KR101787443B1 - Liquid crystal aligning agent, liquid crystal display device, liquid crystal alignment film and polyorganosiloxane compound - Google Patents

Abstract

An object of the present invention is to provide a photo-alignment liquid crystal aligning agent capable of forming a liquid crystal display element having a short electro-optical response time while satisfying characteristics such as voltage holding ratio and light resistance generally required for a liquid crystal display element.
(Solution) The present invention is a liquid crystal aligning agent containing a polymer having a photo-aligning group [A] and a group represented by the following formula (A1). In the formula (A1), R ^A is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group. However, some or all of the hydrogen atoms of these groups may be substituted. R ^B is a linking group including a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom. R ^C is a group having at least two monocyclic structures. a is 0 or 1;

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal display element, a liquid crystal alignment film, and a polyorganosiloxane compound. More particularly, the present invention relates to a liquid crystal alignment agent, a liquid crystal display device, a liquid crystal film,

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

In a liquid crystal display element, a liquid crystal alignment film is formed on a surface of a substrate in order to orient liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the surface of the organic film formed on the substrate surface is rubbed in one direction in the form of rayon or the like. However, when the formation of the liquid crystal alignment film is performed by rubbing treatment, dust or static electricity is likely to be generated during the rubbing process, so that there is a problem that dust adheres to the surface of the alignment film to cause defective display. In addition, ) Device has a problem that the circuit breakage of the TFT element occurs due to the generated static electricity, which causes a decrease in the product yield. As another means for aligning the liquid crystal in the liquid crystal cell, there has been proposed a photo alignment method in which a liquid crystal aligning ability is imparted by irradiating polarized light or non-polarized light to the radiation-sensitive organic thin film formed on the substrate surface (See Patent Documents 1 to 6). According to this optical alignment method, uniform liquid crystal alignment can be formed without generating dust or static electricity during the process (see Patent Documents 7 to 9).

Such a liquid crystal display device is expected to be used as a moving picture display device such as a cellular phone or a liquid crystal television. As a characteristic required for a liquid crystal display device, in order to smoothly display a moving picture and to suppress the afterimage as much as possible, A further increase in the speed is required. With respect to this demand, there has been reported a technique for improving by giving a structure for imparting dielectric anisotropy to the polymer side chain used in the liquid crystal alignment film (see Patent Documents 10 and 11). However, this patent document relates to a liquid crystal alignment film which does not have a photo-alignment function. In addition to speeding up the electro-optical response time, there is no need for electric characteristics such as orientation, voltage- .

From such a situation, development of an optically oriented liquid crystal aligning agent capable of forming a liquid crystal display element having a short electro-optic response time while satisfying characteristics such as voltage holding ratio and light resistance generally required for a liquid crystal display element is desired.

Japanese Patent Application Laid-Open No. 2003-307736 Japanese Laid-Open Patent Publication No. 2004-163646 Japanese Patent Application Laid-Open No. 2002-250924 Japanese Patent Application Laid-Open No. 2004-83810 Japanese Patent Application Laid-Open No. 9-211468 Japanese Patent Application Laid-Open No. 2003-114437 International Publication No. 2009/25385 pamphlet International Publication No. 2009/25386 pamphlet International Publication No. 2009/25388 brochure Japanese Patent Publication No. 2007-521361 Japanese Patent Publication No. 2007-521506

The present invention has been made based on the above-described circumstances, and its object is to provide a liquid crystal display device capable of forming a liquid crystal display element having a short electro-optic response time while satisfying characteristics such as voltage holding ratio and light resistance generally required for a liquid crystal display element An alignment liquid crystal aligning agent, a vertically aligned liquid crystal display element having a liquid crystal alignment film formed of the liquid crystal aligning agent, and a polyorganosiloxane compound suitably used for the liquid crystal aligning agent.

According to an aspect of the present invention,

[A] a liquid crystal aligning agent containing a photo-aligning group and a polymer having a group represented by the following formula (A1) (hereinafter sometimes referred to as "[A] polymer").

(Formula (A1) of, R ¹ is methylene, from 2 to 30 carbon atoms in the alkylene group, a phenylene group or a cyclohexylene group; however, a part or all of the hydrogen atoms with those groups are good and which may be substituted; R ² is R ³ is a group having at least two monocyclic structures, and a is 0 or 1), and the like.

According to the liquid crystal aligning agent of the present invention, the liquid crystal display element comprising the liquid crystal alignment layer formed of the liquid crystal aligning agent contains the [A] polymer having the photo aligning group and the group having the specific structure represented by the formula (A1) , And light resistance, while exhibiting a short electro-optical response time.

It is preferable that the photo-orientable group has a structure represented by the following formula (B1).

(In the formula (B1), R is a fluorine atom or a cyano group; a 'is an integer of 0 to 4; when a' is 2 or more, plural R may be the same or different; .

The liquid crystal aligning agent can improve the sensitivity by having the photo-orientable group having the specific structure described above.

R ^C in the formula (A1) is preferably represented by the following formula (A2).

(Wherein, in the formula (A2), R ^D is a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a divalent heterocyclic group; R ^E is a linking group containing at least one of a methylene group which may have a substituent and an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic group, all or part of which may be substituted; ; R ^F is a (c + 1) -valent group excluding (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or a heterocyclic compound; And R ^G represents a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group B is 0 or 1, c is an integer from 1 to 9, d is 1 or 2, R ^D , R ^E and R ^G A plurality of R ^D , R ^E, and R ^G May be the same or different from each other).

According to the liquid crystal aligning agent, since the R ^C has the specific structure, the effect of the present invention can be further improved.

The polymer [A] preferably has a polyorganosiloxane structure.

The liquid crystal aligning agent can improve the light resistance by the polymer [A] having a polyorganosiloxane structure.

[B] at least one polymer selected from the group consisting of polyamic acid and polyimide (hereinafter sometimes referred to as " [B] polymer ").

The liquid crystal aligning agent may further contain the [B] polymer to improve its solution properties and electric characteristics of the obtained liquid crystal display element.

The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed from the liquid crystal aligning agent.

Since the liquid crystal display element is provided with the liquid crystal alignment layer formed of the liquid crystal aligning agent, the electrooptic response time can be shortened while satisfying the characteristics such as the generally required voltage holding ratio and light resistance.

It is preferable that the liquid crystal display element has two or more regions in which the liquid crystal alignment layers have different orientation orientations.

The liquid crystal display element of the present liquid crystal display element has two or more regions having different orientation orientations, so that the liquid crystal display element can be applied to a 3D display.

The liquid crystal alignment film of the present invention is formed from the liquid crystal aligning agent.

Since the liquid crystal alignment film is formed of the liquid crystal alignment film described above, the liquid crystal display device having the liquid crystal alignment film can exhibit a short electro-optical response time while satisfying generally required characteristics such as voltage holding ratio and light resistance.

In the polyorganosiloxane compound of the present invention,

A photo-aligning group and a group represented by the following formula (A1).

(Formula (A1) of, R ^A is a methylene group, from 2 to 30 carbon atoms in the alkylene group, a phenylene group or a cyclohexylene group; however, a part or all of the hydrogen atoms with those groups are good and which may be substituted; R ^B is R ^c is a group having at least two monocyclic structures, and a is 0 or 1).

Since the polyorganosiloxane compound has a photo aligning group and a group of a specific structure represented by the formula (A1), it can be suitably used as a component of the liquid crystal aligning agent.

According to the present invention, it is possible to provide a liquid crystal aligning agent which can be applied to a photo alignment mode, which can provide a high-speed response and at the same time can form a liquid crystal display element exhibiting excellent light resistance.

1 is an explanatory view showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film manufactured in the embodiment.

(Mode for carrying out the invention)

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention contains a polymer [A] containing a photo-aligning group and a group represented by the formula (A1). This liquid crystal aligning agent can be applied to the photo alignment mode, and the liquid crystal display device having the liquid crystal alignment film formed using the liquid crystal alignment agent can satisfy the characteristics such as voltage holding ratio and light resistance generally required for liquid crystal display elements, The response time becomes short. Further, the liquid crystal aligning agent may contain "[other polymer]" described later such as the [B] polymer. Other optional components may be contained within the range not impairing the effects of the present invention. Each component will be described in detail below.

<[A] Polymer>

[A] The polymer contains a photo-aligning group and a group represented by the formula (A1).

[Optical alignment machine]

As the photo-aligning group, a known photo-orientable group can be appropriately used, but a group having a cinnamate structure, a chalcone structure, and an azobenzene structure is preferable, and a cinnamate structure is particularly preferable in view of sensitivity.

As the photo aligning group, a group having a structure represented by the following formula (B1) is preferable.

In the above formula (B1), R represents a fluorine atom or a cyano group. a 'is an integer of 0 to 4; When a 'is 2 or more, a plurality of R's may be the same or different. * Indicates a combined hand.

As a 'in the above formula (B1), 0 or 1 is preferable, and 0 is more preferable.

As the group having the structure represented by the above formula (B1), a group represented by the following formula (B1-1) and a group represented by the following formula (B1-2) are preferable.

In the formulas (B1-1) and (B1-2), R, a 'and * have the same meanings as in the formula (B1).

In formula (B1-1), R ¹ is a hydrogen atom, a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, or an alkyl group having 1 to 40 carbon atoms. Provided that a part or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom.

X ¹ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-. + Represents a binding hand that binds to R ¹ .

R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group.

X ² is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-. + Represents the bonding hands bonding with R &lt; ² &gt;.

b 'is an integer of 0 to 3;

In the formula (B1-2), R ³ is a hydrogen atom, a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, or an alkyl group having 1 to 40 carbon atoms. Provided that a part or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom.

X ³ is an oxygen atom or a divalent aromatic group.

R ⁴ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group.

X ⁴ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-. + Represents the bonding hands bonding with R ⁴ .

and c 'is an integer of 0 to 3.

Examples of the monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group represented by R ³ in the formula (B1-1) and R ^{1 in} the formula (B1-2) include, for example, A cyclohexyl group having an alkyl group, a bicyclohexyl group, a cholestenyl group, a cholestanyl group and an adamantyl group.

The alkyl group having 1 to 40 carbon atoms represented by R ¹ and R ³ is preferably an alkyl group having 1 to 20 carbon atoms (provided that some or all of the hydrogen atoms of the alkyl group may be substituted by a fluorine atom). Examples of such alkyl groups include n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, N-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, A 4,4,5,5,5-pentafluoropentyl group, a 4,4,5,5,6,6,6-heptafluorohexyl group, a 3,3,4,4-tetrafluorobutyl group, Heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group , A 2- (perfluorooctyl) ethyl group, a 2- (perfluorodecyl) ethyl group, and the like.

By the formula (B1-1) R ² and the formula (B1-2) as the divalent aromatic group of R ^4, for example, 1,4-phenylene, 2-fluoro-in of the 1,4 Phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6-tetrafluoro-1,4-phenylene group and the like.

Examples of the divalent heterocyclic group of R ² and R ⁴ include a 1,4-pyridylene group, a 2,5-pyridylene group and a 1,4-furanylene group.

Examples of the divalent condensed ring group of R ² and R ⁴ include a naphthylene group and the like.

As the group represented by the formula (B1-1), a group represented by the following formula is preferable.

In the above formula, R ¹ and * have the same meanings as in the formula (B1-1). and d is an integer of 1 to 10.

As the group represented by the formula (B1-2), a group represented by the following formula is preferable.

In the above formula, R ³ and * have the same meanings as in formula (Bl-2).

The polymer [A] in the present invention preferably has a structure represented by the above formula (B1) in an amount of 0.2 to 6 mmol / g, more preferably 0.3 to 5 mmol / g.

[The group represented by the formula (A1)

R ^A in the formula (A1) is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group. However, some or all of the hydrogen atoms of these groups may be substituted.

Examples of the alkylene group having 2 to 30 carbon atoms represented by R ^A include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, A tetracosylene group, a pentacosylene group, a hexacosylene group, an octadecylene group, an octadecylene group, an octadecylene group, an eicosylene group, a hemexocylene group, a dococylene group, A heptacosylene group, an octacosylene group, a nonacosylene group, and a triacontylene group. Of these, in order to stably exhibit the liquid crystal alignment, it is preferable to use a silane group such as a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, , Nonadecylene group, eicosylene group and the like is preferably an alkylene group having 5 to 20 carbon atoms.

R ^B is a linking group comprising a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom. Examples of R ^B include an etendiyl group, an ethynediyl group, an ester group, a methanediyloxy group, a fluoromethanediyloxy group, and a difluoromethanediyloxy group. R ^B may contain any of the above bonds, but may contain a combination of these bonds. When R ^A is a phenylene group or a cyclohexylene group, it is preferable that R ^B includes an alkylene group having 1 to 30 carbon atoms, from the viewpoint of the orientation of the formed alignment film and the solubility in a solvent. And a is 0 or 1.

R ^C is a group having at least two monocyclic structures and preferably exhibits positive or negative dielectric anisotropy. The monocyclic structure is a structure which does not have a so-called condensed ring structure in which one cyclic structure exists independently from other cyclic structures and one cyclic structure is shared with other cyclic structures. As the monocyclic structure, any of an alicyclic structure, an aromatic cyclic structure and a heterocyclic structure may be used, or a combination thereof may be used.

R ^C is a group having at least two monocyclic structures, but R ^C is preferably a group represented by the following formula (A2).

(In the formula (A2), R ^D is a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a divalent heterocyclic group. R ^E is a linking group including a methylene group which may have a substituent and an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic ring R ^F is a (c + 1) -valent group excluding (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or a heterocyclic compound. R ^G represents a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group or B is 0 or 1. c is an integer of 1 to 9. d is 1 or 2. When a plurality of R ^D , R ^E and R ^G are plural, plural R ^D and R ^E And R ^G may be the same or different.

By introducing the group represented by the formula (A2) into the side chain of the polymer [A] of the liquid crystal aligning agent, the electrooptic response of the obtained liquid crystal display element can be further increased. In formula (A2), R ^D is a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a divalent heterocyclic group. Examples of the divalent heterocyclic group include a pyridinylene group, a pyridazinylene group, and a pyrimidinylene group.

In the above formula (A2), R ^E is a group represented by R (1), which may be substituted, and includes a methylene group and an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, ^D and R ^F , and can be appropriately selected in accordance with the orientation required for the [A] polymer and the induced anisotropy. Examples of R ^E include a methanediyl group, an ethanediyl group, a propanediyl group, an ethenediyl group, an ethynediyl group, an ether group, an ester group, a methanediyloxy group, an ethanedioxy group, a fluoromethanedioxy group, Methanedioxy group and the like. Among them, an ethanediyl group, an ethynediyl group, an ester group, a methanediyloxy group, and a difluoromethanediyloxy group are preferable. B is an integer of 0 or 1, and R ^E may or may not be included in the design of the side chain structure.

In the formula (A2), R ^F is a (c + 1) -valent group excluding (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or a heterocyclic compound. and c is an integer of 1 to 9. As R ^F , for example, when c is 1, there can be mentioned the same groups as the divalent groups exemplified as R ^D.

In the formula (A2), R ^G is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group and a propoxycarbonyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group and the like , And the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

In the formula (A2), when R ^F has plural substituents (R ^G ), different ones may be used in combination. As a combination when R ^F has plural substituents, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, and a combination of a cyano group and an alkyl group are preferable in order to stably express a desired dielectric anisotropy. Also, c is an integer of 1 to 9.

If the polymer [A] has a photo-aligning group and a group having a structure represented by the formula (A1), a known polymer main chain can be appropriately selected, but a polyorganosiloxane, a polyimide, a polyamic acid, a polyacrylate, It is preferable that the main chain structure is a methacrylate, a poly (styrene-phenylmaleimide) derivative, a cellulose derivative, a polyester, a polyamide, a polystyrene derivative and a polyamic acid ester in view of electrical properties, (Hereinafter sometimes referred to as &quot; [a] polyorganosiloxane compound &quot;).

When the polymer [A] contained in the liquid crystal aligning agent has a polyorganosiloxane structure,

[a] containing a polyorganosiloxane compound,

The polyorganosiloxane compound [a]

A part derived from a polyorganosiloxane having an epoxy group,

A part derived from a compound having a photo-aligning group and a carboxyl group (hereinafter sometimes referred to as &quot; specific carbonic acid A &quot;),

It is preferable to have a moiety derived from a compound having a carboxyl group represented by the following formula (A1-C) (hereinafter sometimes referred to as &quot; specific carbonic acid B &quot;).

In the formula (A1-C), R ^A is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group. Some or all of the hydrogen atoms of these groups may be substituted. R ^B is a linking group including a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom. R ^C is a group having at least two monocyclic structures. a is 0 or 1;

The liquid crystal aligning agent having the specific structure described above has a structure in which a structure having a photo aligning group and a dielectric anisotropy is introduced into the side chain and the liquid crystal aligning element having the liquid crystal alignment layer formed using the liquid crystal aligning agent having the photo aligning property, The electric characteristics and the afterimage characteristics are further improved, and the response time is further shortened. Further, by using the reactivity between the epoxy group and the carboxyl group, it is possible to easily introduce a photo-orientable group as a side chain and a structure having a dielectric anisotropy represented by the formula (A1-C) in the polyorganosiloxane as a main chain.

It is considered that the polyorganosiloxane compound [a] is mainly obtained as a reaction product of the epoxy group of the polyorganosiloxane and the carboxyl group of the specific carbonic acid. However, in order to facilitate the following description, A] polyorganosiloxane compound contained in the liquid crystal aligning agent is divided into a part derived from the organosiloxane (and its derivative) and a part derived from the specific carbon acid.

[Parts derived from a polyorganosiloxane having an epoxy group]

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

Since the [a] polyorganosiloxane compound contains a moiety derived from a polyorganosiloxane having an epoxy group such as a glycidyl group, a glycidyloxy group, or a group containing an epoxycyclohexyl group, the liquid crystal aligning agent has a more oriented And the electrical characteristics such as the voltage holding ratio are improved. The epoxy group is preferably a group represented by the following formula (X ¹ -1-1) or (X ¹ -2-1).

The polyorganosiloxane having an epoxy group may contain a group represented by the formula (X ¹ -1-1) or (X ¹ -2-1) in the polyorganosiloxane of the liquid crystal aligning agent, The side chain group derived from the compound having the structure can be easily introduced.

In the above formulas (X ¹ -1 -1) and (X ¹ -2 -1), * indicates a binding hand.

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

[Method of synthesizing polyorganosiloxane having epoxy group]

The polyorganosiloxane having an epoxy group is preferably obtained by subjecting a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound to hydrolysis in the presence of a suitable organic solvent, Or by hydrolysis and condensation.

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

As other silane compounds, for example,

As a compound having one silicon atom,

Having four hydrolysable groups,

Tetrachlorosilane; Tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,

As having three hydrolyzable groups,

Trihalosilanes such as trichlorosilane; Trialkoxysilanes such as trimethoxysilane and triethoxysilane; Fluorotrichlorosilane; Fluorotrialkoxysilanes such as fluorotrimethoxysilane and fluorotriethoxysilane; Alkyl trichlorosilanes such as methyltrichlorosilane; Alkyltrialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane; Fluorinated alkyl trichlorosilanes such as 2- (trifluoromethyl) ethyl trichlorosilane; Fluorinated alkyltrialkoxysilanes such as 2- (trifluoromethyl) ethyltrimethoxysilane and 2- (trifluoromethyl) ethyltriethoxysilane; Hydroxyalkyl trichlorosilane such as hydroxymethyl trichlorosilane; Hydroxyalkyltrialkoxysilane such as hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane and the like; (Meth) acryloxyalkyltrichlorosilane such as 3- (meth) acryloxypropyltrichlorosilane; (Meth) acryloxyalkyltrialkoxysilane such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane; Mercaptoalkyl trichlorosilanes such as mercaptomethyl trichlorosilane and 3-mercaptopropyl trichlorosilane; Mercaptoalkyltrialkoxysilanes such as mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane; Alkenyl trichlorosilane such as vinyl trichlorosilane and allyl trichlorosilane; Alkenyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and allyltriethoxysilane; Aryl trichlorosilane such as phenyl trichlorosilane; Aryl trialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane, and the like,

As having two hydrolyzable groups,

Alkyldichlorosilane such as methyldichlorosilane; Alkyldialkoxysilanes such as methyldimethoxysilane and methyldiethoxysilane; Dialkyldichlorosilanes such as dimethyldichlorosilane; Dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; (Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane; (Methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane; (Methyl) (3-mercaptopropyl) dichlorosilane, and other mercaptoalkyldichlorosilanes; (Methyl) (3-mercaptopropyl) dimethoxysilane, and other alkyl mercaptoalkyl dialkoxysilanes; (Methyl) (vinyl) dichlorosilane, and other alkylalkenyldichlorosilanes; Dialkenyldichlorosilane such as divinyldichlorosilane; Dialkenyldialkoxysilanes such as divinyldimethoxysilane; Diaryldichlorosilane such as diphenyldichlorosilane; Diaryldialkoxysilanes such as diphenyldimethoxysilane;

Having one hydrolyzable group,

Dialkyl chlorosilanes such as chlorodimethylsilane; Dialkylalkoxysilanes such as methoxydimethylsilane; Trialkylhalosilanes such as chlorotrimethylsilane, bromotrimethylsilane and iodotrimethylsilane; Trialkylalkoxysilanes such as methoxytrimethylsilane; Dialkyl alkenyl chlorosilanes such as (chloro) (vinyl) dimethylsilane; (Methoxy) (vinyl) dimethylsilane, and other dialkylalkenylalkoxysilanes; Diarylalkylchlorosilanes such as (chloro) (methyl) diphenylsilane; And diarylalkylalkoxysilanes such as (methoxy) (methyl) diphenylsilane.

As a commercially available product, 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-212, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, K56002, KF6003, KR- KR5230, KR5235, KR9218 and KR9706 (all manufactured by 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 (manufactured by 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 and XMS-5025 (all manufactured by Chisso Corporation);

Methyl silicate MS51, methyl silicate MS56 (all manufactured by Mitsubishi Chemical Corporation);

Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.);

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

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

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

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

Examples of the 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, cyclohexanone and the like; Examples of the ester compound include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; 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-butyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Of these, water-insoluble ones are preferable. These organic solvents may be used alone or in combination of two or more.

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

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

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

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene; And quaternary organic amines such as tetramethylammonium hydroxide. In view of the fact that the reaction proceeds mildly among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

As the catalyst for 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 desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing a side reaction such as ring opening of an epoxy group, Do. Such a liquid crystal aligning agent containing a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a specific carboxylic acid is suitable because of its excellent storage stability. This is because, as indicated in Chemical Reviews, vol. 95, p1409 (1995), when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis and condensation reaction, a random structure, a ladder- Structure is formed, and a polyorganosiloxane having a small content of silanol groups is obtained. In the case where the condensation reaction between the silanol groups is suppressed because the content of the silanol groups is small and the liquid crystal aligning agent contains the other polymer described later, the condensation reaction between the silanol group and the other polymer is suppressed , Resulting in excellent storage stability.

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

The hydrolysis or hydrolytic condensation reaction in the production of 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.

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

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of this cleaning, it is preferable that the cleaning is performed by washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 mass% or the like. The washing is carried out until the water layer after 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 can be obtained.

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

The [a] polyorganosiloxane compound may be a part derived from a hydrolyzate produced by hydrolysis of the polyorganosiloxane itself having an epoxy group or a hydrolyzed condensate obtained by hydrolysis and condensation of polyorganosiloxanes having an epoxy group And the like. These hydrolysates and hydrolyzed condensates which are constituent materials of this part can also be prepared in the same manner as the hydrolysis and condensation conditions of the polyorganosiloxane having an epoxy group.

[Part derived from a specific carbon acid]

The photo-aligning group or the group represented by the formula (A1) is derived from an epoxy group extending mainly from the main chain of the polyorganosiloxane among the structure of the polyorganosiloxane compound of the component [a] contained in the liquid crystal aligning agent Chain structure in which a structure derived from a carboxyl group bonded to a structure of a carboxyl group is taken as a starting point. However, in the present invention, it is also referred to as &quot; a part derived from a specific carbon acid &quot; including a case where a specific carbon acid bonds to a part other than an epoxy group.

[Specific carbonic acid A]

As the specific carbonic acid A, a compound represented by the following formula (B1-1C) and a compound represented by the formula (B1-2C) having a structure represented by the above formula (B1) are preferable.

R, R ¹ , R ² , X ¹ , X ² , a 'and b' in the above formula (B1-1C) and

R 1, R ³ , R ⁴ , X ³ , X ⁴ , a 'and c' in the formula (B1-2C) have the same meanings as in the formula (B1-1) or the formula (B1-2), respectively.

The formula (B1-1C) of, X ⁵ is a group a single bond, an oxygen atom, a sulfur atom, a methylene group, an alkylene group, having 2 to 10 carbon atoms or an alkenylene group having 2 to 10 carbon atoms of the divalent aromatic group.

When X ⁵ is unity sum, e is 1 and R ⁵ is a hydrogen atom.

When X ⁵ is a methylene group, an alkylene group, an alkenylene group or a bivalent aromatic group, e is 0 or 1 and R ⁵ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR ' Atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH ₂ or SO ₂ Cl.

In the formula (B1-2C), R ⁶ is a divalent aromatic group, a divalent heterocyclic group or a 2-valent fused ring group, X ⁶ is an oxygen atom, -COO- or OCO- ^{+ +.} With the proviso that + represents a bonding hand which bonds with R &lt; ⁶ &gt;.

and f is an integer of 0 to 3.

R ⁷ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH═CH ₂ or SO ₂ Cl. X ⁷ is a single bond, -OCO- (CH ₂ ) _i - ⁺ or O- (CH ₂ ) _j - ⁺ . However, + represents a bonding hand bonding with R ⁷ . i and j are integers of 0 to 10, respectively.

The compound represented by the above formula (B1-1C) is preferably a compound wherein X ⁵ is a single bond and R ⁵ is a hydrogen atom in the formula (B1-1C)

X ⁵ is a methylene group, an alkylene group or a 2-valent aromatic group, and R ⁵ is preferably a carboxyl group compound,

As the compound represented by the formula (B1-2C), a compound in which R ⁷ in the formula (B1-2C) is a carboxyl group is preferable. Hereinafter, such a compound having a carboxyl group is referred to as &quot; carbonic acid (B1) &quot;.

As such a compound represented by the formula (B1-1C), for example, a compound represented by the following formula is preferable as the carbonic acid (B1), more preferably.

In the formula, R ¹ has the same meaning as in the formula (B1-1C). and d is an integer of 1 to 10.

As the compound represented by the above formula (B1-2), a compound represented by the following formula is preferable.

In the above formula, R ³ has the same meaning as in the formula (B1-2C).

[Specific carbonic acid B]

Examples of the specific carbonic acid B include compounds represented by the following formulas (D-1) to (D-25).

In the formulas (D-1) to (D-25), R ^C has the same meaning as in formula (A1-C). m is an integer of 1 to 30;

Examples of the group represented by the formula (A2) include groups represented by the following formulas (E-1) to (E-116).

In the formulas (E-1) to (E-123), R represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Each X independently represents a hydrogen atom or a fluorine atom.

Examples of the alkyl group represented by R include a methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, n-pentyl group and n-hexyl group. Examples of the alkoxy group represented by R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

[Method for synthesizing a specific carbon acid]

The order of synthesis of the specific carbonic acid is not particularly limited, and any of conventionally known methods may be combined. As a typical synthesis procedure, for example, (1) a method in which a compound having a phenol skeleton and a compound in which an alkyl chain portion of a higher fatty acid ester is substituted with a halogen are reacted under basic conditions, and a reaction between a hydroxyl group in the phenol skeleton and a carbon substituted with a halogen (2) reacting a compound having a phenol skeleton with ethylene carbonate to produce a terminal alcohol compound, reacting the hydroxyl group with a halogenated benzenesulfonyl chloride And then reacting the activated portion with methyl benzoate containing a hydroxyl group to produce a bond between the hydroxyl group of the terminal alcohol compound and the hydroxyl group of the methyl benzoate containing a hydroxyl group as a substituent together with the elimination of the sulfonyl moiety, And a method of reducing the ester to give a specific carbonic acid. However, the order of synthesis of the specific carbonic acid is not limited to these.

&Lt; Synthesis method of [a] polyorganosiloxane compound &gt;

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

Here, the specific carbonic acid is used in an amount of preferably 0.001 to 10 mol, more preferably 0.01 to 5 mol, and still more preferably 0.05 to 2 mol, based on 1 mol of the epoxy group of the polyorganosiloxane.

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

In the above formula (4)

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

L ⁰ is a single bond, -O-, -COO- or -OCO-.

L ¹ represents a single bond, methylene group, alkylene group of 2 to 20 carbon atoms, phenylene group, biphenylene group, cyclohexylene group, a cyclohexylene group or by the formula (L ¹ -1) or (L ¹ -2) .

Z is a monovalent organic group capable of reacting with an epoxy group in the [a] polyorganosiloxane compound to form a bonding group.

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

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

Z is preferably a carboxyl group.

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

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

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

In the above formulas (H-1) to (H-3), * represents a bonding hand.

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

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

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

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

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

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

As the catalyst used for the reaction of the epoxy group in the polyorganosiloxane with the compound represented by the formula (4) and the carboxylic acid group-containing compound represented by the other pretilt angle-expressing compound, the reaction between the organic base or the epoxy compound and the acid anhydride A known compound as a so-called curing accelerator may be used.

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene; And quaternary organic amines such as tetramethylammonium hydroxide. Of these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and tetramethylammonium hydroxide are preferable.

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 , Isocyanuric acid adducts of 4-diamino-6- [2'-ethyl-4'-methylimidazolyl (1 ')] ethyl-s-triazine, 2-methylimidazole, Imidazole derivatives such as isocyanuric acid adduct of imidazole and isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl (1 ')] ethyl-s- compound;

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 Ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetra Quaternary phosphonium salts such as fluoroborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate;

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

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

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

Boron compounds such as boron trichloride and triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

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

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

Amine salt type latent curing accelerator;

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

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

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

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

The synthesis reaction of the [a] polyorganosiloxane compound can be carried out in the presence of an organic solvent if necessary. Examples of such an organic solvent include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, and an alcohol compound. Of these, ether compounds, ester compounds, and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of products. The solvent preferably has a solid content concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) of preferably 0.1% by mass or more and 70% by mass or less, more preferably 5% As shown in FIG.

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

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

<Optional ingredients>

The liquid crystal aligning agent may contain, in addition to the [A] polymer, a polymer other than the polymer [A] (hereinafter sometimes referred to as "other polymer"), 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 an &quot; epoxy compound &quot;), a functional silane compound, a surfactant, and the like.

[Other Polymers]

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

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

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

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

In the formula (5), X ^A 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 ^A is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

<[B] Polymer>

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

[Polyamic acid]

The polyamic acid is obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound.

Examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic acid dianhydride. 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 JP-A-2010-97188.

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.

Examples of the aliphatic diamine include, for example, meta-xylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine 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 the like, as well as the diamines described in JP-A-2010-97188.

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, octadecanoxy-2,5-diaminobenzene, cholestanyloxy- Diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid Cholestanol, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3 , 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-aminobenzylamine and 3-aminobenzylamine represented by the following formula (A-1): &lt; EMI ID = ), And the like.

The formula (A-1) of, X ^I is a methylene group or a carbon number of 2 or 3 of an alkylene group, -O-, -COO- or -OCO-. r is 0 or 1; s is an integer of 0 to 2. t is an integer of 1 to 20;

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 0.5 hours to 24 hours, more preferably 2 hours to 12 hours.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. Examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, , Non-protonic polar solvents such as N, N-dimethylimidazolidinone, dimethylsulfoxide,? -Butyrolactone, tetramethylurea and hexamethylphosphotriamide; phenol-based solvents such as m-cresol, xylenol, phenol, and halogenated phenol.

The amount (a) of the organic solvent to be used is preferably 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. Examples of the method of isolating the polyamic acid include a method of drying a precipitate obtained by pouring the reaction solution into a large amount of a poor solvent under reduced pressure, and a method of distilling off the reaction solution under reduced pressure using an expander. As a method for purifying polyamic acid, a method of dissolving an isolated polyamic acid in an organic solvent and then precipitating it in a poor solvent, and a method of distilling off an organic solvent or the like under reduced pressure with a diverter, have.

[Polyimide]

The polyimide can be produced by dehydrating and cyclizing the arid acid structure of the polyamic acid to imidize it. 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, .

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

The reaction temperature in the method (i) is preferably 50 ° C to 200 ° C, more preferably 60 ° C to 170 ° C. If the reaction temperature is less than 50 캜, the dehydration ring-closure reaction does not proceed sufficiently, and if 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 amount of the dehydrating agent to be used is appropriately selected depending on the desired imidization rate, but 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 amount of the dehydration ring-closing catalyst to be used 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 dehydration ring-closing catalyst is larger.

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. The 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.

[Other polyorganosiloxane]

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

In X ^A and Y ^B in the above formula (5)

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

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

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

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

Examples of the raw silane compounds usable herein include the same compounds exemplified as the other silane compounds in the synthesis of the [a] polyorganosiloxane compound. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane, and trimethylethoxysilane are preferable.

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

As the alcohol compound, for example,

Monoalcohol compounds such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol and t-butanol;

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,

Monoketone compounds such as acetone, methyl ethyl ketone, methyl-n-propyl ketone and methyl-n-butyl ketone;

And? -Diketone compounds such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and 2,4-octanedione.

Examples of the amide compound include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylacetamide, N-diethylacetamide, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate,? -Butyrolactone,? -Valerolactone, n-propyl acetate, sec-butyl acetate, sec-butyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, Acetic acid methyl ester, acetic acid ethylene glycol monoethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid ethyleneglycol monomethyl ether, Ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monoacetate T-butyl ether, acetic acid propylene glycol monoethyl ether, acetic acid propylene glycol monopropyl ether, acetic acid propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, Ethyl lactate, n-butyl lactate, diethyl malonate, dimethyl phthalate, di-n-butyl lactate, di-n-butyl lactate, di-n-propyl lactate, Ethyl and the like.

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

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

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

Examples of the metal chelate compound include trialkoxy mono (acetylacetonate) titanium such as triethoxy mono (acetylacetonate) titanium; Dialkoxy bis (acetylacetonate) titanium such as diethoxy bis (acetylacetonate) titanium; Monoalkoxy tris (acetylacetonate) titanium such as monoethoxy tris (acetylacetonate) titanium; Tetrakis (acetylacetonate) titanium; Trialkoxy mono (ethylacetate) titanium such as triethoxy mono (ethylacetate) titanium; Dialkoxy bis (ethylacetate) titanium such as diethoxy bis (ethylacetate) titanium; Monoalkoxy tris (ethylacetate) titanium such as monoethoxy tris (ethylacetate) titanium; Tetrakis (ethylacetate) titanium; And two or more chelate ligands such as mono (acetylacetonate) tris (ethylacetate) titanium, bis (acetylacetonate) bis (ethylacetate) titanium and tris (acetylacetonate) A titanium chelate compound such as a titanium compound;

Trialkoxy mono (acetylacetonate) zirconium such as triethoxy mono (acetylacetonate) zirconium; Dialkoxy bis (acetylacetonate) zirconium such as dimethoxy bis (acetylacetonate) zirconium; Monoalkoxy tris (acetylacetonate) zirconium such as monoethoxy tris (acetylacetonate) zirconium; Tetrakis (acetylacetonate) zirconium; Trialkoxy mono (ethylacetate) zirconium such as triethoxy mono (ethylacetate) zirconium; Dialkoxy bis (ethylacetate) zirconium such as diethoxy bis (ethylacetate) zirconium; Monoalkoxy tris (ethylacetate) zirconium such as monoethoxy tris (ethylacetate) zirconium; Tetrakis (ethylacetate) zirconium; And at least two chelate ligands such as mono (acetylacetonate) tris (ethylacetate) zirconium, bis (acetylacetonate) bis (ethylacetate) zirconium and tris (acetylacetonate) mono A zirconium chelate compound such as a zirconium compound;

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

Examples of the organic acid include aliphatic saturated carboxylic acids such as formic acid, acetic acid and propionic acid; Aliphatic unsaturated carboxylic acids such as malonic acid and fumaric acid; Aromatic carboxylic acids such as salicylic acid, benzoic acid and phthalic acid; aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; Halogen-containing carbonic acids such as monochloroacetic acid, trichloroacetic acid, and trifluoroacetic acid; Citric acid, tartaric acid, and the like.

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

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

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like. These catalysts may be used alone or in combination of two or more.

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

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

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

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

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

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

When the liquid crystal aligning agent contains the [B] polymer, the total amount of the polymer [B] is preferably 100 to 5,000 parts by mass, more preferably 200 to 3,000 parts by mass, relative to 100 parts by mass of the [A] Do.

On the other hand, in the case where the liquid crystal aligning agent and other polyorganosiloxane are contained, the preferred ratio of both of them is from 5 to 2,000 parts by mass as the amount of the other polyorganosiloxane relative to 100 parts by mass of the [A] And preferably 100 to 2,000 parts by mass.

When the liquid crystal aligning agent contains other polymer, the [B] polymer or other polyorganosiloxane is preferable as the other polymer.

[Curing agent, curing catalyst and curing accelerator]

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

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

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

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

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

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

As the curing accelerator, for example, an imidazole compound; A quaternary compound; Quaternary amine compounds; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate and aluminum acetyl acetone complex; Boron compounds such as boron trichloride and triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride; A high melting point dispersing latent curing accelerator such as dicyandiamide, 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 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, and the like.

[Epoxy Compound]

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

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

When the liquid crystal aligning agent contains an epoxy compound, the content thereof is preferably 0.01 to 40 parts by mass per 100 parts by mass of the total amount of the [a] polyorganosiloxane compound and other polymer optionally used, More preferably 0.1 to 30 parts by mass.

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

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the adhesion of the obtained liquid crystal alignment film to the substrate. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silane triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N- Bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. And reaction products of the tetracarboxylic acid dianhydride described in JP-A-63-291922 with a silane compound having an amino group.

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

[Surfactants]

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

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

&Lt; Preparation method of liquid crystal aligning agent &gt;

As described above, the liquid crystal aligning agent may contain a polymer [A] as an essential component and optionally other optional components. Preferably, the liquid crystal aligning agent is a composition in the form of a solution in which each component is dissolved in an organic solvent It is prepared.

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

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

On the other hand, when the liquid crystal aligning agent contains only the [a] polyorganosiloxane compound as the polymer, or when the [a] polyorganosiloxane compound and the other polyorganosiloxane are contained, preferable examples of the organic solvent include For example, 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, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, Diethylene glycol, methyl cellosolve acetates , Ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, 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, n-hexyl acetate , Cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, and the like. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-

The preferred solvent used for preparing the liquid crystal aligning agent may be one or more of the above-mentioned organic solvents depending on whether or not other polymers are used and the kind thereof. In such a solvent, the components contained in the liquid crystal aligning agent are not precipitated at the following preferable solid concentration, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mN / m.

The solid concentration of the liquid crystal aligning agent, that is, the 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., . The liquid crystal aligning agent is applied to the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. However, when the solid concentration is 1% by mass or more, the film thickness of the coating film is less likely to become excessively small and a good liquid crystal alignment film can be obtained. On the other hand, when the solid concentration is 10% by mass or less, it is possible to prevent an excessive film thickness of the coating film from being obtained to obtain a good liquid crystal alignment film, and to prevent the viscosity of the liquid crystal aligning agent from increasing, . A particularly preferable range of the solid concentration is different depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the range of 1.5 to 4.5 mass% is particularly preferable. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9 mass% and the solution viscosity is in the range of 12 to 50 mPa 占 퐏. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 mass%, and the solution viscosity is accordingly in the range of 3 to 15 mPa · s. The temperature at which the liquid crystal aligning agent is prepared is preferably 0 ° C to 200 ° C, and more preferably 0 ° C to 40 ° C.

<Liquid crystal display element>

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

&Lt; Method of forming liquid crystal alignment film &

The liquid crystal aligning agent of the present invention can be suitably used for forming a liquid crystal alignment film by a photo alignment method.

As a method of forming the liquid crystal alignment film, there can be mentioned, for example, a method of applying a liquid crystal alignment film of the present invention on a substrate to form a coating film and then irradiating the coated film with polarized or unpolarized radiation to give a liquid crystal alignment capability .

First, the liquid crystal aligning agent of the present invention is applied to the transparent electroconductive film side of the substrate on which the patterned transparent electroconductive film is formed by a suitable application method such as a roll coating method, a spinner method, a printing method, or an ink jet method. Then, the coated surface is preheated (prebaked) and then baked (post baked) to form a coated film. The prebaking condition is, for example, 0.1 to 5 minutes at 40 to 120 占 폚, and the postbaking condition is preferably 120 to 300 占 폚, more preferably 150 to 250 占 폚, preferably 5 to 200 minutes, More preferably 10 to 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 to 1 占 퐉, and more preferably 0.005 to 0.5 占 퐉.

As the substrate, for example, a transparent substrate made of plastic such as glass such as float glass, soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and cyclic olefin resin can be used.

As the transparent conductive film, a NESA (registered trademark) film made of SnO ₂ , an ITO film made of In ₂ O ₃ -SnO ₂ , or the like can be used. For patterning these transparent conductive films, a known method is used.

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 the adhesion between the substrate or the transparent conductive film and the coating film .

Subsequently, the coating film is irradiated with linearly polarized light or partially polarized radiation or non-polarized light to impart liquid crystal aligning ability. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferable. When the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed in a direction perpendicular to the substrate surface, or may be performed in an oblique direction to give a pre-tilt angle, or in combination. In the case of irradiating non-polarized radiation, the irradiation direction needs to be an oblique direction.

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

<Manufacturing Method of Liquid Crystal Display Element>

The liquid crystal display element of the present invention comprises a liquid crystal alignment layer formed of the liquid crystal aligning agent of the present invention. The liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention is preferable because it can maximally exhibit its advantageous effect when applied to a vertical alignment type liquid crystal display device.

The liquid crystal display element of the present invention can be produced, for example, as follows.

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

In the first method, two substrates are opposed to each other via a gap (cell gap) so that the liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, The liquid crystal is injected and filled in the cell gap defined by the liquid crystal cell, and then the injection port is sealed. Thus, a liquid crystal cell can be manufactured.

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

In either case, it is preferable that the liquid crystal cell is heated to a temperature at which the used liquid crystal has an isotropic phase, and then the liquid crystal cell is gradually cooled to room temperature to remove the flow alignment at the time of filling the liquid crystal.

The liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. Here, when the liquid crystal alignment film is vertically aligned, the cell is configured such that the directions of the easy axis of alignment in the two substrates on which the liquid crystal alignment film is formed are parallel, and the polarizing plate is arranged so that its polarization direction is 45 degrees So that a liquid crystal display element having a vertically aligned liquid crystal cell can be obtained.

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

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal and the like can be preferably used.

In the case of vertically aligned liquid crystal cells, nematic liquid crystals having negative dielectric anisotropy are preferable, and examples thereof include dicyanobenzene-based liquid crystal, pyridazine-based liquid crystal, heptbase-based liquid crystal, Cyclohexane-based liquid crystal or the like is used.

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

The liquid crystal display of the present invention thus manufactured is excellent in various properties such as display characteristics, long-term reliability, and high-speed response.

(Example)

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

The weight average molecular weight (Mw) of the obtained polyorganosiloxane and [E] polyorganosiloxane compound obtained in the following Examples is the polystyrene conversion value measured by GPC in the following specifications.

Column: TSKgelGRCXLII, manufactured by Toso K.K.

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

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

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

[Synthesis Example 1]

100 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube And the mixture was mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise 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% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group As a transparent liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane having the epoxy group, it was found that the peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm in accordance with the theoretical strength, and no side reaction of the epoxy group occurred during the reaction . The weight average molecular weight (Mw) of the polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 was 2,200 and the epoxy equivalent was 186 g / mol.

&Lt; Synthesis of Specific Carbonic Acid &gt;

[Synthesis of Specific Carboxylic Acid 1]

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

[Synthesis Example 2]

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

[Synthesis Example 3]

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

[Synthesis of Specific Carboxylic Acid 2]

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

[Synthesis Example 4]

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

[Synthesis Example 5]

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

[Synthesis Example 6]

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

[Synthesis Example 7]

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

[Synthesis of Specific Carboxylic Acid 3]

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

[Synthesis Example 8]

In Synthesis Example 2, compound No. 5 was obtained in the same manner as in Synthesis Example 2, except that 13.7 g of compound 5 was obtained by using 10.7 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol instead of 4-cyano- g.

[Synthesis Example 9]

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

[Synthesis of Specific Carboxylic Acid 4]

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

[Synthesis Example 10]

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

[Synthesis Example 11]

In Synthesis Example 5, 18.9 g of Compound 6 was used instead of Compound 2 to obtain 24.1 g of Compound 7.

[Synthesis Example 12]

In Synthesis Example 6, 20 g of Compound 7 was used instead of Compound 3 to obtain 15.4 g of Compound 8.

[Synthesis Example 13]

In Synthesis Example 7, 13 g of Compound 8 was used instead of Compound 4 to obtain 11.4 g of a specific carboxylic acid 4.

[Synthesis of Specific Carboxylic Acid 5]

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

[Synthesis Example 14]

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

[Synthesis of Specific Carboxylic Acid 6]

According to the following reaction formula, a specific carbonic acid 6 was synthesized.

[Synthesis Example 15]

In a 500 ml three-necked flask equipped with a condenser tube, 10.1 g of 2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl, 10 g of methyl 11-bromododecanoate, And 200 mL of N, N-dimethylformamide were added and the mixture was heated and stirred at 160 占 폚 for 5 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, followed by mixing and stirring. The precipitated white solid was filtered off and further washed with water. The resulting solid was vacuum-dried at 80 占 폚, thereby obtaining 10.8 g of Compound 9.

[Synthesis Example 16]

Next, 10 g of Compound 9, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 캜 for 4 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, diluted hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered, washed with water and then with ethanol in this order. The obtained solid was vacuum-dried at 80 占 폚 to obtain 6 g of a specific carboxylic acid 6.

[Synthesis of Specific Carboxylic Acid 7]

According to the following reaction formula, a specific carbonic acid 7 was synthesized.

[Synthesis Example 17]

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,3-difluoro-4- -Propyl-cyclohexyl) phenol), 9.1 g of the specific carbonic acid 7 was obtained in the same manner as the synthesis of the specific carbonic acid 6.

[Synthesis of Specific Carboxylic Acid 8]

According to the following reaction formula, a specific carbonic acid 8 was synthesized.

[Synthesis Example 18]

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,2', 3,3'-tetrafluoro (4-propyl-4 "-hydroxyterphenyl) was changed to 12.9 g, in the same manner as in the synthesis of the specific carboxylic acid 6, 7.1 g of the specific carboxylic acid 8 was obtained.

[Synthesis of Specific Carboxylic Acid 9]

According to the following reaction formula, a specific carbonic acid 9 was synthesized.

[Synthesis Example 19]

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,3-difluoro-4- -Propylcyclohexylmethoxy) phenol), the specific carbonic acid 9 was obtained in the same manner as in the synthesis of the above specific carbonic acid 6.

[Synthesis of Specific Carboxylic Acid 10]

According to the following reaction formula, a specific carbonic acid 10 was synthesized.

[Synthesis Example 20]

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,3-difluoro-4' 4-propylphenylethyl) biphenyl) was replaced by 12.6 g, the specific carbonic acid 10 (7.2 g) was obtained in the same manner as the synthesis of the specific carbonic acid 6.

[Synthesis of Specific Carboxylic Acid 11]

According to the following reaction formula, a specific carbonic acid 11 was synthesized.

[Synthesis Example 21]

Except that 10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was replaced with 14.2 g of the compound described in the above reaction formula, 7.6 g of the specific carboxylic acid 11 was obtained in the same manner as in the synthesis.

[Synthesis of Specific Carboxylic Acid 12]

According to the following reaction formula, a specific carbonic acid 12 was synthesized.

[Synthesis Example 22]

In a 500 ml three-necked flask equipped with a condenser tube, 12.5 g of 4- [difluoro (4-pentylcyclohexyl) methoxy] -2,3-difluorophenol, 10 g of methyl 11-bromododecanoate, 14.2 g of potassium and 200 mL of N, N-dimethylformamide were added and the mixture was heated and stirred at 160 DEG C for 5 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, followed by mixing and stirring. The precipitated white solid was filtered off and further washed with water. The resulting solid was vacuum-dried at 80 占 폚 to obtain 14.8 g of Compound 10.

[Synthesis Example 23]

Next, 10 g of Compound 10, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 캜 for 4 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, diluted hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered, washed with water and then with ethanol in this order. The resulting solid was vacuum-dried at 80 占 폚 to obtain 6 g of a specific carboxylic acid 12.

&Lt; Synthesis of cinnamic acid derivative &gt;

[Synthesis of cinnamic acid derivative (A-1)] [

According to the following reaction formula, a cinnamic acid derivative (A-1) was synthesized.

[Synthesis Example 24]

12 g of decylsuccinic anhydride, 8.2 g of 4-aminocinnamic acid and 100 mL of acetic acid were added to 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, and the organic layer was washed with water, dried over magnesium sulfate, purified with a silica column, and further recrystallized from a mixed solvent of ethanol and tetrahydrofuran, 10 g of white crystals (purity: 98.0%) of the derivative (A-1) was obtained.

[Synthesis of cinnamic acid derivative (A-2)] [

According to the following reaction formula, a cinnamic acid derivative (A-2) was synthesized.

[Synthesis Example 25]

82 g of p-hydroxycinnamic acid, 304 g of potassium carbonate and 400 mL of N-methyl-2-pyrrolidone were placed in a 1 L eggplant-shaped flask and stirred at room temperature for 1 hour. Then, 212 g of 1-bromooctane was added, Followed by stirring at 100 ° C for 5 hours. Thereafter, the solvent was distilled off under reduced pressure. 48 g of sodium hydroxide and 400 mL of water were added thereto, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was recovered and recrystallized from ethanol to obtain 80 g of a white crystal of cinnamic acid derivative (A-2).

[Synthesis of cinnamic acid derivative (A-3)] [

According to the following reaction formula, the cinnamic acid derivative (A-3) was synthesized.

[Synthesis Example 26]

107 g of 4-bromo cinnamic acid was refluxed in 83 g of thionyl chloride for 4 hours to obtain a red transparent solution. Next, thionyl chloride was left to distil off the unreacted residue. The residue was recrystallized from toluene and washed with n-hexane to obtain 85 g of white crystals of the compound (A-3-1).

Next, 25.0 g (0.147 mol) of 4-amylcyclohexanol was dissolved in 25 mL of pyridine. While keeping the temperature of the solution at about 3 占 폚, a suspension of 43.3 g (0.176 mole) of the compound (A-3-1) obtained above in 350 ml of pyridine was added dropwise thereto, . The obtained reaction mixture (suspension) was put into 1.3 kg of acidic acidic acidic ice water and the resulting precipitate was filtered, washed with water and dried to obtain 50 g of a crude product (cream-colored powder) of the compound (A- .

125 mL of dry triethylamine was added to a mixture of 50 g of the crude product of the compound (A-3-2) obtained above, 0.28 g of palladium acetate and 1.52 g of tri (o-tolyl) phosphine in a nitrogen atmosphere, . After the preparation of the compound (A-3-2) was completely dissolved, 10.8 g of acrylic acid was injected into the syringe, and the reaction was further continued at 95 캜 for 2 hours. The resulting dark green reaction mixture was poured into 1.3 kg of acidic acid / hydrochloric acid and the resulting precipitate was separated by filtration. The resulting compound was dissolved in 500 mL of ethyl acetate and washed successively with 1N hydrochloric acid and 5% by mass sodium hydrogencarbonate solution. The organic layer was recovered, dried over magnesium sulfate, and the solvent was distilled off to obtain the cinnamic acid derivative A -3) (yellow solid). This crude product was recrystallized from ethanol to obtain 30 g (yield: 55%) of yellow powder of cinnamic acid derivative (A-3).

[Synthesis of cinnamic acid derivative (A-4)] [

According to the following reaction formula, a cinnamic acid derivative (A-4) was synthesized.

[Synthesis Example 27]

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, 1-iodo- And 157.1 g of 4-trifluorobutane were added, and the mixture was stirred at 100 占 폚 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 110 g of white crystals of the compound (A-4-1).

12.41 g of this compound (A-4-1) was placed in a reaction vessel, to which 100 mL of thionyl chloride and 77 μL of N, N-dimethylformamide were added, followed by stirring 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, in a 500 mL three-necked flask different from the above, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutylammonium, 50 mL of tetrahydrofuran, and 100 mL of water were placed. The aqueous solution was ice-cooled, the tetrahydrofuran solution 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 neutralize the solution, extracted with ethyl acetate, dried over magnesium sulfate, concentrated and recrystallized from ethanol to obtain 10.0 g of a white crystal of cinnamic acid derivative (A-4).

[Synthesis of cinnamic acid derivative (A-5)] [

A cinnamic acid derivative (A-5) was synthesized according to the following reaction formula.

[Synthesis Example 28]

31 g of the compound (A-5-1), 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine, 56 mL of triethylamine, 50 g of acrylic acid And 200 mL of N, N-dimethylacetamide were placed, and the reaction was carried out at 120 占 폚 for 3 hours with stirring. After completion of the reaction, the reaction mixture was filtered, and 1 liter of ethyl acetate was added to the resulting filtrate. The obtained organic layer was washed twice with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and then the solvent was removed under reduced pressure. Was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain 15 g of crystals of the cinnamic acid derivative (A-5).

[Synthesis of cinnamic acid derivative (A-6)] [

According to the following reaction formula, the cinnamic acid derivative (A-6) was synthesized.

[Synthesis Example 29]

28 g of the compound (A-6-1), 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine, 56 mL of triethylamine, 50 g of acrylic acid And 200 mL of N, N-dimethylacetamide were placed, and the reaction was carried out at 120 占 폚 for 3 hours with stirring. After completion of the reaction, the reaction mixture was filtered, and 1 liter of ethyl acetate was added to the resulting filtrate. The obtained organic layer was washed twice with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and then the solvent was removed under reduced pressure. Was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain 13 g of crystals of the cinnamic acid derivative (A-6).

[Synthesis of cinnamic acid derivative (A-7)] [

According to the following reaction formula, a cinnamic acid derivative (A-7) was synthesized.

[Synthesis Example 30]

34 g of the compound (A-7-1), 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine, 56 mL of triethylamine, 50 mL of acrylic acid And 200 mL of N, N-dimethylacetamide were placed, and the reaction was carried out at 120 占 폚 for 3 hours with stirring. After completion of the reaction, the reaction mixture was filtered, and 1 liter of ethyl acetate was added to the resulting filtrate. The obtained organic layer was washed twice with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and then the solvent was removed under reduced pressure. Was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain 14 g of crystals of the cinnamic acid derivative (A-7).

[Synthesis of cinnamic acid derivative (A-8)] [

According to the following reaction formula, the cinnamic acid derivative (A-8) was synthesized.

[Synthesis Example 31]

21 g of the compound (A-8-1), 80 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide were placed in a 300 mL branched flask equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, I did. After completion of the reaction, thionyl chloride was distilled off from the reaction mixture, and then 150 mL of methylene chloride was added thereto. The obtained organic layer was washed three times with water. The organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure. To the obtained solid was added 400 mL of tetrahydrofuran.

On the other hand, 16 g of p-hydroxycinnamic acid, 24 g of potassium carbonate, 0.87 g of tetrabutylammonium bromide, 200 mL of water and 100 mL of tetrahydrofuran were placed in a 1 L three-necked flask equipped with a dropping funnel and a thermometer, . The tetrahydrofuran solution was added dropwise over 3 hours, and the reaction was further carried out for 1 hour with stirring. After completion of the reaction, diluted hydrochloric acid was added to the reaction mixture to adjust the pH to 4 or lower. Then, 3 L of toluene and 1 L of tetrahydrofuran were added, and the obtained organic layer was washed with water three times. The organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure. The resulting solid was recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 21 g of cinnamic acid derivative (A-8).

<Synthesis of [a] polyorganosiloxane compound>

[Example 1]

In a 100-mL three-necked flask, 9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 5.0 g of the specific carboxylic acid 1 obtained in Synthesis Example 3, 5.1 g of the nansan derivative (A-1) and 0.20 g of UCAT18X (quaternary amine salt manufactured by San A Pro Co.) were added and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed three times and then the solvent was distilled off to obtain [a] the polyorganosiloxane compound a- 14.5 g of a powder was obtained. The Mw of the polyorganosiloxane compound a-1 was 15,500.

[Examples 2 to 22]

The polyorganosiloxane compound [a] of a-2 to a-22 was obtained in the same manner as in Example 1, except that the kind and amount of the specific carbonic acid and cinnamic acid derivative used were as shown in Table 1.

In Table 1, the amount of modification refers to the introduction ratio of a specific carboxylic acid or cinnamic acid derivative to the amount of epoxy contained in the polyorganosiloxane.

[Comparative Synthesis Example 1]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 5.6 g of the cinnamic acid derivative (A-8) obtained in the above Synthesis Example 31, and 18.6 g of UCAT 18X Manufactured by Nippon Polyurethane Industry Co., Ltd.) were added, and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate. This solution was washed three times, and then the solvent was distilled off to obtain 9.6 g of a polyorganosiloxane compound Ca-1 as a white powder. The Mw of Ca-1 was 9,800.

<Synthesis of [B] polymer>

<Synthesis of polyamic acid>

[Synthesis Example 32]

19.61 g (0.1 mol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 21.23 g (0.1 mol) of 4,4'-diamino 2,2'-dimethylbiphenyl were dissolved in N-methyl- Dissolved in 367.6 g of pyrrolidone, and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 DEG C for 5 hours to obtain 35 g of polyamic acid PA-1.

[Synthesis Example 33]

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

<Synthesis of polyimide>

[Synthesis Example 34]

232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine and 4.9 g of acetic anhydride were added, and the mixture was reacted at 120 ° C for 4 hours to imidize . Subsequently, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to obtain 15 g of polyimide PI-1.

[Synthesis Example 35]

(0.0836 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 7.359 g (0.0681 mol) of p-phenylenediamine as a diamine compound, 3,5-diaminobenzoic acid = 5ξ -Cholestan-3-yl was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 5 hours. The viscosity of this polymerization solution was measured and found to be 2000 mPa · s. Then, 325 g of N-methyl-2-pyrrolidone was added to this solution and stirred for a while. Then, 6.61 g of pyridine and 8.54 g of acetic anhydride were added, followed by dehydration cyclization at 110 ° C for 4 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 DEG C for 15 hours to obtain 26.6 g of polyimide PI-2 having an imidization ratio of 51%.

&Lt; Preparation of liquid crystal aligning agent &

[Example 23]

The polyorganosiloxane compound a-1 (100 parts by weight), which contained the solution containing the polyamic acid PA-1 obtained in Synthesis Example 32 in an amount corresponding to 1,000 parts by weight in terms of polyamic acid PA-1 contained therein, N-methyl-2-pyrrolidone and butyl cellosolve were added to the mixture to obtain a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio) And a solid content concentration of 3.5% by mass. This solution was filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (S-1).

[Examples 24 to 54 and Comparative Examples 1 and 2]

The liquid crystal aligning agents S-2 to S-32 were prepared in the same manner as in Example 23 except that the combination of the polyamic acid or polyimide as the polymer [B] and the polyorganosiloxane compound as shown in Table 2 was used. And CS-1 and CS-2 were prepared.

&Lt; Formation of liquid crystal alignment film &

The liquid crystal aligning agent prepared in the above example was coated on a transparent electrode surface of a glass substrate with a transparent electrode made of ITO film by a spinner and prebaked on a hot plate at 80 DEG C for 1 minute and then the inside of the tube was replaced with nitrogen And then heated in an oven at 200 DEG C for 1 hour to form a coating film having a thickness of 0.08 mu m. 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 shifted from the normal of the substrate by 40 占 using a Hg-Xe lamp and a Gantail prism to obtain a liquid crystal alignment film. The same operation was repeated to form a pair of substrates (two pieces) on which a liquid crystal alignment film was formed.

&Lt; Production of liquid crystal display element &

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 was applied on the outer periphery of the surface having one liquid crystal alignment film among the substrates on which the liquid crystal alignment film was formed by screen printing, So that the projection direction of the optical axis of ultraviolet rays of each substrate to the substrate surface was anti-parallel, and the adhesive was thermally cured at 150 占 폚 for 1 hour. Subsequently, a negative-type liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled in the gap between the substrates rather than the liquid crystal injection hole, and then the 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 at 150 占 폚 and slowly cooled to room temperature. Next, a polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions thereof were orthogonal to each other and the optical axis of the ultraviolet ray of the liquid crystal alignment film was oriented at an angle of 45 degrees with respect to the projection direction of the substrate surface.

[Example 55]

The liquid crystal aligning agent (S-15) prepared in Example 37 was coated on the transparent electrode surface of the glass substrate with a transparent electrode made of ITO film by means of a spinner and prebaked on a hot plate at 80 DEG C for 1 minute , And the tube was heated in an oven where the inside of the tube was replaced with nitrogen at 200 캜 for 1 hour to form a coating film having a thickness of 0.08 탆 and the same operation was repeated to prepare one pair of substrates having a liquid crystal alignment film. On one side of this substrate, polarizing ultraviolet rays 200 J / m 2 containing a bright line of 313 nm were irradiated onto the surface of the coated film from a direction shifted from the normal to the substrate by 40 ° using an Hg-Xe lamp and a Gantry prism. Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 was applied to the outer periphery of the surface having the liquid crystal alignment film of the polarized UV-irradiated substrate by screen printing, and then another pair of substrates (the side not subjected to polarized UV irradiation) And the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a negative-type liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled in the gap between the substrates rather than the liquid crystal injection hole, and then the 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 at 150 占 폚 and slowly cooled to room temperature. Next, a polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions thereof were orthogonal to each other and the optical axis of the ultraviolet ray of the liquid crystal alignment film was oriented at an angle of 45 degrees with respect to the projection direction to the substrate surface.

[Example 56]

20 parts by mass of N, N, N ', N'-tetraglycidyl 4,4'-diaminodiphenylmethane was added to 100 parts by mass of polyimide PI-2 obtained in Synthesis Example 35, N-methyl-2-pyrrolidone and butyl cellosolve were added so as to give methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (by mass ratio) to obtain a solution having a solid concentration of 3.5% by mass. This solution was filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (S-33).

The prepared liquid crystal aligning agent (S-33) was coated on the transparent electrode surface of the glass substrate having the ITO film patterned in the slit shape shown in Fig. 1 by a spinner, prebaked on a hot plate at 80 DEG C for 1 minute , And the tube was heated in an oven in which the inside of the tube was replaced with nitrogen at 200 DEG C for 1 hour to form a coating film having a thickness of 0.08 mu m.

Next, the liquid crystal aligning agent (S-15) prepared in Example 37 was coated on the transparent electrode surface of the glass substrate having the ITO film patterned in the slit shape shown in Fig. 1 by a spinner, Baked for 1 minute, and then heated in an oven in which the inside of the tube was replaced with nitrogen at 200 DEG C for 1 hour to form a coating film having a thickness of 0.08 mu m. An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 was applied to the periphery of the surface having the liquid crystal alignment film of this substrate by screen printing and then the liquid crystal alignment film side of another pair of substrates And the adhesive was heat-cured at 150 DEG C for 1 hour. Subsequently, a negative-type liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled in the gap between the substrates rather than the liquid crystal injection hole, and then the 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 at 150 占 폚 and slowly cooled to room temperature. Thereafter, the cell produced in the state in which AC voltage of 10 V was applied was irradiated with light of 50,000 J / m 2 using a halogen lamp, and then polarizers were polarized perpendicularly to both sides of the outer side of the cell substrate And the liquid crystal display element was manufactured by joining the polarizing UV irradiation at an angle of 45 degrees with respect to the projection direction of the optical axis to the substrate surface.

[Comparative Example 3]

A liquid crystal aligning agent (CS-3) prepared in the same manner as in Example 23 was laminated on a transparent electrode made of an ITO film using the component shown in the following Table 2 ("-" in Table 2 indicates that the component was not used) The transparent electrode surface of the adhered glass substrate was coated with a spinner, prebaked on a hot plate at 80 DEG C for 1 minute, and then heated at 200 DEG C for 1 hour in an oven substituted with nitrogen to remove the solvent, A coating film (liquid crystal alignment film) having a thickness of 0.08 mu m was formed. This operation was repeated to prepare a pair of substrates (two substrates) each having a liquid crystal alignment film.

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

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

<Evaluation>

The following evaluation was made on the liquid crystal display device manufactured using the liquid crystal aligning agent of the above example. The results are shown together in Table 2. In Example 56, since the patterned electrode substrate is used, the measurement of the voltage holding ratio and the light resistance is not performed.

[Voltage Conservation Rate (VHR (%))]

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

[Light Resistance]

VHR after 3,000 hours of irradiation with a weather meter having a carbon arc as a light source was measured in the same manner as described above (voltage of 5 V was applied for 60 seconds and span of 167 milliseconds, voltage after 167 milliseconds The VHR variation was measured to be 1% or less in comparison with the measured value before irradiation, and a value of less than 3% in a range of more than 1% Quot; DELTA &quot;, and 3% or more was evaluated as &quot; x &quot;.

[Response speed (electro-optical response at rising)]

The time of the rise of the liquid crystal response was measured by a device including a polarization microscope, a photodetector and a pulse generator. Here, the liquid crystal response speed is the time (unit: msec.) Required for the manufactured liquid crystal display element to change from a voltage unapplied state to a 90% transmittance at a transmittance of 10% when a voltage of 4V is applied for a maximum of one second. ), And evaluated.

In Table 2, the polyorganosiloxane represents the compounding amount (parts by mass) relative to 100 parts by mass of the [B] polymer.

As is clear from the results in Table 2, the liquid crystal display device having the liquid crystal alignment film formed using the liquid crystal aligning agent of the embodiment not only has excellent light resistance but also has a higher response speed than the liquid crystal display device of the comparative example .

The liquid crystal aligning agent of the present invention can be suitably used for the production of a liquid crystal display element having a short electro-optic response time while satisfying generally required characteristics such as voltage holding ratio and light resistance. Further, the polyorganosiloxane compound of the present invention can be suitably used as a raw material of the liquid crystal aligning agent.

1: ITO electrode
2:
3:

Claims (9)

[A] a photo-alignment layer,
As the group containing no photo-orientable group, a group represented by the following formula (A1)
Respectively,
A liquid crystal aligning agent containing:

(Formula (A1) of, R ^A is a methylene group, from 2 to 30 carbon atoms in the alkylene group, a phenylene group or a cyclohexylene group; however, a part or all of the hydrogen atoms with those groups are good and which may be substituted; R ^B is R ^c is a group having at least two monocyclic structures, and a is 0 or 1), wherein R ^c is a group having at least two monocyclic structures. The method according to claim 1,
Wherein the photo-orientable group has a structure represented by the following formula (B1):

(In the formula (B1), R is a fluorine atom or a cyano group; a 'is an integer of 0 to 4; when a' is 2 or more, plural R may be the same or different; . 3. The method according to claim 1 or 2,
Wherein R ^C in the formula (A1) is a liquid crystal aligning agent represented by the following formula (A2)

(Wherein, in the formula (A2), R ^D is a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a divalent heterocyclic group; R ^E is a linking group containing at least any one of a methylene group which may have a substituent and an alkylene group having from 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic group, all or part of which may be substituted; and; R ^F is a benzene, biphenyl, naphthalene, cyclohexane, bicyclo hexane, cyclohexyl benzene, or except from a heterocyclic compound (c + 1) hydrogen atoms (c + 1) valent group; a part of the hydrogen atoms with groups or all of the well may be substituted; R ^G is a hydrogen atom, a cyano group, a fluorine atom, trifluoromethyl group, alkoxycarbonyl group, alkyl group, alkoxy group, trifluoromethoxy Or an alkyl carbonyl group optionally and; b is 0 or 1; c is an integer from 1 to 9 and; d is 1 or 2; R ^D, R ^E and R ^G is the case of each of the plurality, a plurality of R ^D, R ^E and R ^G may be the same or different from each other). 3. The method according to claim 1 or 2,
[A] the liquid crystal aligning agent wherein the polymer has a polyorganosiloxane structure; 3. The method according to claim 1 or 2,
[B] at least one polymer selected from the group consisting of polyamic acid and polyimide
&Lt; / RTI &gt; A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to any one of claims 1 to 3. The method according to claim 6,
Wherein the liquid crystal alignment film has two or more regions having different orientation orientations. A liquid crystal alignment film formed by the liquid crystal aligning agent according to claim 1 or 2. A photo-
As the group containing no photo-orientable group, a group represented by the following formula (A1)
A polyorganosiloxane compound having the following formula:

(Formula (A1) of, R ^A is a methylene group, from 2 to 30 carbon atoms in the alkylene group, a phenylene group or a cyclohexylene group; however, a part or all of the hydrogen atoms with those groups are good and which may be substituted; R ^B is R ^c is a group having at least two monocyclic structures, and a is 0 or 1), wherein R ^c is a group having at least two monocyclic structures.

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