TWI531615B - Liquid crystal alignment agent, liquid crystal display element, liquid crystal alignment membrane and polyorganicsiloxane compound - Google Patents

Description

Liquid crystal alignment agent, liquid crystal display element, liquid crystal alignment film, and polyorganosiloxane compound

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

In the liquid crystal display device, in order to align liquid crystal molecules in a certain direction with respect to the substrate surface, a liquid crystal alignment film is provided on the surface of the substrate. The liquid crystal alignment film is usually formed by a method (rubbing method) of rubbing the surface of the organic film formed on the surface of the substrate in one direction with a cloth material such as rayon. However, when the formation of the liquid crystal alignment film is performed by the rubbing treatment, dust or static electricity is likely to be generated in the rubbing step. Therefore, dust adheres to the surface of the alignment film, which causes a problem of display failure, and further has the following problem: In the case of a substrate of a TFT (Thin Film Transistor) device, the circuit of the TFT element is damaged due to static electricity generated, which causes a decrease in product yield. Therefore, as another means for aligning the liquid crystal in the liquid crystal cell, a photo-alignment method in which a radiation-sensitive organic thin film formed on the surface of the substrate is irradiated with polarized or unpolarized radiation to impart a liquid crystal alignment ability has been proposed (see Patent Literature 1~6). According to this photo-alignment method, dust or static electricity is not generated in the step, and uniform liquid crystal alignment can be formed (see Patent Documents 7 to 9).

Such a liquid crystal display device is expected to be used as an animation display device such as a mobile phone or a liquid crystal television. As a characteristic required for a liquid crystal display device, it is possible to smoothly display an animation and suppress image sticking as much as possible, thereby requiring an electro-optical effect response. The time is further increased. In response to such a request, a technique for imparting a dielectric anisotropy to a polymer side chain used in a liquid crystal alignment film to improve response time has been reported (see Patent Documents 10 and 11). However, these patent documents are related to liquid crystal alignment films which do not have a photo-alignment function, and have excellent electrical properties such as alignment, voltage retention, and afterimage characteristics, and optical alignment characteristics, which are important in practical use in addition to high speed of photoelectric response time. Not recorded.

Based on such a situation, it is desired to develop a photoalignment liquid crystal alignment agent which can form not only a characteristic of a voltage holding ratio and a light resistance which are generally required as a liquid crystal display element, but also a short photoelectric response time.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-307736

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-163646

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-250924

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-83810

[Patent Document 5] Japanese Patent Laid-Open Publication No. Hei 9-211468

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2003-114437

[Patent Document 7] International Publication No. 2009/25385

[Patent Document 8] International Publication No. 2009/25386

[Patent Document 9] International Publication No. 2009/25388

[Patent Document 10] Japanese Patent Publication No. 2007-521361

[Patent Document 11] Japanese Patent Publication No. 2007-521506

The present invention has been made in view of the above problems, and an object of the invention is to provide a photoalignment liquid crystal alignment agent capable of forming characteristics such as a voltage holding ratio and light resistance which are generally required for a liquid crystal display device, and a short photoelectric response time. A liquid crystal display element comprising a vertical alignment type or the like of a liquid crystal alignment film formed of the liquid crystal alignment agent; and a polyorganosiloxane compound suitable for use as the liquid crystal alignment agent.

The invention proposed to solve the above problems is a liquid crystal alignment agent containing [A] a polymer having a photo-alignment group and a group represented by the following formula (A1) (hereinafter referred to as [A] polymer) ),

In the formula (A1), R ^A is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenyl group or a cyclohexyl group. Among them, some or all of one of the hydrogen atoms of these groups may be substituted. R ^B is a linking group containing any of 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 single ring structures. a is 0 or 1.

The liquid crystal alignment agent of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent by a [A] polymer containing a group having a photo-alignment group and a specific structure represented by the above formula (A1). The liquid crystal display element can not only satisfy characteristics such as voltage holding ratio and light resistance, but also exhibits short photoelectric response time.

The photo-alignment group preferably 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 from 0 to 4. When a' is 2 or more, a plurality of R's may be the same or different. * indicates the connection key.

The liquid crystal alignment agent has the above specific structure in the above photo-alignment group, so that sensitivity can be improved.

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

In the formula (A2), R ^D is a phenyl group, a biphenyl group, a naphthyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylene group or a divalent heterocyclic group. Some or all of one of the hydrogen atoms of these groups may be substituted. R ^E is a linking group including a methylene group which may have a substituent and at least one of an alkylene group, a double bond, a triple bond, an ether bond, an ester bond, and a heterocyclic group having 2 to 10 carbon atoms. R ^F is a (c+1)-valent group from which (c+1) hydrogen atoms are removed from benzene, biphenyl, naphthalene, cyclohexane, dicyclohexane, cyclohexylbenzene or a heterocyclic compound. Some or all of one of the hydrogen atoms having the group may be substituted. 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. b is 0 or 1. c is an integer from 1 to 9. d is 1 or 2. When R ^D , R ^E , R ^G and b are each plural, the plurality of R ^D , R ^E , R ^G and b may be the same or different from each other.

The liquid crystal alignment agent can further improve the effects of the present invention by the above-described specific structure of R ^C .

The [A] polymer preferably has a polyorganosiloxane structure.

The liquid crystal alignment agent has a polyorganosiloxane structure by the [A] polymer, and can improve light resistance.

[B] is preferably a polymer (hereinafter referred to as "[B] polymer") further containing at least one selected from the group consisting of polylysine and polyimine.

The liquid crystal alignment agent can improve the solution characteristics and the electrical characteristics of the obtained liquid crystal display element by further containing the [B] polymer.

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

In the liquid crystal display device, the liquid crystal alignment film formed of the liquid crystal alignment agent described above can satisfy not only the characteristics such as the voltage holding ratio and the light resistance which are normally required, but also the short photoelectric response time.

The liquid crystal display element preferably has a liquid crystal alignment film having two or more regions having different alignment positions.

This liquid crystal display element can be applied to 3D display by having a liquid crystal alignment film having two or more regions having different alignment positions.

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

Since the liquid crystal alignment film is formed of the liquid crystal alignment film, the liquid crystal display element including the liquid crystal display element can satisfy not only the characteristics of the voltage holding ratio and the light resistance which are normally required, but also the short photoelectric response time.

The polyorganosiloxane compound of the present invention has a photo-alignment group 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 phenyl group or a cyclohexyl group. Among them, some or all of one of the hydrogen atoms of these groups may be substituted. R ^B is a linking group including any of a double bond, a triple bond, an ether bond, an ester bond, and an oxygen atom. R ^C is a group having at least 2 single ring structures. a is 0 or 1.

The polyorganosiloxane compound is suitably used as a component of the liquid crystal alignment agent because it has a photo-alignment group and a group having a specific structure represented by the above formula (A1).

According to the present invention, there is provided a liquid crystal alignment agent which can be applied to a light alignment mode and which can provide high-speed responsiveness and can form a liquid crystal display element which exhibits excellent light resistance.

[Formation of the Invention] <Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains a photo-alignment group and a [A] polymer containing a group represented by the above formula (.A1). The liquid crystal alignment agent can be applied to a photo-alignment mode, and the liquid crystal display element having the liquid crystal alignment film formed thereon can satisfy not only the characteristics of voltage holding ratio and light resistance which are generally required for a liquid crystal display element, but also a short photoelectric response time. Further, the liquid crystal alignment agent may contain a "other polymer" to be described later, such as a [B] polymer. Further, other optional components may be contained insofar as the effects of the present invention are not impaired. The details of each component are as follows.

<[A]polymer>

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

[Photoalignment group]

As the photo-alignment group, a well-known photo-alignment group can be suitably used, and a group having a cinnamate structure, a phenylstyrene ketone structure, or an azobenzene structure is preferable, and it is particularly preferable from the viewpoint of sensitivity. It has a cinnamate structure.

The photo-alignment group is preferably a group having a structure represented by the following formula (B1).

In the above formula (B1), R is a fluorine atom or a cyano group. a' is an integer from 0 to 4. When a' is 2 or more, a plurality of R's may be the same or different. * indicates the connection key.

A' in the above formula (B1) is preferably 0 or 1, more preferably 0.

The group represented by the formula (B1) is preferably a group represented by the following formula (B1-1) and a group represented by the formula (B1-2).

In the above formulae (B1-1) and (B1-2), R, a' and * are the same as defined in the above formula (B1).

In the formula (B1-1), R ¹ is a hydrogen atom, a monovalent organic group having 3 to 40 carbon atoms or an alkyl group having 1 to 40 carbon atoms containing an alicyclic group. Some or all of one of the hydrogen atoms of the above alkyl group may be substituted by a fluorine atom.

X ¹ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-. + indicates the connection key to the R ¹ bond.

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

X ² is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-. + indicates the connection key to the R ² bond.

b' is an integer from 0 to 3.

In the formula (B1-2), R ³ is a hydrogen atom, a monovalent organic group having an alicyclic group having 3 to 4 carbon atoms or an alkyl group having 1 to 40 carbon atoms. Here, part or all of one of the hydrogen atoms of the above alkyl group may be substituted by 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 cyclic group.

X ⁴ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO-. + indicates the connection key to the R ⁴ bond.

c' is an integer from 0 to 3.

The monovalent organic group having 3 to 40 carbon atoms and having an alicyclic group as R ¹ in the above formula (B1-1) and R ³ in the above formula (B1-2) can be exemplified, for example. A cyclohexyl group, a dicyclohexyl group, a cholesteryl group, a cholesteryl group, an adamantyl group or the like of an alkyl group having 1 to 10 carbon atoms.

The alkyl group having 1 to 40 carbon atoms of the above R ¹ and R ³ is preferably an alkyl group having 1 to 20 carbon atoms (wherein some or all of the hydrogen atoms of these alkyl groups may be substituted with a fluorine atom). Examples of the alkyl group include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, and the like. N-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, 4,4,4-trifluoro Butyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,5- Heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl) Ethyl, 2-(perfluorodecyl)ethyl and the like.

Examples of the divalent aromatic group of R ² in the above formula (B1-1) and R ⁴ in the above formula (B1-2) include 1,4-phenylene and 2-fluoro-1. 4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, and the like.

Examples of the divalent heterocyclic group of the above R ² and R ⁴ include a 1,4-pyridylpyridyl group, a 2,5-extended pyridyl group, and a 1,4-furanyl group.

The divalent condensed cyclic group of the above R ² and R ⁴ is, for example, a naphthyl group or the like.

The group represented by the above formula (B1-1) is preferably a group represented by the following formula.

In the above formula, R ¹ and * are the same as defined in the above formula (B1-1). d is an integer from 1 to 10.

The group represented by the above formula (B1-2) is preferably a group represented by the following formula.

In the above formula, R ³ and * are the same as defined in the formula (B1-2).

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

[Group represented by the above formula (A1)]

The above-mentioned formula (A1), R ^A is a methylene group, an alkylene group having a carbon number of 2 to 30, phenylene or cyclohexylene. Among them, some or all of one of the hydrogen atoms of these groups may be substituted.

Examples of the alkylene group having 2 to 30 carbon atoms represented by the above R ^A include an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a hydrazine group, and a hydrazine group. Base, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a decadecyl group, an eicosyl group, a stearyl group , dodecyl, thirteen, alkyl, tetracosyl, hexadecyl, hexadecyl, hexadecyl, octadecyl, Twenty-nine alkyl groups, and tridecyl groups are extended. Among these, since the liquid crystal alignment is stably found, it is preferably a pentyl group, a hexyl group, a octyl group, a fluorene group, a decyl group, an undecyl group, a dodecyl group, and a tetradecane. The alkyl group having a carbon number of 5 or more and 20 or less, such as a hexadecyl group, an octadecyl group, a decyl group, and an eicosyl group.

R ^B is a linking group including any of a double bond, a triple bond, an ether bond, an ester bond, and an oxygen atom. Examples of R ^B include an ethylenediyl group, an acetylenediyl group, an ester group, a methanediyloxy group, a fluoromethanediyloxy group, and a difluoromethanediyloxy group. Further, R ^B may be any one containing the above groups, or may contain each group in combination. Further, when R ^A is a phenylene group or a cyclohexyl group, R ^B preferably contains an alkylene group having 1 to 30 carbon atoms from the viewpoint of the alignment property of the formed alignment film or the solubility in a solvent. In addition, a is 0 or 1.

R ^C is a group having at least 2 single ring structures, preferably exhibiting positive or negative dielectric anisotropy. The monocyclic structure means that one ring structure exists independently of the other ring structures, and the bond having no one ring structure is shared with other ring structures, a so-called condensed ring structure. Further, the single ring structure may be any of an alicyclic structure, an aromatic ring structure, and a heterocyclic structure, or a combination thereof.

R ^C is not particularly limited in the range of a group having at least two or more monocyclic structures, but R ^{C is} preferably a group represented by the following formula (A2).

In the above formula (A2), R ^D is a stretching phenyl group, a stretching phenyl group, an anthranyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylene group or a divalent heterocyclic group. Some or all of one of the hydrogen atoms of these groups may be substituted. R ^E is a linking group containing a methyl group which may have a substituent and a stretching alkyl group, a double bond, a triple bond, an ether bond, an ester bond, and a hetero ring having 2 to 10 carbon atoms. R ^F is removed from benzene, biphenyl, naphthalene, cyclohexane, dicyclohexyl, cyclohexyl benzene or heterocyclic compound (c + 1) hydrogen atoms of (c + 1) valent group. Some or all of one of the hydrogen atoms of the group may be substituted. 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. b is 0 or 1. c is an integer from 1 to 9. d is 1 or 2. When R ^D , R ^E , R ^G and b are each plural, a plurality of R ^D , R ^E , R ^G and b may be the same or different from each other.

By introducing the group represented by the above formula (A2) to the side chain of the [A] polymer of the liquid crystal alignment agent, the electro-optical responsiveness of the obtained liquid crystal display element can be further increased. In the formula (A2), R ^D is a phenyl group, a biphenyl group, a naphthyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylene group or a divalent heterocyclic group. As a divalent heterocyclic group, for example, a pyridyl group Basis, pyrimidinyl and the like.

In the above formula (A2), R ^E includes 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. The linking group to which R ^D and R ^F are bonded may be appropriately selected depending on the orientation or dielectric anisotropy necessary for the [A] polymer. Examples of R ^E include a methylenediyl group, an ethylenediyl group, a propylenediyl group, an ethylenediyl group, an acetylenediyl group, an ether group, an ester group, a methyldiyloxy group, an ethylenediyloxy group, and a fluoromethyleneoxy group. Base, difluoromethyldiyloxy and the like. Among these, an ethylenediyl group, an acetylenediyl group, an ester group, a methyldiyloxy group, and a difluoromethyleneoxy group are preferable. Further, b is an integer of 0 or 1, and R ^F may or may not be contained in the design of the side chain structure.

In the above formula (A2), R ^F is (c+1) which removes (c+1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, dicyclohexane, cyclohexylbenzene or a heterocyclic compound. The group of the price. c is an integer from 1 to 9. When R ^{F is} , for example, 1 is c, the same group as the divalent group exemplified as the above R ^D may be used.

In the above 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, a n-butyl group, and an isobutyl group. The linear or branched alkyl group having 1 to 20 carbon atoms may, for example, be a methoxy group, an ethoxy group or a propoxy group.

In the above formula (A2), R ^F has a plurality of substituent groups (R ^G), may be combined in different respective groups R ^F is used. When R ^F is a combination having a plurality of substituents, since a desired dielectric anisotropy is stably found, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, a cyano group and an alkyl group are preferable. combination. In addition, c is an integer of 1 to 9.

[A] When the polymer has a photo-alignment group and a group represented by the above formula (A1), the main chain may suitably be a well-known polymer backbone, such as polyorganosiloxane or polyazide. Amine, polyamic acid, polyacrylate, polymethacrylate, poly(styrene-phenylmaleimide) derivative, cellulose derivative, polyester, polyamine, polystyrene derivative Polyglycolate is preferred as the main chain structure from the viewpoint of electrical characteristics. From the viewpoint of light resistance, polyorganosiloxane (hereinafter referred to as "[a] polyorganosiloxane compound") is preferred.

When the [A] polymer contained in the liquid crystal alignment agent has a polyorganosiloxane structure, it contains a [a] polyorganosiloxane compound, and the [a] polyorganosiloxane compound preferably has a ring. a portion of the polyorganosiloxane having an oxy group, a portion derived from a compound having a photo-alignment group and a carboxyl group (hereinafter referred to as "specific carboxylic acid A"), and a moiety derived from the following formula (A1-C) A moiety of a compound of a carboxyl group (hereinafter referred to as "specific carboxylic acid B").

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

By using the liquid crystal alignment agent having the specific structure described above, that is, introducing a photo-alignment group and a structure having dielectric anisotropy on a side chain, a liquid crystal alignment film having the photo-alignment property is used to form a liquid crystal alignment film. The liquid crystal display element having the liquid crystal alignment film can further improve electrical characteristics and image sticking characteristics, and further shorten the response time. Further, by utilizing the reactivity between the epoxy group and the carboxyl group, it is easy to introduce a photo-alignment group as a side chain on the polyorganosiloxane having a main chain, and the dielectric represented by the above formula (A1-C) Anisotropic structure.

[a] The polyorganosiloxane compound is considered to be mainly a product obtained by reacting an epoxy group of a polyorganosiloxane with a carboxyl group of a specific carboxylic acid, but in order to make the description more convenient, it is classified from having an epoxy group. The portion of the polyorganosiloxane (and its derivative) and the portion derived from the specific carboxylic acid, the [a] polyorganosiloxane compound contained in the liquid crystal alignment agent will be described.

[Part from polyorganosiloxane having an epoxy group]

This portion is a polyorganosiloxane skeleton as a polymer main chain in the structure including the [a] polyorganosiloxane compound, and an epoxy group as a side chain extending from the polyorganosiloxane main chain. Skeleton concept. In the above [a] polyorganosiloxane compound, it is considered that most of the epoxy group reacts with a specific carboxylic acid without having an initial structure, but a specific carboxylic acid may be bonded to a portion other than the epoxy group. Therefore, in the present invention, "a portion derived from a polyorganosiloxane having an epoxy group" including two types of embodiments will be described.

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

By including a group represented by the above formula (X ¹ -1-1) or (X ¹ -2-1) in the polyorganosiloxane having an epoxy group, [a] polyorganism in the liquid crystal alignment agent It is easy to introduce a side chain group derived from a compound having the above specific structure onto a oxoxane compound.

In the above formulae (X ¹ -1-1) and (X ¹ -2-1), * represents a linkage.

The polyorganosiloxane having an epoxy group preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of from 500 to 100,000, more preferably from 1,000 to 50,000, particularly preferably from 1,000 to 20,000. .

[Synthesis method of polyorganosiloxane having epoxy group]

Such an epoxy group-containing polyorganooxane can be preferably a suitable organic solvent or water by a mixture of a decane compound preferably having an epoxy group or a decane compound having an epoxy group and another decane compound. It is synthesized by hydrolysis or hydrolysis ‧ condensation in the presence of a catalyst.

Examples of the above decane compound having an epoxy group include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-epoxypropoxy group. Propylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxy Propyl dimethyl ethoxy decane, 2-glycidoxyethyl trimethoxy decane, 2-glycidoxyethyl triethoxy decane, 2-epoxypropoxy ethyl group Dimethoxy decane, 2-glycidoxyethylmethyldiethoxy decane, 2-glycidoxyethyl dimethyl methoxy decane, 2-glycidoxyethyl Dimethylethoxydecane, 4-glycidoxybutyltrimethoxydecane, 4-glycidoxybutyltriethoxydecane, 4-glycidoxybutylmethyldimethoxy Decane, 4-glycidoxybutylmethyldiethoxydecane, 4-glycidoxybutyldimethylmethoxydecane, 4-glycidoxybutyldimethylethoxydecane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxy Hexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethoxydecane Wait. These may be used alone or in combination of two or more.

As the above other decane compound, for example, a compound having four hydrolyzable groups in a compound having one ruthenium atom, such as tetrachloro decane; tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane a tetraalkoxy decane such as tetraisopropoxy decane, tetra-n-butoxy decane or tetra-butoxy decane; or a compound having three hydrolyzable groups, such as trihalodecane such as trichlorodecane; a trialkyloxydecane such as trimethoxydecane or triethoxysilane; a fluorotrichlorodecane; a fluorotrialkoxide such as fluorotrimethoxydecane or fluorotriethoxydecane; or an alkyl group such as methyltrichlorodecane. Trichloromethane; alkyltrialkoxydecane such as methyltrimethoxydecane or methyltriethoxydecane; fluoroalkyltrichlorononane such as 2-(trifluoromethyl)ethyltrichlorodecane; a fluoroalkyltrialkoxydecane such as (trifluoromethyl)ethyltrimethoxydecane or 2-(trifluoromethyl)ethyltriethoxydecane; or a hydroxyalkyltrichloride such as hydroxymethyltrichlorodecane Hydrane; hydroxyalkyltrialkoxydecane such as hydroxymethyltrimethoxydecane or hydroxyethyltrimethoxydecane; 3-(methyl)propene oxime (meth) propylene oxyalkyl trichloro decane such as propyl trichloro decane; 3-(methyl) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl a (meth) propylene oxyalkyltrial alkoxy oxane such as triethoxy or a decylalkyltrichloro decane such as mercaptomethyltrichlorodecane or 3-mercaptopropyltrichlorodecane; decylmethyltrimethoxy Nonylalkyltrialkaloxane, such as decane, mercaptomethyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxy, etc.; vinyltrichloromethane, allyltriyl Alkenyl trichlorodecane such as chlorodecane; alkenyl trialkoxy decane such as vinyl trimethoxy decane, vinyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy decane An aryltrichlorodecane such as phenyltrichlorodecane; an aryltrialkoxydecane such as phenyltrimethoxydecane or phenyltriethoxydecane; or a compound having two hydrolyzable groups, such as a An alkyl dichlorodecane such as chlorodioxane; an alkyldialkoxy decane such as methyl dimethoxy decane or methyl diethoxy decane; dimethyl dichloro guanidine; a dialkyldichlorodecane such as alkane; a dialkyldialkoxydecane such as dimethyldimethoxydecane or dimethyldiethoxydecane; (methyl)[2-(perfluoro-n-octyl) a difluoroalkyldichlorodecane such as ethyl]dichlorodecane; or a difluoroalkyldialkoxydecane such as (meth)[2-(perfluoro-n-octyl)ethyl]dimethoxydecane; Alkyl ‧ decyl alkyl dichloro decane such as (methyl) (3-mercaptopropyl) dichlorodecane; alkyl phthalyl alkyl dioxane such as (methyl) (3-mercaptopropyl) dimethoxy decane An alkylalkenyl dichloromethane such as (meth)(vinyl)dichlorodecane; a di-alkenyldichlorononane such as divinyldichlorodecane; a chain such as divinyldimethoxydecane; a diaryldichlorodecane such as diphenyldichlorodecane; a diaryldialkoxydecane such as diphenyldimethoxydecane; and a compound having one hydrolyzable group; , such as dialkyl chlorodecane such as chlorodimethyl decane; dialkyl alkoxy decane such as methoxy dimethyl decane; trioxane such as trimethyl chloro decane, trimethyl bromo decane or trimethyl iodonane Trihalodecane; methoxy trimethyl decane, etc. Alkoxy alkane; dialkylalkenyl chlorodecane such as (chloro)(vinyl)dimethyl decane; dialkylalkenyl alkoxy group such as (methoxy)(vinyl)dimethyl decane a arylane; a diarylalkyl chlorodecane such as (chloro)(methyl)diphenyl decane; a diarylalkyl alkoxy oxane such as (methoxy)(methyl)diphenyl decane; and the like.

As commercially available products, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21 can be cited. -5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX , X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X -40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41 -1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N , KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above is manufactured by Shin-Etsu Chemical Co., Ltd.); glass resin (manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411 , SR2416, SR2420 (above is manufactured by Toray ‧ Dow Corning); FZ3711, FZ3722 (above is manufactured by UNICAR, Japan); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42 DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (the above is manufactured by CHISSO); methyl phthalate MS51, methyl phthalate MS56 (above Mitsubishi Chemical Co., Ltd.; ethyl phthalate 28, ethyl decanoate 40, ethyl decanoate 48 (above COLCOAT); GR100, GR650, GR908, GR950 (above, Showa Denko) .

Among these other decane compounds, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, and methyl triethyl are preferable from the viewpoints of the alignment property and storage stability of the obtained liquid crystal display element. Oxydecane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyl triethyl Oxydecane, allyltrimethoxydecane, allyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropane Triethoxy, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane.

Preferably, the polyorganosiloxane having an epoxy group is used in order to introduce a side chain having dielectric anisotropy in a sufficient amount, preferably having an epoxy equivalent of 100 to 10,000 g/mole. More preferably 150~1,000g/mole, especially good 150~300g/mole. Therefore, in synthesizing a precursor of a polyorganosiloxane having an epoxy group, it is preferred to set a ratio of use of a decane compound and other decane compound to obtain an epoxy equivalent of the obtained polyorganosiloxane having an epoxy group. Adjust within the above range. When synthesizing the polyorganosiloxane having an epoxy group used in the present invention, it is more preferred to use only a decane compound and no other decane compound.

Examples of the organic solvent which can be used in the synthesis of the polyorganosiloxane having an epoxy group include a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, an alkanol compound and the like.

Examples of the hydrocarbon compound include toluene and xylene; and examples of the ketone compound include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentanone, diethyl ketone, cyclohexanone, and the like; a compound such as ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate or the like; as the above ether compound, for example, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, two An alkane or the like; examples of the above-mentioned alkanol compound include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 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. Among these, a solvent which is not water-soluble is preferred. These organic solvents may be used singly or in combination of two or more kinds.

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, per 100 parts by mass of the total decane compound. The amount of water used in the production of the polyorganosiloxane having an epoxy group is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles per mole of the total decane compound.

Examples of the catalyst include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound.

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

Examples of the above organic base include ethylamine, diethylamine, and piperazine. Primary and secondary organic amines such as piperidine, pyrrolidine and pyrrole; tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and dinonicycloundecene Organic amine; tetra-organic amine such as tetramethylammonium hydroxide. Among these organic bases, triorganoamines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, etc.; tetramethylammonium hydroxide, etc. are preferable in view of the smooth progress of the reaction. Grade IV organic amine.

As a catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst, a side reaction such as ring opening of an epoxy group is not generated, and a polyorganosiloxane can be obtained with a high hydrolysis rate and a condensation rate, and thus the production stability is excellent. Good. Further, the liquid crystal alignment agent of a polyorganosiloxane having an epoxy group and a reaction product of a specific carboxylic acid synthesized by using an alkali metal compound or an organic base as a catalyst is excellent in storage stability and is very suitable. The reason is as indicated in Chemical Reviews, Vol. 95, p. 1409 (1995). When an alkali metal compound or an organic base is used as a catalyst in the hydrolysis or condensation reaction, it is presumed that a random structure, a ladder structure or a cage is formed. The structure is such that a polyorganosiloxane having a small proportion of sterol groups is obtained. Since the content ratio of the sterol group is small, it is presumed that the condensation reaction between the sterol groups is suppressed, and when the liquid crystal alignment agent contains the other polymer described later, the condensation reaction between the sterol group and the other polymer is suppressed, and thus the preservation is obtained. Excellent stability results.

As the catalyst, an organic base is particularly preferred. The amount of the organic base to be used may be appropriately set depending on the type of the organic base, the reaction conditions, and the like, and is, for example, preferably 0.01 to 3 moles, more preferably 0.05 to 1 mole, based on the total decane compound.

The hydrolysis or hydrolysis ‧ condensation reaction in the production of a polyorganosiloxane having an epoxy group is preferably a solution of a decane compound having an epoxy group and other decane compounds as needed in an organic solvent, the solution and an organic base and water The mixing is carried out, for example, by heating in 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. The heating time is preferably from 0.5 to 12 hours, more preferably from 1 to 8 hours. While heating, the mixture may be stirred or placed under reflux.

After completion of the reaction, the organic solvent layer separated from the reaction liquid is preferably washed with water. In the case of washing, it is preferable to wash the water with a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by mass or the like, from the viewpoint of facilitating the washing operation. The water layer after the cleaning is neutralized to be neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as needed, and then the solvent is removed to obtain the desired polyorganosiloxane having an epoxy group.

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

[a] The polyorganosiloxane compound may also contain a portion derived from a hydrolysis product formed by hydrolysis of a polyorganosiloxane having an epoxy group itself, or a hydrolysis from a hydrolysis and condensation of a polyorganosiloxane having an epoxy group with each other. Part of the condensate. The constituent material of this portion, that is, these hydrolyzed products or hydrolysis condensates, can also be produced under the same hydrolysis and condensation conditions as the polyorganosiloxane having an epoxy group.

[part from a specific carboxylic acid]

The photo-alignment group or the moiety of the group represented by the above formula (A1) corresponds to a side chain structure having a structure derived from a carboxyl group as a starting point, and a polyorganosiloxane of the [a] component contained in the liquid crystal alignment agent In the structure of the compound, a structure derived from an epoxy group mainly extending from a polyorganosiloxane main chain is bonded to the carboxyl group. In the present invention, the case where a specific carboxylic acid is bonded to a moiety other than the epoxy group is also referred to as "a moiety derived from a specific carboxylic acid".

[Specific carboxylic acid A]

The compound having the structure represented by the above formula (B1) as the specific carboxylic acid A is preferably a compound represented by the following formula (B1-1C) or a compound represented by the formula (B1-2C).

R, R ¹ , R ² , X ¹ , X ² , a' and b' in the above formula (B1-1C) and R, R ³ , R ⁴ , X ³ and X in the above formula (B1-2C) ⁴ , a' and c' are respectively the same as those defined by the above formula (B1-1) or formula (B1-2).

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

When X ⁵ is a single bond, e is 1 and R ⁵ is a hydrogen atom.

When X ⁵ is a methylene group, an alkylene group, an alkenyl group or a divalent aromatic group, e is 0 or 1 and R ⁵ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR' (wherein R above) 'is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH=CH ₂ or SO ₂ Cl.

In the above formula (B1-2C), R ⁶ is a divalent aromatic group, a divalent heterocyclic group or a divalent condensed cyclic group, and X ⁶ is an oxygen atom, -COO- ⁺ or OCO- ⁺ . Where + represents the bond to the R ⁶ bond.

f is an integer from 0 to 3.

R ⁷ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (the above 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 - ⁺ . + indicates a linkage that binds to R ⁷ . i and j are integers from 0 to 10, respectively.

The compound represented by the above formula (B1-1C) is preferably a compound of the above formula (B1-1C) wherein X ⁵ is a single bond and R ⁵ is a hydrogen atom, or X ⁵ is a methylene group, an alkylene group or a divalent aromatic group and R ⁵ is a carboxyl group, a compound represented by the above formula (B1-2C), preferably the above formula (B1-2C) in which R ⁷ is carboxy. Hereinafter, such a compound having a carboxyl group is referred to as "carboxylic acid (B1)".

More preferably, such a carboxylic acid (B1) is a compound represented by the above formula (B1-1C), and a compound represented by the following formula is preferable.

In the above formula, R ¹ is the same as defined in the above formula (B1-1C). d is an integer from 1 to 10.

The compound represented by the above formula (B1-2) is preferably a compound represented by the following formula.

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

[Specific carboxylic acid B]

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

In the above formulae (D-1) to (D-25), R ^{C has the} same definition as the above formula (A1-C). m is an integer from 1 to 30.

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

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

Examples of the alkyl group represented by R include a methyl group, an ethyl group, a propyl group, a n-butyl group, an isobutyl group, a n-pentyl group, and a 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.

[Synthesis method of specific carboxylic acid]

The method for synthesizing the specific carboxylic acid is not particularly limited, and it can be carried out by a combination of a conventionally known method. As a typical synthesis method, for example, (1) a compound having a phenol skeleton and a compound in which an alkyl chain moiety of a higher fatty acid ester is substituted with a halogen atom are reacted under basic conditions, and a hydroxyl group and a halogen atom of the phenol skeleton are substituted. The carbon forms a bond, then the ester is reduced to prepare a specific carboxylic acid, and (2) the compound having a phenol skeleton and ethylene carbonate are reacted to form a terminal alkanol compound, and the hydroxyl group is activated by reacting with the halosulfonium chloride. Then, the activated portion is reacted with a methyl group-containing benzoic acid methyl ester, and the sulfonyl group is detached, and the hydroxyl group of the terminal alkanol compound and the hydroxyl group as a substituent contained in the methyl benzoate form a bond, followed by reduction of the ester. A method of preparing a specific carboxylic acid or the like. However, the synthesis method of the specific carboxylic acid is not limited thereto.

<[a] Synthesis method of polyorganosiloxane compound>

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

Here, the specific carboxylic acid is preferably used in an amount of from 0.001 to 10 moles, more preferably from 0.01 to 5 moles, still more preferably from 0.05 to 2 moles, per mole of the epoxy group of the 1 mole of polyorganosiloxane. ear.

In the present invention, a part of the specific carboxylic acid may be used in the form of a compound represented by the following formula (4) in the range which does not impair the effects of the present invention. At this time, the synthesis of the [a] polyorganosiloxane compound is carried out by reacting a polyorganosiloxane having an epoxy group with a mixture of a specific carboxylic acid and a compound represented by the following formula (4).

A ¹ -L ⁰ -L ¹ -Z (4)

In the above formula (4), A ¹ is a linear or branched alkyl group having 1 to 30 carbon atoms, and the number of carbon atoms which may be substituted by an alkyl group having 1 to 20 carbon atoms or an alkoxy group is 3~ A cycloalkyl group of 10 or a hydrocarbon group having from 17 to 51 carbon atoms having a steroid skeleton. Here, a part or all of the hydrogen atom of the above alkyl group and alkoxy group may be substituted with a substituent such as a cyano group, a fluorine atom or a trifluoromethyl group.

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

L ¹ is a single bond, a methylene group, an alkyl group having 2 to 20 carbon atoms, a phenyl group, a phenyl group, a cyclohexylene group, a dicyclohexyl group or the following formula (L ¹ -1) or (L) -2) The group represented.

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

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

The connection keys with "*" in the above formulas (L ¹ -1) and (L ¹ -2) are respectively bonded to Z.

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 above formula (4) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group and a n-butyl group. Base, second butyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-glycol , 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl Base, 2,4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1,3-dimethylpentyl Base, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3,3- Trimethylbutyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methyl Heptyl, 2-ethylhexyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-heptadecyl, n-ten Hexaalkyl, n-heptadecyl, n-octadecyl, n-nonadecyl and the like.

The cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group or an alkoxy group having 1 to 20 carbon atoms may, for example, be a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a cyclic oxime. Base, cyclodecyl, cyclododecyl and the like.

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

In the above formulas (H-1) to (H-3), * indicates a connection key.

In the above formula (4), A ^{1 is} preferably selected from an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and the above formula (H-1) or (H-3). Group.

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

C _u F _2u+1 -C _v H _2v -COOH (4-1)

C _w H _2w+1 -COOH (4-2)

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

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

C ₁₇ H ₃₅ -COOH (5-1)

The compound represented by the above formula (4) is a compound which reacts with a specific carboxylic acid and a polyorganosiloxane having an epoxy group to impart a pretilt angle finding property to the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (4) is hereinafter referred to as "other pretilt angle-detecting compound".

In the present invention, when a specific carboxylic acid and other pretilt angle finding compounds are used, the total use ratio of the specific carboxylic acid and other pretilt angle finding compounds is compared with the epoxy group of 1 mole of polyorganosiloxane. Preferably, it is 0.001 to 1.5 moles, more preferably 0.01 to 1 mole, and even more preferably 0.05 to 0.9 moles. In this case, the other pretilt angle-detecting compound is preferably used in a range of preferably 75 mol% or less, more preferably 50 mol% or less, based on the total amount of the specific carboxylic acid. When the ratio of use of the other pretilt angle-detecting compound exceeds 75 mol%, there is a case where the high-speed responsiveness of the liquid crystal is adversely affected.

The catalyst used in the reaction of the epoxy group in the polyorganosiloxane and the compound represented by the above formula (4) and the carboxylic acid group-containing compound represented by the other pretilt angle-detecting compound can be used to promote an organic base, A compound known as a so-called hardening accelerator for the reaction of an epoxy compound and an acid anhydride.

Examples of the above organic base include ethylamine, diethylamine, and piperazine. Primary, secondary organic amines such as piperidine, pyrrolidine, pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, dinonicycloundecene, etc. Grade organic amine; tetra-organic amine such as tetramethylammonium hydroxide. Among these organic bases, preferred are triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and tetramethylammonium hydroxide.

Examples of the hardening accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; Imidazole, 2-n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2- Cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2 -Phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium trimellitate , 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium trimellitic acid Ester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-all three 2,4-Diamino-6-(2'-n-undecylimidazolyl)ethyl-all three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-all three , a trimeric isocyanate adduct of 2-methylimidazole, a trimeric isocyanate adduct of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl- (1')] ethyl-all three An imidazole compound such as a trimeric isocyanate adduct; an organophosphorus compound such as diphenylphosphine, triphenylphosphine or triphenylphosphite; benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylacetic acid鏻, tetra-n-butyl 鏻 o, o-diethylphosphonium disulfate, tetra-n-butyl benzotriazole, tetra-n-butyl fluorene tetrafluoroborate, tetra-n-butyl fluorene tetraphenyl a quaternary phosphonium salt such as a boronic acid ester or a tetraphenylphosphonium tetraphenylborate; a diterpene bicyclic olefin such as 1,8-difluorenebicyclo[5.4.0]undecene-7 or an organic acid salt thereof Organic metal compound such as zinc octoate, tin octylate, aluminum acetamacetone complex; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, etc. a graded ammonium salt; a boron compound such as boron trifluoride or triphenyl borate; a metal halide such as zinc chloride or tin chloride; an amine addition accelerator such as an addition product of dicyandiamide or an amine and an epoxy resin; High melting point dispersion type latent hardening accelerator; a microcapsule latent curing accelerator coated with a polymer such as an imidazole compound, an organophosphorus compound or a quaternary phosphonium salt; an amine salt type latent curing accelerator; a Lewis acid salt and a Bronsted acid A latent curing accelerator such as a high-temperature dissociable thermal cationic polymerization type latent curing accelerator such as a salt.

Among these catalysts, a quaternary ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred.

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

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

The synthesis reaction of the [a] polyorganosiloxane compound can be carried out in the presence of an organic solvent as needed. Examples of the organic solvent include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, and an alkanol compound. Among these, an ether compound, an ester compound, and a ketone compound are preferable in view of the solubility of a raw material and a product, and the ease of purification of a product. The solid content concentration of the solvent (the ratio of the mass of the component other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 50% by mass or less. use.

The polyaluminoxane compound thus obtained is a polystyrene obtained by gel permeation chromatography, and the converted weight average molecular weight is not particularly limited, and is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000. In such a molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

The [a] polyorganomethoxy siloxane compound of the present invention is a ring-opening addition of an epoxy group to a specific carboxylic acid in a polyorganosiloxane having an epoxy group by a carboxylate moiety of a specific carboxylic acid. The structure of the acid. This production method is simple and can increase the introduction rate of a structure derived from a specific carboxylic acid, and is a very suitable method.

<arbitrary component>

In addition to the [A] polymer, the liquid crystal alignment agent may contain, for example, a polymer other than the [A] polymer (hereinafter referred to as "other polymer"), a hardener, and hardening, within the range in which the effects of the present invention are not impaired. A catalyst, a hardening accelerator, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, a surfactant, and the like.

[Other polymers]

Other polymers are used to further improve the solution characteristics of the liquid crystal alignment agent and the electrical characteristics of the obtained liquid crystal display element. The other polymer may, for example, be at least one polymer selected from the group consisting of polylysine and polyimine ([B] polymer); and is selected from the following formula (5) At least one of the group consisting of a polyorganosiloxane, a hydrolyzate thereof, and a condensate of the hydrolyzate thereof (hereinafter referred to as "other polyorganosiloxane"); polyglycolate, polyester, Polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, and the like.

In the above 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>

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

[polyglycolic acid]

Polylysine is obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types.

Examples of the aliphatic tetracarboxylic dianhydride include tetrabutyric dianhydride and the like.

As the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic 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, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione , 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxo) Heterotetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3 , 5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]oct-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3. 1.02,6] eleven carbon-3,5,8,10-tetraketone, and the like.

The aromatic tetracarboxylic dianhydride is, for example, pyromellitic dianhydride, and the tetracarboxylic dianhydride described in Japanese Patent Application No. 2010-97188.

Among these tetracarboxylic dianhydrides, preferred are alicyclic tetracarboxylic dianhydrides, more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane IV. Formic acid dianhydride, particularly preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

The amount of use of 2,3,5-tricarboxycyclopentylacetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferably 10 mol% based on the total tetracarboxylic dianhydride. The above is more preferably 20 mol% or more, and particularly preferably consists of only 2,3,5-tricarboxycyclopentylacetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

Examples of the diamine compound include an aliphatic diamine, an alicyclic diamine, a diaminoorganosiloxane, an aromatic diamine, and the like. These diamine compounds may be used singly or in combination of two or more kinds.

Examples of the aliphatic diamine include m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, and hexamethylenediamine.

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

Examples of the diamine-based organooxane include, for example, 1,3-bis(3-aminopropyl)-tetramethyldioxane, and the second one described in Japanese Patent Application No. 2009-97188. amine.

Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, and 1,5-diaminonaphthalene. , 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-di Aminoguanidine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminobenzene) , 2, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'- (p-phenylene diiso-propyl) bis(aniline), 4,4'-(meta-phenyl diiso-propyl) bis(aniline), 1,4-bis(4-aminophenoxy) Benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3, 6-Diamino acridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N- Phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N' -Dimethylbenzidine, 1,4-bis-(4-aminophenyl)-peripipeline , 3,5-diamino benzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, fifteen decyloxy-2,4 -diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene , tetradecyloxy-2,5-diaminobenzene, fifteen decyloxy-2,5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, octadecyloxy Base-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4 -diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3,5-diamino benzoic acid cholesteryl, 3,5-diamino benzoic acid cholesteryl, 3 , 5-diaminobenzoic acid lanthanyl, 3,6-bis(4-aminobenzylideneoxy)cholane, 3,6-bis(4-aminophenoxy)cholestane , 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzylideneoxy) ring Hexyl-3,5-diaminobenzoic acid ester, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-double ( 4-((Aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-double (4-((Aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-) (4-heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine and the following formula (A- 1) A diamine compound or the like represented.

The above formula (A-1) in, X ^I is a methylene group or a 2 or 3 carbon atoms, alkylene group, -O -, - COO- or -OCO-. r is 0 or 1. S is an integer from 0 to 2. t is an integer from 1 to 20.

The ratio of use of the tetracarboxylic dianhydride and the diamine compound which provides a synthesis reaction of polylysine is preferably 0.2 based on the amine group contained in one equivalent of the diamine compound. The equivalent amount is 2 equivalents, 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 ° C to 150 ° C, more preferably 0 ° C to 100 ° C. The reaction time is preferably from 0.5 to 24 hours, more preferably from 2 to 12 hours.

The organic solvent is not particularly limited as long as it can dissolve the synthesized polylysine, and examples thereof include N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide. Aprotic systems such as N,N-dimethylformamide, N,N-dimethylimidazolidinone, dimethylhydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine A polar solvent; a phenol solvent such as m-cresol, xylenol, phenol or halophenol.

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

The polyaminic acid solution obtained after the reaction may be supplied to the preparation of the liquid crystal alignment agent as it is, or the poly-proline acid contained in the reaction solution may be separated and then supplied to the liquid crystal alignment agent, or may be purified and separated. The amine acid is then supplied to the preparation of the liquid crystal alignment agent. Examples of the method for separating the polyamic acid include a method in which a precipitate obtained by injecting a large amount of a poor solvent into a reaction solution is dried under reduced pressure, and a method in which a reaction solution is distilled off under reduced pressure using an evaporator. The method for purifying the polyamic acid may be a method in which the separated polylysine is redissolved in an organic solvent and precipitated with a poor solvent, and the organic solvent is distilled off under reduced pressure several times by an evaporator. The method of the steps.

[polyimine]

The polyimine can be produced by dehydrating and ring-opening and hydrazine imidating the proline structure of the above polyamic acid. The polyimine may be a complete hydrazine imide of the proline structure in which the pro-polyglycolic acid has a dehydration ring structure, or may be a part of the valeric acid structure, a dehydration ring closure, a proline structure and a quinone ring. Part of the structure coexisting quinone imide.

Examples of the method for synthesizing the polyimine include (i) a method of heating poly-proline (hereinafter referred to as "method (i)"), and (ii) dissolving poly-lysine in an organic solvent. A method of dehydration ring closure reaction of polylysine such as a method of heating (hereinafter referred to as "method (ii)") by adding a dehydrating agent and a dehydration ring-closure catalyst to the solution.

The reaction temperature of the method (i) is preferably from 50 ° C to 200 ° C, more preferably from 60 ° C to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring closure reaction is insufficient, and when the reaction temperature exceeds 200 ° C, the molecular weight of the obtained polyimine is lowered. The reaction time is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours.

The polyimine obtained in the method (i) may be supplied to the preparation of the liquid crystal alignment agent as it is, or may be separated from the preparation of the liquid crystal alignment agent by the separation of the polyimine or the purified polyimine. In the preparation of liquid crystal alignment agent.

The dehydrating agent in the method (ii) may, for example, be an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride.

The amount of the dehydrating agent to be used can be appropriately selected depending on the desired ruthenium iodide ratio, but the guanamine structure with respect to 1 mol of polylysine is preferably 0.01 mol to 20 mol.

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

The amount of the dehydration ring-closure catalyst to be used is preferably from 0.01 mol to 10 mol based on the dehydrating agent per 1 mol of the dehydrating agent. Further, the more the content of the above dehydrating agent and the dehydration ring-closing agent, the higher the niobium iodization rate.

The organic solvent to be used in the method (ii) may, for example, be an organic solvent similar to the organic solvent used for the synthesis of polyamic acid.

The reaction temperature in the method (ii) is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 0.5 to 20 hours, more preferably from 1 to 8 hours. When the reaction conditions are in the above range, the dehydration ring-closure reaction can be sufficiently carried out, and the molecular weight of the obtained polyimine can be controlled to an appropriate range.

A reaction solution containing polyienimine is obtained in the method (ii). The reaction solution may be supplied to the preparation of the liquid crystal alignment agent as it is, or may be supplied to the liquid crystal alignment agent after the dehydration agent and the dehydration ring closure catalyst are removed from the reaction solution, or may be separated from the polyimine and then supplied to the liquid crystal. The preparation of the alignment agent or the purification of the separated polyimine is followed by the preparation of the liquid crystal alignment agent. As a method of removing a dehydrating agent and a dehydration ring-closing catalyst from a reaction solution, the method of solvent substitution etc. are mentioned, for example. The separation method and the purification method of the polyimine are, for example, the same as those of the separation method and the purification method of the polyaminic acid.

[Other polyorganosiloxanes]

The liquid crystal alignment agent may also contain other polyorganosiloxanes other than the [a] polyorganosiloxane compound. The other polyorganosiloxane is preferably at least one selected from the group consisting of polyorganooxane represented by the above formula (5), a hydrolyzate thereof, and a condensate of the hydrolyzate thereof. Further, when the liquid crystal alignment agent contains another polyorganosiloxane, most of the other polyorganosiloxanes are independently present as the [a] polyorganosiloxane compound, or a part thereof may be aggregated with [a]. A condensate of an organic oxoxane compound is present.

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, a n-propyl group, a n-butyl group, a n-pentyl group, and a n-hexyl group. N-heptyl, n-octyl, n-decyl, n-decyl, n-lauryl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, N-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, etc.; as alkoxy having 1 to 16 carbon atoms, for example, a methoxy group, an ethoxy group, etc.; An aryl group having 6 to 20 atoms, such as a phenyl group.

The other polyorganosiloxane may be hydrolyzed, for example, by at least one decane compound (hereinafter referred to as "raw decane compound") selected from the group consisting of water and a catalyst in a preferably suitable organic solvent. The mixture was synthesized by hydrolysis and condensation, and the group consisted of an alkoxydecane compound and a halodecane compound.

The raw material decane compound which can be used here may, for example, be a compound similar to the other decane compound in the synthesis of the above [a] organopolyoxy siloxane compound. Among these, preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, Dimethyldimethoxydecane, dimethyldiethoxydecane, trimethylmethoxydecane, trimethylethoxydecane.

In the case of synthesizing another polyorganosiloxane, examples of the organic solvent which can be used arbitrarily include an alkanol compound, a ketone compound, a guanamine compound or an ester compound or other aprotic compound. These compounds and each solvent compound may be used alone or in combination of two or more.

Examples of the alkanol compound include monoalkanol compounds such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, and third butanol; ethylene glycol; 2-propanediol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2- a polyalkanol compound such as ethyl hexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol or tripropylene glycol; ethylene glycol monomethyl 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-ethylenebutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, two Glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol single a partial ether of a polyhydric alkanol compound such as diethyl ether or dipropylene glycol monopropyl ether.

Examples of the ketone compound include monoketone compounds such as acetone, methyl ethyl ketone, methyl-n-acetone, and methyl-n-butanone; acetamidine acetone, 2,4-hexanedione, 2,4-heptanedione, and 3,5. a β-diketone compound such as heptanedione or 2,4-octanedione.

Examples of the above guanamine compound include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-di Methylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpyridylpyridinium, N-ethylidene Porphyrin, N-ethinylpiperidine, N-ethinylpyrrolidine, and the like.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl carbonate, ethyl acetate, γ-butyrolactone, γ-valerolactone, and n-propyl acetate. , isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, acetic acid 2-ethylbutyl ester, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, ethyl hydrazine carbonate, ethyl acetate, ethyl acetate Glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl acetate , propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxy triethylene glycol acetate, ethyl propionate, propionic acid Butyl ester, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, lactate B , N-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

Examples of the other aprotic compound include acetonitrile, dimethyl hydrazine, N, N, N', N'-tetraethyl sulfonamide, trimethylamine hexamethyl phosphate, and N-methyl group. Porphyrin, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylper , N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- Imidazolinone, 1,3-dimethyltetrahydro-2(1H)-pyrimidinone. Among these solvents, a polyvalent alkanol compound, a partial ether of a polyvalent alkanol compound, or an ester compound is particularly preferred.

The amount of water used in the synthesis of the other polyorganosiloxane is 1 mol, preferably 0.01 to 100 mol, more preferably 0.1 to 30 mol, based on the total of the alkoxy group and the halogen atom of the starting decane compound. Further better is 1 to 1.5 m.

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

Examples of the metal chelate compound include a trialkoxy group such as triethoxy ‧ mono(acetyl acetonate) titanium; titanium mono(acetylpyruvate); diethoxy bis (acetyl acetonate) Titanium et al., dialkyloxy bis (acetyl acetonate) titanium; monoethoxy ethoxy tris(acetylpyruvate) titanium, etc. monoalkoxy ‧ tris(acetylpyruvate) titanium; tetra (acetyl acetonate) Titanium; triethoxyl mono(ethylacetamidineacetic acid) titanium such as trialkoxy ‧ mono (ethyl acetoacetate) titanium; diethoxy ‧ bis (ethyl acetoacetate) titanium and other dioxane Oxy ‧ bis (ethyl acetonitrile ) titanium; monoethoxy octa (ethyl acetoacetic acid) titanium and other monoalkoxy ‧ tri (ethyl acetonitrile ) titanium; tetra (ethyl acetoacetic acid) Titanium; mono(acetylpyruvate) tris(ethylacetamidineacetic acid) titanium, bis(acetamidinepyruvate) bis(ethylacetamidineacetic acid) titanium, tris(acetylpyruvate) mono(ethyl acetamidine) a titanium chelate compound such as a titanium compound containing a chelating ligand such as titanium acetate; or a trialkyloxy ‧ mono(acetylpyruvyl) zirconium such as triethoxy ‧ mono(acetylpyruvyl) zirconium; Di-alkoxy bis (acetyl acetonate) zirconium such as diethoxy bis (acetyl acetonate) zirconium; monoethoxy Tris(acetylpyruvyl)zirconium monoalkoxy ‧ tris(acetylpyruvate) zirconium; tetrakis(acetonitrile pyruvate) zirconium; triethoxy ‧ mono(ethylacetamidineacetic acid) zirconium and the like Zirconium (ethyl acetoacetate) zirconium; diethoxy bis (ethyl ethanoacetic acid) zirconium and other dialkoxy bis (ethyl acetoacetate) zirconium; monoethoxy ‧ three (B Ethylene acetoacetate, zirconium, etc. monoalkoxy ‧ tris(ethyl acetoacetate) zirconium; tetrakis(ethyl acetoacetate) zirconium; mono (acetyl acetonate) tris(ethyl acetoacetate) zirconium, double Zirconium chelate such as zirconium compound containing chelating ligand, such as bis(ethylacetylacetic acid) zirconium, tris(ethylpyruvylacetate) mono(ethylacetonitrile acetic acid) zirconium or the like An aluminum chelate compound such as aluminum tris(acetate pyruvate) or aluminum tris(ethylacetonitrileacetate).

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; and aromatic acids such as salicylic acid, benzoic acid, and phthalic acid. a carboxylic acid; an aromatic sulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid; a halogen-containing carboxylic acid such as monochloroacetic acid, trichloroacetic acid or trifluoroacetic acid; citric acid, tartaric acid or the like.

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

Examples of the above organic base include pyridine, pyrrole, and piperidin. , pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyldiethanolamine, triethanolamine, dioxodicyclooctane, dioxodicyclodecane , bis-bicycloundecene, tetramethylammonium hydroxide, and the like.

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

Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred. More preferably, the metal chelate compound is a titanium chelate compound.

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, per 100 parts by mass of the starting decane compound.

The catalyst may be previously added to the decane compound as a raw material or to a solution formed by dissolving a decane compound in an organic solvent, or dissolved or dispersed in the added water.

The water added at the time of synthesis of the other polyorganosiloxane may be added intermittently or continuously to the decane compound as a raw material or in a solution formed by dissolving the decane compound in an organic solvent.

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

When the liquid crystal alignment agent contains another polymer, the content of the other polymer is preferably 10,000 parts by mass or less based on 100 parts by mass of the [A] polymer. The preferred content of other polymers may vary depending on the type of other polymer.

When the liquid crystal alignment agent is used in the [B] polymer, the total amount of the [B] polymer is preferably 100 to 5,000 parts by mass, more preferably 200, based on 100 parts by mass of the [A] polymer. ~ 3,000 parts by mass.

On the other hand, when the liquid crystal alignment agent contains other polyorganosiloxanes, the preferred ratio of the two is relative to 100 parts by mass of the [A] polymer, and the amount of other polyorganosiloxanes is 5 to 2,000. It is preferably 100 to 2,000 parts by mass.

When the liquid crystal alignment agent contains another polymer, the other polymer is preferably a [B] polymer or another polyorganosiloxane.

[hardener, hardening catalyst and hardening accelerator]

The hardener and the hardening catalyst may be contained in the liquid crystal alignment agent for the purpose of making the crosslinking reaction of the [A] polymer stronger. The hardening accelerator is contained in the liquid crystal alignment agent in order to promote the hardening reaction of the hardener.

As the curing agent, a curing agent generally used for curing may be used, including a curable composition which hardens a hardening compound having an epoxy group or a compound having an epoxy group. Examples of such a curing agent include polyamines, polycarboxylic anhydrides, and polycarboxylic acids.

Examples of the polycarboxylic acid anhydride include cyclohexane tricarboxylic anhydride and other polycarboxylic acid anhydrides.

Examples of the cyclohexane tricarboxylic anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, Cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, and the like. Examples of the other polycarboxylic acid anhydride include 4-methyltetrahydrophthalic anhydride, methyl nordecene dianhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, and phthalic anhydride. And trimellitic anhydride, a compound represented by the following formula (6), a tetracarboxylic dianhydride which is generally used for the synthesis of polyglycine, and a conjugated double bond such as α-terpinene or bellerolene. Diels-Alder reaction products of alicyclic compounds and maleic anhydride, hydrogenated products thereof and the like.

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

As the curing catalyst, for example, a ruthenium hexafluoride compound, a phosphorus hexafluoride compound, aluminum triacetate pyruvate or the like can be used. These catalysts may be catalysts for cationic polymerization of epoxy groups by heating.

Examples of the above-mentioned hardening accelerator include an imidazole compound; a quaternary phosphonium compound; a quaternary ammonium compound; and a diazepam such as 1,8-difluorenebicyclo[5.4.0]undecene-7 or an organic acid salt thereof. Alkenes; organometallic compounds such as zinc octoate, tin octylate, aluminum acetamacetone complex; boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and tin chloride; dicyandiamide; a high-melting-point-dispersion latent hardening accelerator such as an amine addition accelerator such as an amine and an epoxy resin; a microcapsule latent curing accelerator covered with a surface polymer such as a quaternary phosphonium salt; and an amine salt type potential A hardening accelerator; a high temperature dissociative thermal cationic polymerization type latent hardening accelerator such as a Lewis acid salt or a Buchhol acid salt.

[epoxy compound]

The epoxy compound may be included in the liquid crystal alignment agent in view of improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate.

As the epoxy compound, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl- 2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Alkane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,-diglycidyl-benzylamine, N,N-diglycidyl Amino-aminomethylcyclohexane.

When the liquid crystal alignment agent contains an epoxy compound, the content ratio thereof is 100 parts by mass or more, preferably 0.01 to 40 parts by mass or less, based on the total of the above [a] polyorganosiloxane compound and any other polymer used arbitrarily. It is 0.1 to 30 parts by mass.

Further, when the liquid crystal alignment agent contains an epoxy compound, it may be used in combination with a basic catalyst such as 1-benzyl-2-methylimidazole in order to make the crosslinking reaction more efficient.

[functional decane compound]

The functional decane compound can be used for the purpose of improving the adhesion between the obtained liquid crystal alignment film and the substrate. Examples of the functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyl group. Triethoxy, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Decane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-ureidopropyltrimethoxydecane, N-ethoxycarbonyl- 3-ureidopropyltriethoxy, N-triethoxycarbamidopropyltriethylamine, N-trimethoxycarbamidopropyltriethylamine, 10-trimethoxy Mercaptoalkyl-1,4,7-trioxane, 10-triethoxycarboxylidene-1,4,7-trioxane, 9-trimethoxyformamido-3,6- Dimercaptoacetate, 9-triethoxycarbamido-3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxy, N-bis(oxygen) Ethyl extended ethyl 3-aminopropyl trimethoxy Decane, N-bis(oxyethyl)-3-aminopropyltriethoxy, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl) Further, it may be a reaction product of tetracarboxylic dianhydride and a decane compound having an amine group described in JP-A-63-291922, in addition to ethyltrimethoxy decane.

When the liquid crystal alignment agent contains a functional decane compound, the content ratio 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 of the [A] polymer and any other polymer used arbitrarily.

[Surfactant]

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a polyoxyalkylene surfactant, a polyoxyalkylene surfactant, and a fluorine-containing interface. Active agent, etc.

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

<Preparation method of liquid crystal alignment agent>

As described above, the liquid crystal alignment agent contains the [A] polymer as an essential component, and may contain other optional components as necessary. However, it is preferred to dissolve the components in an organic solvent to form a solution-like composition.

As the organic solvent which can be used for the preparation of the liquid crystal alignment agent, a solvent which can dissolve the [A] polymer and other components used arbitrarily but does not react therewith is preferable. The organic solvent which can be preferably used in the liquid crystal alignment agent differs depending on the type of other polymer to be added.

When the liquid crystal alignment agent contains the [A] polymer and the [B] polymer, the above-exemplified organic solvents used in the synthesis of the polyamic acid are exemplified as preferred organic solvents. In this case, a solvent used in the synthesis of the polyamic acid of the present invention may be used in combination with a poor solvent. These organic solvents may be used singly or in combination of two or more kinds.

On the other hand, the liquid crystal alignment agent is a preferred organic solvent when the polymer contains only the [a] polyorganosiloxane compound or the [a] polyorganosiloxane compound and other polyorganosiloxane. 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, dipropylene glycol propyl ether, Dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monopentyl ether, ethylene glycol single Hexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl Carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, acetic acid second Amyl ester, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, acetic acid N-hexyl ester, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, and the like. Among these, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, dibutyl acetate, n-amyl acetate, and second amyl acetate are preferred.

The solvent to be used in the preparation of the liquid crystal alignment agent can be obtained by combining one or more of the above organic solvents depending on the presence or absence of other polymers and their types. Such a solvent is a substance which does not cause the analysis of the respective components contained in the liquid crystal alignment agent at a preferable solid concentration, and the surface tension of the liquid crystal alignment agent is controlled to be in the range of 25 to 40 mN/m.

The solid content concentration of the liquid crystal alignment agent, that is, the ratio of the total mass of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent in the liquid crystal alignment agent is selected in consideration of viscosity, volatility, etc., preferably in the range of 1 to 10% by mass. . The liquid crystal alignment agent is applied to the surface of the substrate to form a coating film composed of a liquid crystal alignment film. When the solid content concentration is 1% by mass or more, the film thickness of the coating film does not become too small, and a good liquid crystal can be obtained. Orientation film. On the other hand, when the solid content concentration is 10% by mass or less, the film thickness of the coating film can be suppressed from being excessively large, and a favorable liquid crystal alignment film can be obtained, and the viscosity of the liquid crystal alignment agent can be prevented from increasing, and the coating property can be improved. The range of the particularly preferable solid content concentration differs depending on the method used when the liquid crystal alignment agent is coated on the substrate. For example, according to the spin coating method, it is particularly preferably in the range of 1.5 to 4.5% by mass. According to the printing method, the solid content concentration is controlled in the range of 3 to 9% by mass, and the solution viscosity is particularly preferably in the range of 12 to 50 mPa·s. According to the inkjet method, the solid content concentration is controlled in the range of 1 to 5% by mass, and the solution viscosity is particularly preferably in the range of 3 to 15 mPa·s. The temperature at which the liquid crystal alignment agent is prepared is preferably from 0 ° C to 200 ° C, more preferably from 0 ° C to 40 ° C.

<Liquid crystal display element>

The driving method of the liquid crystal display device of the present invention is not particularly limited, and the present technology can be applied to various well-known methods such as TN, STN, IPS, FFS, VA (including VA-MVA method, VA-PVA method, etc.), and the like. The liquid crystal element includes the liquid crystal alignment film formed of the liquid crystal alignment agent. In general, a liquid crystal display device includes a pair of substrates in which a transparent electrode and a liquid crystal alignment film are sequentially laminated on a surface, and the pair of substrates are disposed to face each other, and a liquid crystal is filled between the pair of substrates, and the periphery is sealed with a sealant. .

<Method of Forming Liquid Crystal Alignment Film>

The liquid crystal alignment agent of the present invention can be suitably used in a liquid crystal alignment film formed by a photo-alignment method.

As a method of forming the liquid crystal alignment film, for example, a liquid crystal alignment film of the present invention is applied onto a substrate to form a coating film, and then irradiation with polarized light or unpolarized light is applied to the coating film to impart alignment ability to the liquid crystal. Method, etc.

First, the liquid crystal alignment agent of the present invention is applied on the transparent conductive film side of the substrate on which the pattern-shaped transparent conductive film is provided by a suitable coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. Next, the coated surface is prebaked, and then a coating film is formed by postbake. The preheating condition is, for example, 40 to 120 ° C for 0.1 to 5 minutes, the post heating condition is preferably 120 to 300 ° C, more preferably 150 to 250 ° C, preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-heating is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

As the substrate, for example, glass such as floating glass or soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, cyclic olefin resin or the like can be used. Transparent substrate made of plastic, etc.

As the transparent conductive film, a NESA (registered trademark) film made of SnO ₂ or an ITO film made of In ₂ O ₃ -SnO ₂ can be used. The imaging of these transparent conductive films can be carried out using a well-known method.

In the application of the liquid crystal alignment agent, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, a functional decane compound, a titanate compound or the like may be applied to the substrate and the transparent conductive film in advance.

Next, the liquid crystal alignment ability can be imparted by irradiating the coating film with radiation of linearly polarized light or partially polarized light or radiation of unpolarized light. Here, as the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferably used. When the radiation to be used is linearly polarized light or partially polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, and may be performed in a direction of inclination or in combination in order to impart a pretilt angle. When irradiating radiation of unpolarized light, the direction of irradiation must be oblique.

The irradiation amount of radiation, preferably 1J / m ² or more and less 10,000J / m ^2, more preferably 10 ~ 3,000J / m ^2. In addition, when the liquid crystal alignment ability is imparted to the coating film formed by the conventionally known liquid crystal alignment agent, the amount of radiation irradiation of 10,000 J/m ² or more is required. However, when the liquid crystal alignment agent of the present invention is used, the radiation irradiation amount in the photo-alignment method is 3,000 J/m ² or less, and further, the liquid crystal alignment ability can be imparted at 1,000 J/m ² or less, which is advantageous for lowering the liquid crystal display element. Manufacturing costs.

<Method of Manufacturing Liquid Crystal Display Element>

The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is particularly preferable when it is applied to a liquid crystal display device of a vertical alignment type to maximize the advantageous effects.

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 was formed were prepared as described above, and a liquid crystal cell was produced by disposing liquid crystal between the two substrates. For the production of the liquid crystal cell, for example, the following two methods can be employed.

In the first method, the two substrates are first disposed opposite to each other with a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portion of the two substrates is bonded by a sealant, which is divided by the surface of the substrate and the sealant. A liquid crystal cell is manufactured by filling a liquid crystal cell by filling a liquid crystal cell after filling the liquid crystal with a method of closing the injection hole.

The second method is a method called the ODF (Liquid Crystal Drop) method. It is applied to a predetermined position on the substrate of one of the two substrates forming the liquid crystal alignment film, for example, by applying an ultraviolet curable sealing material, and further, after the liquid crystal is dropped on the liquid crystal alignment film surface, another piece is bonded to the liquid crystal alignment film. The substrate is then irradiated with ultraviolet light over the entire surface of the substrate, and the liquid crystal cell is manufactured by hardening the sealant.

For any of the methods, it is desirable to gradually cool the liquid crystal cell to a temperature at which the liquid crystal is in an isotropic phase, and then slowly cool to room temperature to remove the flow alignment when the liquid crystal is filled.

Next, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Here, when the liquid crystal alignment film has a vertical alignment property, the alignment direction of the easy magnetization axes of the two substrates forming the liquid crystal alignment film is formed in a parallel manner, and the polarizing plate is attached thereto so that the polarization direction thereof and the easy axis alignment direction are At a 45° angle, it is possible to produce a liquid crystal display element having a vertical alignment type liquid crystal cell.

As the sealing agent, for example, an epoxy resin containing an alumina ball and a curing agent as a separator can be used.

As the liquid crystal, for example, a nematic liquid crystal, a matrix liquid crystal, or the like can be preferably used.

In the case of a vertical alignment type liquid crystal cell, it is preferred to use a nematic liquid crystal having a negative dielectric anisotropy, such as a dicyanobenzene liquid crystal or a ruthenium. A liquid crystal, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or the like.

Examples of the polarizing plate used on the outer side of the liquid crystal cell include a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film, or a polarizing plate composed of an H film itself, and the like. The light film is obtained by stretching polyvinyl alcohol while absorbing iodine.

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

[Examples]

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

The weight average molecular weight (Mw) of the polyorganosiloxane having an epoxy group and the [E] polyorganosiloxane compound obtained in the following examples is a converted value of polystyrene measured by the following GPC method. .

Pipe column: manufactured by Tosoh Corporation, TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf/cm ²

Further, the amount of the raw material compound and the polymer used in the following examples is required to ensure that the synthesis of the starting compound and the polymer at the synthesis scale shown in the following synthesis examples can be repeated as needed.

<Synthesis of polyorganosiloxane having an epoxy group> [Synthesis Example 1]

In a reaction vessel equipped with a stirrer, a temperature meter, a dropping funnel and a reflux condenser, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECETS) 100.0 g, methyl isobutyl ketone was added. 500 g and 10.0 g of triethylamine were mixed at room temperature. Then, 100 g of deionized water was added dropwise thereto over 30 minutes using a dropping funnel, and the mixture was reacted at 80 ° 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% by mass aqueous solution of ammonium nitrate until the water after washing was neutral, and then the solvent and water were distilled off under reduced pressure to obtain an epoxy group-containing polycondensate as a viscous transparent liquid. Organic oxirane.

The ¹ H-NMR analysis of the polyorganosiloxane having an epoxy group was carried out, and the theoretical strength was obtained according to the peak of the epoxy group in the vicinity of the chemical shift (δ) = 3.2 ppm, and it was confirmed that the epoxy group did not undergo side reaction in the reaction. . The polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 had a weight average molecular weight (Mw) of Mw = 2,200 and an epoxy equivalent of 186 g/mole.

<Synthesis of specific carboxylic acids> [Synthesis of specific carboxylic acid 1]

The specific carboxylic acid 1 was synthesized according to the following synthetic route.

[Synthesis Example 2]

In a 500 mL three-necked flask equipped with a condenser, 6.3 g of 4-cyano-4'-hydroxybiphenyl, 10 g of methyl 11-bromoundate, 14.2 g of potassium carbonate, and N,N-dimethylformamidine were added. 200 mL of the amine was heated and stirred at 160 ° C for 5 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was added to 500 mL of water and mixed and stirred. The precipitated white solid was filtered and washed with water. The obtained solid was dried under vacuum at 80 ° C to give 11 g of Compound 1.

[Synthesis Example 3]

Next, 10 g of Compound 1, 1.6 mL of lithium hydroxide ‧ monohydrate, 30 mL of methanol, and 15 mL of water were placed in a 200 mL three-necked flask equipped with a condenser, and the mixture was heated and stirred at 80 ° C for 4 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was slowly added dropwise with dilute hydrochloric acid to the reaction solution while stirring. The precipitated solid was filtered and washed successively with water and ethanol. The obtained solid was dried under vacuum at 80 ° C to obtain 8 g of the specific carboxylic acid 1.

[Synthesis of specific carboxylic acid 2]

The specific carboxylic acid 2 was synthesized according to the following synthetic route.

[Synthesis Example 4]

In a 500 mL three-necked flask equipped with a condenser, 15 g of 4-cyano-4'-hydroxybiphenyl, 13.5 g of ethylene carbonate, 2.5 g of tetrabutylammonium bromide (TBAB), and N,N-dimethylmethyl were added. 300 mL of guanamine was heated and stirred at 150 ° C for 9 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was subjected to liquid separation washing with a mixed solution of 300 mL of ethyl acetate and 100 mL of a 1N-aqueous sodium hydroxide solution. After the organic layer was taken out, the liquid separation was carried out in the order of 100 mL of a 1N-aqueous sodium hydroxide solution and 100 mL of water. After the organic layer was dried over magnesium sulfate, the organic solvent was evaporated. The obtained solid was vacuum dried, and then recrystallized from ethanol (100 mL) / hexane (250 mL) to give 13.1 g of Compound 2.

[Synthesis Example 5]

Into a 200 mL three-necked flask equipped with a condenser and a dropping funnel, 12 g of a compound 2, 12.7 g of 4-chlorobenzenesulfonyl chloride, and 60 mL of dehydrated dichloromethane were placed and mixed. In the state where the reaction solution was cooled in an ice bath, 10 mL of an anhydrous dichloromethane solution containing 6.6 g of triethylamine was added dropwise over 10 minutes. The mixture was kept in an ice bath, stirred for 30 minutes, and returned to room temperature and stirred for another 6 hours. 150 mL of chloroform was added to the reaction solution, and liquid separation was carried out 4 times with 100 mL of water. The extracted organic layer was dried over magnesium sulfate, and the organic solvent was evaporated. The obtained solid was washed with ethanol to obtain 16.1 g of Compound 3.

[Synthesis Example 6]

In a 300 mL three-necked flask equipped with a condenser, 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 and heated at 80 ° C. 9 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water and mixed and stirred. The precipitated white solid was filtered and washed with ethanol. The obtained solid was dried under vacuum at 80 ° C 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 placed in a 100 mL three-necked flask equipped with a condenser, and the mixture was stirred under heating at 80 ° C for 4 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was stirred, and dilute hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered and washed successively with water and ethanol. The obtained solid was vacuum dried at 80 ° C to obtain 9 g of a specific carboxylic acid 2.

[Synthesis of specific carboxylic acid 3]

The specific carboxylic acid 3 was synthesized according to the following synthetic route.

[Synthesis Example 8]

In Synthesis Example 2, instead of 4-cyano-4'-hydroxybiphenyl, 10.7 g of 2,3,5,6-tetrafluoro-4-(pentafluorophenyl)phenol was used to obtain 13.7 g of Compound 5.

[Synthesis Example 9]

In Synthesis Example 3, 13.5 g of the compound 5 was used instead of the compound 1, and 11.2 g of the specific carboxylic acid 3 was obtained.

[Synthesis of specific carboxylic acid 4]

The specific carboxylic acid 4 was synthesized according to the following synthetic route.

[Synthesis Example 10]

In Synthesis Example 4, instead of 4-cyano-4'-hydroxybiphenyl, 25.5 g of 2,3,5,6-tetrafluoro-4-(pentafluorophenyl)phenol was used to obtain 23.1 g of Compound 6.

[Synthesis Example 11]

In Synthesis Example 5, instead of the compound 2, 18.9 g of the compound 6 was used, and 24.1 g of the compound 7 was obtained.

[Synthesis Example 12]

In Synthesis Example 6, instead of the compound 3, 20 g of the compound 7 was used, and 15.4 g of the compound 8 was obtained.

[Synthesis Example 13]

In Synthesis Example 7, in place of Compound 4, 13 g of Compound 8 was used, and 11.4 g of a specific carboxylic acid 4 was obtained.

[Synthesis of specific carboxylic acid 5]

The specific carboxylic acid 5 was synthesized according to the following synthetic route.

[Synthesis Example 14]

As with the synthesis of the specific carboxylic acid 1, 15 g of the specific carboxylic acid 5 having a methylene group number changed from 10 to 5 was synthesized.

[Synthesis of specific carboxylic acid 6]

The specific carboxylic acid 6 was synthesized according to the following synthetic route.

[Synthesis Example 15]

2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl 10.1 g, methyl 11-bromoundecanoate 10 g, carbonic acid in a 500 mL three-necked flask equipped with a condenser Potassium 14.2 g and 200 mL of N,N-dimethylformamide were heated and stirred at 160 ° C for 5 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water and mixed and stirred. The precipitated white solid was filtered and washed with water. The obtained solid was dried under vacuum at 80 ° C to obtain 10.8 g of Compound 9.

[Synthesis Example 16]

Next, 10 g of the compound 9, 1.6 g of lithium hydroxide ‧ monohydrate, 30 mL of methanol, and 15 mL of water were placed in a 200 mL three-necked flask equipped with a condenser, and the mixture was stirred under heating at 80 ° C for 4 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. While the reaction solution was under stirring, dilute hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered and washed successively with water and ethanol. The obtained solid was vacuum dried at 80 ° C to obtain 6 g of a specific carboxylic acid 6.

[Synthesis of a specific carboxylic acid 7]

The specific carboxylic acid 7 was synthesized according to the following synthetic route.

[Synthesis Example 17]

In addition to changing the starting compound (2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) 10.1 g to the compound described in the above synthetic route (2,3-difluoro In the same manner as the above-mentioned specific carboxylic acid 6 except for 9.1 g of -4-(4-propyl-cyclohexyl)phenol), 5.9 g of the specific carboxylic acid 7 was obtained.

[Synthesis of specific carboxylic acid 8]

The specific carboxylic acid 8 was synthesized according to the following synthetic route.

[Synthesis Example 18]

In addition to changing the starting compound (2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) 10.1 g to the compound (2, 2', 3 described in the above synthetic route, In the same manner as the above specific carboxylic acid 6 except for the synthesis of the above specific carboxylic acid 6 except for the above-mentioned synthesis of the above specific carboxylic acid 6, 7.1 g of the specific carboxylic acid 8 was obtained.

[Synthesis of a specific carboxylic acid 9]

The specific carboxylic acid 9 was synthesized according to the following synthetic route.

[Synthesis Example 19]

In addition to the starting compound (2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) 10.1 g was changed to the compound described in the above synthetic route (2,3-difluoro- In the same manner as the above-mentioned specific carboxylic acid 6 except for the synthesis of the above specific carboxylic acid 6 except for the above 4-(4-propylcyclohexylmethoxy)phenol), 6.5 g of the specific carboxylic acid 9 was obtained.

[Synthesis of a specific carboxylic acid 10]

The specific carboxylic acid 10 was synthesized according to the following synthetic route.

[Synthesis Example 20]

In addition to the starting compound (2,2',3,3'-tetrafluoro-4,-propyl-4-hydroxybiphenyl) 10.1 g was changed to the compound described in the above synthetic route (2,3-difluoro- In the same manner as the above specific carboxylic acid 6 except for the synthesis of 4'-(4-propylphenylethyl)biphenyl), 7.2 g of the specific carboxylic acid 10 was obtained.

[Synthesis of Specific Carboxylic Acid 11]

The specific carboxylic acid 11 was synthesized according to the following synthetic route.

[Synthesis Example 21]

In addition to the starting compound (2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) 10.1 g, which was changed to 14.2 g of the compound described in the above synthetic route, and the above specific carboxy group In the same manner as the synthesis of the acid 6, 7.6 g of the specific carboxylic acid 11 was obtained.

[Synthesis of Specific Carboxylic Acid 12]

The specific carboxylic acid 12 was synthesized according to the following synthetic route.

[Synthesis Example 22]

In a 500 mL three-necked flask equipped with a condenser, 12.5 g of 4-[difluoro(4-pentylcyclohexyl)methoxy]-2,3-difluorophenol and 10 g of methyl 11-bromoundate were added. 14.2 g of potassium carbonate and 200 mL of N,N-dimethylformamide were heated and stirred at 160 ° C for 5 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water and mixed and stirred. The precipitated white solid was filtered and washed with water. The obtained solid was dried under vacuum at 80 ° C to obtain 14.8 g of Compound 10.

[Synthesis Example 23]

Next, 10 g of Compound 10, lithium hydroxide ‧ monohydrate 1.6 g, methanol 30 mL, and water 15 mL were placed in a 200 mL three-necked flask equipped with a condenser, and the mixture was heated and stirred at 80 ° C for 4 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. While the reaction solution was under stirring, dilute hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered, and washed with water and ethanol in that order. The obtained solid was vacuum dried at 80 ° C to obtain 6 g of a specific carboxylic acid 12.

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

The cinnamic acid derivative (A-1) was synthesized according to the following synthetic route.

[Synthesis Example 24]

In a 200 mL eggplant-shaped flask equipped with a reflux tube, 12 g of mercapto succinic anhydride, 8.2 g of 4-aminocinnamic acid, and 100 mL of acetic acid were added, and the mixture was refluxed for 2 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over magnesium sulfate, and then purified with a ruthenium dioxide column and recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 10 g of cinnamic acid derivative. White crystal of (A-1) (purity: 98.0%).

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

The cinnamic acid derivative (A-2) was synthesized according to the following synthetic route.

[Synthesis Example 25]

In a 1 L eggplant-shaped flask, 82 g of p-hydroxycinnamic acid, 304 g of potassium carbonate, and 400 mL of N-methyl-2-pyrrolidone were added, and the mixture was stirred at room temperature for 1 hour, and then 1-bromooctane 212 g was added thereto at 100 g. Stir at ° C for 5 hours. Then, the solvent was distilled off under reduced pressure. At this time, 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 the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was recovered, and recrystallized from ethanol to obtain white crystals of 80 g of the cinnamic acid derivative (A-2).

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

The cinnamic acid derivative (A-3) was synthesized according to the following synthetic route.

[Synthesis Example 26]

107 g of 4-bromocinnamic acid was refluxed in 83 g of sulfinium chloride for 4 hours to obtain a red transparent solution. Then, the unreacted sulfinium chloride was distilled off, and the residue was recrystallized from toluene and washed with n-hexane to obtain white crystals of 85 g of compound (A-3-1).

Next, 25.0 g (0.147 mol) of 4-pentylcyclohexanol was dissolved in 25 mL of pyridine. The temperature of the solution was maintained at about 3 ° C, at which time a suspension of 43.3 g (0.176 mol) of the compound (A-3-1) obtained above in 350 mL of pyridine was added dropwise, followed by a reaction for 3 hours. . The obtained reaction mixture (suspension) was poured into 1.3 kg of hydrochloric acid acidic ice water, and the resulting precipitate was filtered, washed with water, and dried to obtain 50 g of a crude product (cream powder) of the compound (A-3-2).

In a mixture of 50 g of the compound (A-3-2) obtained above, 0.28 g of palladium acetate and 1.52 g of tris(o-tolyl)phosphine, 125 mL of dry triethylamine was added under a nitrogen atmosphere. , carry out the reaction. After the crude product of the compound (A-3-2) was completely dissolved, 10.8 g of acrylic acid was injected through a syringe, and the reaction was further continued at 95 ° C for 2 hours. The dark green reaction mixture obtained was placed in 1.3 kg of hydrochloric acid acidic ice water, and separated by filtration to form a precipitate. The obtained compound was dissolved in 500 mL of ethyl acetate, and washed successively with 1N hydrochloric acid and 5% by mass of sodium hydrogen carbonate solution, and then the organic layer was collected, dried over magnesium sulfate, and the solvent was evaporated to give 56 g of cinnamic acid derivatives. Crude product (yellow solid) of (A-3). This crude product was recrystallized from ethanol to obtain 30 g of a yellow powder of cinnamic acid derivative (A-3) (yield 55%).

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

The cinnamic acid derivative (A-4) was synthesized according to the following synthetic route.

[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 added to a 1 L eggplant-shaped flask, and after stirring at room temperature for 1 hour, 1-iodo-4 was added. 157.1 g of 4,4-trifluorobutane was stirred at 100 ° C for 5 hours. After the reaction was completed, reprecipitation was carried out with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain white crystals of 110 g of Compound (A-4-1).

12.41 g of the compound (A-4-1) was taken out and placed in a reaction vessel, and 100 mL of sulfoxide chloride and 77 μL of N,N-dimethylformamide were added thereto, and the mixture was stirred at 80 ° C for 1 hour. Next, the sulfinium chloride was distilled off under reduced pressure, dichloromethane was added, and the mixture was washed with a sodium hydrogencarbonate aqueous solution, dried over magnesium sulfate, and concentrated, and then the mixture was evaporated to afford a solution.

Next, 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 in a separate 500 mL three-necked flask. The aqueous solution was ice-cooled, and the above tetrahydrofuran solution was slowly added dropwise thereto, followed by stirring for 2 hours. After completion of the reaction, the mixture was neutralized with hydrochloric acid, and ethyl acetate was extracted, dried over magnesium sulfate, and concentrated, and then recrystallized from ethanol to obtain white crystals of 10.0 g of cinnamic acid derivative (A-4).

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

The cinnamic acid derivative (A-5) was synthesized according to the following synthetic route.

[Synthesis Example 28]

In a 500 mL three-necked flask equipped with a reflux tube, a temperature meter, and a nitrogen introduction tube, 31 g of the compound (A-5-1), 0.23 g of palladium acetate, 1.2 g of tris(o-tolyl)phosphine, 56 mL of triethylamine, and acrylic acid were added. 8.2 mL and 200 mL of N,N-dimethylacetamide were stirred at 120 ° C for 3 hours to carry out a reaction. After the reaction was completed, the reaction mixture was filtered, and the organic layer obtained by adding 1 L of ethyl acetate to the obtained filtrate was washed twice with dilute hydrochloric acid and then washed three times with water, dried over magnesium sulfate, and the solvent was removed under reduced pressure. The solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of 15 g of the cinnamic acid derivative (A-5).

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

The cinnamic acid derivative (A-6) was synthesized according to the following synthetic route.

[Synthesis Example 29]

In a 500 mL three-necked flask equipped with a reflux tube, a temperature meter, and a nitrogen gas introduction tube, 28 g of the compound (A-6-1), 0.23 g of palladium acetate, 1.2 g of tris(o-tolyl)phosphine, 56 mL of triethylamine, and 8.2 of acrylic acid were added. 200 mL of mL and N,N-dimethylacetamide were stirred at 120 ° C for 3 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was filtered, and the obtained organic layer was washed twice with dilute hydrochloric acid and washed three times with water, dried over magnesium sulfate, and then evaporated. The solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of 13 g of the cinnamic acid derivative (A-6).

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

The cinnamic acid derivative (A-7) was synthesized according to the following synthetic route.

[Synthesis Example 30]

In a 500 mL three-necked flask equipped with a reflux tube, a temperature meter, and a nitrogen gas introduction tube, 34 g of the compound (A-7-1), 0.23 g of palladium acetate, 1.2 g of tris(o-tolyl)phosphine, 56 mL of triethylamine, and 8.2 of acrylic acid were added. 200 mL of mL and N,N-dimethylacetamide were stirred at 120 ° C for 3 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was filtered, and the organic layer obtained by adding 1 L of ethyl acetate to the obtained filtrate was washed twice with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and then evaporated. The solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of 14 g of the cinnamic acid derivative (A-7).

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

The cinnamic acid derivative (A-8) was synthesized according to the following synthetic route.

[Synthesis Example 31]

21 g of compound (A-8-1), 80 mL of sulfinium chloride and 0.1 mL of N,N-dimethylformamide were added to a 300 mL eggplant-shaped flask equipped with a reflux tube and a nitrogen introduction tube, and stirred at 80 ° C. The reaction was carried out for 1 hour. After completion of the reaction, sulfinium chloride was distilled off from the reaction mixture, followed by the addition of 150 mL of dichloromethane, and the obtained organic layer was washed three times with water. After the organic layer was dried over magnesium sulfate, solvent was evaporated under reduced pressure, and 400 mL of tetrahydrofuran was added to the obtained solid.

On the other hand, in a 1-L three-necked flask equipped with a dropping funnel and a temperature meter, 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 added, and the mixture was ice-cooled at 5 ° C or lower. . Here, the above tetrahydrofuran solution was added dropwise over 3 hours, and the reaction was further carried out while stirring for 1 hour. After completion of the reaction, dilute hydrochloric acid was added to the reaction mixture, and after pH 4 or less, 3 L of toluene and 1 L of tetrahydrofuran were added, and the obtained organic layer was washed three times with water. After the organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure, and the obtained solid was recrystallized from a solvent mixture of ethanol and tetrahydrofuran to obtain 21 g of cinnamic acid derivative (A-8).

<[a] Synthesis of polyorganosiloxane products> [Example 1]

9.8 g of the polyorganooxynonane having an epoxy group obtained in the above Synthesis Example 1, 28 g of methyl isobutyl ketone, and 5.0 g of the specific carboxylic acid obtained in the above Synthesis Example 3, 5.1 g, were placed in a 100 mL three-necked flask. The cinnamic acid derivative (A-1) obtained in the above Synthesis Example 24 and 0.20 g of UCAT18X (a quaternary amine salt manufactured by SANAPRO) were stirred at 80 ° C 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. After washing the solution three times, the solvent was distilled off to obtain 14.5 g of a [a] polyorganosiloxane compound as a white powder. A-1. The Mw of the polyorganosiloxane compound a-1 was 15,500.

[Examples 2 to 22]

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

In the above Table 1, the modified mass means the ratio of the specific carboxylic acid or the cinnamic acid derivative to the amount of the epoxy which the polyorganosiloxane has.

[Comparative Synthesis Example 1]

9.8 g of the polyorganosiloxane having an epoxy group obtained in the above Synthesis Example 1, 28 g of methyl isobutyl ketone, and 5.6 g of the cinnamic acid derivative obtained in the above Synthesis Example 31 were added to a 100 mL three-necked flask (A- 8) and 0.10 g of UCAT18X (a quaternary amine salt manufactured by SANAPRO), and stirred at 80 ° C for 12 hours. After completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate. After washing the solution three times, the solvent was distilled off to obtain 9.6 g of a polyorganoxane compound Ca-1 as a white powder. The Mw of Ca-1 was 9,800.

<[B] Synthesis of Polymers> <Synthesis of polylysine> [Synthesis Example 32]

19.76 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mol) 4,4' were dissolved in 367.6 g of N-methyl-2-pyrrolidone. -Diamino-2,2'-dimethylbiphenyl was reacted at room temperature for 6 hours. Next, the reaction mixture was poured into an excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried at 40 ° C for 5 hours under reduced pressure to obtain 35 g of poly phthalic acid PA-1.

[Synthesis Example 33]

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g (0.1 mol) of cyclohexane bis (329.3 g) in N-methyl-2-pyrrolidone Amine), reacted at 60 ° C for 6 hours. Next, the reactant was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 32 g of poly phthalic acid PA-2.

<Synthesis of Polyimine> [Synthesis Example 34]

17.5 g of the polyamic acid PA-2 obtained in the above Synthesis Example 33 was added, and 232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine, and 4.9 g of acetic anhydride were added thereto, and reacted at 120 ° C for 4 hours. , carrying out hydrazine imidization. Next, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure for 15 hr to afford 15 g of polyimine.

[Synthesis Example 35]

18.75 g (0.0836 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 7.359 g (0.0681 mol) dissolved in 140 g of N-methyl-2-pyrrolidone As the diamine compound, p-phenylenediamine, 8.895 g (0.0170 mol) of 3,5-diaminobenzoic acid = 5 ξ-cholest-3-yl group was reacted at 60 ° C for 5 hours. The viscosity of the polymerization solution was measured and found to be 2000 mPa·s. Next, 325 g of N-methyl-2-pyrrolidone was added to the solution, and after stirring for a while, 6.61 g of pyridine and 8.54 g of acetic anhydride were added, and dehydration ring closure was carried out at 110 ° C for 4 hours. Then, the reaction solution was poured into an excessive amount of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 °C for 15 hours to obtain 26.6 g of polyimine PI-2 having a ruthenium iodide ratio of 51%.

<Preparation of liquid crystal alignment agent> [Example 23]

In the solution containing the poly-proline acid PA-1 obtained in Synthesis Example 32, [a] polyorganosiloxane compound a was added in an amount corresponding to 1,000 parts by mass of the polyamic acid PA-1 contained therein. -1 (100 parts by mass), further adding N-methyl-2-pyrrolidone and butyl cellosolve to prepare a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 ( A mass ratio) of 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 μm to prepare a liquid crystal alignment agent (S-1).

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

As a combination of polyamine or polyiminamide of [B] polymer and [a] polyorganosiloxane compound as described in Table 2, a liquid crystal alignment agent S- was prepared in the same manner as in Example 23. 2~S-32 and CS-1 and CS-2.

<Formation of liquid crystal alignment film>

The liquid crystal alignment agent prepared in the above Example was applied onto the transparent electrode surface of the glass substrate having the transparent electrode made of the ITO film by a spinner, and preheated on a hot plate at 80 ° C for 1 minute. The inside of the incubator which was replaced with nitrogen was heated at 200 ° C for 1 hour to form a coating film having a film thickness of 0.08 μm. Next, a Hg-Xe lamp and a Glan-Taylor prism polarizer were used for the surface of the coating film, and polarized ultraviolet rays (200 J/m ² ) containing a bright line of 313 nm were irradiated in a direction inclined by 40° with respect to the normal direction of the substrate. Liquid crystal alignment film. The same operation was repeated to produce a pair of (two pieces) substrates on which the liquid crystal alignment film was formed.

<Manufacture of liquid crystal display element>

A liquid crystal alignment film of a pair of substrates is formed by screen-printing an epoxy resin adhesive having a diameter of 3.5 μm on a peripheral surface of a substrate on which one of the liquid crystal alignment films is formed by a liquid crystal alignment film. The surface was pressed against the projection direction of the substrate surface of the ultraviolet light axis of each substrate so as to be opposite to each other, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (manufactured by Merck, MLC-6608) was filled in the gap between the substrates by a liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow alignment during liquid crystal injection, it was heated to 150 ° C and then slowly cooled to room temperature. Next, a polarizing plate was bonded to both outer surfaces of the substrate so that the polarization directions of the polarizing plates were perpendicular to each other, and the liquid crystal display element was manufactured at an angle of 45° with respect to the projection direction of the substrate surface of the ultraviolet light axis of the liquid crystal alignment film.

[Example 55]

The liquid crystal alignment agent (S-15) prepared in the above Example 37 was applied onto the transparent electrode surface of the glass substrate provided with the transparent electrode made of the ITO film, and preheated for 1 hour on a hot plate at 80 ° C. Thereafter, the film was heated at 200 ° C for 1 hour in an oven substituted with nitrogen gas to form a coating film having a film thickness of 0.08 μm, and the same operation was repeated to prepare a pair of (two pieces) substrates having a liquid crystal alignment film. For one of the substrates, a polarized ultraviolet ray (200 J/m ² ) containing a 313 nm bright line was irradiated on the surface of the coating film using a Hg-Xe lamp and a Glan-Taylor prism in a direction inclined by 40° along the normal line of the substrate. Then, on the outer periphery of the surface on which the polarized light UV is irradiated with the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 3.5 μm is coated by a screen printing method, and the other pair of substrates is irradiated. The liquid crystal alignment film surface of the light UV was pressed against each other, and the adhesive was thermally hardened at 150 ° C for 1 hour. Next, a negative liquid crystal (manufactured by Merck, MLC-6608) was filled in the gap between the substrates by a liquid crystal injection port, and then the liquid crystal injection port was closed with an epoxy adhesive. Further, in order to remove the flow alignment during liquid crystal injection, it was heated to 150 ° C and then slowly cooled to room temperature. Next, a polarizing plate is bonded to both outer surfaces of the substrate so that the polarizing directions of the polarizing plates are perpendicular to each other, and the liquid crystal display element is manufactured at an angle of 45° with respect to the projection direction of the substrate surface of the ultraviolet light axis of the liquid crystal alignment film. .

[Example 56]

N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane 20 was added to 100 parts by mass of the polyimine imine PI-2 obtained in the above Synthesis Example 35, respectively. The mass fraction and the solvent composition are N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (mass ratio) of N-methyl-2-pyrrolidone and butyl cellosolve, and the solid concentration is 3.5% by mass of the solution. This solution was filtered with a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent S-33.

On the transparent electrode surface of the glass substrate having the ITO film imaged in the slit shape as shown in FIG. 1, the liquid crystal alignment agent (S-33) prepared above was applied by a spinner, and was preliminarily prepared on a hot plate at 80 ° C. After heating for 1 minute, it was heated at 200 ° C for 1 hour in an incubator which was internally purged with nitrogen to form a coating film having a film thickness of 0.08 μm.

Next, the liquid crystal alignment agent (S-15) prepared in the above Example 37 was applied by a spinner on the transparent electrode surface of the glass substrate having the ITO film imaged in the slit shape shown in Fig. 1, at 80 °C. After preheating for 1 minute on a hot plate, it was heated at 200 ° C for 1 hour in an oven which was replaced with nitrogen gas to form a coating film having a film thickness of 0.08 μm. On the outer periphery of the liquid crystal alignment film of the substrate, an epoxy resin adhesive having a diameter of 3.5 μm is applied by screen printing, and the liquid crystal alignment of the other pair of substrates (which is not irradiated with polarized light UV) is applied. The film surface was pressed against each other and the adhesive was thermally hardened at 150 ° C for 1 hour. Next, a negative liquid crystal (manufactured by Merck, MLC-6608) was filled in the gap between the substrates by a liquid crystal injection port, and then the liquid crystal injection port was closed with an epoxy adhesive. Further, in order to remove the flow alignment during liquid crystal injection, it was heated to 150 ° C and then slowly cooled to room temperature. Then, the liquid crystal cell manufactured by applying the AC voltage of 10 V was irradiated with light of 50,000 J/m ² using a halogen lamp, and then a polarizing plate was attached to both outer surfaces of the unit substrate so that the polarization direction of the polarizing plate was made. The liquid crystal display element was manufactured to be perpendicular to each other and at an angle of 45 to the projection direction of the substrate surface of the optical axis when irradiated with polarized light UV.

[Comparative Example 3]

Using the components shown in the following Table 2 ("-" in Table 2 indicates that the component was not used), the liquid crystal alignment agent CS-3 prepared in the same manner as in Example 23 was applied by a spinner to a transparent electrode made of an ITO film. The transparent electrode surface of the glass substrate was preheated on a hot plate at 80 ° C for 1 minute, and then heated at 200 ° C for 1 hour in an incubator substituted with nitrogen to remove the solvent to form a coating film having a film thickness of 0.08 μm. (Liquid crystal alignment film). This operation was repeated to produce a pair of (two pieces) substrates having a liquid crystal alignment film.

On the outer periphery of the surface of the substrate having the liquid crystal alignment film, the epoxy resin adhesive having a diameter of 3.5 μm is applied by screen printing, and then the liquid crystal alignment film surfaces of the pair of substrates are pressed against each other. Heating at 150 ° C for 1 hour, heat hardening the adhesive. Next, a liquid crystal injection port is filled with a negative liquid crystal (manufactured by Merck, MLC-6608) to the gap of the substrate, and then the liquid crystal injection port is sealed with an epoxy adhesive, and further, in order to remove the flow alignment during liquid crystal injection, it is 150 ° C. After heating for 10 minutes, it was slowly cooled to room temperature.

Further, a polarizing plate is attached to both outer surfaces of the substrate so that the polarization directions of the two polarizing plates are perpendicular to each other, thereby manufacturing a liquid crystal display element.

<evaluation>

The liquid crystal display element manufactured using the liquid crystal alignment agent of the above examples was subjected to the following evaluation. The results are shown together in Table 2. Further, in Example 56, since the pattern electrode substrate was used, the voltage holding ratio and the light resistance were not measured.

[Voltage Retention Rate (VHR (%))]

On the liquid crystal display element manufactured above, a voltage of 5 V was applied with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from the release of the application was measured. The measuring device used VHR-1 manufactured by Dongyang Technica.

[light resistance]

In the meteorological instrument using a carbon arc as a light source, the same measurement as described above was performed on the VHR after 3,000 hours of irradiation (after applying a voltage of 5 V with an application time of 60 μsec and a span of 167 msec, the measurement was 167 msec after the release of the application. The voltage holding rate of the measuring device is VHR-1) manufactured by Toyo Technica, and the amount of change in VHR is 1% or less as compared with the measured value before irradiation, and is more than 1% and less than 3%. For "△", 3% or more is marked as "╳".

[Response speed (electro-optic responsiveness at the beginning)]

The start time of the liquid crystal response was measured by a device including a polarizing microscope, a photodetector, and a pulse generator. Here, the liquid crystal response speed is defined as a time period in which a voltage is applied to the manufactured liquid crystal display element to a voltage of 4 V from a state where no voltage is applied for a maximum of one second. The time (in milliseconds) required to change the rate from 10% to 90%.

In the above Table 2, the polyorganosiloxane is represented by a mixing amount (parts by mass) with respect to 100 parts by mass of the [B] polymer.

As is clear from the results of Table 2, the liquid crystal display element including the liquid crystal alignment film formed of the liquid crystal alignment agent of the example was excellent in light resistance, and the response speed of the liquid crystal was higher than that of the liquid crystal display element of the comparative example.

[Industry use possibility]

The liquid crystal alignment agent of the present invention can be suitably used for producing a liquid crystal display element which can satisfy not only a generally required voltage holding ratio and light resistance but also a short photoelectric response time. Further, the organopolysiloxane compound of the present invention can be suitably used as a raw material of the liquid crystal alignment agent.

1. . . ITO electrode

2. . . Slit portion

3. . . Sunscreen

Fig. 1 is a view showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film produced in Examples.

Claims (9)

A liquid crystal alignment agent containing [A] a polymer having a photo-alignment group and a group represented by the following formula (A1) (but not including a photo-alignment group), In the formula (A1), R ^A is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenyl group or a cyclohexylene group, and some or all of 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, and R ^C is a group having at least two monocyclic structures, and a is 0 or 1. The liquid crystal alignment agent of the first aspect of the invention, wherein the photo-alignment group has a structure represented by the following formula (B1), In the formula (B1), R is a fluorine atom or a cyano group, and 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, and * represents a linkage. The liquid crystal alignment agent of claim 1, wherein R ^C in the above formula (A1) is represented by the following formula (A2), In the formula (A2), R ^D is a phenyl group, a biphenyl group, a naphthyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylphenyl group or a divalent heterocyclic group, and these groups have a hydrogen atom. Some or all of them may be substituted, and R ^E is 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. a linking group, R ^F is a (c+1) valence of (c+1) hydrogen atoms removed from benzene, biphenyl, naphthalene, cyclohexane, dicyclohexane, cyclohexylbenzene or a heterocyclic compound a group having a part or all of a hydrogen atom which may be substituted, and R ^G is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, or a trifluoromethyl group. Oxy or alkylcarbonyloxy, b is 0 or 1, c is an integer from 1 to 9, d is 1 or 2, and when R ^D , R ^E , R ^G and b are each plural, plural R ^D , R ^E , R ^G and b may be the same or different from each other. The liquid crystal alignment agent of claim 1, wherein the [A] polymer has a polyorganosiloxane structure. The liquid crystal alignment agent according to any one of claims 1 to 4, further comprising [B] at least one polymer selected from the group consisting of polyproline and polyimine. A liquid crystal display element comprising a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 5. The liquid crystal display element of claim 6, wherein the liquid crystal alignment film has two or more regions having different alignment positions. A liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of claims 1 to 5. A polyorganosiloxane compound having a photo-alignment group and a group represented by the following formula (A1) (but not including a photo-alignment group), In the formula (A1), R ^A is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenyl group or a cyclohexylene group, and some or all of 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, and R ^C is a group having at least two monocyclic structures, and a is 0 or 1.