KR101709526B1 - Liquid crystal aligning agent, liquid crystal alignment film, method for forming the liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

[PROBLEMS] To provide a liquid crystal alignment film which satisfactorily satisfies properties such as liquid crystal alignment property, voltage holding ratio and light resistance required in practical use as a liquid crystal display device, excellent storage stability suitable as a material for forming the liquid crystal alignment film and a liquid crystal alignment film, A liquid crystal aligning agent capable of forming a liquid crystal alignment film by employing a photo alignment method and a liquid crystal alignment film comprising the liquid crystal alignment film.
(Solution) The present invention is a liquid crystal aligning agent containing a polyorganosiloxane compound having at least one structure selected from the group consisting of [A] piperidine structure, phenol structure and aniline structure.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film,

The present invention relates to a liquid crystal aligning agent which is suitable as a material for forming a liquid crystal alignment film, a liquid crystal alignment film formed by the liquid crystal aligning agent, a method for forming a liquid crystal alignment film, and a liquid crystal display device comprising the liquid crystal alignment film.

Liquid crystal display elements are widely used in liquid crystal display devices such as cellular phones and liquid crystal televisions since they have advantages such as small power consumption, small size, and easy flattening. As a display mode of such a liquid crystal display device, for example, Patent Documents 1 to 4 disclose a twisted nematic type (TN type), a super twisted nematic type (STN type), an in-plane switching type (IPS type), and Vertical Alignment type (VA type).

The principle of operation of such various liquid crystal display elements is roughly classified into a transmissive type and a reflective type. The transmission type display is performed by a backlight source from the back surface of the device. The liquid crystal alignment film provided in this transmissive liquid crystal display element is exposed to light from a backlight source for a long time, and therefore, when irradiated with a backlight source of high illumination intensity such as a metal halide lamp, there is a problem of leading to a rise in temperature. On the other hand, since the reflection type display is performed by light reflected from the outside such as sunlight without using a light source for backlight, power consumption is lower than that of the transmissive type, but it is exposed to strong ultraviolet rays. In addition, in the process of manufacturing a liquid crystal display element, the liquid crystal dropping method that can be employed from the viewpoint of process shortening or the like includes an ultraviolet light irradiation process. Therefore, any liquid crystal display element is required to have excellent heat resistance and light resistance. In addition, recent liquid crystal display devices are required to have excellent electric characteristics such as liquid crystal alignability and voltage holding ratio, and do not cause a problem of after-images.

Thus, a technique of a liquid crystal alignment film formed by a specific polysiloxane solution and considered to have excellent heat resistance and light resistance has been developed (see Patent Document 5). However, according to this technique, the required performance is not satisfied due to recent production environment and severe use environment, and additionally, storage stability of the coating liquid is insufficient, so that convenience in industrial use is not high.

From such a situation, a liquid crystal aligning agent having satisfactory characteristics such as liquid crystal alignability, voltage preservation rate and light resistance required for practical use as a liquid crystal display element and having excellent storage stability capable of forming a liquid crystal alignment film by employing a photo alignment method Development is demanded.

Japanese Patent Application Laid-Open No. 4-153622 Japanese Patent Application Laid-Open No. 60-107020 Japanese Laid-Open Patent Publication No. 56-91277 U.S. Patent No. 5,928,733 Japanese Patent Application Laid-Open No. 9-281502 Japanese Patent Application Laid-Open No. 6-287453 Japanese Patent Application Laid-Open No. 2003-307736 Japanese Laid-Open Patent Publication No. 2004-163646

The present invention has been made based on the above-described circumstances, and its object is to provide a liquid crystal alignment film which satisfactorily satisfies properties such as liquid crystal alignment property, voltage holding ratio and light resistance required for practical use as a liquid crystal display device, a method of forming the liquid crystal alignment film A liquid crystal aligning agent which is excellent in storage stability as a material for forming a liquid crystal alignment film and which can form a liquid crystal alignment film by employing a photo alignment method and a liquid crystal alignment film.

According to an aspect of the present invention,

Is a liquid crystal aligning agent containing a [A] polyorganosiloxane compound having a piperidine structure, a phenol structure or an aniline structure.

The liquid crystal aligning agent is excellent in storage stability and the liquid crystal alignment film formed of the liquid crystal aligning agent sufficiently satisfies the properties such as liquid crystal aligning property, voltage holding ratio and light resistance required for practical use as a liquid crystal display element.

It is preferable that the piperidine structure is represented by the following formula (A-1 '), the phenol structure is represented by the following formula (A-2') and the aniline structure is represented by the following formula (A-3 '):

(In the formula (A-1 '),

R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms or a 1,3-dioxobutyl group;

R ² to R ⁵ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms;

X ¹ is a single bond, a carbonyl group or ^** -CONH-; X ^{2 to} X ⁵ each independently represent a single bond, a carbonyl group, ^** -CH ₂ -CO- or ^** -CH ₂ -CH (OH) -; Bonded to the piperidine ring;

Bonded to the backbone or side chain of the polyorganosiloxane backbone);

(In the formula (A-2 '), R ⁶ is an alkyl group having 1 to 16 carbon atoms, provided that the alkyl group has an oxygen atom, a sulfur atom, a carbonyl group, an ester group or a combination of two or more thereof in the skeleton chain N is an integer from 0 to 4; and the bonded hands represented by * are bonded to the main chain or side chain of the polyorganosiloxane skeleton);

(In the formula (A-3 '), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 16 carbon atoms, provided that the alkyl group has an oxygen atom, a sulfur atom, a carbonyl group, May be combined with each other to form a polyorganosiloxane skeleton; and * the bonded hands represented by * are bonded to the main chain or side chain of the polyorganosiloxane skeleton).

Wherein the polyorganosiloxane compound [A] is at least one member selected from the group consisting of a polyorganosiloxane having a structural unit represented by the following formula (1), a condensate of the hydrolyzate thereof and a hydrolyzate, (A-1), a compound derived from at least one compound selected from the group consisting of compounds represented by the following formulas (A-1), (A-2) and desirable:

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

(In the formula (A-1), R ¹ to R ⁵ and X ^{1 to} X ⁵ have the same meanings as in the formula (A-1 ');

In the formula (A-2), R ⁶ has the same meaning as in the formula (A-2 ');

In the formula (A-3), R ⁷ and R ⁸ have the same meanings as in the formula (A-3 ');

In the formulas (A-1) to (A-3), Y is a single bond or an alkanediyl group having 1 to 16 carbon atoms; The alkanediyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, or a combination of two or more thereof in the structure; And Z is a carboxyl group or a hydroxyl group).

The liquid crystal aligning agent according to any one of [1] to [4], wherein the polyorganosiloxane compound [A] comprises at least one member selected from the group consisting of a polyorganosiloxane having a structural unit represented by the formula (1), a hydrolyzate thereof and a condensate of a hydrolyzate , A structure having a radical capturing ability such as a piperidine structure can be easily introduced into the [A] polyorganosiloxane compound, and as a result, the light resistance is improved.

The method of claim art liquid crystal orientation, is of X ^a in the above formula (1), the formula (X ^a -1) or formula (X ^a -2) due to be preferred, and represented by the formula (X ^a -1- 1) or (X ^a -2-1):

Wherein s is an integer of 0 to 3, t is an integer of 1 to 6, u is an integer of 0 to 2, and v is an integer of 0 to 6 (in the formula (X ^a -1) and (X ^a -2) And the bonded hands represented by * are bonded to a silicon atom;

(Of the formulas (X ^a -1-1) and (X ^a -2-1), a bonded hand represented by * bonds to a silicon atom).

(A-1), (A-2), or (A-2) or (A-2) is added to the polyorganosiloxane compound [A] of the liquid crystal aligning agent, -3) can be introduced easily.

In the liquid crystal aligning agent, it is preferable that the [A] polyorganosiloxane compound includes a structure having liquid crystal aligning ability. When the [A] polyorganosiloxane compound contains a structure having liquid crystal aligning ability, the liquid crystal aligning ability can be further improved.

The structure having the liquid crystal aligning ability is preferably an organic group having a steroid skeleton and having 17 to 51 carbon atoms, an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, an alkoxy group having 2 to 20 carbon atoms An alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms, a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, and a fluoroalkoxycyclohexyl group having a fluoroalkoxy group having 1 to 20 carbon atoms And at least one kind of group selected from the group consisting of By having the structure having the liquid crystal aligning ability mentioned above (hereinafter sometimes referred to as " liquid crystal aligning group "), it is possible to impart a better liquid crystal alignment ability to the liquid crystal aligning agent.

The structure having the liquid crystal aligning ability preferably has a structure represented by the following formula (B-1):

(In the formula (B-1), m is an integer of 0 to 4).

Since the structure having the liquid crystal aligning ability has the specific structure described above, the liquid crystal alignment film can be formed from the liquid crystal aligning agent by the photo alignment method.

The liquid crystal aligning agent preferably further contains at least one polymer selected from the group consisting of [B] polyamic acid and polyimide (hereinafter sometimes referred to as " [B] polymer "). By producing a liquid crystal alignment film using a liquid crystal aligning agent further containing [B] polymer, a liquid crystal display device having improved electric characteristics such as a voltage holding ratio can be obtained.

The liquid crystal aligning agent may further contain [C] a polyorganosiloxane compound having a structural unit represented by the following formula (2) (hereinafter sometimes referred to as "[C] other polyorganosiloxane compound" Preferably:

(Wherein X ^b represents 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 ^b is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms ).

By further containing the liquid crystal aligning agent [C] other polyorganosiloxane compound, the crosslinking of the polyorganosiloxane compound [A] can be promoted, and as a result, the voltage holding ratio and the like of the obtained liquid crystal display element can be further improved .

The method for forming a liquid crystal alignment film of the present invention comprises:

(1) a step of applying a liquid crystal aligning agent containing a structure having a liquid crystal aligning ability, wherein the polyorganosiloxane compound [A] has a structure represented by the formula (B-1)

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation

Respectively.

According to the forming method of the present invention using the liquid crystal aligning agent, it is possible to form a liquid crystal alignment film which satisfactorily satisfies properties such as liquid crystal aligning property, voltage holding ratio and light resistance required for practical use as a liquid crystal display element.

A liquid crystal alignment film formed of the liquid crystal aligning agent and a liquid crystal display device having the liquid crystal alignment film are also included in the present invention. The liquid crystal display element of the present invention including a liquid crystal alignment film formed of the liquid crystal aligning agent can be used in various fields such as a clock, a portable game, a word processor, a notebook type personal computer, a car navigation system, a camcorder, a portable information terminal, Various monitors, liquid crystal televisions, and the like.

In addition, the R ¹ represents an aryl group of 6 to 20 carbon atoms, an aralkyl group, R ² an alkyl group having a carbon number of 1~6 ~R ⁵ is shown having a carbon number of 7-13, 6-12 carbon atoms in the aryl group and aralkyl of 7-13 carbon atoms Some or all of the hydrogen atoms of the alkyl group may be substituted.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid crystal alignment film which satisfactorily satisfies properties such as liquid crystal alignment property, voltage holding ratio and light resistance required for practical use as a liquid crystal display device, excellent storage stability suitable as a material for forming the liquid crystal alignment film, , And a liquid crystal aligning agent capable of forming a liquid crystal alignment film by employing a photo alignment method and a liquid crystal alignment film. The liquid crystal display element of the present invention including a liquid crystal alignment film formed of the liquid crystal aligning agent can be used in various fields such as a clock, a portable game, a word processor, a notebook type personal computer, a car navigation system, a camcorder, a portable information terminal, Various monitors, liquid crystal televisions, and the like.

(Mode for carrying out the invention)

Hereinafter, embodiments of the present invention will be described in detail.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention contains a [A] polyorganosiloxane compound having at least one structure selected from the group consisting of a piperidine structure, a phenol structure and an aniline structure. The liquid crystal aligning agent is excellent in storage stability and the liquid crystal alignment film formed of the liquid crystal aligning agent sufficiently satisfies the properties such as liquid crystal aligning property, voltage holding ratio and light resistance required for practical use as a liquid crystal display element. The [A] polyorganosiloxane compound preferably contains a structure having liquid crystal aligning ability, and the liquid crystal aligning agent is preferably a polymer other than the [A] polyorganosiloxane compound (hereinafter referred to as &quot; other polymer &quot; ), And the liquid crystal aligning agent may contain an arbitrary component as long as the effect of the present invention is not impaired. Hereinafter, the [A] polyorganosiloxane compound, the structure having liquid crystal aligning ability, other polymers and optional components will be described in detail.

<[A] polyorganosiloxane compound>

The polyorganosiloxane compound [A] has at least one structure selected from the group consisting of a piperidine structure, a phenol structure and an aniline structure. Further, the [A] polyorganosiloxane compound is preferably a polyorganosiloxane having a part derived from a polyorganosiloxane having a structural unit represented by the above formula (1) (hereinafter sometimes referred to as "polyorganosiloxane having an epoxy group") and , A compound derived from at least one compound selected from the group consisting of compounds represented by the above formulas (A-1), (A-2) and (A-3) Such [A] polyorganosiloxane compound is obtained by reacting a polyorganosiloxane having an epoxy group with a compound represented by the formula (A-1), the formula (A-2) or the formula (A-3) Loses. Wherein the polyorganosiloxane compound [A] is at least one selected from the group consisting of a polyorganosiloxane having a structural unit represented by the formula (1), a condensate of the hydrolyzate thereof and a hydrolyzate, The structure having radical capturing ability such as a piperidine structure can be easily introduced into the [A] polyorganosiloxane compound, and as a result, the light resistance is improved. Hereinafter, the polyorganosiloxane having a piperidine structure, a phenol structure, an aniline structure and an epoxy group will be described in detail.

[Structure of piperidine]

As the piperidine structure of the polyorganosiloxane compound [A], a structure represented by the above formula (A-1 ') is preferable.

The [A] polyorganosiloxane compound having such a piperidine structure is obtained by reacting a polyorganosiloxane having an epoxy group with a compound represented by the above formula (A-1).

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ⁵ include a straight chain or branched chain, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ include a phenyl group, a naphthyl group and an anthranyl group. It is also preferred that some or all of the hydrogen atoms of the aromatic ring of the aryl group are substituted with formyl groups or alkoxyl groups of 1 to 4 carbon atoms.

Examples of the aralkyl group having 7 to 13 carbon atoms represented by R ¹ to R ⁵ include a benzyl group and a phenethyl group. It is preferable that a part or all of hydrogen atoms contained in the aromatic ring of the aralkyl group is substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms.

Examples of the aryl group having 6 to 12 carbon atoms represented by R ² to R ⁵ include a phenyl group and a naphthyl group. It is preferable that some or all of the hydrogen atoms contained in the aromatic ring of the aryl group are substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ² to R ⁵ include methoxy group, ethoxy group and n-propoxy group.

For example, the compound represented by the following formulas (A-1-1) to (A-1-4) is preferably a carboxyl group in the formula (A- Can be mentioned as preferable examples.

[A] poly organo Examples (A-1 ') the ratio of the structure of the siloxane compound, with respect to X ^a, and 2 mole% to 80 mole%, far preferably from 5 mol% to 75 mol%, more preferably, 25 mol % To 60 mol% is particularly preferable.

[Phenol structure]

The phenol structure of the polyorganosiloxane compound [A] is preferably a structure represented by the above formula (A-2 ').

The [A] polyorganosiloxane compound having such a phenol structure is obtained by reacting a polyorganosiloxane having an epoxy group with a compound represented by the above formula (A-2).

Examples of the alkyl group having 1 to 16 carbon atoms represented by R ⁶ may be straight chain or branched chain, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.

For example, the compound represented by the following formulas (A-2-1) to (A-2-7) is preferably a compound represented by the formula (A-2) Can be mentioned as preferable examples.

[A] As the ratio of the polyorganosiloxane (A-2 ') in the compound, with respect to X ^a, is 10 mol% to 90 mol% preferably from 20 mol% to 80 mol% is more preferable, and 25 mol% To 75 mol% is particularly preferable.

[Aniline structure]

As the aniline structure of the polyorganosiloxane compound [A], a structure represented by the above formula (A-3 ') is preferable.

The [A] polyorganosiloxane compound having such an aniline structure is obtained by reacting a polyorganosiloxane having an epoxy group with a compound represented by the above formula (A-3).

Examples of the alkyl group having 1 to 16 carbon atoms represented by R ⁷ and R ⁸ include the same ones described in the above formula (A-2).

For example, the compound represented by the following formulas (A-3-1) to (A-3-8) is preferably a compound represented by the formula (A-3) Can be mentioned as preferable examples.

[A] As the ratio of the polyorganosiloxane (A-3 ') in the compound, with respect to X ^a, is 10 mol% to 90 mol% preferably from 20 mol% to 80 mol% is more preferable, and 25 mol% To 75 mol% is particularly preferable.

[Polyorganosiloxane Having an Epoxy Group]

The polyorganosiloxane having an epoxy group means a polyorganosiloxane skeleton as a polymer main chain and a skeleton containing an epoxy group as a polymer main chain branched from the polyorganosiloxane in the structure of the polyorganosiloxane compound [A] .

The monovalent organic group having an epoxy group represented by X ^a in the formula (1) is not particularly limited as long as it is a monovalent organic group having an epoxy group, and examples thereof include a glycidyl group, a glycidyloxy group and an epoxycyclohexyl group And the like. Among them, X ^a is preferably a group represented by the formula (X ^a -1) or (X ^a -2), and the formula (X ^a -1-1) or (X ^a -2-1) Is more preferable. (A-1), the formula (A-2) or the formula (A-2) is added to the [A] polyorganosiloxane compound of the liquid crystal aligning agent by employing the specific group as the monovalent organic group having an epoxy group. 3) can be introduced easily.

Examples of the alkoxy group having 1 to 10 carbon atoms represented by Y ^a in the formula (1) include methoxy, ethoxy, n-propoxy, isopropoxy, n- .

Examples of the alkyl group having 1 to 20 carbon atoms represented by Y ^a in the formula (1) include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, A decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group.

Examples of the aryl group having 6 to 20 carbon atoms represented by Y ^a in the formula (1) include a phenyl group and a naphthyl group.

[Method of synthesizing polyorganosiloxane having epoxy group]

The polyorganosiloxane having an epoxy group is preferably a mixture of a silane compound having an epoxy group or a silane compound having an epoxy group and another silane compound in the presence of a suitable organic solvent, 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-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2 - (3,4-epoxycyclohexyl) ethyltriethoxysilane, 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, tri-n-butoxysilane, tri-n-butoxysilane, tri-n-butoxysilane, tri-n-butoxysilane, Fluorotris-sec-butoxysilane, fluorotri-n-butoxysilane, fluorotriethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, N-propoxysilane, methyltri-n-butoxysilane, methyltri-n-butoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri- butoxy silane, 2- (trifluoromethyl) ethyl trichlorosilane, 2- (trifluoro Ethyltriethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri- butoxy silane, 2- (trifluoromethyl) ethyl tri-n-butoxy silane, 2- (trifluoromethyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- (Perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (Perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri- Octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro- (Perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- Octyl) ethyltri-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyltri- butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri- Propyl tri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3- 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxy Silane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, n-propoxysilane, vinyltri-sec-butoxysilane, aryltrichlorosilane, aryltrimethoxysilane, aryltriethoxysilane, vinyltriethoxysilane, N-propoxysilane, aryltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, N-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec- Butoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, Sec-butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-sec-butoxy silane, dimethyldimethoxy silane, dimethyl diethoxy silane, dimethyl di- (Methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro- n-octyl) ethyl] dichlorosilane, (Perfluoro-n-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro- (Methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (Methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) di (Methyl) (3-mercaptopropyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) Butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (3-mercaptopropyl) di- Propyloxy silane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl) Vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane , Divinyldi-i-propoxy silane, divinyl di-n-butoxy silane, divinyl di-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyl Di-n-propoxy silane, diphenyl di-i-propoxy silane, diphenyl di-n-butoxy silane, diphenyl di- n-propoxytrimethylsilane, n-propoxytrimethylsilane, n-propoxytrimethylsilane, n-butoxytrimethylsilane, n-propoxytrimethylsilane, n-propoxytrimethylsilane, butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, Silane compounds having one silicon atom such as (methoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane and (ethoxy) . These may be used alone or in combination of two or more.

Examples of commercially available products include, for example,

KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X- X-22-170B, X-22-170D, X-22-170DX, X-22-176B, X-22-170B, X- 22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X- X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, KR-217, KR-217, KR-220, KR-292, KR-271, KR-281, KR-300, KR-311, KR-401, KR-500, KR-510, KR-5206, KR-5230, KR- 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.);

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

Of these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltri But are not limited to, ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aryltrimethoxysilane, aryltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane are preferable.

The epoxy equivalent of the epoxy group-having polyorganosiloxane is preferably 100 g / mol to 10,000 g / mol, more preferably 150 g / mol to 1,000 g / mol, and particularly preferably 150 g / mol to 300 g / mol. Therefore, in the synthesis of the polyorganosiloxane having an epoxy group, it is preferable to set the epoxy equivalent of the obtained polyorganosiloxane to be in the above range in the ratio of the silane compound having an epoxy group and the other silane compound.

Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane having an epoxy group include a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, and an alcohol compound. These may be used alone or in combination of two or more.

Examples of the hydrocarbon compound include toluene, xylene, and the like.

Examples of the ketone compound include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone.

Examples of the ester compound include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate.

Examples of the ether compound include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like.

Examples of the alcohol compound 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.

The amount of the organic solvent to be used is preferably 10 parts by mass to 10,000 parts by mass, more preferably 50 parts by mass to 1,000 parts by mass, per 100 parts by mass of the total silane compound.

The amount of water used when synthesizing the polyorganosiloxane having an epoxy group is preferably from 0.5 times to 100 times by mole, more preferably from 1 time to 30 times by mole, based on the total amount of the silane compound.

Examples of the catalyst include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. These may be used alone or in combination of two or more.

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

As the organic base, for example,

Primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene;

And quaternary organic amines such as tetramethylammonium hydroxide.

As the catalyst for producing 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, a polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing a side reaction such as ring opening of an epoxy group, Stability is excellent.

The polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and the compound represented by the formula (A-1), the formula (A-2) or the formula (A-3) The liquid crystal aligning agent containing the reactant is suitable because it has excellent storage stability. This is because, as indicated in the science of sol-gel method (Agneshoff, 1988, pp. 154-161), when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis and condensation reaction , A random structure or a cage-like structure is formed and a polyorganosiloxane having a small content of silanol groups is obtained. That is, in such a polyorganosiloxane, when the condensation reaction between the silanol groups is suppressed because the content of the silanol groups is small, and when the liquid crystal aligning agent of the present invention contains the other polymer described later, the silanol groups and other It is deduced that the condensation reaction with the polymer is inhibited, resulting in excellent storage stability.

As the catalyst, an organic base is more preferable, and a tertiary organic amine and a quaternary organic amine are particularly preferable. The amount of the organic base to be used differs depending on the kind of the organic base and the reaction conditions such as the temperature. For example, the amount is preferably 0.01 to 3 times, more preferably 0.05 to 1 times as much as the total silane compound .

The hydrolysis or hydrolytic condensation reaction in the synthesis of a 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, by heating with an oil bath or the like.

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

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of cleaning, it is preferable to wash with a water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 mass% from the viewpoint of facilitating the cleaning operation. The washing is carried out until the water layer after the washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain a polyorganosiloxane having a desired epoxy group Siloxane is 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 weight average molecular weight (hereinafter sometimes referred to as &quot; Mw &quot;) of the polyorganosiloxane having an epoxy structure in terms of polystyrene measured by gel permeation chromatography is preferably 500 to 100,000, more preferably 1,000 to 10,000 And particularly preferably from 1,000 to 5,000. In the present specification, Mw is the polystyrene reduced value measured by gel permeation chromatography of the following method.

Column: TSKgelGRCXLII, Toso K.K.

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 6.8 MPa

&Lt; Structure having liquid crystal aligning ability &gt;

In the liquid crystal aligning agent, it is preferable that the [A] polyorganosiloxane compound includes a structure having liquid crystal aligning ability. When the [A] polyorganosiloxane compound contains a structure having liquid crystal aligning ability, the liquid crystal aligning ability can be further improved.

As the group of the structure having the liquid crystal aligning ability, the above-mentioned liquid crystal aligning group is preferable. The structure having the liquid crystal aligning ability has the above-mentioned specific group, so that the liquid crystal aligning agent can give excellent liquid crystal aligning ability.

The organic group having a steroid skeleton and having from 17 to 51 carbon atoms is preferably a monovalent organic group having from 17 to 30 carbon atoms and having a steroid skeleton. For example, a cholestan-3-yl group, a cholesta- , A cholesta-24-en-3-yl group, a cholesta-5,24-dien-3-yl group and a lanostan-3-yl group.

Examples of the alkyl group having 2 to 20 carbon atoms include an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, N-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, And the like. The number of carbon atoms of the alkyl group is more preferably from 4 to 20.

Examples of the fluoroalkyl group having 1 to 20 carbon atoms include a trifluoromethyl group, a perfluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a 4, Pentafluoropentyl group, 3,3,4,4,5,5,5,5-heptafluoropentyl group, and the like.

Examples of the alkoxyaryl group having an alkyl group having 2 to 20 carbon atoms include n-propyloxyaryl, n-butyloxyaryl, n-pentyloxyaryl, n-hexyloxyaryl, n-heptyloxyaryl And n-octyloxyaryl group.

Examples of the alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms include an n-propylcyclohexyl group, an n-butylcyclohexyl group, an n-pentylcyclohexyl group, an n-hexylcyclohexyl group, Hexyl group, n-octylcyclohexyl group, and the like.

Examples of the fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms include a trifluoromethylcyclohexyl group.

Examples of the fluoroalkoxycyclohexyl group having a fluoroalkoxy group having 1 to 20 carbon atoms include, for example, 4,4,4-trifluorobutoxycyclohexyl group, 4,4,5,5,5-pentafluoro Pentoxycyclohexyl group and the like.

The structure having the liquid crystal aligning ability preferably has a structure represented by the above formula (B-1). Since the structure having the liquid crystal aligning ability has a specific structure, a liquid crystal alignment film can be formed from the liquid crystal aligning agent by the photo alignment method.

The [A] polyorganosiloxane compound containing a structure having liquid crystal aligning ability is obtained by a reaction between a polyorganosiloxane having an epoxy group and a compound having liquid crystal aligning ability represented by the following formula (B-2) .

R ^E -T (B-2)

In the formula (B-2), R ^E is a group including a structure having a liquid crystal aligning ability. T is a carboxyl group or a hydroxyl group.

Preferable examples of the formula (B-2) include compounds represented by the following formulas (B-2-1) to (B-2-8).

In the above formula (B-2-1), R ^f is the above-mentioned liquid crystal aligning group. ^Xc represents a single bond, an oxygen atom, a sulfur atom, a phenylene group, a cyclohexylene group, -COO-, -NHCO-, -CONH-, -CO-, -OCO- or a combination of two or more of these . X ^d is a single bond, an oxygen atom, a phenylene group, -CO-, -OCO-, - (CH ₂ ) _a - or a linking group combining two or more of them. a is an integer of 1 to 6; T has the same meaning as in the above formula (B-2).

In the formula (B-2-2), R ^f , X ^d and T have the same meanings as in the formula (B-2-1). ^Xe represents a single bond, an oxygen atom, a sulfur atom, a phenylene group, -COO-, -NHCO-, -CONH-, -CO-, -OCO-, or a linking group combining two or more of them.

In the formula (B-2-3), R ^f and T have the same meanings as in the formula (B-2-1). X ^f is a single bond, an oxygen atom, -CO-, - (CH ₂ ) _a -, or a linking group combining two or more of them. a is an integer of 1 to 6; m is an integer of 0 to 4;

In the formulas (B-2-4) to (B-2-6), R ^f and T have the same meanings as in the formula (B-2-1). X ^g is a single bond, an oxygen atom, a sulfur atom, -COO-, -NHCO-, -CONH-, -CO-, -OCO-, or a linking group combining two or more of them. X ^h is a single bond, an oxygen atom, a sulfur atom, - (CH ₂ ) _a -, -CO-, or a linking group combining two or more of them. a is an integer of 1 to 6;

In the formulas (B-2-7) and (B-2-8), R ^f and T have the same meanings as in the formula (B-2-1). X ^j is a single bond, an oxygen atom, -COO-, -OCO-, - (CH ₂ ) _a, or a linking group combining two or more of them. a is an integer of 1 to 6;

In the above formulas (B-2-1) to (B-2-8), it is assumed that the combination of the O-O bond or the substituent forming the?,? - diketo structure is not allowed.

Among the above-mentioned formulas (B-2-1) to (B-2-8), compounds represented by the following formulas (B-2-1-1) to (B-2-8-2) are more preferable.

In the formulas (B-2-1-1) to (B-2-8-2), R ^f has the same meaning as in formula (B-2-1). A is an integer of 1 to 6.

Other preferred examples of the compound having a liquid crystal aligning ability in the case of a group containing the structure represented by the formula (B-1) include, for example, compounds represented by the following formulas (B-2-1-1 ' -1 ').

In the above, R ^f has the same meaning as in the formula (B-2-1).

On the other hand, when R ^E in the formula (B-2) is an organic group having 17 to 51 carbon atoms having a steroid skeleton, an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, An alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms, a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, and a fluoroalkoxy group having a fluoroalkoxy group having 1 to 20 carbon atoms. (B-2) is at least one compound selected from the group consisting of a compound represented by the following formula (B-1) and a compound represented by the following formula 9) to (B-2-11).

R ^f and T in the formulas (B-2-9) to (B-2-11) have the same meanings as those of the formula (B-2-1). X ^k is a single bond, an oxygen atom, -COO- or -OCO-.

In the above formula (B-2-11), p is 1 or 2.

Examples of the compound wherein T is a carboxyl group in the formula (B-2-9) include n-butanoic acid, n-pentanoic acid, n-hexanoic acid, n- n-heptadecanoic acid, n-heptadecanoic acid, n-heptadecanoic acid, n-octadecanoic acid, n-octadecanoic acid, n-nonadecanoic acid, n-eicosanoic acid, tetrahydroabietic acid, monocholestanyl succinate, monocholestanyl glutarate, compounds represented by the following formulas, and the like.

_{C h F 2h +1 -C i H} 2i -COOH

In the formula, h is an integer of 1 to 3. i is an integer of 3 to 18;

Examples of the compound having a hydroxyl group as T in the above formula (B-2-9) include 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, Octadecanol, 1-undecanol, 1-undecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, Ol, 1-eicosanol, and the like.

Examples of the compound wherein T is a carboxyl group in the above formula (B-2-10) include 4-methylbenzoic acid, 4-ethylbenzoic acid, 4- (n-propyl) benzoic acid, 4- (n-pentyl) benzoic acid, 4- (n-hexyl) benzoic acid, 4- (n-pentyl) benzoic acid, 4- Benzoic acid, 4- (n-dodecyl) benzoic acid, 4- (n-octadecyl) benzoic acid, 4- Benzoic acid, 4- (n-pentyloxy) benzoic acid, 4- (n-pentyloxy) benzoic acid, 4- Benzoic acid, 4- (n-octadecyloxy) benzoic acid, 4- (n-decyloxy) benzoic acid, 4- And the like.

In the above formula, j is an integer of 5 to 20. k is an integer of 1 to 3; and ma is an integer of 0 to 18. n is an integer of 1 to 18;

Examples of the compound in which T is a carboxyl group in the formula (B-2-11) include 4- (n-butyl) cyclohexylcarboxylic acid, 4- (n-pentyl) cyclohexylcarboxylic acid, 4- Butyl) bicyclohexylcarboxylic acid, and 4- (n-pentyl) bicyclohexylcarboxylic acid.

&Lt; Synthesis method of compound having liquid crystal aligning ability &gt;

The compounds represented by the above formulas (B-2-1) to (B-2-11) are commercially available or can be synthesized by appropriately combining the methods of organic chemistry. It will be readily understood by those skilled in the art that the synthesis method will be described by taking the compound wherein R ^f is an alkyl group as an example but that R ^f can also be synthesized by a similar procedure to a compound other than an alkyl group or by a synthetic method analogous thereto .

The compound represented by the above formula (B-2-1-1) can be produced by, for example, heating and reacting hydroxycinnamic acid and a halogenated alkyl having an alkyl group corresponding to R ^f in the presence of a suitable base such as potassium carbonate, By hydrolysis with an appropriate aqueous alkali solution such as sodium hydroxide.

The compound represented by the formula (B-2-1-2) can be obtained by, for example, hydroxycinnamic acid and an alkylcarbonic acid chloride having an alkyl group corresponding to R ^f in the presence of a suitable base such as potassium carbonate at a temperature of 0 ° C to room temperature &Lt; / RTI &gt;

The compound represented by the above formula (B-2-1-4) can be produced, for example, by reacting methyl hydroxybenzoate with a halogenated alkyl having an alkyl group corresponding to R ^f or a tosylated alkyl in the presence of a suitable base such as potassium carbonate at room temperature to 100 And then hydrolyzing the resultant with an appropriate alkaline aqueous solution such as sodium hydroxide and further converting it into an acid chloride with thionyl chloride and then reacting it with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate, Lt; 0 &gt; C to room temperature.

The compound represented by the above formula (B-2-1-5) can be obtained by, for example, reacting hydroxybenzoic acid and an alkylcarbonic acid chloride having an alkyl group corresponding to R ^f in the presence of a suitable base such as triethylamine at a temperature of 0 ° C to room temperature And then reacting the resulting product with hydrochloric acid in the presence of a suitable base such as potassium carbonate at a temperature of 0 ° C to room temperature.

The compound represented by the above formula (B-2-1-6) can be obtained by, for example, using 4-alkylbenzoic acid as an acid chloride with thionyl chloride and treating it with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate Lt; 0 &gt; C to room temperature.

The compound represented by the above formula (B-2-1-7) can be produced, for example, by reacting methyl 4-hydroxycyclohexylcarbonate with an alkyl halide having an alkyl group corresponding to R ^f in the presence of a suitable alkali such as sodium hydride or sodium metal The reaction is carried out to give an ether which is then hydrolyzed with an aqueous alkaline solution such as sodium hydroxide and further with thionyl chloride chloride to obtain an acid chloride which is then reacted with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate, At room temperature.

As the compound represented by the above formula (B-2-1-8), for example, a 4-alkylcyclohexylcarboxylic acid having an alkyl group equivalent to R ^f is prepared from thionyl chloride with an acid chloride, With a hydroxycinnamic acid in the presence of a suitable base at a temperature of 0 ° C to room temperature.

The compound represented by the above formula (B-2-1-9) is obtained by reacting a halogenated alkyl having an alkyl group corresponding to R ^f with hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond, Benzoic acid is obtained by Aldol condensation in the presence of sodium hydroxide. Compounds represented by the above formulas (B-2-1-10) to (B-2-1-15) can also be obtained by a method analogous thereto.

The compound represented by the above formula (B-2-2-1) can be produced, for example, by reacting 4-iodophenol and an alkyl acrylate having an alkyl group corresponding to R ^f with a palladium and amine catalyst Followed by ring-opening addition of the desired cyclic acid anhydride such as succinic anhydride or glutaric anhydride to the reaction product.

The compound represented by the formula (B-2-2-2) is obtained by aldol condensation of 4-alkyl acetophenone having an alkyl group corresponding to R ^f and 4-formylbenzoic acid in the presence of sodium hydroxide. The compound represented by the above formula (B-2-2-3) can also be obtained by a method analogous thereto.

The compound represented by the above formula (B-2-2-4) is obtained by aldol condensation of 4-alkyl acetophenone having an alkyl group corresponding to R ^f and 4-hydroxybenzaldehyde in the presence of sodium hydroxide. The compound represented by the formula (B-2-2-5) can also be obtained by a method similar thereto.

The compound represented by the formula (B-2-3-1) is obtained by a method of obtaining an acrylic acid ester having an alkyl group corresponding to R ^f and 4-bromosuccinic acid using a palladium catalyst. A compound represented by the above formula (B-2-3-2) can also be obtained by the same method as described above.

The compounds represented by formula (B-2-4-1), for example, R ^f is of the alkyl succinic anhydride with 4-aminocinnamic acid having an alkyl group corresponding to include, when R ^f is an alkyl group, in the acetic acid In a solvent such as toluene or xylene under reflux or in the presence of a suitable base catalyst such as triethylamine, and when R ^f is a fluoroalkyl group, maleic anhydride may be reacted with p-toluidine , Followed by coupling with a Grignard reaction with a fluoroalkyl iodine having a fluoroalkyl group corresponding to R &lt; ^{1 &} gt ;, followed by deprotection by hydrolysis, followed by dehydration ring closure, and then 4- With an amino cinnamic acid.

The compound represented by the above formula (B-2-4-2) can be synthesized by any of the following methods, for example. As a first method, maleic anhydride is protected with an appropriate protecting group such as p-toluidine, and then an alcohol having an alkyl group corresponding to R ^f is Michael added in the presence of a suitable base with potassium carbonate, Followed by dehydration ring closure, and the resulting product is reacted with 4-aminocinnamic acid in the same manner as in the synthesis of the compound represented by the formula (B-2-4-1) . As a second method, methyl malate and a halogenated alkyl having an alkyl group corresponding to R ^f are reacted in the presence of, for example, silver oxide to obtain an ether, followed by hydrolysis and dehydration ring closure, -2-4-1) with 4-aminocinnamic acid in the same manner as in the synthesis of the compound represented by formula (I).

Except that the compound represented by the formula (B-2-4-3) are, for example thionyl having an alkyl group corresponding to R ^f in place of the alcohol having an alkyl group corresponding to R ^f has the formula (B- 2-4-2). &Lt; tb &gt;&lt; TABLE &gt;

The compound represented by the above formula (B-2-5-1) can be obtained by, for example, converting 1,2,4-tricarboxycyclohexane anhydride to thionyl chloride chloride and then reacting an alcohol having an alkyl group corresponding to R ^f In the presence of a suitable base such as triethylamine to give an ester which is reacted with 4-aminocinnamic acid in the same manner as in the synthesis of the compound represented by the formula (B-2-4-1) .

The compound represented by the above formula (B-2-6-1) can be obtained by, for example, reacting a compound R ^f -OH corresponding to a desired compound with an anhydrous trimellitic acid halide to synthesize an ester compound as an intermediate, Can be synthesized by reacting a compound with 4-aminocinnamic acid. The synthesis of the intermediate ester compound is preferably carried out in a suitable solvent in the presence of a basic compound. Examples of the solvent that can be used include tetrahydrofuran and the like, and examples of the basic compound include triethylamine and the like. The reaction between the ester compound and 4-aminocinnamic acid can be carried out by, for example, a method of refluxing both of them in acetic acid, a method of reacting the two with an appropriate catalyst in toluene or xylene (for example, an acid catalyst such as sulfuric acid or a base catalyst such as triethylamine) And refluxing in the presence of a solvent.

The compound represented by the above formula (B-2-6-2) can be obtained by subjecting 5-hydroxyphthalic acid to, for example, refluxing in diethylbenzene to effect dehydration cyclization to give an acid anhydride, followed by treatment with 4-aminocinnamic acid And then reacting the imide compound with a compound R ^f -H (H is a halogen atom) corresponding to the desired compound. At this time, it is preferably carried out in a suitable solvent in the presence of a basic compound. Examples of the solvent that can be used include amide compounds such as N, N-dimethylacetamide, and the like. Examples of basic compounds include potassium carbonate and the like.

The compound represented by the above formula (B-2-7-1) is obtained by, for example, reacting 4-nitrocinnamic acid with an alkyl halide having an alkyl group corresponding to R ^f in the presence of potassium carbonate to give an ester, For example, by reduction with tin chloride to give an amino group, and then reacting the product with 1,2,4-tricarboxycyclohexylcyclohexane anhydride. The latter reaction can be carried out, for example, by refluxing the starting compound in acetic acid or refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine. A compound represented by the above formula (B-2-8-1) can be synthesized by a method analogous thereto.

The compound represented by the above formula (B-2-8-2) is a compound represented by the above formula (B-2-7-1) in place of 1,2,4-tricarboxycyclohexylcyclohexane anhydride Synthesizing a cinnamic acid derivative having an imide ring using hydroxyphthalic acid, and then reacting it with succinic anhydride or glutaric anhydride.

The compound represented by the above formula (B-2-1-1 ') is obtained by reacting a halogenated alkyl having an alkyl group corresponding to R ^f and 4-hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond , Obtained by aldol condensation of 4-hydroxyacetophenone in the presence of sodium hydroxide. Compounds represented by the above formulas (B-2-1-2 ') to (B-2-1-7') are also obtained by the above-described method.

The compound represented by the above formula (B-2-2-1 ') is obtained, for example, by reacting 4-iodophenol and an alkyl acrylate having an alkyl group corresponding to R ^f with palladium and amine as catalysts.

The compound represented by the above formula (B-2-2-2 ') is obtained by aldol condensation of 4-alkyl acetophenone having an alkyl group corresponding to R ^f and 4-hydroxybenzaldehyde in the presence of sodium hydroxide. The compound represented by the above formula (B-2-1-3 ') is also obtained by the above-mentioned method.

The compound represented by the above formula (B-2-8-1 ') can be obtained by, for example, converting 4-nitrocinnamic acid into an acid chloride with thionyl chloride and then reacting with an alcohol having an alkyl group corresponding to R ^f to give an ester , Reducing the nitro group with, for example, tin chloride to obtain an amino group, and reacting the resulting product with hydroxyphthalic anhydride. The latter reaction can be carried out, for example, by refluxing the starting compound in acetic acid or refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine.

Among these compounds (B-2), the compounds represented by the formulas (B-2-1-1), (B-2-1-3), (B- 2-1-6) to (B-2-1-8), (B-2-1-16), (B-2-1-19) , (B-2-4-1), (B-2-4-2), (B-2-5-1) and (B-2-7-1).

Examples of the structure having a liquid crystal aligning ability that does not have a structure represented by the above formula (B-1) include n-butanoic acid, n-hexanoic acid, n-octanoic acid, n- 4-n-octadecylbenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-dodecylbenzoic acid, 4-n-octylbenzoic acid, 1-heptanethiol, 1-heptanethiol, 1-octanethiol, 1-nonantiol, 1-decanethiol, 1-undecanethiol, 1-dodecanethiol, 1-tetradecanethiol, 1-hexadecanethiol, 1-octadecanethiol, monocholestanyl succinate, and compounds represented by the following formulas.

In the present specification, a compound having a structure having a liquid crystal aligning ability and having no structure represented by the formula (B-1) is referred to as "other pretilt angle-expressing compound". As the ratio of the structure having such a polyester liquid crystal aligning capability of the organosiloxane compound, with respect to X ^a, 10 mole% to 90 mole%, far preferably from 20 mol% to 80 mol% is more preferred, and 25 to 75 mole% Mol% is particularly preferable.

The polyorganosiloxane compound [A] in the present invention preferably has a part of Si-X ^a bonds remaining in the polyorganosiloxane having an epoxy structure. Therefore, when the reaction is carried out, the total number of moles of the compound (A-1), the compound (A-2), the compound (A-3) and the compound having a liquid crystal aligning ability and the polyorganosiloxane having an epoxy structure Is preferably smaller than the number of moles of the group X ^a . In this case, when the proportion of the compound having a liquid crystal aligning ability having a group represented by the formula (B-1) is preferably 50 mol% or more based on the total amount of the compound, the ratio of the [A] polyorganosiloxane compound The liquid crystal aligning agent contained therein can form a liquid crystal alignment film exhibiting good liquid crystal alignability by the photo alignment method.

<Method of synthesizing polyorganosiloxane compound [A]

The polyorganosiloxane compound [A] is preferably a polyorganosiloxane having an epoxy group, a compound represented by the above formulas (A-1) to (A-3) , In an organic solvent. This manufacturing method is convenient in that it is simple and can increase the introduction rate of each structure.

The compounds represented by formulas (A-1) to (A-3) and the compounds having liquid crystal aligning ability may be used alone or in combination of two or more.

When the compound represented by formulas (A-1) to (A-3) and the structure having liquid crystal aligning ability have a carboxyl group, a part of the compound may be substituted with other carbonic acid to carry out the reaction. In this case, the use ratio of the other carbonic acid is preferably 50 mol% or less based on the total amount of the compound and the other carbonic acid.

As the catalyst, for example, a so-called curing accelerator which promotes the reaction of an organic base or an epoxy compound with an acid anhydride is used.

As the organic base, for example,

Primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene;

And quaternary organic amines such as tetramethylammonium hydroxide. Of these, tertiary organic amines and quaternary organic amines are preferred.

As the curing accelerator, for example,

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- Ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s- Triazine, 2,4-di Methyl-imidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adducts of 2-methylimidazole, 2-phenylimidazole Imidazole compounds such as isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine;

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenphosphate;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphor N-butylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium, O, O-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, Quaternary phosphonium salts such as tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate;

Diazabicyclo [5.4.0] undecene-7 and its organic acid salts;

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 dicyandiamide or an amine addition type accelerator such as an adduct of an amine and an epoxy resin;

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

Amine salt type latent curing accelerator;

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

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

The amount of the catalyst to be used is preferably 100 parts by mass or less, more preferably 0.01 parts by mass to 100 parts by mass, and particularly preferably 0.1 parts by mass to 20 parts by mass, based on 100 parts by mass of the polyorganosiloxane having an epoxy group.

The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The reaction time is preferably 0.1 hour to 50 hours, more preferably 0.5 hours to 20 hours.

Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane compound [A] include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, and an alcohol compound. Of these, ether compounds, ester compounds and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of products. The content of the solvent is preferably 0.1% by mass or more, and more preferably 5% by mass to 50% by mass, based on the solids concentration (the ratio of the total mass of the components other than the solvent in the reaction solution to the total mass of the solution) Lt; / RTI &gt;

The Mw of the polyorganosiloxane compound [A] is preferably 1,000 to 10,000,000, more preferably 2,000 to 100,000, and particularly preferably 3,000 to 50,000.

<Other Polymers>

The other polymer may suitably be contained in the liquid crystal aligning agent in order to further improve the solution properties of the liquid crystal aligning agent and the electrical characteristics of the obtained liquid crystal alignment film. Examples of the other polymer include at least one polymer selected from the group consisting of [B] polyamic acid and polyimide, [C] other polyorganosiloxane compound, polyamic acid ester, polyester, polyamide, cellulose derivative, Polyacetal, polystyrene derivatives, poly (styrene phenylmaleimide) derivatives, and poly (meth) acrylates.

Of these, the [B] polymer and the [C] other polyorganosiloxane compound are preferable. A liquid crystal display element having improved electric characteristics such as a voltage holding ratio can be obtained by producing a liquid crystal alignment film using the liquid crystal aligning agent further containing the liquid crystal aligning agent [B] polymer. Further, by further containing the [C] other polyorganosiloxane compound in the liquid crystal aligning agent, the crosslinking of the polyorganosiloxane compound [A] can be promoted, and as a result, the voltage holding ratio and the like of the obtained liquid crystal display element Can be improved. Hereinafter, the [B] polymer and the [C] other polyorganosiloxane compound will be described in detail.

<[B] Polymer>

[Polyamic acid]

[B] The polyamic acid as the polymer is obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

Examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic acid dianhydride. Besides these, tetracarboxylic dianhydrides described in Japanese Patent Application No. 2009-157556 can be used. These tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

Examples of the aliphatic tetracarboxylic acid dianhydride include butane tetracarboxylic dianhydride.

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

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride and the like, and tetracarboxylic dianhydrides described in Japanese Patent Application No. 2009-84462.

Among these tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic dianhydrides are preferable, and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferable. Especially preferred is 2,3,5-tricarboxycyclopentylacetic acid dianhydride.

The amount of 2,3,5-tricarboxycyclopentylacetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride is preferably 10 mol% or more based on the total tetracarboxylic dianhydride, More preferably 20 mol% or more, and it is particularly preferable that it is composed of only 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride.

Examples of the diamine compound include an aliphatic diamine, an alicyclic diamine, a diaminoorganosiloxane, and an aromatic diamine. These diamine compounds may be used alone or in combination of two or more. In addition to these, diamines described in Japanese Patent Application No. 2009-157556 may be used.

The aliphatic diamines include, for example, meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) cyclohexane.

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and diamines described in Japanese Patent Application No. 2009-84462.

Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9- 4,4'- (m-tert-butylphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 - diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl- , 6-diaminocarbazole, N- (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis (4-aminophenyl) -Bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy 2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy- 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecanoxy- Diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-dia Diaminobenzene, cholestenyloxy-2,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesterol 3, 6-bis (4-aminobenzoyloxy) cholestane, 3, 5-diaminobenzoic acid, , 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyl) Oxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 4-heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallyl aniline, 4-aminobenzylamine, 3-aminobenzylamine and the following formula And the like.

In the formula (6), Za represents an alkyl group having 1 to 3 carbon atoms, -O-, -COO- or -OCO-. pa is 0 or 1. q is an integer of 0 to 2; r is an integer of 1 to 20;

Examples of the C _r H _{2r + 1} group in the formula (6) include linear or branched groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, There may be mentioned a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group.

Examples of the diamine compound represented by the formula (6) include compounds represented by the following formulas (6-1) to (6-5).

The ratio of the tetracarboxylic acid 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 with respect to 1 equivalent of the amino group contained in the diamine compound, More preferably 0.3 equivalents to 1.2 equivalents.

The synthesis reaction is preferably carried out in an organic solvent. The reaction temperature is preferably -20 占 폚 to 150 占 폚, more preferably 0 占 폚 to 100 占 폚. The reaction time is preferably 0.1 hour to 24 hours, more preferably 0.5 hours to 12 hours.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized, and examples thereof include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, Aprotic polar solvents such as N, N-dimethylimidazolidinone, dimethylsulfoxide,? -Butyrolactone, tetramethylurea and hexamethylphosphoramide; m-cresol, xylenol, phenol, halogenated phenol And the like.

The amount (a) of the organic solvent to be used is preferably from 0.1% by mass to 50% by mass, more preferably from 5% by mass to 5% by mass, based on the sum (a + b) of the total amount (b) of the tetracarboxylic acid dianhydride and the diamine compound and the amount And more preferably from 30% by mass to 30% by mass.

The polyamic acid solution obtained after the reaction 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. After the isolated polyamic acid is purified, It may be provided in the preparation of the article. As a method of isolating the polyamic acid, for example, there may be mentioned a method of drying a precipitate obtained by pouring a reaction solution into a large amount of a poor solvent under reduced pressure, and a method of distilling off the reaction solution by a vacuum distillation. Examples of the method for purifying polyamic acid include a method of dissolving an isolated polyamic acid in an organic solvent and then precipitating it with a poor solvent, and a method of performing a step of distilling off an organic solvent or the like under reduced pressure once or plural times have.

[Polyimide]

The polyimide as the [B] polymer can be produced by imidizing the amic acid structure of the above-mentioned polyamic acid by dehydration cyclization.

The polyimide may be a completely imide cargo which is subjected to dehydration ring closure of all of the arboric acid structure possessed by the polyamic acid which is the precursor thereof. The polyimide may be a partially imide cargo having only a part of the arboric acid structure, . The imidization ratio of the polyimide is preferably 30% or more, and more preferably 40% to 80%. Further, the imidation rate in polyimide can be measured by injecting a solution of polyimide into purified water, drying the resulting precipitate under reduced pressure at room temperature, dissolving it in heavy hydride dimethylsulfoxide, and using tetramethylsilane as a reference material ¹ H-NMR was measured at room temperature, and the value was determined from the obtained ¹ H-NMR spectrum by the following equation (7).

Imidization rate (%) = {1- (A ¹ / A ² ) × α} × 100 (7)

In the formula (7), A ¹ is the peak area (10 ppm) derived from the proton of the NH group. A ² is the peak area derived from the other protons. and? is the number ratio of the other protons to one proton of the NH group in the polyamic acid.

Examples of the method for synthesizing polyimide include (i) a method of heating a polyamic acid (hereinafter sometimes referred to as "method (i)"), (ii) (Ii) a method of adding a dehydrating agent and a dehydrating ring-closing catalyst, and heating them if necessary (hereinafter referred to as "method (ii)").

The reaction temperature in the method (i) is preferably 50 ° C to 200 ° C, more preferably 60 ° C to 170 ° C. When the reaction temperature is less than 50 캜, the dehydration ring closure reaction does not progress sufficiently, and when the reaction temperature exceeds 200 캜, the molecular weight of the obtained polyimide may be lowered. The reaction time is preferably 0.5 hours to 48 hours, more preferably 2 hours to 20 hours.

The polyimide obtained in the method (i) may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, after the polyimide is isolated, the polyimide may be supplied to the preparation of the liquid crystal aligning agent, And may be provided in the preparation of the liquid crystal aligning agent after purification.

Examples of the dehydrating agent in the method (ii) include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride.

The content of the dehydrating agent is appropriately selected depending on the desired imidization rate, but it is preferably 0.01 mol to 20 mol based on 1 mol of the acid structure of the polyamic acid.

Examples of the dehydration ring closure catalyst in the method (ii) include pyridine, collidine, lutidine, triethylamine, and the like.

The content of the dehydration ring-closing catalyst is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent contained. The imidization rate can be increased as the content of the dehydrating agent and the dehydrating ring closure agent increases.

Examples of the organic solvent used in the method (ii) include the same organic solvents as those exemplified for the synthesis of polyamic acid.

The reaction temperature in the method (ii) is preferably 0 ° C to 180 ° C, more preferably 10 ° C to 150 ° C. The reaction time is preferably 0.5 hours to 20 hours, more preferably 1 hour to 8 hours. By setting the reaction conditions within the above range, the dehydration ring-closure reaction proceeds sufficiently, and the molecular weight of the obtained polyimide can be made appropriate.

In the method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided to the preparation of the 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 and provided in the preparation of the liquid crystal aligning agent After the polyimide having good or isolation is purified, it may be added to the preparation of the liquid crystal aligning agent.

Examples of the method for removing the dehydrating agent and the dehydration cyclization catalyst from the reaction solution include a method of solvent substitution. Examples of the polyimide isolation and purification methods include the same methods as those exemplified as the polyamic acid isolation and purification methods.

&Lt; [C] Other polyorganosiloxane compound &gt;

The liquid crystal aligning agent preferably further contains a [C] other polyorganosiloxane compound in addition to the [A] polyorganosiloxane compound, and the [C] other polyorganosiloxane compound is preferably a compound represented by the formula (2) More preferred are polyorganosiloxanes having the structural units shown. Further, when the liquid crystal aligning agent comprises [C] other polyorganosiloxane compound, most of the [C] other polyorganosiloxane compound is present independently of the [A] polyorganosiloxane compound, And some of them may exist as a condensate with a specific polyorganosiloxane compound.

In the formula (2), X ^b 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 ² is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, A nonadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group and the like can be given.

Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and isobutoxy group.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.

The Mw of the [C] other polyorganosiloxane compound is preferably 500 to 100,000, more preferably 500 to 10,000.

The [C] other polyorganosiloxane compound 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 "raw silane compound"), Can be synthesized by hydrolysis or hydrolysis / condensation in a suitable organic solvent in the presence of water and a catalyst.

As the raw material silane compound, for example,

Butoxy silane, tetra-sec-butoxy silane, tetra-tert-butoxy silane, tetra-n-propoxy silane, tetra- Tetrachlorosilane and the like;

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-butoxysilane, ethyl tri-tert-butoxysilane, ethyl trichlorosilane, phenyl trimethoxysilane, phenyl triethoxysilane, phenyl trichlorosilane and the like;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane and the like;

Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and the like.

Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane or trimethylethoxysilane is preferred.

Examples of the organic solvent that can optionally be used when the [C] other polyorganosiloxane compound is synthesized include an alcohol compound, a ketone compound, an amide compound, an ester compound or other aprotic compound. These may be used alone or in combination of two or more.

As the alcohol compound, for example,

Propanol, n-butanol, i-butanol, sec-butanol, t-butanol, Butanol, 2-ethylhexanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol sec-octadecyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, n-octanol, n-nonyl alcohol, 2,6- , Monoalcohol compounds such as 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.

As the ketone compound, for example,

But are not limited to, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, Ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-petanthion, acetyl acetone, acetophenone, fenchone ;

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.

Examples of the amide compound include N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-ethylacetoamide, N, N-diethylacetoamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N -Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, methyl acetate, ethyl acetate,? -Butyrolactone,? -Valerolactone, n-propyl acetate, i-propyl acetate, Butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, Acetic acid ethyleneglycol monomethylether, acetic acid ethylene glycol monomethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid di Ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, methoxytriglycol acetate, ethyl propionate, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, N-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, .

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, NMP, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyltetrahydro-2 (1H) -pyrimidone.

Among these solvents, polyhydric alcohol compounds, partial ethers of polyhydric alcohol compounds and ester compounds are preferable.

The amount of water used in the synthesis of the [C] other polyorganosiloxane compound is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, per 1 mole of the total of the alkoxy group and the halogen atom contained in the raw material silane compound And particularly preferably 1 mol to 1.5 mol.

Examples of the catalyst that can be used in the synthesis of the [C] other polyorganosiloxane compound include metal chelate compounds, organic acids, inorganic acids, organic bases, alkali metal compounds, alkaline earth metal compounds and ammonia. These may be used alone or in combination of two or more.

As the metal chelate compound, for example,

(Acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, tri-n-butoxy mono (Acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di-n-butoxy bis (acetylacetonate) titanium, di-sec- (Acetylacetonate) titanium, di-t-butoxy bis (acetylacetonate) titanium, monoethoxy tris (acetylacetonate) titanium, mono-n-propoxy tris (acetylacetonate) Mono-i-propoxy tris (acetylacetonate) titanium, mono-butoxy tris (acetylacetone Butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy mono (Acetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) (Ethyl acetoacetate) titanium, di-n-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis Ethylacetoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-n-butoxy bis (ethylacetoacetate) titanium, di- , Di-t-butoxy bis (ethylacetoacetate) titanium, monoethoxy Tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i-propoxy tris (ethylacetoacetate) titanium, mono-n-butoxy tris ) Titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-t-butoxy tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono Titanium acetylacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium and tris (acetylacetonate) mono (ethylacetoacetate) titanium;

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, acetic acid, butyric acid, malic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, Dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

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

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine , Triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide and the like.

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

Examples of the alkaline earth metal compound include barium hydroxide, calcium hydroxide and the like.

Of these, metal chelate compounds, organic acids and inorganic acids are preferable, and titanium chelate compounds and organic acids are more preferable.

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

Water to be added in the synthesis of the [C] other polyorganosiloxane compound 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 catalyst may be added in advance in the silane compound as a raw material or in a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.

The reaction temperature in the synthesis of the [C] other polyorganosiloxane compound is preferably 0 ° C to 100 ° C, more preferably 15 ° C to 80 ° C. The reaction time is preferably 0.5 hours to 24 hours, more preferably 1 hour to 8 hours.

[Content of other polymer]

When the liquid crystal aligning agent and the other polymer are contained, the content of the other polymer varies depending on the kind of the other polymer, but is preferably 10,000 parts by mass or less based on 100 parts by mass of the [A] polyorganosiloxane compound.

When the liquid crystal aligning agent contains the [B] polymer, the content of the total amount of the polyamic acid and the polyimide is preferably 200 parts by mass to 5,000 parts by mass based on 100 parts by mass of the [A] polyorganosiloxane compound.

When the liquid crystal aligning agent contains the [C] other polyorganosiloxane compound, the content of the [C] other polyorganosiloxane compound is preferably 100 parts by mass to 2000 parts by mass relative to 100 parts by mass of the polyorganosiloxane Do.

When the liquid crystal aligning agent contains other polymer, the other polymer is preferably the [B] polymer or the [C] other polyorganosiloxane compound, more preferably the [B] polymer.

<Optional ingredients>

Examples of optional components include a curing agent, a curing catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule (hereinafter sometimes referred to as "epoxy compound"), a functional silane compound, and a surfactant . Hereinafter, these optional components will be described in detail.

[Curing agent, curing catalyst and curing accelerator]

The curing agent and the curing catalyst may be contained in the liquid crystal aligning agent for the purpose of making the crosslinking reaction of the [A] polyorganosiloxane compound stronger. The curing accelerator may be contained 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 composition containing an epoxy group or a compound having an epoxy group can be used. For example, a curing agent such as a polyvalent amine, a polyvalent carboxylic acid anhydride, .

Examples of the polyvalent carboxylic acid anhydride include anhydrides of cyclohexanetricarboxylic acid and other polyvalent carboxylic acid anhydrides. Examples of the cyclohexanetricarboxylic anhydride include cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid -2,3-anhydride, and the like.

Examples of other polyvalent carboxylic acid anhydrides include polyvalent carboxylic acids such as 4-methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride and polyamic acid , A Diels-Alder reaction product of an alicyclic compound having a conjugated double bond such as? -Terpinene and alo cymene with maleic anhydride, a hydrogenation product thereof, and the like, .

The use ratio of the curing agent is preferably 100 parts by mass or less based on 100 parts by mass of the [A] polyorganosiloxane compound.

As the curing catalyst, for example, an antimony hexafluoride compound, a hexafluorophosphate compound, and aluminum trisacetylacetonate can be given. The use ratio of the curing catalyst is preferably 2 parts by mass or less based on 100 parts by mass of the [A] polyorganosiloxane compound.

As the curing accelerator, for example,

Imidazole compounds;

A quaternary compound;

Quaternary amine compounds;

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

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

Boron compounds such as boron trifluoride, triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

Amine-type accelerators such as dicyandiamide, adducts of amines and epoxy resins, and the like;

A microcapsulated latent curing accelerator in which a surface of a quaternary phosphonium salt or the like is coated with a polymer;

Amine salt type latent curing accelerator;

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

The use ratio of the curing accelerator is preferably 10 parts by mass or less based on 100 parts by mass of the [A] polyorganosiloxane compound.

[Epoxy Compound]

The epoxy compound may be contained in the liquid crystal aligning agent for the purpose of further improving the adhesiveness of the formed liquid crystal alignment film to the substrate surface.

As the epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- -Aminomethylcyclohexane, and the like.

The content of the epoxy compound is preferably 40 parts by mass or less, more preferably 0.1 parts by mass to 30 parts by mass, relative to 100 parts by mass of the total amount of the polyorganosiloxane compound and other polymer optionally contained. 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 a crosslinking reaction.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the adhesion of the liquid crystal alignment film to the substrate surface.

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, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetracarboxylic dianhydride and A reaction product of a tetracarboxylic acid dianhydride and a silane compound having an amino group, which are described in JP-A-63-291922, and the like, as well as a reaction product with a silane compound having an amino group.

The content of the functional silane compound is preferably 50 parts by mass or less, more preferably 20 parts by mass or less based on 100 parts by mass of the total amount of the polyorganosiloxane compound and the other polymer optionally contained.

[Surfactants]

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

The ratio of the surfactant to be used 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 &gt;

The liquid crystal aligning agent, as described above, contains the [A] polyorganosiloxane compound as an essential component and, if necessary, contains other components. Preferably, the liquid crystal aligning agent is a liquid phase in which each component is dissolved in an organic solvent .

As the organic solvent, it is preferred that the [A] polyorganosiloxane compound and optionally other components are dissolved and not reacted with them. The organic solvent which can be preferably used for the liquid crystal aligning agent is different depending on the kind of the other polymer optionally contained.

Preferred examples of the organic solvent in the case where the liquid crystal aligning agent contains the [A] polyorganosiloxane compound and the [B] polymer include the organic solvents exemplified for use in the synthesis of polyamic acid. 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 only the [A] polyorganosiloxane compound as the polymer or when the polyorganosiloxane compound [A] and the [C] other polyorganosiloxane compound are contained Such as 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, Ethylene glycol monoethyl 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 Propylcarbitol, butylcarbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, Butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, acetic acid n -Hexyl, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate and the like. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-

The preferred solvent used for preparing the liquid crystal aligning agent is obtained by combining 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 respective 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 mN / m to 40 mN / m.

The solid concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the total mass of the liquid crystal aligning agent other than the solvent in the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., To 10% by mass. When the solid concentration is less than 1% by mass, the film thickness of the liquid crystal alignment film formed with the liquid crystal aligning agent becomes too small to obtain a good liquid crystal alignment film. On the other hand, if the solid concentration exceeds 10% by mass, the film thickness of the coating film becomes excessively large and a good liquid crystal alignment film may not be obtained. In addition, the viscosity of the liquid crystal aligning agent may increase and the coating property may be insufficient. The preferable range of the solid content concentration differs 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 solid content concentration is preferably 1.5% by mass to 4.5% by mass. In the case of the printing method, it is preferable that the solid concentration is set in the range of 3% by mass to 9% by mass, and the solution viscosity is accordingly set in the range of 12 mPa · s to 50 mPa · s. In the case of the ink-jet method, it is preferable that the solid concentration is in the range of 1% by mass to 5% by mass, and the solution viscosity is accordingly in the range of 3 mPa · s to 15 mPa · s.

The temperature at which the liquid crystal aligning agent is prepared is preferably 0 ° C to 200 ° C, more preferably 10 ° C to 60 ° C.

&Lt; Liquid crystal alignment film and method for forming the same &

A liquid crystal alignment film formed with the liquid crystal aligning agent is also suitably included in the present invention. As a method for forming a liquid crystal alignment film using the liquid crystal aligning agent, it is preferable that the structure [B] having a liquid crystal aligning ability in the [A] polyorganosiloxane compound does not have a structural unit represented by the formula (B-1) (Hereinafter, the forming method in this case is referred to as "forming method (i)") and the structure having liquid crystal aligning ability has a structural unit represented by the above formula (B-1) (Hereinafter referred to as &quot; forming method (ii) &quot;). Hereinafter, the formation methods (i) and (ii) will be described in detail.

[Formation method (i)]

First, two pairs of substrates on which a patterned transparent conductive film is formed are paired, and the liquid crystal aligning agent is applied onto each of the transparent conductive film forming surfaces by a roll coater method, a spinner method, a printing method, By an appropriate application method of the above. Next, the coated surface is subjected to preheating (prebaking), and then a coating film is formed by baking (post baking). The prebaking condition is, for example, 0.1 to 5 minutes at 40 to 120 캜. The post-baking conditions are preferably 120 deg. C to 300 deg. C, more preferably 150 deg. C to 250 deg. C, and preferably 5 min to 200 min, more preferably 10 min to 100 min. The film thickness of the coated film after post-baking is preferably 0.001 mu m to 1 mu m, more preferably 0.005 mu m to 0.5 mu m.

Examples of the substrate include glass substrates such as float glass and soda glass, and transparent substrates including plastic substrates such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, and polycarbonate.

Examples of the transparent conductive film include a NESA film containing SnO ₂ , an ITO film containing In ₂ O ₃ -SnO ₂ , and the like. As a method of patterning these transparent conductive films, for example, a photo-etching method, a method using a mask when forming a transparent conductive film, and the like can be given.

In applying the liquid crystal aligning agent, a functional silane compound, a titanate compound, or the like may be previously coated on the substrate and the transparent conductive film in order to further improve adhesion between the substrate or the transparent conductive film and the coating film.

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

The rubbing treatment is carried out by rubbing a cloth made of fibers such as nylon, rayon, and cotton, for example, in a given direction. In this case, as described in, for example, Japanese Unexamined Patent Application Publication No. 6-222366 and Japanese Unexamined Patent Application Publication No. 6-281937, a liquid crystal alignment film is formed by irradiating a part of the liquid crystal alignment film with ultraviolet light The tilt angle may be changed, or after a resist film is formed on a part of the surface of the formed liquid crystal alignment film as described in JP-A-5-107544, rubbing treatment may be performed in a direction different from the above rubbing treatment , The resist film may be removed and the liquid crystal alignment film may have a liquid crystal aligning ability different from region to region to improve the visual characteristics of the obtained horizontal liquid crystal display element.

[Formation method (ii)]

The method (ii) for forming a liquid crystal alignment layer, which is included in the present invention,

(1) a step in which the polyorganosiloxane compound [A] is coated on a substrate with a liquid crystal aligning agent containing a structure having a liquid crystal aligning ability having a structural unit represented by the above formula (B-1) to form a coating film And

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation

. According to the forming method of the present invention using the liquid crystal aligning agent, it is possible to form a liquid crystal alignment film which satisfactorily satisfies properties such as liquid crystal aligning property, voltage holding ratio and light resistance required for practical use as a liquid crystal display element.

As the coating film forming step (1), the same step as the coating film forming step described in the forming method (i) can be applied.

In the forming method (ii), a liquid crystal alignment film can be produced by the step of irradiating at least a part of the coating film formed in the step (1) in place of the rubbing treatment described in the forming method (i) have.

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

Examples of the light source to be used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp and an excimer laser. The ultraviolet rays in the above-mentioned preferable wavelength range are obtained by a means for using the light source together with, for example, a filter, a diffraction grating, or the like.

The irradiation dose of the radiation is preferably 1 J / m 2 or more and less than 10,000 J / m 2, more preferably 10 J / m 2 to 3,000 J / m 2. When a liquid crystal aligning ability is imparted to a coating film formed by a conventionally known liquid crystal aligning agent by the photo alignment method, a radiation dose of 10,000 J / m 2 or more is required. Therefore, when the liquid crystal aligning agent is used, It is possible to impart a good liquid crystal aligning ability even when the irradiation dose is 3,000 J / m 2 or less, more preferably 1,000 J / m 2 or less, particularly 500 J / m 2 or less, thereby contributing to a reduction in manufacturing cost of the liquid crystal display element.

<Liquid crystal display element>

A liquid crystal display element having the liquid crystal alignment film is also suitably included in the present invention. Accordingly, the liquid crystal display element of the present invention including the liquid crystal alignment film formed of the liquid crystal aligning agent can be used in various applications such as a clock, a portable game, a word processor, a notebook type personal computer, a car navigation system, a camcorder, Telephones, various monitors, liquid crystal televisions, and the like.

<Manufacturing Method of Liquid Crystal Display Element>

This liquid crystal display element can be manufactured, for example, as follows.

As a first method, a conventionally known method is as follows. First, two substrates are opposed to each other with a gap (cell gap) interposed therebetween such that the respective liquid crystal alignment films face each other, and a peripheral portion of the two substrates is sealed After the liquid crystal is injected and filled in the cell gap defined by the surface of the substrate and the sealant, the liquid crystal cell can be manufactured by sealing the injection hole.

As a second method, a so-called ODF (One Drop Fill) method is employed in which a sealant of, for example, an ultraviolet light curing property is applied to a predetermined place on one of the two substrates on which a liquid crystal alignment film is formed, The liquid crystal cell can be manufactured by dropping the liquid crystal on the liquid crystal alignment film surface, bonding the other substrate so that the liquid crystal alignment film is opposed thereto, and then irradiating ultraviolet light to the entire surface of the substrate to cure the sealant.

In either case, it is preferable that the liquid crystal cell used in the liquid crystal cell is heated to a temperature at which the liquid crystal using the liquid crystal is in an isotropic phase, and then gradually cooled to room temperature to remove the flow alignment upon liquid crystal filling. Then, the polarizing plate is bonded to the outer surface of the liquid crystal cell to obtain the liquid crystal display element of the present invention.

As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a spacer and a curing agent can be given.

Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable. 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-based liquid crystal, dioxane- Quaternary liquid crystal, and the like. Further, a key sold as cholesteric liquid crystal (Merck, "C-15", "CB-15") such as cholesteryl chloride, cholesteryl nonoate, cholesteryl carbonate, A strong dielectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate may be further added.

On the other hand, in the case of a vertically aligned liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferable. Examples of such a liquid crystal include a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a cypher base-based liquid crystal, an agar watch liquid crystal, a biphenyl-based liquid crystal, and a phenylcyclohexane-based liquid crystal.

Examples of the polarizing plate used for the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called &quot; H film &quot; in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state is sandwiched between cellulose acetate protective films or a polarizing plate made of H film itself.

(Example)

Hereinafter, the present invention will be described in detail on the basis of examples, but the present invention is not limitedly interpreted based on the description of this example.

The necessary amounts of raw material compounds and polymers used in the following examples were ensured by repeating the synthesis of raw material compounds and polymers in a synthesis scale as shown in the following synthesis examples, if necessary. The epoxy equivalent was measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105. The solution viscosity (mPa 占 퐏) was measured at 25 占 폚 using an E-type rotational viscometer for a solution prepared by adjusting the polymer concentration of the polymer solution in each synthesis example to 10% by mass.

&Lt; Synthesis of polyorganosiloxane having epoxy group &gt;

[Synthesis Example 1]

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, And mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 mass% aqueous ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group (EPS- 1) was obtained as a viscous transparent liquid.

(EPS-1) was subjected to ¹ H-NMR analysis. As a result, it was confirmed that a peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm in accordance with theoretical strength and a side reaction of an epoxy group was not occurring during the reaction . (EPS-1) had an Mw of 2,200 and an epoxy equivalent of 186 g / mol.

&Lt; Synthesis of Compound (A-1-1)

[Synthesis Example 2]

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

23.6 g of 2,2,6,6-tetramethyl-4-hydroxypiperidine, 15.0 g of succinic anhydride and 200 mL of pyridine were placed in a 500 mL eggplant type flask, and the reaction was carried out at 80 DEG C for 9 hours with stirring. After completion of the reaction, the mixture was allowed to stand at room temperature for one day to precipitate crystals, and the solvent was removed to obtain 37.1 g of white crystals of the compound (A-1-1).

&Lt; Synthesis of compound having liquid crystal aligning ability &gt;

[Synthesis Example 3]

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

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

[Synthesis Example 4]

Compound (b-2) was synthesized according to the following reaction formula.

91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 mL of N-methyl-2-pyrrolidone were placed in a 1 L eggplant-shaped flask and stirred at room temperature for 1 hour. Then, 99.7 g And the reaction was carried out at 100 占 폚 under stirring for 5 hours. After completion of the reaction, re-precipitation was performed with water. Next, to this precipitation, 48 g of sodium hydroxide and 400 mL of water were added and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain white crystals (104 g) of the compound (b-2 '). 104 g of the compound (b-2 ') was placed in a reaction vessel, and 1 L of thionyl chloride and 770 N of N, N-dimethylformamide were added thereto, followed by stirring at 80 캜 for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, and methylene chloride was added thereto, followed by washing with an aqueous solution of sodium hydrogencarbonate, drying with magnesium sulfate, concentration and then adding tetrahydrofuran to obtain a solution. Next, 74 g of 4-hydroxycinnamic acid, 138 g of potassium carbonate, 4.8 g of tetrabutylammonium, 500 mL of tetrahydrofuran, and 1 L of water were placed in a 5 L three-necked flask different from the above. This aqueous solution was ice-cooled (ice-cooled), and a tetrahydrofuran solution containing a reaction product of the compound (b-2 ') and thionyl chloride was slowly added dropwise and the reaction was further carried out for 2 hours with stirring. After completion of the reaction, hydrochloric acid was added to the reaction mixture to neutralize and extracted with ethyl acetate. The extract was dried with magnesium sulfate, concentrated and recrystallized with ethanol to obtain 90 g of white crystals of the compound (b-2).

[Synthesis Example 5]

Compound (b-3) was synthesized according to the following reaction formula.

82 g of methyl 4-hydroxybenzoate, 166 g of potassium carbonate and 400 mL of N, N-dimethylacetamide were placed in a 1 L eggplant-shaped flask and stirred at room temperature for 1 hour. Then, 4,4,4-trifluoro- 95 g of iodobutane was added and the reaction was carried out at room temperature for 5 hours with stirring. After completion of the reaction, re-precipitation was performed with water. Subsequently, 32 g of sodium hydroxide and 400 mL of water were added to this precipitation, and the mixture was refluxed for 4 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 80 g of white crystals of the compound (b-3 '). 46.4 g of the compound (b-3 ') was placed in a reaction vessel, to which 200 ml of thionyl chloride and 0.2 ml of N, N-dimethylformamide were added and the mixture was stirred at 80 ° C for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, and methylene chloride was added thereto, followed by washing with an aqueous solution of sodium hydrogencarbonate, drying with magnesium sulfate, concentration and then adding tetrahydrofuran to obtain a solution. Next, 36 g of 4-hydroxycinnamic acid, 55 g of potassium carbonate, 2.4 g of tetrabutylammonium, 200 mL of tetrahydrofuran, and 400 mL of water were placed in a 2 L three-necked flask different from the above. This aqueous solution was ice-cooled to slowly drop a tetrahydrofuran solution containing a reaction product of the above compound (b-3 ') and thionyl chloride, and the reaction was further carried out for 2 hours with stirring. After completion of the reaction, hydrochloric acid was added to the reaction mixture to neutralize and extracted with ethyl acetate. The extract was dried with magnesium sulfate, concentrated and recrystallized with ethanol to obtain 39 g of white crystals of the compound (b-3).

[Synthesis Example 6]

Compound (b-4) was synthesized according to the following reaction formula.

(B-4) was obtained in the same manner as in Synthesis Example 4, except that 9.91 g of 4-pentyl-trans cyclohexylcarboxylic acid was used instead of the compound (b-2 ' 13 g of crystals were obtained.

[Synthesis Example 7]

Compound (b-5) was synthesized according to the following reaction formula.

31 g of the compound (b-5 '), 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine, 56 mL of triethylamine, and 8.2 g of acrylic acid were added to a 500 mL three-necked flask equipped with a reflux condenser, mL and N, N-dimethylacetamide (200 mL) were placed, and the reaction was carried out at 120 ° C for 3 hours with stirring. After the completion of the reaction, the reaction solution was filtered, and 1 liter of ethyl acetate was added to the filtrate. The obtained organic layer was washed twice with dilute hydrochloric acid and three times with water. Thereafter, the organic layer was dried with magnesium sulfate, concentrated and dried, and then recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain 15 g of crystals of the compound (b-5).

[Synthesis Example 8]

Compound (b-6) was synthesized according to the following reaction formula.

16 g of the compound (b-6) was obtained in the same manner as in the above Synthesis Example 7 except that 36 g of the compound (b-6 ') was used instead of the compound (b-5').

[Synthesis Example 9]

Compound (b-7) was synthesized according to the following reaction formula.

12 g of decylsuccinic anhydride, 8.2 g of 4-aminocinnamic acid and 100 mL of acetic acid were placed in a 200 mL eggplant-shaped flask equipped with a reflux tube, and the reaction was carried out under reflux for 2 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, the organic layer was washed with water, dried over magnesium sulfate, purified with a silica column, and further recrystallized with a mixed solvent of ethanol and tetrahydrofuran to obtain the compound b-7) (purity: 98.0%).

[Synthesis Example 10]

(B-8 ') represented by the following formula was used in place of the compound (b-5') in Synthesis Example 7, 8) was obtained in an amount of 14 g.

[Synthesis Example 11]

Compound (b-9) was synthesized according to the following reaction formula.

39 g of? -Cholestanol, 20 g of succinic anhydride, 1.5 g of N, N-dimethylaminopyridine, 200 mL of ethyl acetate and 17 mL of triethylamine were placed in a 500 mL three-necked flask equipped with a reflux condenser and a nitrogen inlet tube, The reaction was carried out under reflux. After completion of the reaction, 200 ml of tetrahydrofuran was added to the reaction mixture, and the resulting organic layer was washed with 1N hydrochloric acid water and twice with water three times in succession, dried over magnesium sulfate, and then the solvent was removed under reduced pressure. Ethyl, whereby 38 g of a white crystal of the compound (b-9) was obtained.

<Synthesis of [A] polyorganosiloxane compound>

[Synthesis Example 12]

10.0 g of (EPS-1), 69.5 g of methyl isobutyl ketone and 2.77 g of the compound (A-1-1) (20 mol% based on the epoxy group of the polyorganosiloxane EPS-1) (Equivalent to 30 mol% based on the epoxy group of the polyorganosiloxane (EPS-1)) and 1.00 g of tetrabutylammonium bromide, and the reaction was carried out at 100 DEG C for 8 hours with stirring. After completion of the reaction, the polyorganosiloxane compound (S-1) was dissolved in ethyl acetate to obtain a solution, and the solution was washed five times with water and then the solvent was distilled off, 15.8 g was obtained as a white powder.

[Synthesis Example 13 to Synthesis Example 33]

The polyorganosiloxane compounds (S-2) to (S-22) were synthesized by operating in the same manner as in Synthesis Example 12, except that the kind and compounding amount of the compound to be compounded were changed as shown in Table 1, respectively. In addition, the use ratio of the compound in Table 1 is the mole% relative to the epoxy group of (EPS-1). Mws of the polyorganosiloxanes (S-1) to (S-22) are also shown in Table 1. In addition, the structures of salicylic acid and 4-diethylaminobenzoic acid are shown below in order.

[Comparative Synthesis Example 1]

10.0 g of (EPS-1), 58.4 g of methyl isobutyl ketone, 4.60 g of stearic acid (corresponding to 30 mol% based on the epoxy group of the polyorganosiloxane EPS-1) and tetrabutylammonium 1.00 g of bromide was added, and the reaction was carried out at 100 占 폚 under stirring for 8 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed five times with water and then the solvent was distilled off to obtain a white powder 12.4 of polyorganosiloxane (CS-1) g.

[Comparative Synthesis Examples 2 to 4]

The polyorganosiloxanes (CS-2) to (CS-4) were synthesized in the same manner as in Comparative Synthesis Example 1, with the kind and compounding amount of the compound to be compounded as shown in Table 1, respectively. Mws of the polyorganosiloxanes (CS-1) to (CS-4) are also shown in Table 1.

&Lt; Synthesis of [B] polymer (polyamic acid) &gt;

[Synthesis Example 34]

(1.0 mole) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as tetracarboxylic dianhydride, 212 g (1.0 mole) of 2,2'-dimethyl-4,4'-diaminobiphenyl as a diamine, Was dissolved in 4,050 g of NMP and reacted at 40 占 폚 for 3 hours to obtain a polyamic acid solution (PA-1) having a solid content concentration of 10 mass% and a solution viscosity of 170 mPa 占 퐏.

[Synthesis Example 35]

86.3 g (0.44 mol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 96.0 g (0.44 mol) of pyromellitic dianhydride as a tetracarboxylic dianhydride, 2,2'-dimethyl- (0.90 mol) of 4'-diaminobiphenyl were dissolved in 1,490 g of NMP, and reacted at 40 ° C for 4 hours. Then, NMP was further added to obtain a solution having a solid concentration of 10% by mass and a solution viscosity of 43 mPa.s To obtain an acid solution (PA-2).

&Lt; Synthesis of [B] polymer (polyimide) &gt;

[Synthesis Example 36]

(0.093 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 9.2 g (0.085 mole) of p-phenylenediamine as a diamine and 4.9 g of a compound represented by the following formula (DA) (0.009 mol) were dissolved in 140 g of NMP and reacted at 60 DEG C for 4 hours. A small amount of the obtained polyamic acid solution was collected and NMP was added to obtain a polyamic acid solution having a solid concentration of 10 mass% and a solution viscosity of 126 mPa.s . Subsequently, 325 g of NMP was added to the obtained polyamic acid solution, and 7.4 g of pyridine and 9.5 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with fresh NMP to obtain about 210 g of a solution containing 16.1% by mass of a polyimide (PI-1) having an imidization rate of about 54%. A small amount of the polyimide solution was collected, and NMP was added thereto to measure a solid content concentration of 10 mass%. As a result, the solution viscosity was 75 mPa 占 퐏.

[Synthesis Example 37]

20.0 g (0.089 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 6.8 g (0.063 mole) of p-phenylenediamine as diamine, 4,4'-diaminodiphenylmethane And 4.7 g (0.009 mol) of the compound represented by the above formula (DA) were dissolved in 140 g of NMP and reacted at 60 DEG C for 4 hours to obtain a solution having a solids concentration of 20 mass% and a solution viscosity of 2,200 mPa.s An acid solution was obtained. Subsequently, 325 g of NMP was added to the obtained polyamic acid solution, 10.5 g of pyridine and 13.6 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration cyclization reaction, the solution in the system was replaced with a fresh NMP solvent to obtain a polyimide (PI-2) solution (solid concentration 20% by mass) having an imidization rate of about 65%, about 160 g.

[Synthesis Example 38]

19.2 g (0.086 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 5.2 g (0.034 mol) of 3,5-diaminobenzoic acid as diamine and 25.5 g 0.052 mol) was dissolved in 200 g of NMP and reacted at 60 占 폚 for 4 hours to obtain a polyamic acid solution having a solid content concentration of 20 mass% and a solution viscosity of 1,450 mPa 占 퐏. Next, 250 g of NMP was added to the obtained polyamic acid solution, 10.2 g of pyridine and 13.2 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solution in the system was replaced with fresh NMP to obtain about 230 g of a solution containing 20% by mass of a polyimide (PI-3) having an imidization rate of about 67%.

<Synthesis of [C] other polyorganosiloxane compound>

[Synthesis Example 39]

20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol were placed in a 200-mL three-necked flask equipped with a cooling tube, and the mixture was heated to 60 DEG C and stirred. Thereto was added an aqueous maleic anhydride solution prepared by dissolving 0.26 g of maleic anhydride in 10.8 g of water, which was prepared in another flask having a capacity of 20 mL, and the reaction was further carried out at 60 DEG C for 4 hours with stirring. After completion of the reaction, the solvent was distilled off from the obtained reaction mixture, 1-ethoxy-2-propanol was added to the residue, and the solution was concentrated again to obtain a polyorganosiloxane (PS-1) solution having a solid concentration of 10 mass%. Mw was 5,100.

&Lt; Preparation of liquid crystal aligning agent &

[Example 1]

100 parts by mass of the polyorganosiloxane (S-1) and 1,000 parts by mass of the solution containing polyamic acid (PA-1) in terms of polyamic acid (PA-1) And ethylene glycol-mono-n-butyl ether were added to obtain a solution having a solvent composition of NMP: ethylene glycol-mono-n-butyl ether = 50: 50 (mass ratio) and a solid content concentration of 3.0% by mass. This solution was filtered with a filter having a pore diameter of 1 탆 to prepare a liquid crystal aligning agent (AF-1).

[Examples 2 to 39 and Comparative Examples 1 to 7]

(AF-2) to (AF-39) and (CAF-1) to (AFF-2) were carried out in the same manner as in Example 1, CAF-7) were prepared and used in Examples 2 to 39 and Comparative Examples 1 to 7.

<Storage stability>

The storage stability of each liquid crystal compounding agent was evaluated by the following (Method 1) or (Method 2). The results are shown in Table 2.

(Method 1)

(AF-1) to (AF-12) and (CAF-1) to (CAF-3) were coated on a glass substrate by spin coating at a variable number of revolutions, The coating film was formed by heating for 60 minutes, and the number of revolutions at which the thickness of the coating film after removal of the solvent became 1000 angstroms was investigated. Next, a part of the liquid crystal aligning agent was taken and stored at -15 占 폚 for 5 weeks. The liquid crystal aligning agent after storage was visually observed, and when the precipitation of insoluble matter was observed, the storage stability was judged as &quot; poor &quot;. When no insoluble matter was observed after 5 weeks of storage, the glass substrate was further coated with a liquid crystal aligning agent after storage by spin coating at a revolution number of 1,000 angstroms before storage, followed by 200 Lt; 0 &gt; C for 60 minutes to form a coating film, and the film thickness after solvent removal was measured. When the film thickness was changed by 10% or more from 1,000 ANGSTROM, the storage stability was judged as &quot; defective &quot;, and when the film thickness was less than 10%, the storage stability was judged as &quot; positive &quot;. Further, the film thickness of the coating film was measured using an etching-type stepped film deposition apparatus manufactured by KLA-Tencor Corporation.

(Method 2)

The liquid crystal aligning agents (AF-13) to (AF-39) and (CAF-4) to (CAF-7) were stored at -15 ° C for 6 months. Viscosity was measured by an E-type viscometer at 25 캜 before and after storage. When the change rate of the solution viscosity before and after storage was less than 10%, the storage stability was evaluated as &quot; positive &quot;, and when it was 10% or more, the storage stability was evaluated as &quot; defective &quot;.

&Lt; Production of liquid crystal display element &

[Example 40]

A liquid crystal aligning agent AF-1 was applied on the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner and pre-baked on a hot plate at 80 DEG C for 1 minute, And the solvent was removed by heating at 200 占 폚 for 1 hour to form a coating film having a thickness of 0.1 占 퐉. 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 5.5 mu m was applied to the periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing and then the surfaces of the liquid crystal alignment film of the pair of substrates were superimposed on each other, For 1 hour to thermally cure the adhesive. 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. In order to further eliminate the flow alignment during liquid crystal injection, After being heated at 150 DEG C for 10 minutes, it was gradually cooled to room temperature. A polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions of the two polarizing plates were orthogonal to each other. Thus, a vertical alignment type liquid crystal display device was manufactured.

[Examples 41 to 51, Comparative Examples 7 to 9]

Liquid crystal display devices were produced in the same manner as in Example 40 using the liquid crystal aligning agents AF-2 to AF-12 and (CAF-1) to (CAF-3) To 51 and Comparative Examples 7 to 9, respectively.

[Example 52]

A liquid crystal aligning agent AF-13 was applied on the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner and pre-baked on a hot plate at 80 DEG C for 1 minute, And the solvent was removed by heating at 200 占 폚 for 1 hour to form a coating film having a thickness of 0.1 占 퐉. Subsequently, a polarizing ultraviolet ray 200 J / m 2 containing a bright line of 313 nm was irradiated onto the surface of the coating film from a direction inclined 40 ° from the normal to the substrate using a Hg-Xe lamp and a Gantry prism to form a liquid crystal alignment film. The same operation was repeated to prepare a pair of substrates (two pieces) having a liquid crystal alignment film. An epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 mu m was applied to the periphery of the surface having one liquid crystal alignment film in the substrate by screen printing and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, So that the projection direction of the optical axis of ultraviolet light to the substrate surface was antiparallel, and the adhesive was thermally cured at 150 占 폚 for 1 hour. Subsequently, a gap between the substrates was filled with a negative type liquid crystal (Merck Co., MLC-6608) from the liquid crystal injection port, and then a liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to exclude the flow orientation at the time of injecting the liquid crystal, it was heated to 150 占 폚 and then slowly cooled to room temperature. Next, the polarizing plate is bonded to both outer sides of the substrate so that the polarization directions thereof are orthogonal to each other and the optical axis of the ultraviolet ray of the liquid crystal alignment film is at an angle of 45 degrees with respect to the projection direction of the substrate surface, And this was designated as Example 52. [

[Examples 53 to 78, Comparative Examples 10 to 13]

Liquid crystal display devices were produced in the same manner as in Example 52 using the liquid crystal aligning agents AF-13 to AF-39 and (CAF-4) to (CAF-7) To 78 and Comparative Examples 10 to 13, respectively.

The liquid crystal display devices of Examples 40 to 78 and Comparative Examples 7 to 13 were evaluated as follows. The results are shown in Table 3.

<Liquid crystal alignment property>

The presence or absence of an abnormal (abnormal) domain in the change of light and dark when a voltage of 5 V was turned ON / OFF (applied / released) to the liquid crystal display device manufactured as described above was visually observed. A case in which no light leakage from the cell was observed at the time of voltage OFF, and a case where the cell driving region was white at the time of voltage application and no light leakage from the other region was determined as &quot; positive &quot; The case where light leakage from the cell at the time of voltage OFF or light leakage from the region other than the cell driving region at the time of voltage ON was observed was defined as &quot; poor &quot;

<Voltage Conservation Rate>

A voltage of 5 V was applied to the liquid crystal display device prepared above at an environmental temperature of 60 캜 for 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 measurement apparatus used was VHR-1 manufactured by Toyota Technica Co., Ltd. The case where the voltage holding ratio was 97% or more was evaluated as &quot; positive voltage holding ratio &quot;.

<Light resistance>

The initial voltage holding ratio was measured on the liquid crystal display device manufactured as described above under the same conditions as the evaluation of the voltage holding ratio. Thereafter, it was placed at a distance of 5 cm under a 100-watt white fluorescent lamp, irradiated with light for 500 hours, and then the voltage maintenance rate was measured again under the same conditions as above. A "when the rate of decrease of the voltage holding ratio was less than 1% with respect to the initial value," B "when the rate was more than 1% but less than 2%, and" C "when the rate exceeded 2%.

As apparent from the results of Tables 2 and 3, it was found that the liquid crystal aligning agent of the present invention is excellent in storage stability. It has also been found that the liquid crystal alignment film formed from the liquid crystal aligning agent sufficiently satisfies the liquid crystal alignment property, the voltage holding ratio and the light resistance required for practical use as a liquid crystal display element.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid crystal alignment film which satisfactorily satisfies properties such as liquid crystal alignment property, voltage holding ratio and light resistance required for practical use as a liquid crystal display device, a method of forming the liquid crystal alignment film, , And a liquid crystal aligning agent capable of forming a liquid crystal alignment film by employing a photo alignment method and a liquid crystal alignment film. The liquid crystal display element of the present invention including a liquid crystal alignment film formed of the liquid crystal aligning agent can be used in various fields such as a clock, a portable game, a word processor, a notebook type personal computer, a car navigation system, a camcorder, a portable information terminal, Various monitors, liquid crystal televisions, and the like.

Claims (17)

[A] a polyorganosiloxane compound having at least one structure selected from the group consisting of a piperidine structure, a phenol structure and an aniline structure
And a liquid crystal aligning agent. The method according to claim 1,
A liquid crystal aligning agent wherein the piperidine structure is represented by the following formula (A-1 '), the phenol structure is represented by the following formula (A-2') and the aniline structure is represented by the following formula (A-

(In the formula (A-1 '),
R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms or a 1,3-dioxobutyl group;
R ² to R ⁵ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms;
X ¹ is a single bond, a carbonyl group or ^** -CONH-; X ^{2 to} X ⁵ each independently represent a single bond, a carbonyl group, ^** -CH ₂ -CO- or ^** -CH ₂ -CH (OH) -; Bonded to the piperidine ring;
Bonded to the backbone or side chain of the polyorganosiloxane backbone);

(In the formula (A-2 '), R ⁶ is an alkyl group having 1 to 16 carbon atoms, provided that the alkyl group has an oxygen atom, a sulfur atom, a carbonyl group, an ester group or a combination of two or more thereof in the skeleton chain N is an integer from 0 to 4; and the bonded hands represented by * are bonded to the main chain or side chain of the polyorganosiloxane skeleton);

(In the formula (A-3 '), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 16 carbon atoms, provided that the alkyl group has an oxygen atom, a sulfur atom, a carbonyl group, May be combined with each other to form a polyorganosiloxane skeleton; and * the bonded hands represented by * are bonded to the main chain or side chain of the polyorganosiloxane skeleton). The method according to claim 1,
The polyorganosiloxane compound [A]
A part derived from at least one member selected from the group consisting of a polyorganosiloxane having a structural unit represented by the following formula (1), a hydrolyzate thereof and a condensate of a hydrolyzate,
A part derived from at least one compound selected from the group consisting of compounds represented by the following formulas (A-1), (A-2) and (A-3)
A liquid crystal aligning agent having:

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

(In the formula (A-1), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms or a 1,3-dioxobutyl group;
R ² to R ⁵ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms;
X ¹ is a single bond, a carbonyl group or ^** -CONH-; X ^{2 to} X ⁵ each independently represent a single bond, a carbonyl group, ^** -CH ₂ -CO- or ^** -CH ₂ -CH (OH) -; Bonded to the piperidine ring;
In the formula (A-2), R ⁶ is an alkyl group having 1 to 16 carbon atoms; The alkyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group, or a combination of two or more thereof in the skeleton chain; n is an integer from 0 to 4;
In the formula (A-3), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 16 carbon atoms; The alkyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group, or a combination of two or more thereof in the skeleton chain;
In the formulas (A-1) to (A-3), Y is a single bond or an alkanediyl group having 1 to 16 carbon atoms; The alkanediyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, or a combination of two or more thereof in the structure; And Z is a carboxyl group or a hydroxyl group). The method of claim 3,
A liquid crystal aligning agent wherein X ^a in the formula (1) is a group represented by the following formula (X ^a -1) or (X ^a -2)

Wherein s is an integer of 0 to 3, t is an integer of 1 to 6, u is an integer of 0 to 2, and v is an integer of 0 to 6 (in the formula (X ^a -1) and (X ^a -2) And the bonded hands represented by * are bonded to silicon atoms). 5. The method of claim 4,
Wherein the group represented by the formula (X ^a -1) or the formula (X ^a -2) is a group represented by the following formula (X ^a -1-1) or (X ^a -2-1)

(Of the formulas (X ^a -1-1) and (X ^a -2-1), a bonded hand represented by * bonds to a silicon atom). The method according to claim 1,
A liquid crystal aligning agent wherein the polyorganosiloxane compound [A] comprises a structure having liquid crystal aligning ability. The method according to claim 6,
Wherein the structure having the liquid crystal aligning ability is selected from the group consisting of organic groups having a steroid skeleton and having 17 to 51 carbon atoms, an alkyl group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, an alkoxy group having 2 to 20 carbon atoms An alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms, a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, and a fluoroalkoxycyclohexyl group having a fluoroalkoxy group having 1 to 20 carbon atoms And at least one kind of group selected from the group consisting of The method according to claim 6,
Wherein the structure having the liquid crystal aligning ability is a liquid crystal aligning agent represented by the following formula (B-1)

(In the formula (B-1), m is an integer of 0 to 4). 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. The method according to claim 1,
[C] a liquid crystal aligning agent further comprising a polyorganosiloxane compound having a structural unit represented by the following formula (2)

(Wherein X ^b represents 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 ^b is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms ). (1) a step of applying the liquid crystal aligning agent according to any one of claims 8, 9 and 10 on a substrate to form a coating film, and
(2) A method for forming a liquid crystal alignment film having a step of irradiating at least a part of a coating film formed in the step (1) with radiation. A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1 to 10. A liquid crystal display element comprising the liquid crystal alignment film according to claim 12. delete delete delete delete