KR101787445B1 - Liquid crystal aligning agent, liquid crystal display device and its manufacturing method - Google Patents

Abstract

(식 (1) 중, R¹은 적어도 2개의 단환 구조를 갖는 기이고; R²는 이중 결합, 삼중 결합, 에테르 결합, 에스테르 결합 또는 산소 원자를 포함하는 연결기이고; a는 0∼1의 정수임).[PROBLEMS] To provide a liquid crystal aligning agent capable of forming a PSA type liquid crystal display element having excellent properties such as high-speed response, a PSA type liquid crystal display element having a liquid crystal alignment film formed of the liquid crystal aligning agent, And a method thereof.
(A) a liquid crystal aligning agent for forming a liquid crystal alignment film in a liquid crystal display element of a PSA system, characterized by comprising a compound having a group represented by the following formula (1).

(Wherein R ¹ is a group having at least two monocyclic structures; R ² is a linking group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom; a is an integer of 0 to 1 ).

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal display element, and a method of manufacturing the same. BACKGROUND ART [0002] Liquid crystal display devices,

The present invention relates to a liquid crystal aligning agent, a liquid crystal display element, and a method for producing a liquid crystal display element.

In recent years, liquid crystal display devices have advantages such as low power consumption, small size, and easy flattening. Therefore, they are widely used in a wide range of applications, from small liquid crystal display devices such as cellular phones to large screen liquid crystal display devices such as liquid crystal televisions .

(Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and the like are used as driving modes of liquid crystal display devices in accordance with changes in the orientation Are known. In addition, in the VA mode, a multi-domain vertical alignment (MVA) method or a patterned vertical alignment (PVA) method is employed in order to increase the viewing angle by the alignment division. Further, , The adoption of PSA (Polymer Sustained Aligmentent) method has been studied.

In this PSA method, a monomer capable of being polymerized by light or heat is mixed in a liquid crystal, and a voltage is applied to polymerize the monomer in a state where the liquid crystal molecules are inclined (Japanese Patent Application Laid-Open -357830, JP-A-2003-307720, and JP-A-2003-177418). In the liquid crystal display element using the PSA method, for example, since the liquid crystal molecules are supported in an inclined state very slightly with respect to the substrate interface, the liquid crystal molecules can surely fall down in the oblique direction upon application of a voltage, As a result, the response speed is fast.

The alignment state of the liquid crystal molecules in the liquid crystal display element is controlled by the liquid crystal alignment film, and the liquid crystal alignment film takes charge of the control of the functional characteristics of the liquid crystal display element with considerable weight. Also in the PSA system, a liquid crystal display device which defines the composition of a liquid crystal aligning agent used for forming this liquid crystal alignment film has been developed (JP-A-2006-215326) It is required to further improve the performance of the display device.

Japanese Patent Application Laid-Open No. 2002-357830 Japanese Patent Application Laid-Open No. 2003-307720 Japanese Patent Application Laid-Open No. 2003-177418 Japanese Laid-Open Patent Publication No. 2006-215326

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-described circumstances, and has as its object to provide a liquid crystal aligning agent capable of forming a liquid crystal display element of a PSA system excellent in properties such as high speed response and the like, a PSA Type liquid crystal display element and a method of manufacturing such a liquid crystal display element.

According to an aspect of the present invention,

As a liquid crystal aligning agent for forming a liquid crystal alignment film in a PSA type liquid crystal display element,

[A] A compound having a group represented by the following formula (1) (hereinafter also referred to as "[A] compound").

(Wherein R ¹ is a group having at least two monocyclic structures; R ² is a linking group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom; a is an integer of 0 to 1 )

The liquid crystal aligning agent contains the [A] compound having the group having the dielectric anisotropy, and has excellent alignment controllability of the liquid crystal molecules. Therefore, the liquid crystal display element of the PSA system including the liquid crystal alignment film formed using the liquid crystal aligning agent has good orientation of the liquid crystal molecules, and the response time can be shortened.

The compound [A]

A part derived from a polyorganosiloxane having an epoxy group,

(Hereinafter also referred to as " specific carbonic acid ") represented by the following formula (2).

(Wherein R ¹ , R ² and a have the same meanings as in the formula (1), R ³ is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group, Group may further have a substituent).

According to the liquid crystal aligning agent, the structure having the dielectric anisotropy represented by the formula (1) as a side chain can be easily introduced into the polyorganosiloxane as the main chain as the [A] compound by utilizing the reactivity between the epoxy group and the carboxyl group have. Therefore, the liquid crystal aligning agent can impart high-speed responsiveness to the obtained liquid crystal display element effectively.

Provided that R ¹ is a group represented by the following formula (3).

(Wherein R ⁴ 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, R ⁵ is benzene, (B + 1) -valent groups other than (b + 1) hydrogen atoms from biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or a heterocyclic compound, these groups may further have substituents; ⁶ is a methylene group, an alkylene group, a double bond having 2 to 10 carbon atoms, a linking group containing any of a triple bond, an ether bond, an ester bond, and a heterocyclic ring, these groups may further have a substituent; R ⁷ are each independently A biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle, these groups may further have a substituent; Is an integer of 9; b is 2 or more, a plurality of R ⁴ may be the same or different is; c is an integer from 0 to 1 and; d is an integer from 1 to 2, and; if d is 2, a plurality of R ⁶ And R ⁷ may be the same or different.

By introducing the structure represented by the formula (3) into the [A] compound of the liquid crystal aligning agent, the responsiveness of the resulting liquid crystal display element can be further increased.

The epoxy group may be a group represented by the following formula (X ¹ -1) or (X ¹ -2).

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

In formula (X ¹ -2), j is an integer of 0 to 6).

The group represented by the formula (1) is easily introduced into the [A] compound of the liquid crystal aligning agent by including the group represented by the formula (X ¹ -1) or (X ¹ -2) in the polyorganosiloxane .

The liquid crystal aligning agent may further contain at least one polymer selected from the group consisting of [B] polyamic acid and polyimide (hereinafter also referred to as " [B] polymer "). [B] When a liquid crystal alignment film is formed using a liquid crystal aligning agent containing a polymer, a liquid crystal display device with improved high-speed response can be obtained.

The liquid crystal display element of the present invention is a PSA type liquid crystal display element having a liquid crystal alignment film formed from the liquid crystal aligning agent. According to the liquid crystal display element, since the liquid crystal alignment film is formed of the liquid crystal alignment agent, the liquid crystal alignment property is high and excellent high-speed response can be exhibited.

In the method of manufacturing a liquid crystal display element of the present invention,

A step of forming a liquid crystal alignment film on each inner surface of a pair of substrates having transparent electrodes by the liquid crystal aligning agent,

A step of arranging the pair of substrates so as to face each other with their inner surfaces facing each other, filling the polymerizable liquid crystal composition between the substrates,

A step of curing the polymerizable liquid crystal composition with a voltage applied thereto

Of the liquid crystal display element of the PSA type.

According to this manufacturing method, since the liquid crystal alignment film is formed of the liquid crystal aligning agent, a liquid crystal display device of the PSA type having a high liquid crystal alignment property and excellent high-speed response can be produced.

INDUSTRIAL APPLICABILITY As described above, according to the liquid crystal aligning agent of the present invention, it is possible to form a liquid crystal display element of a PSA system excellent in properties such as high-speed response. Further, the liquid crystal display element of the present invention can exhibit high response and the like as a PSA type device. According to the manufacturing method of the present invention, it is possible to manufacture a liquid crystal display element of the PSA system with high responsiveness and the like.

1 is a schematic cross-sectional view showing a liquid crystal display element according to an embodiment of the present invention.
2 is a schematic cross-sectional view showing a liquid crystal display element according to a different embodiment from the liquid crystal display element of FIG.
3 is a schematic view of the liquid crystal display element manufactured in the embodiment.

(Mode for carrying out the invention)

Hereinafter, embodiments of the liquid crystal aligning agent, liquid crystal display element and liquid crystal display element of the present invention will be described in detail.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is characterized by containing a [A] compound as a liquid crystal aligning agent for forming a liquid crystal alignment film in a PSA type liquid crystal display device. Further, the liquid crystal aligning agent may contain "other polymer" described later such as [B] polymer. The liquid crystal aligning agent may contain other optional components within the range not to impair the effect of the present invention. Each component will be described in detail below.

<[A] compound>

The [A] compound is a compound having a group represented by the above formula (1). The group represented by the formula (1) has dielectric anisotropy, and the liquid crystal aligning agent containing the [A] compound has excellent alignment controllability of the liquid crystal molecules. Therefore, the liquid crystal display element of the PSA system including the liquid crystal alignment film formed using the liquid crystal aligning agent has good orientation of the liquid crystal molecules, and the response time can be shortened.

In the formula (1), R ¹ is a group having at least two monocyclic structures, and preferably exhibits positive or negative dielectric anisotropy. The monocyclic structure is a structure which does not have a so-called condensed ring structure in which one cyclic structure exists independently from other cyclic structures and one cyclic structure is shared with other cyclic structures. As the monocyclic structure, any of an alicyclic structure, an aromatic cyclic structure and a heterocyclic structure may be used, or a combination thereof may be used.

R ¹ is not particularly limited as long as it is a group having at least two monocyclic structures, and typically, R ¹ is preferably a group represented by the formula (3). By introducing the structure represented by the formula (3) into the side chain of the [A] compound of the liquid crystal aligning agent, the electro-optical responsiveness of the obtained liquid crystal aligning element can be further increased.

In the formula (3), R ⁴ is any of a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group and an alkylcarbonyloxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group and a propoxycarbonyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group and an isobutyl group, Examples of the alkoxy group such as a straight chain or branched chain alkyl group having 1 to 20 carbon atoms include methylcarbonyloxy group and ethylcarbonyloxy group as the alkylcarbonyloxy group such as methoxy group, ethoxy group and propoxy group, .

In the above formula (3), when there are a plurality of R ⁴ , different ones may be used in combination. As a combination of a plurality of R ^{4 s} , a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, and a combination of a cyano group and an alkyl group are preferable in order to stably express the desired dielectric anisotropy. B is an integer of 0 to 9;

In the above formula (3), R ⁵ represents (b + 1) -valent (b + 1) hydrogen atoms other than (b + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or heterocyclic compound Group, and these groups may further have a substituent. Examples of the heterocyclic compound include pyridine, pyridazine, and pyrimidine.

In the formula (3), R ⁶ is a methylene group, an alkylene group, a double bond having 2 to 10 carbon atoms, a triple bond, an ether bond, connect, R ⁵ and R ^7, which comprises any one of an ester bond and a heterocyclic , And these groups (alkylene group or heterocycle) may further have a substituent. Examples of R ⁶ include a methanediyl group, an ethanediyl group, a propanediyl group, an ethanediyl group, an ethynediyl group, an ether group, an ester group, a methanediyloxy group, an ethanedioxy group, a fluoromethanedioxy group, Methanedioxy group and the like. Among them, an ethanediyl group, an ethynediyl group, an ester group, a methanediyloxy group, and a difluoromethanediyloxy group are preferable. [A] can be appropriately selected in accordance with the orientation and induced anisotropy required for the compound. Since c is an integer of 0 or 1, R ⁶ may or may not be included.

In the above formula (3), each R ⁷ independently represents a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle. Examples of the heterocyclic ring include a pyridine ring, a pyridazine ring, and a pyrimidine ring.

In the formula (3), d is an integer of 1 to 2. When d is 2, plural R &lt; ⁶ &gt; and R &lt; ⁷ &gt; May be the same or different from each other.

Examples of the group represented by the formula (3) include groups represented by the following formulas (D-1) to (D-123).

In the formulas (D-1) to (D-123), R represents an alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, n- butyl group, isobutyl group, n- Or an alkoxy group having 1 to 20 carbon atoms (methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, etc.). Each X independently represents a hydrogen atom or a fluorine atom.

In the above formula (1), R ² is a linking group containing any of a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom. R ² may contain any of the above bonds, but may contain a combination of these bonds. Examples of R ² include an etendiyl group, an ethynediyl group, an ester group, a methanediyloxy group, a fluoromethanediyloxy group, and a difluoromethanediyloxy group. When R ³ described below is a phenylene group or a cyclohexylene group, it is preferable that R ² includes an alkylene group having 1 to 30 carbon atoms, from the viewpoint of the orientation of the formed alignment film and the solubility in a solvent. Also, a is an integer of 0 to 1.

The compound [A] is not particularly limited as long as it has a group represented by the above formula (1), but is preferably a polymer having a group represented by the formula (1) in its side chain, and a polyorganosiloxane, a polyimide, It is more preferable in view of electrical properties that the main chain structure of poly (meth) acrylate, poly (styrene phenyl maleimide) derivative, cellulose derivative, polyester, polyamide, polystyrene derivative and poly It is more preferable that the organosiloxane has a backbone structure.

The compound [A] having a polyorganosiloxane as a main chain structure is preferably a compound having a part derived from a polyorganosiloxane having an epoxy group and a part derived from a specific carbonic acid represented by the formula (2). A liquid crystal display device comprising a liquid crystal alignment film formed using the liquid crystal aligning agent and having a structure having dielectric anisotropy introduced into the side chain by having the specific structural unit of the [A] compound in the liquid crystal aligning agent, Is shortened. Further, by utilizing the reactivity between the epoxy group and the carboxyl group, a structure having the dielectric anisotropy represented by the above formula (1) as a side chain can be easily introduced into the polyorganosiloxane as a main chain.

When the compound [A] has a part derived from a polyorganosiloxane having an epoxy group and a part derived from the specific carbonic acid, a reaction product of an epoxy group of a polyorganosiloxane and a carboxyl group of a specific carboxylic acid In order to facilitate the following explanation, the [A] compound is divided into a part derived from a polyorganosiloxane (and a derivative thereof) having an epoxy group for convenience and a part derived from a specific carbon acid.

[Parts derived from a polyorganosiloxane having an epoxy group]

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

When the [A] compound has an epoxy group such as a glycidyl group, a glycidyloxy group or a group containing an epoxycyclohexyl group, the liquid crystal aligning agent improves electrical properties such as orientation and fast response. The epoxy group is preferably a group represented by the formula (X ¹ -1) or (X ¹ -2). Introducing a group represented by the formula (1) into the side chain using a specific carbonic acid in the [A] compound by including in the polyorganosiloxane a group represented by the formula (X ¹ -1) or (X ¹ -2) It gets easier.

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

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

[Method of synthesizing polyorganosiloxane having epoxy group]

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

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

As other silane compounds, for example,

As a compound having one silicon atom,

Having four hydrolysable groups,

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

As having three hydrolyzable groups,

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

As having two hydrolyzable groups,

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

Having one hydrolyzable group,

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

As a commercially available product, for example,

KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X- X-22-170B, X-22-170D, X-22-170DX, X-22-176B, X-22-170B, X- 22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X- X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, KR-212, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, K56002, KF6003, KR- KR5230, KR5235, KR9218, KR9706 (all, Shin-Etsu Chemical Co., Ltd.);

GLASS RESIN (manufactured by Showa Denko K.K.);

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

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

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

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

Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, Kolkot K.K.);

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

Among these silane compounds, from the viewpoints of orientation and storage stability of the obtained liquid crystal aligning agent, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltri (Meth) acrylates such as methoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane are preferable Do.

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

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

Examples of the hydrocarbons include toluene, xylene and the like; Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and the like; Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; As the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; Examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Of these, non-water-soluble ones are preferable. These organic solvents may be used alone or in combination of two or more.

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

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

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

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

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

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used varies depending on the kind of the organic base, the reaction conditions such as the temperature, and the like, and is appropriately set. For example, it is preferably 0.01 to 3 times by mole, more preferably 0.05 It is ~ 1x mall.

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

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

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. Is washed with water containing 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 washing is carried out until the water layer after the washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain a polyorganosiloxane having a desired epoxy group Siloxane can be obtained.

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

The [A] compound is a compound derived from a hydrolyzate produced by hydrolysis of an epoxy group-containing polyorganosiloxane per se, or a part derived from a hydrolyzed condensation product in which polyorganosiloxanes having an epoxy group are hydrolyzed and condensed with each other May be included. These hydrolysates and hydrolyzed condensates which are constituent materials of this part can also be prepared in the same manner as the hydrolysis and condensation conditions of the polyorganosiloxane having an epoxy group.

[Part derived from a specific carbon acid]

This portion derived from the specific carbonic acid represented by the formula (2) is bonded to a structure derived from an epoxy group mainly extending from the main chain of the polyorganosiloxane in the structure of the [A] compound contained in the liquid crystal aligning agent Chain structure having a structure derived from a carboxyl group as a starting point. However, in the present invention, the term &quot; a part derived from a specific carbonic acid &quot; is also referred to as &quot; a part derived from a specific carbonic acid &quot; including a case where a specific carbonic acid bonds to a part other than an epoxy group.

In the formula (2), R ¹ and R ² are the same meanings as R ¹ and R ² in the aforementioned formula (1).

R ³ in the formula (2) is a methylene group or an alkylene group, a phenylene group or a cyclohexylene group having 2 to 30 carbon atoms, which may further have a substituent.

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

Examples of the compound having a carboxyl group represented by the formula (2) include compounds represented by the following formulas (E-1) to (E-25).

In formulas (E-1) to (E-25), R ¹ has the same meaning as in formula (2). m is an integer of 1 to 30;

[Method for synthesizing a specific carbon acid]

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

&Lt; Synthesis method of [A] compound &gt;

The method for synthesizing the [A] compound is not particularly limited and can be synthesized by a generally known method. When the [A] compound has a part derived from a polyorganosiloxane having an epoxy group and a part derived from a specific carbonic acid, the polyorganosiloxane having an epoxy group and the specific carbonic acid are preferably reacted in the presence of a catalyst And the like.

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

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

In the above formula (4)

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

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

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

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

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

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

Z is preferably a carboxyl group.

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

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

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

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

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

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

Of these compounds, compounds represented by the following formulas (4-7) to (4-13) are more preferable.

　

　

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

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

As the catalyst used in the reaction of the epoxy group in the polyorganosiloxane with other pretilt angle-expressing compound, a known compound as a so-called curing accelerator which promotes the reaction of an organic base or an epoxy compound with an acid anhydride can be used .

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

As the curing accelerator, for example,

Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine and triethanolamine;

2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) 1- (2-cyanoethyl) -2-n-octylimidazole, 1- (2-cyanoethyl) 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- (2-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate (2- cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- (2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s - triazine, 2 , Isocyanuric acid adduct of 4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl- An isocyanuric acid adduct of phenylimidazole, an isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s- Imidazole compounds;

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

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

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

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

Boron compounds such as boron trichloride and triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

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

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

Amine salt type latent curing accelerator;

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

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

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

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

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

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

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

<Optional ingredients>

The liquid crystal aligning agent may contain, in addition to the above-mentioned [A] compound, a polymer other than the [A] compound (hereinafter sometimes referred to as "other polymer"), a curing agent, A catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule (hereinafter sometimes referred to as an &quot; epoxy compound &quot;), a functional silane compound, and a surfactant.

[Other Polymers]

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

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

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

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

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

<[B] Polymer>

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

[Polyamic acid]

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

Examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic acid dianhydride. These tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

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

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

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride and the like, and tetracarboxylic dianhydrides described in JP-A-2010-97188.

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

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

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

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

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

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

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

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

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

The synthesis reaction is preferably carried out in an organic solvent. The reaction temperature is preferably -20 占 폚 to 150 占 폚, more preferably 0 占 폚 to 100 占 폚. The reaction time is preferably 0.5 hours to 24 hours, more preferably 2 hours to 12 hours.

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

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

The polyamic acid solution obtained after the reaction may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent. After the isolated polyamic acid is purified, It may be provided in the preparation of the article. Examples of the method of isolating the polyamic acid include a method of drying a precipitate obtained by pouring the reaction solution into a large amount of a poor solvent under reduced pressure, and a method of distilling off the reaction solution under reduced pressure using an expander. Examples of the method for purifying polyamic acid include a method in which an isolated polyamic acid is dissolved again in an organic solvent and then precipitated with a poor solvent, and a method in which a step of distilling off an organic solvent or the like under reduced pressure is carried out once or plural times have.

[Polyimide]

The polyimide can be produced by dehydrating and cyclizing the arid acid structure of the polyamic acid to imidize it. The polyimide may be a completely imide cargo which is subjected to dehydration ring closure of all of the arboric acid structure possessed by the polyamic acid which is the precursor thereof. The polyimide may be a partially imide cargo having only a part of the arboric acid structure, .

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

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

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

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

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

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

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

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

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

In the method (ii), a reaction solution containing polyimide is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, after the dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, the reaction solution may be supplied to the preparation of the liquid crystal aligning agent. After the polyimide is isolated, Or may be provided in the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. Examples of the method for removing the dehydrating agent and the dehydration cyclization catalyst from the reaction solution include a method of solvent substitution. Examples of the polyimide isolation and purification methods include the same methods as those exemplified as the polyamic acid isolation and purification methods.

[Other polyorganosiloxane]

The liquid crystal aligning agent may contain other polyorganosiloxane in addition to the [A] compound containing a moiety derived from the polyorganosiloxane. The other polyorganosiloxane is preferably at least one selected from the group consisting of a polyorganosiloxane represented by the formula (5), a hydrolyzate thereof and a condensate of the hydrolyzate thereof. When the liquid crystal aligning agent contains other polyorganosiloxane, most of the other polyorganosiloxanes are present independently of the [A] compound, and some of them are condensed with the [A] compound It may be present.

In X ¹ and Y ¹ in the formula (5)

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

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

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

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

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

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

As the alcohol compound, for example,

Propanol, n-butanol, i-butanol, sec-butanol, t-butanol, Butanol, 2-ethylhexanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol sec-octadecyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, n-octanol, n-nonyl alcohol, 2,6- , Monoalcohol compounds such as cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

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

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

As the ketone compound, for example,

But are not limited to, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, Monoketone compounds such as ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone and fenchone;

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Water to be added in the synthesis of other polyorganosiloxanes can be added intermittently or continuously in a silane compound as a raw material or in a solution in which a silane compound is dissolved in an organic solvent.

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

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

In the case where the liquid crystal aligning agent contains the [A] compound and the [B] polymer, the ratio of the total amount of the [B] polymer to 100 parts by mass of the [A] compound is preferably 100 to 5,000 parts by mass , More preferably 200 to 3,000 parts by mass.

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

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

[Curing agent, curing catalyst and curing accelerator]

The curing agent and the curing catalyst may be included in the liquid crystal aligning agent for the purpose of making the crosslinking reaction of the [A] compound stronger. The curing accelerator may be included in the liquid crystal aligning agent for the purpose of accelerating the curing reaction of the curing agent.

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

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

Examples of the cyclohexanetricarboxylic acid anhydrides include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic-3,5- Hexane-1,2,3-tricarboxylic acid-2,3-anhydride and the like. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, In addition to the compounds shown, tetracarboxylic acid dianhydrides generally used for the synthesis of polyamic acids, the reaction products of the alicyclic compounds having a conjugated double bond such as? -Terpinene and alo cymene with maleic anhydride, Hydrogenated products, and the like.

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

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

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

[Epoxy Compound]

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

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

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

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

[Functional silane compound]

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

When the liquid crystal aligning agent contains a functional silane compound, the content thereof is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the total of 100 parts by mass of the compound [A] Or less.

[Surfactants]

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

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

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

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

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

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

On the other hand, as the preferred organic solvent when the liquid crystal aligning agent contains only the [A] compound as the polymer or the [A] compound and other polyorganosiloxane, for example, 1-ethoxy- -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 monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, Acetate, ethyl cellosolve acetate, propyl cellosol Butyl acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, Propyl acetate, sec-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, , Isoamyl acetate, and the like. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-

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

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

<Liquid crystal display element>

The liquid crystal display element of the present invention is a PSA type liquid crystal display element having a liquid crystal alignment film formed from the liquid crystal aligning agent. According to the liquid crystal display element, since the liquid crystal alignment film is formed of the liquid crystal alignment agent, the liquid crystal alignment property is high and excellent high-speed response can be exhibited. Hereinafter, an embodiment of a liquid crystal display element will be described with reference to Figs. 1 and 2. Fig.

[First Embodiment]

The liquid crystal display element 1 of Fig. 1 comprises a pair of substrates 2 arranged opposite to each other, a pair of liquid crystal alignment films 3 laminated on the inner surface side of the pair of substrates 2, And a liquid crystal layer 4 filled between the alignment films 3 and formed of a polymerizable liquid crystal composition.

Examples of the pair of substrates 2 include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and alicyclic polyolefin can be used.

On the inner surfaces of the pair of substrates 2, transparent electrodes 5a and 5b are provided. The transparent electrode 5a is a common electrode, and the transparent electrode 5b is a pixel electrode. As the transparent electrode 5, for example, an ITO film made of a NESA film (registered by the US PPG company) and indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) . This transparent electrode is connected to a TFT, a bus line, and the like (not shown), similarly to a known liquid crystal display device.

On the surface (opposite surface side) of both the transparent electrodes 5a and 5b, a linear projection (a bank-shaped alignment regulation structure) 6 is formed. The size of the linear protrusions is, for example, 1.5 占 퐉 in height and 10 占 퐉 in width, and is 25 占 퐉, for example. The liquid crystal molecules are aligned and divided by the linear protrusions 6.

A liquid crystal alignment film 3 is formed on the inner surface side of the pair of substrates 2 with transparent electrodes 5a and 5b and linear projections 6 interposed therebetween. The liquid crystal alignment film 3 is a vertical alignment film and is formed by the above-mentioned liquid crystal aligning agent. The surface of the liquid crystal alignment film 3 may or may not be subjected to treatment such as rubbing treatment or photo alignment treatment. According to the liquid crystal display element, since the liquid crystal alignment film is formed of the liquid crystal alignment agent, the liquid crystal alignment property is excellent, and excellent high-speed responsiveness can be exhibited.

The liquid crystal alignment layer 3 is filled with a liquid crystal layer 4 formed of a polymerizable liquid crystal composition. This liquid crystal layer 4 has negative dielectric anisotropy. As such a liquid crystal, for example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a cypher base-based liquid crystal, an agglutinative liquid crystal, a biphenyl-based liquid crystal, a phenylcyclohexane-based liquid crystal and the like are used. The polymerizable liquid crystal composition is not particularly limited and may be any known one. For example, a monomer having an acryloyl group and a liquid crystal skeleton may be added to a negative (negative dielectric anisotropy) type liquid crystal together with a polymerization initiator . The amount of the monomer added is, for example, from 0.1 mass% to 1 mass%. The thickness of the liquid crystal layer 4 is, for example, about 4 mu m.

In this liquid crystal display element 1, the liquid crystal layer 4 is formed of the polymerizable liquid crystal composition, so that the polymer layer 7 is formed at the interface with the liquid crystal alignment film 3 in the liquid crystal layer 4 . The polymer layer 7 imparts a pretilt angle to the liquid crystal molecules 4a in the liquid crystal layer 4 at a predetermined angle? P.

In the liquid crystal display element 1, a polarizing plate (not shown) is laminated on both outer surfaces of the substrate 2, similarly to a known liquid crystal display element. The polarizing plate is not particularly limited, but a polarizing plate in which a polarizing film called &quot; H film &quot; in which iodine is absorbed while a polyvinyl alcohol film is oriented in a stretched orientation is sandwiched by a cellulose acetate protective film or a polarizing plate made of the H film itself have.

According to the liquid crystal display element 1, since the liquid crystal alignment film 3 is formed of the liquid crystal alignment agent, the liquid crystal alignment property is high and excellent high-speed response can be exhibited.

[Second Embodiment]

The liquid crystal display element 11 of Fig. 2 (a) includes a pair of substrates 2 arranged opposite to each other, a pair of liquid crystal alignment films 3 laminated on the inner surface side of the pair of substrates 2, , And a liquid crystal layer (4) filled between the liquid crystal alignment layers (3) and formed of a polymerizable liquid crystal composition. In the liquid crystal display element 11, similarly to the liquid crystal display element 1, a polarizing plate (not shown) is laminated on both outer surfaces of the substrate 2.

The liquid crystal display element 11 performs alignment division of liquid crystal molecules by the patterned transparent electrodes 15 instead of the linear protrusions 6 of the liquid crystal display element 1. [ The substrate 2, the liquid crystal alignment film 3, the liquid crystal layer 4 and the one transparent electrode 5a (common electrode) in the liquid crystal display element 11 are the same as the liquid crystal display element 1 in Fig. 1 The description is omitted.

On one inner surface of the substrate 2, a transparent electrode 15 (pixel electrode) patterned in a fish-eye pattern is disposed. By using such a patterned transparent electrode 15, the liquid crystal molecules 4a in the liquid crystal layer 4 can be aligned along the transparent electrode 15, and the alignment can be divided (see Fig. 2 (b)), . Further, this transparent electrode is connected to a TFT, a bus line, and the like (not shown) similarly to a known liquid crystal display element.

In this liquid crystal display element 11, the oblique direction of the liquid crystal molecules in the liquid crystal layer can be stored by curing the liquid crystal layer in a state in which the voltage is applied, thereby functioning as a PSA type liquid crystal display element.

Since the liquid crystal alignment film is formed of the liquid crystal alignment film by the liquid crystal display element 11 as well, the liquid crystal alignment property is excellent, and excellent high-speed response can be exhibited.

[Other Embodiments]

In this liquid crystal display element, in the liquid crystal layer, a cured portion for expressing PSA may be formed as the polymer layer 4 like the liquid crystal display element 1 in Fig. 1, or partially or entirely in the liquid crystal layer There may be. Instead of the above-mentioned linear projections or patterned electrodes, alignment division may be performed by a slit, a barrier rib, or the like. In any case, according to the liquid crystal display element, for example, the liquid crystal molecules are supported so as to be inclined very slightly with respect to the substrate interface, and since the liquid crystal alignment film is formed of the liquid crystal alignment agent, The liquid crystal molecules can be reliably tilted in the oblique direction, and the responsiveness at this time can be increased.

<Manufacturing Method of Liquid Crystal Display Element>

An example of the method of manufacturing the liquid crystal display element will be described as an example of the liquid crystal display element 1 of Fig.

As a method for producing the liquid crystal display element 1,

A step of forming a liquid crystal alignment film 3 on each inner surface of a pair of substrates 2 having transparent electrodes 5a or 5b and linear projections 6 by the liquid crystal aligning agent,

A step of arranging the pair of substrates (2) so as to face each other with their inner surfaces facing each other, filling the polymerizable liquid crystal composition between the substrates,

And a step of curing the polymerizable liquid crystal composition with a voltage applied thereto.

The liquid crystal alignment film can be formed by applying a liquid crystal aligning agent and curing it by heating.

Examples of the curing method of the polymerizable liquid crystal composition include photo-curing using ultraviolet rays or thermal curing by heat application. The irradiation dose in the case of photo-curing is not particularly limited, but is, for example, about 1,000 to 5,000 mJ / cm 2 as an ultraviolet irradiation dose. The applied voltage at the time of polymerization is not particularly limited, but is about 0 to 20 V.

By thus curing (polymerizing) while applying a voltage to form a liquid crystal layer, the liquid crystal molecules can be supported in an inclined state to effectively control the orientation of the liquid crystal molecules. Further, according to this production method, since the liquid crystal alignment film is formed of the liquid crystal aligning agent, it is possible to produce a PSA type liquid crystal display device having a high liquid crystal alignability and a high speed response.

(Example)

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples, but the present invention is not limited to these Examples.

The weight average molecular weight (Mw) of the epoxy compound-containing polyorganosiloxane and the [A] compound obtained in the following Examples is a polystyrene reduced value measured by GPC under the following specifications.

Column: TSKgelGRCXLII, Toso K.K.

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

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

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

[Synthesis Example 1]

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

As a result of ¹ H-NMR analysis of the polyorganosiloxane having the epoxy group, a peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm as the theoretical intensity, and a side reaction of the epoxy group occurred during the reaction .

[Synthesis Examples 2 to 3]

A polyorganosiloxane having an epoxy group was obtained as a viscous transparent liquid by operating in the same manner as in Synthesis Example 1 except that the starting materials were as shown in Table 1 below.

Mw and epoxy equivalent of the epoxy group-containing polyorganosiloxane obtained in Synthesis Examples 1 to 3 are shown in Table 1. The abbreviations of the raw material silane compounds in Table 1 have the following meanings.

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

MTMS: methyltrimethoxysilane

PTMS: phenyltrimethoxysilane

&Lt; Synthesis of Specific Carbonic Acid &gt;

[Synthesis of Specific Carboxylic Acid 1]

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

[Synthesis Example 4]

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

[Synthesis Example 5]

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

[Synthesis of Specific Carboxylic Acid 2]

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

[Synthesis Example 6]

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

[Synthesis Example 7]

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

[Synthesis Example 8]

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

[Synthesis Example 9]

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

[Synthesis of Specific Carboxylic Acid 3]

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

[Synthesis Example 10]

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

[Synthesis Example 11]

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

[Synthesis of Specific Carboxylic Acid 4]

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

[Synthesis Example 12]

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

[Synthesis Example 13]

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

[Synthesis Example 14]

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

[Synthesis Example 15]

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

[Synthesis of Specific Carboxylic Acid 5]

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

[Synthesis Example 16]

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

[Synthesis of Specific Carboxylic Acid 6]

A specific carbonic acid 6 was synthesized according to the following reaction formula.

[Synthesis Example 17]

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

[Synthesis Example 18]

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

[Synthesis of Specific Carboxylic Acid 7]

A specific carbonic acid 7 was synthesized according to the following reaction formula.

[Synthesis Example 19]

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

[Synthesis of Specific Carboxylic Acid 8]

A specific carbonic acid 8 was synthesized according to the following reaction formula.

[Synthesis Example 20]

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

[Synthesis of Specific Carboxylic Acid 9]

A specific carbonic acid 9 was synthesized according to the following reaction formula.

[Synthesis Example 21]

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

[Synthesis of Specific Carboxylic Acid 10]

A specific carbonic acid 10 was synthesized according to the following reaction formula.

[Synthesis Example 22]

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

[Synthesis of Specific Carboxylic Acid 11]

A specific carbonic acid 11 was synthesized according to the following reaction formula.

[Synthesis Example 23]

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

[Synthesis of Specific Carboxylic Acid 12]

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

[Synthesis Example 24]

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

[Synthesis Example 25]

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

&Lt; Synthesis of [A] compound &gt;

[Synthesis Example 26]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 5.0 g of the specific carbonic acid 1 obtained in Synthesis Example 5, 5.0 g of the specific carbonic acid 1 obtained in the above Synthesis Example 1, 3.3 g of 4-octyloxybenzoic acid represented by the formula (4-11) exemplified as one of the compounds and 0.20 g of UCAT 18X (quaternary amine salt of San A Pro Co.) were added and the mixture was stirred at 80 캜 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed three times with water and then the solvent was distilled off to obtain Compound [A] g. [A] The Mw of the compound A-1 was 6,500.

[Synthesis Example 27]

12.8 g of a white powder of the compound [A] A-2 was obtained in the same manner as in Synthesis Example 26 except that 4 g of the specific carboxylic acid 2 obtained in Synthesis Example 9 was used instead of the specific carbonic acid 1. [A] The Mw of the compound A-2 was 6,000.

[Synthesis Example 28]

The procedure of Synthetic Example 26 was repeated except that 6.8 g of the specific carboxylic acid 3 obtained in Synthesis Example 11 was used in place of the specific carbonic acid 1 to obtain 14.7 g of a white powder of the compound [A] A-3. [A] The Mw of Compound A-3 was 8,100.

[Synthesis Example 29]

Compound [A] was synthesized in the same manner as in Synthesis Example 26 except that 5.6 g of the specific carbonic acid 4 obtained in Synthesis Example 15 was used instead of the specific carbonic acid 1. As a result, 15.0 g of a white powder of the compound [A] 4 was obtained. [A] The Mw of Compound A-4 was 7,500.

[Synthesis Example 30]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 10 g of the specific carboxylic acid 1 obtained in the above Synthesis Example 5 and 10 g of UCAT 18X (manufactured by San- Of quaternary amine salt), and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate. The solution was washed three times with water and then the solvent was distilled off to obtain 16.0 g of [A] Compound A-5 as a white powder. [A] The Mw of the compound A-5 was 8,500.

[Synthesis Example 31]

12.4 g of white powder of Compound A-A was obtained in the same manner as in Synthesis Example 26 except that 4.1 g of the specific carbonic acid 5 obtained in Synthesis Example 16 was used instead of the specific carbonic acid 1. [A] The Mw of Compound A-6 was 6,200.

[Synthesis Example 32]

(4-pentylcyclohexyl) benzoic acid represented by the formula (4-13) exemplified as one of the compounds represented by the formula (4) was used instead of 4-octyloxybenzoic acid in Synthesis Example 26 To obtain 13.4 g of a white powder of Compound [A] A-7. [A] The Mw of Compound A-7 was 7,900.

[Synthesis Example 33]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 8.0 g of the specific carbonic acid 1 obtained in the above Synthesis Example 5, 8.0 g of the formula (4-13) 1.4 g of 4- (4-pentylcyclohexyl) benzoic acid represented by the following formula and UCAT 18X (quaternary amine salt of San A's Co., Ltd.) (0.20 g) were placed and 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. The solution was washed three times with water and then the solvent was distilled off to obtain 13.9 g of [A] compound A-8 as a white powder. [A] The Mw of Compound A-8 was 8,900.

[Synthesis Example 34]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 2.0 g of the specific carbonic acid 1 obtained in Synthesis Example 5, 5.8 g of 4- (4-pentylcyclohexyl) benzoic acid represented by the following formula, and 0.20 g of UCAT 18X (quaternary amine salt of San A Pro Co.) were added and 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. The solution was washed three times with water and then the solvent was distilled off to obtain Compound A-9 of [A] as a white powder g. [A] The Mw of Compound A-9 was 7,600.

[Synthesis Example 35]

9.8 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 8.0 g of the specific carbonic acid 1 obtained in Synthesis Example 5, 8.0 g of the formula (4-12) , And 0.20 g of UCAT 18X (quaternary amine salt of San A Pro Co.), and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol. The precipitate was dissolved in ethyl acetate. The solution was washed three times with water, and then the solvent was distilled off to obtain 15.5 g of [A] Compound A-10 as a white powder. [A] The Mw of Compound A-10 was 9,200.

[Synthesis Example 36]

18.4 g of a white powder of the compound [A] 11 was obtained in the same manner as in Synthesis Example 26 except that 6.1 g of the specific carbonic acid 6 obtained in Synthesis Example 18 was used instead of the specific carbonic acid 1. [A] The Mw of the compound A-11 was 7,300.

[Synthesis Example 37]

17.5 g of a white powder of the [A] compound A-12 was obtained in the same manner as in Synthesis Example 26 except that 5.7 g of the specific carbonic acid 7 obtained in Synthesis Example 19 was used instead of the specific carbonic acid 1. [A] The Mw of Compound A-12 was 7,600.

[Synthesis Example 38]

19.1 g of a white powder of the compound [A] 13 was obtained in the same manner as in Synthesis Example 26 except that 7.2 g of the specific carbonic acid 8 obtained in Synthesis Example 20 was used instead of the specific carbonic acid 1. [A] The Mw of the compound A-13 was 7,000.

[Synthesis Example 39]

18.1 g of a white powder of the compound [A] 14 was obtained in the same manner as in Synthesis Example 26 except that 6.2 g of the specific carbonic acid 9 obtained in Synthesis Example 21 was used instead of the specific carbonic acid 1. [A] The Mw of the compound A-14 was 6,900.

[Synthesis Example 40]

19.4 g of a white powder of the compound [A] 15 was obtained in the same manner as in Synthesis Example 26 except that 7.0 g of the specific carbonic acid 10 obtained in Synthesis Example 22 was used instead of the specific carbonic acid 1. [A] The Mw of Compound A-15 was 7,500.

[Synthesis Example 41]

20.1 g of a white powder of the compound [A] 16 was obtained in the same manner as in Synthesis Example 26 except that 8.4 g of the specific carboxylic acid 11 obtained in Synthesis Example 23 was used instead of the specific carbonic acid 1. [A] The Mw of the compound A-16 was 7,300.

[Synthesis Example 42]

19.5 g of a white powder of the compound [A] 17 [A] was obtained by operating in the same manner as in Example 26 except that 7.2 g of the specific carbonic acid 12 obtained in Synthesis Example 25 was used instead of the specific carbonic acid 1. [A] The Mw of Compound A-17 was 7,300.

[Comparative Synthesis Example 1]

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

<Synthesis of polyamic acid>

[Synthesis Example 43]

19.61 g (0.1 mole) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 21.23 g (0.1 mole) of 4,4'-diamino-2,2'- -Pyrrolidone, and the reaction was carried out at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 35 g of polyamic acid PA-1.

[Synthesis Example 44]

(0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g (0.1 mol) of cyclohexane bis (methylamine) were dissolved in 329.3 g of N-methyl-2-pyrrolidone to obtain 60 Lt; 0 &gt; C for 6 hours. The reaction was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 占 폚 for 15 hours to obtain 32 g of polyamic acid PA-2.

<Synthesis of polyimide>

[Synthesis Example 45]

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

[Synthesis Example 46]

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

&Lt; Preparation of liquid crystal aligning agent &

[Example 1]

The amount of the solution containing the polyamic acid PA-1 obtained in Synthesis Example 43, which was converted into polyamic acid PA-1 contained therein, was taken as an amount equivalent to 1,000 parts by mass, and the amount of [A] Compound A-1 (100 parts by mass) Methyl-2-pyrrolidone and butyl cellosolve were added to the mixture to prepare a solution having a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio) 3.0% by mass. This solution was filtered with a filter having a pore diameter of 10.2 占 퐉 to prepare liquid crystal aligning agent S-1.

[Examples 2 to 21 and Comparative Example 1]

The liquid crystal aligning agents S-2 to S-2 were obtained in the same manner as in Example 1 except that the combination of the polyamic acid or polyimide as the polymer [B] and the polyorganosiloxane compound as the component [A] -21 and CS-1 were prepared.

[Comparative Example 2]

To the polyimide PI-2 obtained in Synthesis Example 46 were added N-methyl-2-pyrrolidone and butyl (2-pyrrolidone) such that the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = And cellosolve, respectively, to prepare a solution having a solid content concentration of 3.0% by mass. This solution was filtered with a filter having a pore size of 0.2 탆 to prepare liquid crystal aligning agent CS-2. In the table, &quot; - &quot; indicates that the corresponding component was not used.

&Lt; Production of liquid crystal display element &

A 15-inch XGA panel (pixel pitch: 297 占 퐉, pixel number: 1024 占 768) was produced as the liquid crystal display element using the liquid crystal aligning agent S-1 of Example 1. 3 is a schematic view showing one pixel of this panel (liquid crystal display element). A transparent electrode 21 patterned on one of the substrates was formed. On this substrate, a TFT 22 and a bus line 23 are provided so that the transparent electrode 21 functions as a pixel electrode. As shown in Fig. 3, the patterned transparent electrode 21 is extended in four directions (right top, bottom right, left top, left bottom) from the pixel central portion. Here, the electrode width of the patterned transparent electrode 21 in the vicinity of the boundary (backbone) was 2 占 퐉, the space width was 4 占 퐉, the electrode width in the region apart from the boundary was 4 占 퐉, and the space width was 2 占 퐉 . The distance (x) from the boundary end to the pattern width changing portion was 5 mu m. On the other substrate, a transparent electrode (common electrode) was formed. As the substrate material, a glass substrate OA-2 (manufactured by Nippon Denshikarasu Co., Ltd.) having a thickness of 0.7 mm was used.

On these substrates, a liquid crystal alignment film was formed by a printing method using liquid crystal aligning agent S-1, and heat treatment was performed at 180 占 폚 for 60 minutes. Further, these substrates were bonded to each other with spacers (manufactured by Sekisui Fine Chemical Co., Ltd.) having a diameter of 4 탆, and empty cells of liquid crystal un-injected were prepared. To this cell, a negative liquid crystal (manufactured by Merck Co., Ltd.) in which a small amount of a photopolymerizable monomer (manufactured by Dainippon Ink and Chemicals, Incorporated) was added was injected. The addition amount of the photopolymerizable monomer was 2.4% by mass. Next, a voltage was applied to the cell to irradiate ultraviolet rays, and the monomer was polymerized and polymerized. The liquid crystal display element of Example 1 was fabricated by joining the polarizing plate on both outer sides of the substrate so that the polarizing directions of the two polarizing plates were orthogonal to each other. The applied voltage at the time of polymerization was 10 V and the UV irradiation amount was 2,000 mJ / cm 2 (? = 365 nm).

A liquid crystal display device using the liquid crystal aligning agents of Examples 2 to 20 and Comparative Examples 1 and 2 was fabricated by the same operation as above except that the liquid crystal aligning agent shown in Table 2 was used in place of the liquid crystal aligning agent S-1.

<Evaluation>

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

[Orientation]

With respect to the liquid crystal display device manufactured as described above, the presence or absence of light leakage and orientation disturbance in a voltage unapplied state was observed by visual inspection under backlight, and a case where there was no light leakage / orientation disorder was evaluated as &quot;Quot;, and a case where light leakage and orientation disorder were present in a part were &quot; DELTA &quot;, and those in which no vertical alignment state was obtained at all were evaluated as &quot; x &quot;.

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

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

As apparent from the results of Table 2, the liquid crystal display device comprising the liquid crystal alignment film produced by using the liquid crystal aligning materials of Examples 1 to 21 has excellent orientation properties and the response speed of the liquid crystal, As compared with about 2/3.

The liquid crystal aligning agent of the present invention can be suitably used for the production of a liquid crystal display element of the PSA system excellent in high-speed responsiveness.

1, 11: liquid crystal display element
2: substrate
3: Liquid crystal alignment film
4: liquid crystal layer
4a: liquid crystal molecule
5, 5a, 5b: transparent electrodes
6: Linear projection
7: polymer layer
15: Patterned transparent electrode
21: Transparent electrode
22: TFT
23: Bus line

Claims (7)

As a liquid crystal aligning agent for forming a liquid crystal alignment film in a PSA type liquid crystal display element,
[A] a compound having a part derived from a polyorganosiloxane having an epoxy group and a part derived from a compound represented by the following formula (2)
Wherein the liquid crystal aligning agent comprises:

(In the formula (2), R ¹ is a group represented by the following formula (3) and R ² is an ethynyl group, an ethynyl group, an ester group, a methanediyl group, a fluoromethanedioxy group or a difluoromethane A is an integer of 0 to 1; R ³ is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group, and these groups may further have a substituent;

(Wherein R ⁴ 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, R ⁵ is benzene, (B + 1) -valent groups other than (b + 1) hydrogen atoms from biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or a heterocyclic compound, these groups may further have substituents; ⁶ represents a group selected from the group consisting of a methanediyl group, an ethanediyl group, a propanediyl group, an ethenediyl group, an ethynediyl group, an ether group, an ester group, a methanediyloxy group, an ethanedioxy group, a fluoromethanedioxy group, And R ⁷ are each independently a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle, and these groups may further have a substituent ; b is an integer of 1 to 9, b is 2 or more, a plurality of R ⁴ may be the same or different, c is an integer of 0 to 1, d is an integer of 1 to 2, A plurality of R ⁶ and R ⁷ may be the same or different from each other). delete delete The method according to claim 1,
The liquid crystal aligning agent in which the epoxy group is a group represented by the following formula (X ¹ -1) or (X ¹ -2)

(Formula (X ¹ -1) of, A is an oxygen atom or a single bond; h is an integer of 1~3; i is an integer from zero to six; however, if i is 0, A is a single bond and ;
In formula (X ¹ -2), j is an integer of 0 to 6). The method according to claim 1 or 4,
[B] a liquid crystal aligning agent further comprising at least one polymer selected from the group consisting of polyamic acid and polyimide. A liquid crystal display element of a PSA type comprising a liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1 to 4. A step of forming a liquid crystal alignment film by the liquid crystal aligning agent according to any one of claims 1 to 4 on each inner surface of a pair of substrates having transparent electrodes,
A step of arranging the pair of substrates so as to face each other with their inner surfaces facing each other, filling the polymerizable liquid crystal composition between the substrates,
A step of curing the polymerizable liquid crystal composition with a voltage applied thereto
Of the liquid crystal display element.

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