with ethanol to obtain 16.1 g of Compound 3.

[Synthesis Example 8]

15 g of Compound 3, 11 g of methyl 4-hydroxybenzoate, 12.5 g of potassium carbonate and 180 mL of N, N-dimethylformamide were added to a 300 mL three-necked flask equipped with a cooling tube and the mixture was heated and stirred at 80 DEG C for 9 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, followed by mixing and stirring. The precipitated white solid was filtered off and further washed with ethanol. The resulting solid was vacuum-dried at 80 占 폚, thereby obtaining 10 g of Compound 4.

[Synthesis Example 9]

9.5 g of Compound 4, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, 15 mL of tetrahydrofuran and 15 mL of water were added to a 100 mL three-necked flask equipped with a cooling tube and the mixture was heated and stirred at 80 캜 for 4 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, diluted hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered and washed with water and ethanol in this order. The resulting solid was vacuum-dried at 80 占 폚 to obtain 9 g of a specific carboxylic acid 2.

A specific carbonic acid 3 was synthesized according to the following reaction formula.

[Synthesis Example 10]

Compound No. 5 was obtained in the same manner as in Synthesis Example 4 except that 10.7 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol was used instead of 4-cyano-4'- g.

[Synthesis Example 11]

In Synthesis Example 5, 13.5 g of Compound 5 was used instead of Compound 1 to obtain 11.2 g of a specific carboxylic acid 3.

A specific carbonic acid 4 was synthesized according to the following reaction formula.

[Synthesis Example 12]

Compound 6 was obtained by using 25.5 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol instead of 4-cyano-4'-hydroxybiphenyl in Synthesis Example 6 23.1 g.

[Synthesis Example 13]

In Synthesis Example 7, 18.9 g of Compound 6 was used instead of Compound 2 to obtain 24.1 g of Compound 7.

[Synthesis Example 14]

In Synthesis Example 8, 20 g of Compound 7 was used instead of Compound 3 to obtain 15.4 g of Compound 8.

[Synthesis Example 15]

In Synthesis Example 9, 13 g of Compound 8 was used instead of Compound 4 to obtain 11.4 g of a specific carbonic acid 4.

A specific carbonic acid 5 was synthesized according to the following reaction formula.

[Synthesis Example 16]

15 g of the specific carboxylic acid 5 in which the number of methylene groups was changed from 10 to 5 was synthesized in the same manner as the synthesis of the specific carbonic acid 1.

<Synthesis of [A] polyorganosiloxane compound>

[Example 1]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 5.0 g of the specific carbonic acid 1 obtained in Synthesis Example 5, 5.0 g of the compound represented by the formula (5) 3.3 g of 4-octyloxybenzoic acid represented by the formula (5-5) shown as an example and 0.20 g of UCAT 18X (quaternary amine salt of San A Pro Co.) were added and stirred at 80 占 폚 for 12 hours. After completion of the reaction, the polyorganosiloxane compound (A-1) was obtained by repeating the steps of [A] repeating the reaction with methanol, dissolving the precipitate in ethyl acetate to obtain a solution, rinsing the solution three times with water, As a white powder. The Mw of the polyorganosiloxane compound (A-1) of [A] was 6,500.

[Example 2]

12.8 g of a white powder of the polyorganosiloxane compound (A-2) [A] was obtained in the same manner as in Example 1 except that 4 g of the specific carboxylic acid 2 obtained in Synthesis Example 9 was used instead of the specific carbonic acid 1. The Mw of A-2 was 6,000.

[Example 3]

14.7 g of a white powder of the polyorganosiloxane compound (A-3) [A] was obtained in the same manner as in Example 1 except that 6.8 g of the specific carboxylic acid 3 obtained in Synthesis Example 11 was used instead of the specific carbonic acid 1 . The Mw of A-3 was 8,100.

[Example 4]

A polyorganosiloxane compound [A] was synthesized in the same manner as in Example 1 except that 5.6 g of the specific carbonic acid 4 obtained in Synthesis Example 15 was used instead of the specific carbonic acid 1. As a result, 15.0 g of a white powder of the [A] polyorganosiloxane compound (A-4) was obtained. The Mw of A-4 was 7,500.

[Example 5]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 10 g of the specific carboxylic acid 1 obtained in the above Synthesis Example 5 and 10 g of UCAT 18X (produced by Sana Kogyo Co., Ltd.) Quaternary amine salt) were added, and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water, and then the solvent was distilled off to obtain a polyorganosiloxane compound (A-5) as a white powder Was obtained. The Mw of A-5 was 8,500.

[Example 6]

12.4 g of a white powder of the polyorganosiloxane compound (A-6) [A] was obtained in the same manner as in Example 1 except that 4.1 g of the specific carbonic acid 5 obtained in Synthesis Example 16 was used instead of the specific carbonic acid 1. The Mw of A-6 was 6,200.

[Example 7]

(4-pentylcyclohexyl) benzoic acid represented by the formula (5-7) exemplified as one of the compounds represented by the formula (5) instead of 4-octyloxybenzoic acid was used in the same manner as in Example 1 To obtain 13.4 g of a white powder of the [A] polyorganosiloxane compound (A-7). The Mw of A-7 was 7,900.

[Example 8]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 8.0 g of the specific carboxylic acid 1 obtained in Synthesis Example 5, 8.0 g of the compound represented by the formula (5-7) 1.4 g of the resulting 4- (4-pentylcyclohexyl) benzoic acid and 0.20 g of UCAT 18X (quaternary amine salt of San A Pro Co.) were added and the mixture was stirred at 80 ° C for 12 hours. After the completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water and then the solvent was distilled off to obtain a polyorganosiloxane compound (A-8) as a white powder Was obtained. The Mw of A-8 was 8,900.

[Example 9]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 2.0 g of the specific carbonic acid 1 obtained in Synthesis Example 5 and 2.0 g of the compound represented by the formula (5-7) were added to a 100-mL three- 5.8 g of the resulting 4- (4-pentylcyclohexyl) benzoic acid and 0.20 g of UCAT 18X (quaternary amine salt of San A Pro Co.) were added and the mixture was stirred at 80 ° C for 12 hours. After completion of the reaction, the polyorganosiloxane compound (A-9) was obtained by repeating the steps of reprecipitation with methanol, dissolving the precipitate in ethyl acetate to obtain a solution, washing the solution three times with water, To obtain 13.4 g of a white powder. The Mw of A-9 was 7,600.

[Example 10]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 8.0 g of the specific carbonic acid 1 obtained in Synthesis Example 5, 8.0 g of the compound represented by the formula (5-6) 2.6 g of the resulting carboxylic acid derivative and 0.20 g of UCAT 18X (quaternary amine salt of San A Pro Co.) were added and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water and then the solvent was distilled off to obtain a polyorganosiloxane compound (A-10) as a white powder Was obtained. The Mw of A-10 was 9,200.

[Comparative Synthesis Example 1]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 3.3 g of 4-octyloxybenzoic acid and 4 g of UCAT 18X (quaternary amine salt of San A Pro Co.) were added to a 100-mL three- , And the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed with water three times, and the solvent was distilled off to obtain a polyorganosiloxane compound (A-1) as a white powder 9.6 g was obtained. The Mw of CA-1 was 6,000.

<Synthesis of polyamic acid>

[Synthesis Example 17]

19.61 g (0.1 mol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 21.23 g (0.1 mol) of 4,4'-diamino 2,2'-dimethylbiphenyl were dissolved in N-methyl- Dissolved in 367.6 g of pyrrolidone, and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 35 g of polyamic acid (PA-1).

[Synthesis Example 18]

22.4 g (0.1 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g (0.1 mole) of cyclohexane bis (methylamine) were dissolved in 329.3 g of N-methyl-2-pyrrolidone, Lt; 0 &gt; C for 6 hours. The reaction was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 占 폚 for 15 hours to obtain 32 g of polyamic acid (PA-2).

<Synthesis of polyimide>

[Synthesis Example 19]

17.5 g of the polyamic acid (PA-2) obtained in the above Synthesis Example 18 was added, 232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine and 4.9 g of acetic anhydride were added, And imidation was carried out. Subsequently, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to obtain 15 g of polyimide (PI-1).

[Synthesis Example 20]

19.88 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 6.83 g of p-phenylenediamine as a diamine compound, 3.58 g of diaminodiphenylmethane and 3.58 g of diaminodiphenylmethane represented by the formula (G-4) Diamine were dissolved in 140 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 60 DEG C for 4 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried at 40 DEG C for 24 hours under reduced pressure to obtain 32.8 g of polyamic acid. 30 g of the obtained polyamic acid was dissolved in 400 g of N-methyl-2-pyrrolidone, and 12.0 g of pyridine and 15.5 g of acetic anhydride were added and subjected to dehydration cyclization at 110 DEG C for 4 hours to precipitate, wash, To obtain 25 g of a polyimide (PI-2) having Mw = 92,000, Mw / Mn = 4.19 and an imidization ratio of 79%.

&Lt; Preparation of liquid crystal aligning agent &

[Example 11]

A solution containing polyamic acid (PA-1) obtained in Synthesis Example 17 in an amount corresponding to 1,000 parts by mass in terms of the polyamic acid (PA-1) contained therein was used as the polyorganosiloxane compound (A) Methyl-2-pyrrolidone and butyl cellosolve were added to the solution, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio), and a solid content concentration of 3.0 mass%. This solution was filtered with a filter having a pore diameter of 0.2 탆 to prepare a liquid crystal aligning agent (S-1).

[Examples 12 to 24 and Comparative Example 1]

(B) A liquid crystal aligning agent (S-2 to S-2) was obtained in the same manner as in Example 11 except that the combination of polyamic acid or polyimide as the polymer and polyorganosiloxane compound as the component [A] 14) and (CS-1) were prepared.

[Comparative Example 2]

To the polyimide (PI-2) obtained in Synthesis Example 20 was added N-methyl-2-pyrrolidone (NMP) such that the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = And butyl cellosolve, respectively, to prepare a solution having a solid concentration of 3.0% by mass. This solution was filtered with a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (CS-2). In the table, &quot; - &quot; indicates that the corresponding component was not used.

&Lt; Production of liquid crystal display element &

The liquid crystal aligning agent (S-1) prepared in Example 11 was coated on the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by using a spinner and prebaked on a hot plate at 80 DEG C for 1 minute , And the solvent was removed by heating in an oven substituted with nitrogen at 200 DEG C for 1 hour to form a coating film (liquid crystal alignment film) having a film thickness of 0.08 mu m. This operation was repeated to prepare a pair of substrates (two substrates) each having a liquid crystal alignment film.

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 was applied to the periphery of the surface having one liquid crystal alignment film of the above substrate by screen printing and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, The adhesive was heated and cured at 150 ° C for 1 hour. Subsequently, a negative-type liquid crystal (Merck, MLC-6608) 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, Lt; 0 &gt; C for 10 minutes and then slowly cooled to room temperature.

A polarizing plate was bonded to both sides of the substrate so that the polarizing directions of the two polarizing plates were orthogonal to each other, thereby producing a liquid crystal display device. Examples 12 to 24 and Comparative Examples 1 to 2

Was used to manufacture a liquid crystal display device.

&Lt; Liquid crystal display element having two or more regions having different orientation directions &

[Example 25]

A liquid crystal display element having two or more regions having different orientation orientations was produced in the same manner as in the production of the liquid crystal display element except that the patterned transparent electrode shown in Fig. 1 was used.

[Example 26]

The liquid crystal aligning agent (S-1) prepared in Example 11 was applied on a substrate having a transparent electrode formed thereon, further baked on a hot plate at 80 DEG C for 1 minute, Deg.] C for 1 hour to remove the solvent, thereby forming a coating film (liquid crystal alignment film) having a thickness of 0.08 mu m. This operation was repeated to prepare a pair of substrates (two substrates) each having a liquid crystal alignment film. These substrates were rubbed through a mask for dividing one pixel into four parts. A liquid crystal display element having two or more regions having different orientation directions was manufactured by operating in the same manner as in the production of the above liquid crystal display element except that the rubbing treatment was performed so that one pixel had a region having two or more different orientation orientations did.

<Evaluation>

The liquid crystal display device manufactured was evaluated as follows. The results are also shown in Table 2.

[Orientation]

With respect to the liquid crystal display device manufactured as described above, the presence or absence of light leakage and orientation disturbance in a voltage unapplied state was observed with a naked eye under the condition of a backlight, and a case where there was no light leakage / Quot; and &quot; No &quot; at which no vertical alignment state was obtained at all.

[Voltage Conservation Rate]

A voltage of 5 V was applied to the liquid crystal display device manufactured in the above manner at an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio (%) after 167 milliseconds after the application was released was measured. The measuring device used was Toyo Technica VHR-1 manufactured by Kabushiki Kaisha.

[Afterimage characteristics]

A voltage of 17 V DC was applied to the liquid crystal display device manufactured in the same manner as above for 20 hours at an environmental temperature of 100 캜 for 20 hours and the voltage (residual DC voltage) remaining in the liquid crystal cell immediately after the application of the DC voltage, It was obtained by the erasure method.

[Response speed (electro-optical responsiveness at the start)] [

The start time of the liquid crystal response was measured with a device including a polarization microscope, a photodetector and a pulse generator. Here, the liquid crystal response speed was set to the time (msec.) Necessary for the transmittance to change from 90% to 90% at a transmittance of 10% when a voltage of 5 V was applied to the produced liquid crystal display element for a maximum of 1 second .

[Contrast]

The contrast of the liquid crystal display device using the liquid crystal aligning agent prepared in Example 11 and the liquid crystal display device having two or more regions having different orientation orientations prepared in Examples 25 and 26 were evaluated. The liquid crystal cell prepared as described above was placed between two polarizing plates and fixed on a light box. One polarizing plate was rotated to measure the minimum intensity of transmitted light to obtain the minimum transmittance. Further, the same polarizing plate was rotated to measure the maximum intensity of transmitted light, and the maximum transmittance was obtained. The maximum transmittance-minimum transmittance was defined as a relative transmittance, and the relative transmittance was used as a substitute indicator of contrast. When the relative transmittance is 40 or more, it can be judged to be good.

As a result, the relative transmittance of the liquid crystal display element prepared in Example 11 was 20. The relative transmittance of the liquid crystal display element prepared in Examples 25 and 26 having two or more regions having different alignment orientations was 49. [ Also, when the liquid crystal display element having two or more regions having different orientation orientations using the patterned transparent electrodes shown in Figs. 2 and 3 was produced, the same relative transmittance was obtained.

As is apparent from the results of Table 2, the liquid crystal display device comprising the liquid crystal alignment film produced using the liquid crystal aligning agents of Examples 11 to 24 had the generally required alignment property, voltage holding ratio and afterimage property I could. As to the response speed of the liquid crystal, it was found that the liquid crystal display device of Comparative Example 1 had a speed difference of about 24% or more as compared with the liquid crystal display device of Comparative Example 1 in terms of the smallest difference. Further, it was found that the liquid crystal display element having two or more regions having different orientation orientations produced by using the composition had excellent contrast.

[Industrial Availability]

According to the present invention, it is possible to provide a liquid crystal aligning agent capable of forming a liquid crystal display element excellent in orientation, capable of high-speed response, and excellent in performances such as voltage characteristics and afterimage characteristics. Therefore, the liquid crystal display element can be suitably applied also in a driving mode such as TN, STN, IPS, and VA (including MVA, PVA, optical vertical alignment, PSA, etc.).

1: ITO film
2: slit
3: transparent substrate

Claims (11)

[A] A composition containing a polyorganosiloxane compound,
The polyorganosiloxane compound [A]
A part derived from a polyorganosiloxane having an epoxy group,
A liquid crystal aligning agent having a moiety derived from a compound having a carboxyl group represented by the following formula (1)

[In the formula (1), R ¹ is a methylene group or an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group; These groups may have a substituent;
R ² is a linking group comprising a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom;
R ³ is a group having at least two monocyclic structures and represented by the following formula (2); a is an integer of 0 to 1;

[Wherein R ⁴ and R ⁶ are each a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle, May have;
R ⁵ is a linking group containing any of an alkylene group, a double bond, a triple bond, an ether bond, an ester bond and a heterocycle having 1 to 10 carbon atoms which may have a substituent;
R ⁷ is any of a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group and an alkoxy group, provided that at least R ⁷ includes a cyano group or a fluorine atom;
b is an integer from 0 to 1;
and c is an integer of 1 to 9, provided that when c is an integer of 2 to 9, a plurality of R ^{7 s} may be the same or different. delete The method according to claim 1,
The liquid crystal aligning agent in which the epoxy group is a group represented by the following formula (X ¹ -1) or (X ¹ -2)

[Wherein, in the formula (X ¹ -1), A is an oxygen atom or a single bond;
h is an integer from 1 to 3;
i is an integer from 0 to 6; Provided that when i is 0, A is a single bond;
Formula (X ¹ -2) of the, j is 2;
"*" Indicates a combined hand). The method according to claim 1,
[B] a liquid crystal aligning agent further comprising at least one polymer selected from the group consisting of polyamic acid and polyimide. A liquid crystal display element comprising a liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1, 3 and 4. 6. The method of claim 5,
A transparent electrode,
And a liquid crystal alignment film laminated on the transparent electrode,
The liquid crystal alignment mode is vertical, and the liquid crystal display device has two or more regions having different orientation orientations. The method according to claim 6,
Wherein the two or more regions having different orientation orientations are obtained by using a transparent electrode patterned as the transparent electrode or by imparting an alignment division function to the liquid crystal alignment film. A transparent electrode,
And a liquid crystal alignment film laminated on the transparent electrode,
As a liquid crystal aligning agent for forming a liquid crystal alignment film in a liquid crystal display element having two or more regions in which the liquid crystal alignment mode is vertical and the alignment direction is different,
A liquid crystal aligning agent characterized by containing a polyorganosiloxane compound having a group represented by the following formula (3)

[In the formula (3), R ² is a linking group comprising a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom;
R ³ is a group having at least two monocyclic structures and represented by the following formula (2);
a is an integer of 0 to 1;
&Quot; * &quot; indicates a combined hand);

[Wherein R ⁴ and R ⁶ are each a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle, May have;
R ⁵ is a linking group containing any of an alkylene group, a double bond, a triple bond, an ether bond, an ester bond and a heterocycle having 1 to 10 carbon atoms which may have a substituent;
R ⁷ is any of a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group and an alkoxy group, provided that at least R ⁷ includes a cyano group or a fluorine atom;
b is an integer from 0 to 1;
and c is an integer of 1 to 9, provided that when c is an integer of 2 to 9, a plurality of R ^{7 s} may be the same or different. 9. The method of claim 8,
Wherein at least two regions having different orientation orientations use a patterned transparent electrode or a liquid crystal alignment film having an alignment division function. A liquid crystal display element comprising two or more regions in which the liquid crystal alignment mode is vertical and the orientation direction is different, and a liquid crystal alignment film formed by the liquid crystal aligning agent according to Claim 8 or 9. A part derived from a polyorganosiloxane having an epoxy group,
A polyorganosiloxane compound having a moiety derived from a compound having a carboxyl group represented by the following formula (1):

[In the formula (1), R ¹ is a methylene group or an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group; These groups may have a substituent;
R ² is a linking group comprising a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom;
R ³ is a group having at least two monocyclic structures and represented by the following formula (2); a is an integer of 0 to 1;

[Wherein R ⁴ and R ⁶ are each a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle, May have;
R ⁵ is a linking group containing any of an alkylene group, a double bond, a triple bond, an ether bond, an ester bond and a heterocycle having 1 to 10 carbon atoms which may have a substituent;
R ⁷ is any of a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group and an alkoxy group, provided that at least R ⁷ includes a cyano group or a fluorine atom;
b is an integer from 0 to 1;
and c is an integer of 1 to 9, provided that when c is an integer of 2 to 9, a plurality of R ^{7 s} may be the same or different.

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