CN102604652A - Liquid crystal aligning agent,liquid crystal display element and manufacture method thereof - Google Patents

Abstract

The invention refers to a liquid crystal aligning agent, a liquid crystal display element and a manufacture method thereof, aiming to provide an SPA type liquid crystal aligning agent which can perform excellent properties such as high speed response, an SPA type liquid crystal display element which possesses a liquid crystal aligning film formed by the liquid crystal aligning agent and a manufacture method of the liquid crystal display element. The invention provides the liquid crystal aligning agent for forming the liquid crystal aligning film in the liquid crystal display element, characterized by comprising (A) a compound (also referred as A compound as follows) represented by formula (1). In the formula (1), R1 is perssad comprising at least two monocyclic structures; R2 comprises a link group comprising double bonds, triple bonds, ether bonds, ester bonds or oxygen atoms; a is an integer of 0-1.

Description

Liquid crystal aligning agent, liquid crystal display device and method of manufacture thereof

Technical field

The present invention relates to liquid crystal aligning agent, liquid crystal display device and liquid crystal display device

Method of manufacture.

Background technology

In recent years, liquid crystal display device because have that consumes electric power is little, advantage such as miniaturized and flattening are easy, the purposes of the such wide region of large-screen lc display unit that therefore is applied to from the small-sized liquid crystal indicator of mobile phone etc. to LCD TV etc.

At present, the drive pattern of liquid crystal indicator is according to the variation of orientation (arrangement) state of liquid crystal molecule, and known have TN (twisted-nematic), STN (supertwist is to row), IPS (plane conversion), a VA (vertical orientated) etc.In addition; With regard to the VA pattern, improve the visual angle in order to cut apart through orientation, adopting has MVA (multi-domain vertical alignment) mode, PVA (image is vertical orientated) mode; In order further to improve high-speed response property, panel aperture opening ratio, studying PSA (polymer stabilizing orientation) mode that adopts.

This PSA mode is meant; Can sneak into liquid crystal through the monomer of light or thermopolymerization in advance; Make monomer polymerization under the state after applying voltage to make liquid crystal molecules tilt, thereby the technology (with reference to TOHKEMY 2002-357830 communique, TOHKEMY 2003-307720 communique, TOHKEMY 2003-177418 communique) of the vergence direction of liquid crystal molecule is lived in memory.With regard to the liquid crystal display device that has used the PSA mode; Because for example liquid crystal molecule is supported under the state after tilting with respect to substrate interface minimumly; Therefore when applying voltage, can make liquid crystal molecule positively swing to this vergence direction, consequently response speed is fast.

The state of orientation of the liquid crystal molecule in such liquid crystal display device is controlled by liquid crystal orientation film, and liquid crystal orientation film is being undertaken the manifesting, control of functional performance of liquid crystal display device on sizable degree.Aspect the PSA mode; In order to improve functions such as response speed; Also developing a kind of liquid crystal indicator (TOHKEMY 2006-215326 communique) of composition of the liquid crystal aligning agent of having stipulated to be used to form this liquid crystal orientation film; But, require to realize improvement further in order to realize the high performance of response speed etc.

The prior art document

[patent documentation]

Patent documentation 1: TOHKEMY 2002-357830 communique

Patent documentation 2: TOHKEMY 2003-307720 communique

Patent documentation 3: TOHKEMY 2003-177418 communique

Patent documentation 4: TOHKEMY 2006-215326 communique

Summary of the invention

The present invention is based on the situation of above-mentioned that kind and carry out, its purpose is to provide: can form all excellents such as high-speed response property the PSA mode liquid crystal display device liquid crystal aligning agent, possess liquid crystal display device and the method for manufacture of such liquid crystal display device of the PSA mode of the liquid crystal orientation film that forms by this liquid crystal aligning agent.

The invention of developing in order to solve above-mentioned problem is characterised in that; The liquid crystal aligning agent of using for the liquid crystal orientation film in a kind of liquid crystal display device of the PSA of formation mode; Containing [A] has by the compound of the group of following formula (1) expression (below, also be called " [A] compound ")

In the formula (1), R ¹For having the group of two single ring architectures at least.R ²For comprising the binding group of two keys, triple bond, ehter bond, ester bond or Sauerstoffatom.A is 0～1 integer.

This liquid crystal aligning agent contains [A] compound, should possess the above-mentioned group with dielectric anisotropy, the controlled excellence of the orientation of liquid crystal molecule by [A] compound.Thus, possess in the liquid crystal display device of PSA mode of the liquid crystal orientation film that uses this liquid crystal aligning agent and form, the orientation of liquid crystal molecule is good and can shorten the time of response.

[A] compound can have: be derived from the organopolysiloxane with epoxy group(ing) part, be derived from part by the compound of following formula (2) expression (below, also be called " specific carboxylic acid "),

In the formula (2), R ¹, R ²And a and the same definition of above-mentioned formula (1).R ³Be alkylidene group, phenylene or the cyclohexylidene of methylene radical, carbonatoms 2～30, these groups can further have substituting group.

According to this liquid crystal aligning agent, through utilizing the reactivity of epoxy group(ing) and carboxyl, thereby can in as the organopolysiloxane of main chain, import structure easily, with as [A] compound with dielectric anisotropy by above-mentioned formula (1) expression as side chain.Therefore, this liquid crystal aligning agent can be given the liquid crystal display device that obtained effectively with high-speed response property.

Above-mentioned R ¹Can be group by following formula (3) expression,

In the formula (3), R ⁴Be Wasserstoffatoms, cyanic acid, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxyl group, trifluoromethoxy or alkyl-carbonyl oxygen base.R ⁵For remove the group of (b+1) valency that (b+1) individual Wasserstoffatoms obtains from benzene, biphenyl, naphthalene, hexanaphthene, bis cyclohexane, phenylcyclohexane or heterogeneous ring compound, these groups can further have substituting group.R ⁶Be any the binding group in the alkylidene group that comprises methylene radical, carbonatoms 2～10, two key, triple bond, ehter bond, ester bond and the heterocycle, these groups can further have substituting group.R ⁷Be phenylene, biphenylene, naphthyl, cyclohexylidene, two cyclohexylidene, cyclohexylidene phenylene or heterocycle independently of one another, these groups can further have substituting group.B is 1～9 integer.B is under the situation more than 2, a plurality of R ⁴Can be identical also can be different.C is 0～1 integer.D is 1～2 integer.D is under 2 the situation, a plurality of R ⁶, R ⁷And c can be the same or different separately.

Through in [A] of this liquid crystal aligning agent compound, importing structure, thereby the responsiveness of the liquid crystal display device of acquisition is become more at a high speed by above-mentioned formula (3) expression.

Above-mentioned epoxy group(ing) can be by following formula (X ¹-1) or (X ¹-2) group of expression,

Formula (X ¹-1) in, A is Sauerstoffatom or singly-bound.H is 1～3 integer.I is 0～6 integer.Wherein, i is that A is a singly-bound under 0 the situation.

Formula (X ¹-2) in, j is 0～6 integer.

Through in above-mentioned organopolysiloxane, comprising by above-mentioned formula (X ¹-1) or (X ¹-2) group of expression, thus be easy in [A] of this liquid crystal aligning agent compound, import group by above-mentioned formula (1) expression.

This liquid crystal aligning agent can further contain at least a polymkeric substance selected in the group that [B] be made up of polyamic acid and polyimide (below, also be called " [B] polymkeric substance ").Use contains the liquid crystal aligning agent of [B] polymkeric substance and when forming liquid crystal orientation film, can obtain high-speed response property and obtain the liquid crystal display device that improves more.

Liquid crystal display device of the present invention is the liquid crystal display device that possesses the PSA mode of the liquid crystal orientation film that is formed by this liquid crystal aligning agent.According to this liquid crystal display device, through forming liquid crystal orientation film by above-mentioned liquid crystal aligning agent, thereby liquid crystal aligning property is high, and can bring into play excellent high-speed response property.

The method of manufacture of liquid crystal display device of the present invention is the method for manufacture of the liquid crystal display device of PSA mode, and it has following operation:

Form the operation of liquid crystal orientation film at each internal surface of a pair of substrate with transparency electrode by this liquid crystal aligning agent,

Above-mentioned a pair of substrate according to the mode subtend configuration that internal surface faces each other, is filled the operation of polymerizable liquid crystal compound between this substrate, and

Under the state that has applied voltage, make above-mentioned polymerizable liquid crystal compound solidified operation.

According to this method of manufacture, through forming liquid crystal orientation film, thereby can make the liquid crystal display device that liquid crystal aligning property is high and have the PSA mode of excellent high-speed response property by above-mentioned liquid crystal aligning agent.

That kind as described above according to liquid crystal aligning agent of the present invention, can form the liquid crystal display device of the PSA mode of all excellents such as high-speed response property.In addition, liquid crystal display device of the present invention as the element of PSA mode, can be brought into play high responsiveness etc.Manufacturing method according to the invention can be made the liquid crystal display device of the PSA mode that possesses high responsiveness etc.

Description of drawings

Fig. 1: the pattern sectional view of the liquid crystal display device of expression an embodiment of the invention.

Fig. 2 (a)～Fig. 2 (b): the pattern sectional view of representing the liquid crystal display device of the form different with the liquid crystal display device of Fig. 1.

Fig. 3: the mode chart of the liquid crystal display device of making by embodiment.

Embodiment

Below, the embodiment of the method for manufacture of liquid crystal aligning agent of the present invention, liquid crystal display device and liquid crystal display device is detailed.

< liquid crystal aligning agent >

Liquid crystal aligning agent of the present invention is characterised in that it contains [A] compound for the liquid crystal aligning agent that the liquid crystal orientation film in the liquid crystal display device that forms the PSA mode is used.In addition, this liquid crystal aligning agent can contain " other the polymkeric substance " stated behind [B] polymkeric substance etc.Further, this liquid crystal aligning agent also can contain other optional member in the scope of not damaging effect of the present invention.Below each composition is detailed.

< [A] compound >

[A] compound is for having the compound by the group of above-mentioned formula (1) expression.Group by above-mentioned formula (1) expression has dielectric anisotropy, and the liquid crystal aligning agent that comprises [A] compound is excellent aspect controlled in the orientation of liquid crystal molecule.Thus, for the liquid crystal display device of the PSA mode that possesses the liquid crystal orientation film that uses this liquid crystal aligning agent and form, the orientation of liquid crystal molecule is good and can shorten the time of response.

In the above-mentioned formula (1), R ¹For having the group of two single ring architectures at least, preferably manifest the dielectric anisotropy of plus or minus.Single ring architecture is meant: ring structure is independent of other ring structure and exists, and the key of a ring structure and the total structure that does not have so-called condensed ring structure of other ring structure.In addition, as single ring architecture, can be any in ester ring type structure, fragrant ring type structure, the hetero ring type structure, also capable of being combined they and have.

R ¹So long as have the group of two single ring architectures at least, not special so the qualification, but say R typically ¹Be preferably group by above-mentioned formula (3) expression.Through in the side chain of [A] of this liquid crystal aligning agent compound, importing structure, thereby can make the further high speed of electrooptics responsiveness of the liquid crystal aligning element of acquisition by above-mentioned formula (3) expression.

In the above-mentioned formula (3), R ⁴Be in Wasserstoffatoms, cyanic acid, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxyl group, trifluoromethoxy and the alkyl-carbonyl oxygen base any.As alkoxy carbonyl, for example enumerate out methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl etc.; As alkyl, for example enumerating out carbonatomss such as methyl, ethyl, propyl group, normal-butyl, isobutyl-is straight or branched alkyl of 1～20 etc.; As alkoxyl group, for example enumerate out methoxyl group, oxyethyl group, propoxy-etc.; As the alkyl-carbonyl oxygen base, for example enumerate out methyl ketonic oxygen base, ethyl ketonic oxygen base etc.

In above-mentioned formula (3), R ⁴There is under a plurality of situation the group that has nothing in common with each other also capable of being combined and using.As having a plurality of R ⁴Situation under combination, in order stably to manifest desirable dielectric anisotropy, the combination of combination, cyanic acid and the alkyl of combination, fluorine atom and the alkyl of preferred fluorine atom and cyanic acid.Again, b is 0～9 integer.

In above-mentioned formula (3), R ⁵For remove the group of (b+1) valency that (b+1) individual Wasserstoffatoms obtains from benzene, biphenyl, naphthalene, hexanaphthene, bis cyclohexane, phenylcyclohexane or heterogeneous ring compound, these groups can further have substituting group.As above-mentioned heterogeneous ring compound, for example can enumerate out pyridine, pyridazine, pyrimidine etc.

In above-mentioned formula (3), R ⁶Be any the binding R in the alkylidene group that comprises methylene radical, carbonatoms 2～10, two key, triple bond, ehter bond, ester bond and the heterocycle ⁵And R ⁷The binding group, these groups (alkylidene group, heterocycle) can further have substituting group.As R ⁶, enumerate out methane two bases, ethane two bases, propane two bases, ethene two bases, acetylene two bases, ether, ester group, methane two basic oxygen bases, ethane two basic oxygen bases, fluoromethane two basic oxygen bases, methylene fluoride two basic oxygen bases etc.Among them, be preferably ethane two bases, acetylene two bases, ester group, methane two basic oxygen bases, methylene fluoride two basic oxygen bases.Can come suitably to select according to the necessary orientation of [A] compound, dielectric anisotropy.Because c is 0 or 1 integer, thereby can comprises also and can not comprise R again, ⁶

In above-mentioned formula (3), R ⁷Be phenylene, biphenylene, naphthyl, cyclohexylidene, two cyclohexylidene, cyclohexylidene phenylene or heterocycle independently of one another.As heterocycle, for example enumerate out pyridine ring, pyridazine ring, pyrimidine ring etc.

In the above-mentioned formula (3), d is 1～2 integer.D is under 2 the situation, a plurality of R ⁶, R ⁷And c can be the same or different separately.

As group by above-mentioned formula (3) expression, for example enumerate out group by following formula (D-1)～(D-123) expression,

In the formula (D-1)～(D-123), R is the alkyl (methyl, ethyl, propyl group, normal-butyl, isobutyl-, n-pentyl, n-hexyl etc.) of carbonatoms 1 to 20 or the alkoxyl group (methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy etc.) of carbonatoms 1～20.X is Wasserstoffatoms or fluorine atom independently of one another.

In the above-mentioned formula (1), R ²For comprising any the binding group in two keys, triple bond, ehter bond, ester bond and the Sauerstoffatom.R ²Any that comprises in the above-mentioned key gets final product, but each key also capable of being combined and comprising.As R ², for example enumerate out ethene two bases, acetylene two bases, ester group, methane two basic oxygen bases, fluoromethane two basic oxygen bases, methylene fluoride two basic oxygen bases etc.Again, the R that states after ³Under the situation for phenylene or cyclohexylidene, consider R from the orientation of formed alignment films, deliquescent viewpoint solvent ²The preferred package carbon atom quantity is 1～30 alkylidene group.Again, a is 0～1 integer.

As [A] compound; As long as the group that has above-mentioned formula (1) expression does not just limit especially; But preferably has polymkeric substance by the group of formula (1) expression at side chain; Consider more preferably organopolysiloxane, polyimide, polyamic acid, polyacrylic ester, Rohm tech inc from the aspect of electrical characteristic, gather the polymkeric substance that (vinylbenzene-phenyl maleimide) verivate, derivatived cellulose, polyester, polymeric amide, polystyrene derivative, poly amic acid ester are processed backbone structure, consider further preferably organopolysiloxane to be processed the polymkeric substance of backbone structure from sunproof aspect.

As [A] compound of organopolysiloxane being processed backbone structure, be preferably and have: part that is derived from organopolysiloxane and the compound that is derived from by the part of the specific carboxylic acid of above-mentioned formula (2) expression with epoxy group(ing).Because [A] compound in this liquid crystal aligning agent has the specific structure unit, thereby can import the structure with dielectric anisotropy at side chain, the liquid crystal display device that possesses the liquid crystal orientation film that uses this liquid crystal aligning agent and form can shorten the time of response more.In addition, through utilizing the reactivity between epoxy group(ing) and the carboxyl, thereby can in as the organopolysiloxane of main chain, import structure easily with dielectric anisotropy by above-mentioned formula (1) expression as side chain.

[A] compound has under the situation of part that is derived from the organopolysiloxane with epoxy group(ing) and the part that is derived from above-mentioned specific carboxylic acid; Can think mainly can be with the mode of the reactant of the carboxyl of the epoxy group(ing) of organopolysiloxane and specific carboxylic acid and obtain; But in order explanation thereafter to be carried out easily, is divided into easily part that is derived from organopolysiloxane (and verivate) and the part that is derived from specific carboxylic acid with explanation [A] compound with epoxy group(ing).

[being derived from the part of organopolysiloxane] with epoxy group(ing)

The notion of this part comprises: among the structure of [A] compound as the organopolysiloxane skeleton of main polymer chain with from the extended skeleton that contains epoxy group(ing) of this organopolysiloxane main chain as side chain.Can think as above-mentioned in [A] compound, most epoxy group(ing) and specific carboxylic acid reaction and do not have its initial structure, but also can there be specific carboxylic acid and epoxy group(ing) part bonded situation in addition.Therefore, the form that comprises the two in the present invention is called " part that is derived from the organopolysiloxane with epoxy group(ing) ".

[A] thus compound makes the such electrical characteristic of orientation, high-speed response property of this liquid crystal aligning agent improve more through having the epoxy group(ing) such as group that comprise glycidyl, glycidyl oxygen base, epoxycyclohexyl.Be preferably by above-mentioned formula (X as epoxy group(ing) ¹-1) or (X ¹-2) group of expression.Through in organopolysiloxane, comprising by above-mentioned formula (X ¹-1) or (X ¹-2) group of expression, thereby in [A] compound, easily through using specific carboxylic acid to import to side chain by the base of above-mentioned formula (1) expression.

Above-mentioned formula (X ¹-1) or (X ¹-2) among, be preferably the group of representing by following formula,

The weight-average molecular weight through polystyrene conversion that organopolysiloxane with epoxy group(ing) is measured by GPC (GPC) is preferably 500～100, and 000, more preferably 1,000～50,000, be preferably 1,000～20,000 especially.

[compound method] with organopolysiloxane of epoxy group(ing)

Organopolysiloxane like this with epoxy group(ing) can be preferably through as get off synthetic: will have the silane compound of epoxy group(ing) or have the mixture hydrolysis or the hydrolytic condensation of the silane compound and other the silane compound of epoxy group(ing), preferably hydrolysis or hydrolytic condensation in the presence of suitable organic solvent, water and catalyzer.

As above-mentioned silane compound with epoxy group(ing); For example enumerate out 3-glycidyl ether oxygen base propyl trimethoxy silicane, 3-glycidyl ether oxygen base propyl-triethoxysilicane, 3-glycidyl ether oxygen base propyl group methyl dimethoxysilane, 3-glycidyl ether oxygen base propyl group methyldiethoxysilane, 3-glycidyl ether oxygen base propyl-dimethyl methoxy silane, 3-glycidyl ether oxygen base propyl-dimethyl Ethoxysilane, 2-glycidyl ether oxygen base ethyl trimethoxy silane, 2-glycidyl ether oxygen base ethyl triethoxysilane, 2-glycidyl ether oxygen base ethyl-methyl dimethoxy silane, 2-glycidyl ether oxygen base ethyl-methyl diethoxy silane, 2-glycidyl ether oxygen base ethyl dimethyl methyl TMOS, 2-glycidyl ether oxygen base ethyl dimethylethoxysilane, 4-glycidyl ether oxygen base butyl trimethoxy silane, 4-glycidyl ether oxygen Ji Dingji triethoxyl silane, 4-glycidyl ether oxygen base butyl methyl dimethoxy silane, 4-glycidyl ether oxygen base butyl methyl diethoxy silane, 4-glycidyl ether oxygen Ji Dingji dimethyl methyl TMOS, 4-glycidyl ether oxygen Ji Dingji dimethylethoxysilane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3; The 4-epoxycyclohexyl) ethyl triethoxysilane, 3-(3; The 4-epoxycyclohexyl) propyl trimethoxy silicane, 3-(3, the 4-epoxycyclohexyl) propyl-triethoxysilicane etc.They can use or use two or more separately.

As above-mentioned other silane compound, for example for having the compound of 1 Siliciumatom, and

As other silane compound with 4 hydrolization groups; Enumerate out tetrachloro silicane, tetraalkoxysilanes such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec.-butoxy silane etc.;

As other silane compound with 3 hydrolization groups; Enumerate out trihalosilanes such as trichlorosilane; Trialkoxy silane such as Trimethoxy silane, triethoxyl silane; The fluorine trichlorosilane; Fluorine trialkoxy silanes such as fluorine Trimethoxy silane, fluorine triethoxyl silane; Alkyl trichlorosilanes such as METHYL TRICHLORO SILANE; Alkyltrialkoxysilaneand such as methyltrimethoxy silane, Union carbide A-162, fluoro-alkyl trichlorosilanes such as 2-(trifluoromethyl) ethyl trichlorosilane, fluoro-alkyl trialkoxy silanes such as 2-(trifluoromethyl) ethyl trimethoxy silane, 2-(trifluoromethyl) ethyl triethoxysilane; Hydroxyalkyl trichlorosilanes such as hydroxymethyl trichlorosilane; Hydroxyalkyl trialkoxy silanes such as hydroxymethyl Trimethoxy silane, hydroxyethyl Trimethoxy silane, (methyl) acryloxyalkyl trichlorosilanes such as 3-(methyl) acryloxy propyltrichlorosilan, (methyl) acryloxyalkyl trialkoxy silanes such as 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane; Mercaptoalkyl trichlorosilanes such as mercapto methyl trichlorosilane, 3-sulfydryl propyltrichlorosilan; Mercaptoalkyl trialkoxy silanes such as mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, thiazolinyl trichlorosilanes such as vinyl trichloro silane, allyltrichlorosilane, thiazolinyl trialkoxy silanes such as vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane; Aryl trichlorosilanes such as phenyl-trichloro-silicane, aryl trialkoxy silanes such as phenyltrimethoxysila,e, phenyl triethoxysilane etc.;

As other silane compound with 2 hydrolization groups; Enumerate out alkyl dichlorosilanes such as dimethyl dichlorosilane (DMCS); Alkyl-dialkoxysilanes such as methyl dimethoxysilane, methyldiethoxysilane; Dialkyldichlorosilan,s such as dimethyldichlorosilane(DMCS), dialkyl dialkoxy silicanes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, two fluoro-alkyl dichlorosilanes such as (methyl) [2-(perfluor n-octyl) ethyl] dichlorosilane; Two fluoro-alkyl dialkoxy silicanes such as (methyl) [2-(perfluor n-octyl) ethyl] dimethoxy silane; Alkyl thiol alkyl dichlorosilanes such as (methyl) (3-sulfydryl propyl group) dichlorosilane, alkyl thiol alkyl-dialkoxysilanes such as (methyl) (3-sulfydryl propyl group) dimethoxy silane, alkyl thiazolinyl dichlorosilanes such as (methyl) (vinyl) dichlorosilane; Two (thiazolinyl) dichlorosilanes such as divinyl dichlorosilane; Two (thiazolinyl) dialkoxy silicanes such as divinyl dimethoxy silane, diaryl dichlorosilanes such as diphenyl dichlorosilane, diaryl dialkoxy silicanes such as dimethoxydiphenylsilane;

As other silane compound with 1 hydrolization group; Enumerate out dialkyl group chlorosilanes such as Chlorodimethyl silane; Dialkyl group organoalkoxysilanes such as methoxyl group dimethylsilane, trialkyl halogenated silanes such as chlorine trimethyl silane, trimethylammonium bromide silane, iodine trimethyl silane, trialkyl organoalkoxysilanes such as methoxytrimethylsilane; Dialkyl group thiazolinyl chlorosilanes such as (chlorine) (vinyl) dimethylsilane; Dialkyl group alkenyl alkoxy silanes such as (methoxyl group) (vinyl) dimethylsilane, alkyl diaryl chlorosilanes such as (chlorine) (methyl) diphenyl silane, alkyl diaryl organoalkoxysilanes such as (methoxyl group) (methyl) diphenyl silane etc.

As commercially available article, for example enumerate out:

KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (more than, chemical industry commercial firm of SHIN-ETSU HANTOTAI system);

グ ラ ス レ ジ Application (clear and electrician commercial firm system);

SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, more than the SR2420(, eastern レ ダ ウ コ one ニ Application グ commercial firm system);

FZ3711, FZ3722 (more than, Japanese ユ ニ カ one commercial firm's system);

DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (more than, チ Star ソ commercial firm system);

Methyl silicate MS51, methyl silicate MS56 (more than, Mitsubishi Chemical Ind's system);

Tetraethyl silicate 28, ethyl silicate 40, tetraethyl silicate 48 (more than, コ Le コ one ト commercial firm system);

The partial condensate of GR100, GR650, GR908, GR950 (more than, clear with electrician commercial firm system) etc.

Among these other the silane compound; Consider preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162,3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane from the orientation of the liquid crystal aligning agent that obtained and the viewpoint of storage stability.

The preferred organopolysiloxane with epoxy group(ing) that uses imports the side chain with dielectric anisotropy among the present invention with sufficient amount in order to make; Its epoxy equivalent (weight) is preferably 100～10,000g/ mole, more preferably 150～1; The 000g/ mole is preferably 150～300g/ mole especially.Therefore; When synthesizing the precursor of organopolysiloxane with epoxy group(ing); Usage ratio with silane compound and other silane compound of epoxy group(ing) is preferably set according to the mode that the epoxy equivalent (weight) of the organopolysiloxane with epoxy group(ing) that is obtained is modulated into above-mentioned scope.In synthetic the present invention, use have the organopolysiloxane of epoxy group(ing) the time, more preferably only use the silane compound that has the silane compound of epoxy group(ing), do not use other.

As spendable organic solvent when synthesizing organopolysiloxane, for example enumerate out hydrocarbon compound, ketone compound, ester cpds, ether compound, alkylol cpd etc. with epoxy group(ing).

As above-mentioned hydrocarbon, for example enumerate out toluene, YLENE etc.; As above-mentioned ketone, for example enumerate out methylethylketone, MIBK, methyl-n-amyl ketone, metacetone, pimelinketone etc.; As above-mentioned ester, for example enumerate out ETHYLE ACETATE, n-butyl acetate, Isoamyl Acetate FCC, propylene glycol methyl ether acetate, 3-methoxyl group butylacetic acid ester, ethyl lactate etc.; As above-mentioned ether, for example enumerate out ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, THF 、 diox etc.; As above-mentioned alcohol, for example enumerate out 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol monomethyl n-propyl ether, glycol monomethyl n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, Ucar 35 list n-propyl ether etc.Preferred non-water-soluble organic solvent among them.These organic solvents can use or use two or more separately.

Consumption about organic solvent is preferably 10～10 with respect to persilylated compound 100 mass parts, 000 mass parts, more preferably 50～1,000 mass parts.The consumption of the water during organopolysiloxane that manufacturing has epoxy group(ing) is preferably 0.5～100 times of mole with respect to persilylated compound, more preferably 1～30 times of mole.

As above-mentioned catalyzer, for example can use acid, alkali metal cpd, organic bases, titanium compound, zirconium compounds etc.

As above-mentioned alkali metal cpd, for example enumerate out sodium hydroxide, Pottasium Hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc.

As above-mentioned organic bases; For example can enumerate out organic primary amine～organic secondary amine such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles respectively; Trimethylamines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene, organic quaternary amine such as TMAH etc.Among these organic basess, consider the viewpoint that reacting balance carries out, trimethylamines such as preferred triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, organic quaternary amine such as TMAH.

Catalyzer during the organopolysiloxane that has epoxy group(ing) as manufacturing, preferred as alkali compound or organic bases.Through with alkali metal cpd or organic bases as catalyzer, thereby the side reactions such as open loop of epoxy group(ing) do not take place, can obtain the organopolysiloxane of target with high hydrolytic condensation speed, so so production stability is excellent preferred.In addition, contain and use alkali metal cpd or organic bases as catalyzer and synthetic has the organopolysiloxane of epoxy group(ing) and this liquid crystal aligning agent of the reactant of specific carboxylic acid, its storage stability is extremely excellent, therefore convenient use.Its reason can be inferred for as follows: like ChemicalReviews, 95 volumes, point out in the 1409th page (nineteen ninety-five); When in hydrolysis, condensation reaction, using alkali metal cpd or organic bases as catalyzer; Form random structure, ladder shape structure or basket type structure, can obtain containing of silanol group of proportional few organopolysiloxane.Can infer: because containing of silanol group is proportional few; Therefore silanol group condensation reaction each other is suppressed; Further; Under the situation of the polymkeric substance of other that state after this liquid crystal aligning agent contains, because the condensation reaction of silanol group and other polymkeric substance is suppressed, so the result is an excellent storage stability.

As catalyzer, preferred especially organic bases.The consumption of organic bases is different because of reaction conditionss such as the kind of organic bases, temperature etc., should suitably set, but for example is preferably 0.01～3 times of mole with respect to persilylated compound, more preferably 0.05～1 times of mole.

Preferred following enforcement of hydrolysis during organopolysiloxane that manufacturing has epoxy group(ing) or hydrolysis-condensation reaction: will have the silane compound of epoxy group(ing) and other silane compound as required is dissolved in organic solvent; This solution is mixed with organic bases and water, thereby for example implement through heating such as oil baths.

When hydrolysis-condensation reaction, the Heating temperature of oil bath is preferably below 130 ℃, and more preferably 40～100 ℃, preferably heated 0.5～12 hour, more preferably heated 1～8 hour.Add and pine for, can mixed solution be stirred, also can be placed on and reflux down.

Behind the reaction terminating, preferred water will wash from the organic solvent layer that reaction solution is obtained.In this when washing, through with comprising the water of a spot of salt, for example use washings such as aqueous ammonium nitrate solution about 0.2 quality %, thereby be prone to the washing operation transfiguration, considers this viewpoint and preferred.The water layer that washing proceeds to after the washing becomes neutrality, thereafter as required with organic solvent layer with siccative dryings such as anhydrous calciumsulphate, molecular sieves after, the removal solvent, thus can obtain the organopolysiloxane with epoxy group(ing) of target.

In the present invention, also can use as organopolysiloxane and commercially available product with epoxy group(ing).As so commercially available article, for example enumerate out DMS-E01, DMS-E12, DMS-E21, EMS-32 (more than, チ Star ソ commercial firm) etc.

[A] compound also can comprise: be derived from the hydrolysis of the organopolysiloxane with epoxy group(ing) own and the part of the hydrolyzate that produces, be derived from organopolysiloxane hydrolytic condensation and the part of the hydrolytic condensate that obtains each other with epoxy group(ing).These hydrolyzates, hydrolytic condensate as the constituent material of this part also can likewise prepare with hydrolysis, the condensation condition of the organopolysiloxane with epoxy group(ing).

[being derived from the part of specific carboxylic acid]

This part that is derived from by the specific carboxylic acid of above-mentioned formula (2) expression is equivalent to: in this liquid crystal aligning agent among the structure of contained [A] compound with the structure that is derived from carboxyl side-chain structure as starting point, the said structure that is derived from carboxyl mainly combines with the structure that is derived from from the extended epoxy group(ing) of organopolysiloxane main chain.But be called " part that is derived from specific carboxylic acid " that also comprises in the present invention, specific carboxylic acid and the part bonded situation except epoxy group(ing).

R in the above-mentioned formula (2) ¹And R ²With the R in the above-mentioned formula (1) ¹And R ²Identical.

The R of above-mentioned formula (2) ³Be alkylidene group, phenylene or the cyclohexylidene of methylene radical or carbonatoms 2～30, they can further have substituting group.

As the alkylidene group of carbonatoms 2～30, enumerate out ethylidene, propylidene, butylidene, pentylidene, hexylidene, octylene, nonamethylene, inferior decyl, inferior undecyl, inferior dodecyl, inferior tetradecyl, inferior hexadecyl, inferior octadecyl, inferior nonadecyl, inferior eicosyl, inferior heneicosyl, inferior docosyl, inferior tricosyl, inferior tetracosyl, inferior pentacosyl, inferior cerylic, inferior heptacosyl, inferior octacosyl, inferior nonacosyl and inferior triacontyl etc.Among them, being preferably carbonatomss such as pentylidene, hexylidene, octylene, nonamethylene, inferior decyl, inferior undecyl, inferior dodecyl, inferior tetradecyl, inferior hexadecyl, inferior octadecyl, inferior nonadecyl, inferior eicosyl in order stably to manifest liquid crystal aligning is the alkylidene group below 20 more than 5.

As compound with carboxyl by above-mentioned formula (2) expression, for example enumerate out compound by following formula (E-1)～(E-25) expression,

In the formula (E-1)～(E-25), R ¹With the same definition of above-mentioned formula (2).M is 1～30 integer.

[compound method of specific carboxylic acid]

The synthesis procedure of specific carboxylic acid is not special to be limited, known method in the past capable of being combined and carrying out.As representational synthesis procedure; For example illustration goes out following method: (1) makes the alkyl chain part of compound with phenol skeleton and high-grade aliphatic ester replaced by halogen under alkaline condition and the compound reaction that obtains; The hydroxyl of phenol skeleton with form key by the substituted carbon of halogen; Ester reduction processed the method for specific carboxylic acid thereafter; (2) compound with phenol skeleton and ethylene carbonate are reacted and generate the terminal alcohol compound, its hydroxyl and halogeno-benzene SULPHURYL CHLORIDE are reacted and activation, activated partial and the oil of Niobe that comprises hydroxyl are reacted; Generate key thereby the disengaging of alkylsulfonyl part and the hydroxyl of terminal alcohol compound take place with comprising the hydroxyl of hydroxyl, then the ester reduction is processed the method for specific carboxylic acid etc. as substituent oil of Niobe.But the synthesis procedure of specific carboxylic acid is not subject to them.

< compound method of [A] compound >

As the compound method of [A] compound, not special the qualification can be synthesized through general known method.[A] compound has under the situation of the part that is derived from the organopolysiloxane with epoxy group(ing) and the part that is derived from specific carboxylic acid, can be through making organopolysiloxane and specific carboxylic acid reaction with epoxy group(ing), and preferably in the presence of catalyzer, react and synthesize.

Specific here carboxylic acid preferably uses 0.001～10 mole for 1 mole with respect to the epoxy group(ing) that organopolysiloxane had, and more preferably uses 0.01～5 mole, 0.05～2 mole of further preferred use.

In the present invention, replace the part of specific carboxylic acid and use at the also available compound of the scope of not damaging effect of the present invention by following formula (4) expression.In the case, the synthetic of [A] compound carries out through making organopolysiloxane with epoxy group(ing) and, specific carboxylic acid and being reacted by the mixture of the compound of following formula (4) expression.

A ¹-L ⁰-L ¹-Z (4)

In the above-mentioned formula (4), A ¹For the straight chain shape of carbonatoms 1～30 or branched-chain alkyl, can or have the alkyl of the carbonatoms 17～51 of steroid backbone by the naphthenic base of the alkyl of carbonatoms 1～20 or the substituted carbonatoms 3～10 of alkoxyl group.Wherein, the Wasserstoffatoms of abovementioned alkyl and alkoxyl group a part or all also can replace by substituting groups such as cyanic acid, fluorine atom, trifluoromethyls.

L ⁰Be singly-bound, *-O-, *-COO-or *-OCO-.Key end and A with " * " ¹In conjunction with.

L ¹For the alkylidene group of singly-bound, carbonatoms 1～20, phenylene, biphenylene, cyclohexylidene, two cyclohexylidene or by following formula (L ¹-1) or (L ¹-2) group of expression.

Z is for forming the organic group of 1 valency of linking group with the epoxy reaction in [A] polyorganosiloxane compounds.

Wherein, at L ¹L during for singly-bound ⁰Be singly-bound.

Above-mentioned formula (L ¹-1) and (L ¹-2) the key end with " * " in combines with Z respectively.

Z is preferably carboxyl.

As A in above-mentioned formula (4) ¹The straight chain shape or the branched-chain alkyl of represented carbonatoms 1～30 are for example enumerated out: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethyl propyl, n-hexyl, 4-methyl amyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 3; 3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2; 2-dimethylbutyl, 1,2-dimethylbutyl, 1,2-dimethylbutyl, 1; 1-dimethylbutyl, n-heptyl, 5-methyl hexyl, 4-methyl hexyl, 3-methyl hexyl, 2-methyl hexyl, 1-methyl hexyl, 4,4-dimethyl-amyl group, 3,4-dimethyl-amyl group, 2; 4-dimethyl-amyl group, 1,4-dimethyl-amyl group, 3,3-dimethyl-amyl group, 2; 3-dimethyl-amyl group, 1,3-dimethyl-amyl group, 2,2-dimethyl-amyl group, 1; 2-dimethyl-amyl group, 1; 1-dimethyl-amyl group, 2,3,3-trimethylammonium butyl, 1; 3; 3-trimethylammonium butyl, 1,2,3-trimethylammonium butyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, NSC 172782 base, Octadecane base, NSC 77136 base etc.

As can for example enumerating out cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, cyclo-dodecyl etc. by the naphthenic base of the alkyl or the substituted carbonatoms 3～10 of alkoxyl group of carbonatoms 1～20.

As the alkyl of the carbonatoms with steroid backbone 17～51, for example enumerate out group by following formula (A-1)～(A-3) expression.

As the A in the above-mentioned formula (4) ¹, be preferably fluoroalkyl and the above-mentioned formula (A-1) of the alkyl that is selected from carbonatoms 1～20, carbonatoms 1～20 or (A-3) in group.

As compound, preferably by the compound of each expression in following formula (4-1)～(4～6) by above-mentioned formula (4) expression.

C _uF _2u+1-C _vH _2v-COOH (4-1)

C _wH _2w+1-COOH (4-2)

In the above-mentioned formula (4-1)～(4-6), u is 1～5 integer.V is 1～18 integer.W is 1～20 integer.K is 1～5 integer.P is 0 or 1.Q is 0～18 integer.R is 0～18 integer.S and t are 0～2 integer independently of one another.

Among these compounds, the compound of more preferably representing by following formula (4-7)～(4-13).

C ₁₇H ₃₅-COOH (4-7)

Compound by above-mentioned formula (4) expression is: with specific carboxylic acid together with the organopolysiloxane reaction with epoxy group(ing), and form and can give the liquid crystal orientation film that obtained compound with the position of the manifesting property of slope (tilt angle) of regulation.Sometimes will be called " other manifesting property of tilt angle compound " by the compound of above-mentioned formula (4) expression in this manual.

In the present invention; Together use under other the situation of manifesting property of tilt angle compound with specific carboxylic acid; The usage ratio of the total of specific carboxylic acid and other manifesting property of tilt angle compound is preferably 0.001～1.5 mole for 1 mole with respect to the epoxy group(ing) that organopolysiloxane had; More preferably 0.01～1 mole, further be preferably 0.05～0.9 mole.In the case, other manifesting property of tilt angle compound with respect to the total of itself and specific carboxylic acid preferably with 75 moles below the %, more preferably use with 50 moles of scopes below the %.When the usage ratio of other manifesting property of tilt angle compound surpasses 75 moles of %, have and occurring dysgenic situation aspect the high-speed response property of liquid crystal.

The catalyzer that uses in the reaction as epoxy group(ing) in the organopolysiloxane and other manifesting property of tilt angle compound can use organic bases or as so-called curing catalyst and the known compound of the reaction that can promote epoxy compounds and acid anhydrides.

As above-mentioned organic bases, for example enumerate out organic primary amine～organic secondary amine such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles; Trimethylamines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene; Organic quaternary amine such as TMAH etc.Among these organic basess, preferred triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, TMAH.

As above-mentioned curing catalyst, for example enumerate out:

Benzyl dimethyl amine, 2,4, tertiary amines such as 6-three (dimethylaminomethyl) phenol, cyclohexyl dimethyl amine, trolamine;

Glyoxal ethyline, 2-n-heptyl imidazoles, 2-n-undecane base imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1; 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-glyoxal ethyline, 1-(2-cyanoethyl)-2-n-undecane base imidazoles, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazoles, 2-phenyl-4; 5-two (hydroxymethyl) imidazoles, 1-(2-cyanoethyl)-2-phenyl-4; 5-two [(2 '-cyanic acid oxyethyl group) methyl] imidazoles, 1-(2-cyanoethyl)-2-n-undecane base imidazoles trimellitate, 1-(2-cyanoethyl)-2-phenylimidazole trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole trimellitate, 2; 4-diamino--6-[2 '-methylimidazolyl-(1 ')] ethyl s-triazine, 2; 4-diamino--6-(2 '-n-undecane base imidazolyl) ethyl s-triazine, 2; 4-diamino--6-[2 '-ethyl-4 '-methylimidazolyl-(1 ')] ethyl s-triazine, the isocyanuric acid affixture of glyoxal ethyline, the isocyanuric acid affixture, 2 of 2-phenylimidazole, the imidazolium compoundss such as isocyanuric acid affixture of 4-diamino--6-[2 '-methylimidazolyl-(1 ')] ethyl s-triazine;

Organo phosphorous compoundss such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; Benzyl triphenyl phosphonium chloride squama, tetran-butylphosphonium bromide squama, methyltriphenylphospbromide bromide squama, ethyl triphenyl bromination squama, normal-butyl triphenyl bromination squama, tetraphenylphosphonibromide bromide squama, ethyltriphenylphosphiodide iodide squama, ethyl triphenyl squama acetic ester, tetra-n-butyl squama o, season squama salt such as o-diethyl phosphorothioate, tetra-n-butyl squama benzotriazole salt, tetra-n-butyl squama a tetrafluoro borate, tetra-n-butyl squama tetraphenyl borate salts, tetraphenyl squama tetraphenyl borate salts;

1, Diazabicycloalkenes such as 8-diazabicyclo [5.4.0] 11 carbon-7-alkene, its organic acid salt;

Organometallic compounds such as zinc octoate, stannous octoate, acetopyruvic acid aluminium coordination compound;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride;

Boron cpd such as boron trifluoride, triphenyl borate;

Metal halide such as zinc chloride, tin chloride compound;

HMP decentralized potentiality curing catalysts such as amine add-on type promotor such as the affixture of Dyhard RU 100, amine and epoxy resin;

By the surface coverage microcapsule-type potentiality curing catalyst that obtain of polymkeric substance with above-mentioned imidazolium compounds, organo phosphorous compounds, season curing catalyst such as squama salt;

Amine salt type potentiality curing catalyst;

Potentiality curing catalysts such as the hot cationic polymerization type potentiality curing catalyst of high temperature dissociative types such as lewis acid, Bronsted hydrochlorate etc.

Among these catalyzer, quaternary ammonium salts such as preferred tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride.

Catalyzer with respect to 100 mass parts of the organopolysiloxane with epoxy group(ing) preferably with below 100 mass parts, more preferably with 0.01～100 mass parts, further preferably use with the amount of 0.1～20 mass parts.

Temperature of reaction is preferably 0～200 ℃, more preferably 50～150 ℃.Reaction times is preferably 0.1～50 hour, more preferably 0.5～20 hour.

The building-up reactions of [A] compound can be carried out in the presence of organic solvent as required.As above-mentioned organic solvent, for example enumerate out hydrocarbon compound, ether compound, ester cpds, ketone compound, amide compound, alkylol cpd etc.Among them, consider viewpoint and preferred ether compound, ester cpds, the ketone compound of purified easness of solvability and the product of raw material and product.Solvent with solid component concentration (quality of the composition except solvent in the reaction soln in the total mass of solution shared ratio) be preferably more than the 0.1 quality % below the 70 quality %, more preferably the amount below the 50 quality % is used more than the 5 quality %.

[A] compound that obtains is so converted and the weight-average molecular weight that obtains does not limit especially through vinylbenzene what gel permeation chromatograph was measured, still is preferably 1,000～200,000, and more preferably 2,000～20,000.Through being in such molecular weight ranges, thereby can guarantee orientation and stability that liquid crystal display device is good.

With regard to above-mentioned [A] compound, thereby the carboxylate moiety through specific carboxylic acid has to the open loop addition of epoxy group(ing) to import in the organopolysiloxane of epoxy group(ing) the structure that is derived from specific carboxylic acid is being arranged.This method of manufacture considers it is preferable methods extremely from viewpoint easy and that can improve the importing rate of the structure that is derived from specific carboxylic acid.

< optional member >

With regard to this liquid crystal aligning agent; Except above-mentioned [A] compound; Only otherwise damage effect of the present invention; For example so also can contain other optional member such as compound (below, be sometimes referred to as " epoxy compounds "), functional silanes compound, tensio-active agent of having at least one epoxy group(ing) except [A] polymkeric substance the compound (below, be sometimes referred to as " other polymkeric substance "), solidifying agent, curing catalysts, curing catalyst, at intramolecularly.

[other polymkeric substance]

With regard to other polymkeric substance, can use for the electrical characteristic of changing solution properties of being apt to this liquid crystal aligning agent and the liquid crystal display device that is obtained.As other polymkeric substance, for example enumerate out:

At least a polymkeric substance of selecting in the group that forms by polyamic acid and polyimide ([B] polymkeric substance);

By the organopolysiloxane of following formula (5) expression, its hydrolyzate with and the group formed of the condenses of hydrolyzate at least a (below, be sometimes referred to as " other organopolysiloxane ");

Poly amic acid ester, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, gather (vinylbenzene-phenyl maleimide) verivate, gather (methyl) propenoate etc.,

In the formula (5), X ¹Be the alkyl of hydroxyl, halogen atom, carbonatoms 1～20, the alkoxyl group of carbonatoms 1～6 or the aryl of carbonatoms 6～20.Y ¹Alkoxyl group for hydroxyl or carbonatoms 1～10.

< [B] polymkeric substance >

At least a polymkeric substance of [B] polymkeric substance for selecting in the group that forms by polyamic acid and polyimide.Below, polyamic acid and polyimide are detailed.

[polyamic acid]

Polyamic acid obtains through tetracarboxylic dianhydride and diamine compound are reacted.

As the tetracarboxylic dianhydride, for example enumerate out aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.These tetracarboxylic dianhydrides can use separately or make up two or more and use.

As the aliphatics tetracarboxylic dianhydride, for example enumerate out butane tetracarboxylic acid dianhydride etc.

As the ester ring type tetracarboxylic dianhydride, for example enumerate out 1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, 2,3; 5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2; 5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1,3-diketone, 1,3,3a, 4; 5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1,3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(THF-2 '; 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-ethyloic norbornane-2:3,5:6-dianhydride, 2; 4,6,8-tetracarboxylic dicyclo [3.3.0] octane-2:4,6:8-dianhydride, 4,9-dioxa three ring 5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone etc.

As aromatic tetracarboxylic acid's dianhydride, except for example enumerating out pyromellitic acid dianhydride etc., also enumerate out the special tetracarboxylic dianhydride who is willing to record in 2010-97188 number of Japan.

Among these tetracarboxylic dianhydrides, preferred ester ring type tetracarboxylic dianhydride, more preferably 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride or 1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, preferred especially 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride.

With regard to 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride or 1,2; 3, the consumption of 4-tetramethylene tetracarboxylic acid dianhydride is preferably 10 moles more than the % with respect to whole tetracarboxylic dianhydrides, more preferably 20 moles more than the %; Especially preferably only comprise 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride or 1; 2,3,4-tetramethylene tetracarboxylic acid dianhydride.

As diamine compound, for example enumerate out aliphatie diamine, ester ring type diamines, diamino-organo-siloxane, aromatic diamine etc.These diamine compounds can use separately or make up two or more and use.

As aliphatie diamine, for example enumerate out m-xylene diamine, 1,3-tn, tetramethylene-diamine, five methylene diamine, hexanediamine etc.

As the ester ring type diamines, for example enumerate out 1,4-DACH, 4,4 '-methylene-bis (hexahydroaniline), 1, two (amino methyl) hexanaphthenes of 3-etc.

As the diamino-organo-siloxane,, outside two (3-the aminopropyl)-tetramethyl disiloxanes of 3-etc., also enumerate out the special diamines of being willing to record in 2009-97188 number of Japan except for example enumerating out 1.

As aromatic diamine, for example enumerate out Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1; 5-diaminonaphthalene, 2,2 '-dimethyl--4,4 '-benzidine, 4,4 '-diamino--2; 2 '-two (trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2, two [4-(4-amino-benzene oxygen) phenyl] propane, 9 of 2-; Two (4-aminophenyl) fluorenes, 2 of 9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas, 2 of 2-, two (4-aminophenyl) HFC-236fas, 4 of 2-, 4 '-(to phenylene two isopropylidenes) two (aniline), 4; 4 '-(metaphenylene two isopropylidenes) two (aniline), 1, two (4-amino-benzene oxygen) benzene, 4 of 4-, 4 '-two (4-amino-benzene oxygen) biphenyl, 2,6-diamino-pyridine, 3; 4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamino-carbazole, N-methyl-3; 6-diamino-carbazole, N-ethyl-3,6-diamino-carbazole, N-phenyl-3,6-diamino-carbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, N; N '-two (4-aminophenyl)-N, N '-tolidine, 1,4-pair-(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2; 4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2; 4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxyaniline-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2; 5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane oxygen base-3,5-diaminobenzene, cholestene oxygen base-3; 5-diaminobenzene, cholestane oxygen base-2,4-diaminobenzene, cholestene oxygen base-2,4-diaminobenzene, 3; 5-diaminobenzoic acid cholestane ester, 3,5-diaminobenzoic acid cholestene ester, 3,5-diaminobenzoic acid lanostane ester, 3; Two (the 4-aminobenzoic acyl-oxygen base) cholestane of 6-, 3, two (4-amino-benzene oxygen) cholestane of 6-; 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethyl benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 1; Two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexanes, 1 of 1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptyl hexanaphthenes, 1 of 1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptyl hexanaphthenes, 1 of 1-; Two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthenes, 2 of 1-, 4-diamino-N, N-diallyl aniline, 4-amino-benzylamine, 3-amino-benzylamine and by the diamine compound of following formula (A-1) expression etc.

In the above-mentioned formula (A-1), X ¹For the alkylidene group of methylene radical or carbonatoms 2 or 3 ,-O-,-COO-or-OCO-.R is 0 or 1.S is 0～2 integer.T is 1～20 integer.

As the tetracarboxylic dianhydride of the building-up reactions that is supplied in polyamic acid and the usage ratio of diamine compound; With respect to amino contained in the diamine compound 1 equivalent; Preferred tetracarboxylic dianhydride's anhydride group is 0.2 equivalent～2 equivalents, more preferably 0.3 equivalent～1.2 equivalents.

Preferred building-up reactions is carried out in organic solvent.As temperature of reaction, be preferably-20 ℃～150 ℃, more preferably 0 ℃～100 ℃.As the reaction times, be preferably 0.5 hour～24 hours, more preferably 2 hours～12 hours.

As organic solvent; If the then not special restriction of the organic solvent of solubilized institute synthetic polyamic acid; For example enumerate out N-N-methyl-2-2-pyrrolidone N-(NMP), DMAC N,N, N, dinethylformamide, N; N-methylimidazole alkane ketone, DMSO 99.8MIN., gamma-butyrolactone, 4-methyl urea, hexamethyl phosphinylidyne triamide etc. are non-proton to be polar solvent, phenol series solvents such as meta-cresol, xylenol, phenol, halogenated phenol.

As the consumption (a) of organic solvent, the total (a+b) with respect to the consumption (a) of the total amount (b) of tetracarboxylic dianhydride and diamine compound and organic solvent is preferably 0.1 quality %～50 quality %, more preferably 5 quality %～30 quality %.

The polyamic acid solution that obtains after the reaction can directly supply the preparation in liquid crystal aligning agent; Also can be in independent separating reaction solution supply preparation on the basis of contained polyamic acid, also can on the basis of refining independent isolated polyamic acid, supply preparation in liquid crystal aligning agent in liquid crystal aligning agent.As the independent separation method of polyamic acid, for example enumerate out: under reduced pressure will be through reaction soln being injected the precipitate exsiccant method that a large amount of poor solvents obtains, through vaporizer with the reaction soln distilled method etc. that reduces pressure.As the process for purification of polyamic acid, enumerate out: once more independent isolated polyamic acid is dissolved in organic solvent, the method for separating out by poor solvent, 1 time or repeatedly carry out with the method for vaporizer with decompression distilled operations such as organic solvents.

[polyimide]

Polyimide, thus can make by imidization through the amido acid structure that above-mentioned polyamic acid had is carried out dehydration closed-loop.Polyimide can be for carrying out the complete imidization thing that dehydration closed-loop obtains to the amido acid structure that polyamic acid had of whole its precursors of conduct, also can be the part imidization thing that only part of amido acid structure is carried out dehydration closed-loop, made amido acid structure and imide ring structure and deposit.

Compound method as polyimide; For example enumerate out (i) polyamic acid heating means (below; Be sometimes referred to as " method (i) "), (ii) polyamic acid is dissolved in organic solvent; In this solution, add dewatering agent and dehydration closed-loop catalyzer, as required and the method that the method for heating (below, be sometimes referred to as " method (ii) ") waits the dehydration closed-loop based on polyamic acid to react.

As the temperature of reaction in the method (i), be preferably 50 ℃～200 ℃, more preferably 60 ℃～170 ℃.During 50 ℃ of temperature of reaction less thaies, insufficient the carrying out of dehydration closed-loop reaction, the molecular weight of the polyimide that temperature of reaction is obtained when surpassing 200 ℃ reduces sometimes.As the reaction times, be preferably 0.5 hour～48 hours, more preferably 2 hours～20 hours.

The polyimide that obtains in the method (i) can directly supply the preparation in liquid crystal aligning agent; Also can on the basis of separating polyimide separately, supply preparation, or also can supply preparation on the basis of the refining polyimide of telling separately or on the basis of the refining polyimide that is obtained in liquid crystal aligning agent in liquid crystal aligning agent.

As the dewatering agent of method in (ii), for example enumerate out acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.

As the consumption of dewatering agent, come suitably to select according to desirable imidization rate, but, be preferably 0.01 mole～20 moles with respect to 1 mole on the amido acid structure of polyamic acid.

As the dehydration closed-loop catalyzer of method in (ii), for example enumerate out pyridine, trimethylpyridine, lutidine, triethylamine etc.

As the dehydration closed-loop catalyst consumption, with respect to 1 mole of the dewatering agent that contains, preferred 0.01 mole～10 moles.Again, with regard to the imidization rate, the content of above-mentioned dewatering agent and dehydration closed-loop agent more at most can be high more.

As the organic solvent that method is used in (ii), for example enumerate out: with as the organic solvent that uses in polyamic acid synthetic and the same organic solvent of illustrative organic solvent etc.

As the temperature of reaction of method in (ii), be preferably 0 ℃～180 ℃, more preferably 10 ℃～150 ℃.As the reaction times, be preferably 0.5 hour～20 hours, more preferably 1 hour～8 hours.Through making reaction conditions is above-mentioned scope, and the dehydration closed-loop sufficient reacting is carried out, and in addition, the molecular weight that can make the polyimide that is obtained is appropriate molecular weight.

Can obtain to contain the reaction soln of polyimide in (ii) in method.Can this reaction soln directly be supplied the preparation in liquid crystal aligning agent; Also can supply preparation on the basis of having removed dewatering agent and dehydration closed-loop catalyzer from reaction soln in liquid crystal aligning agent; Also can on the basis of separating polyimide separately, supply preparation, or also can on the basis of refining independent isolated polyimide, supply preparation in liquid crystal aligning agent in liquid crystal aligning agent.As the method for removing dewatering agent and dehydration closed-loop catalyzer from reaction soln, for example enumerate out the method for solvent exchange etc.As the independent separation method and the process for purification of polyimide, for example enumerate out with as the independent separation method of polyamic acid and process for purification and the same method of illustrative method etc.

[other organopolysiloxane]

This liquid crystal aligning agent also can comprise other organopolysiloxane except [A] that comprises the part that is derived from organopolysiloxane the compound.Other organopolysiloxane be preferably by the organopolysiloxane of above-mentioned formula (5) expression, its hydrolyzate with and the group that forms of the condenses of hydrolyzate in select at least a.Again, this liquid crystal aligning agent comprises under other the situation of organopolysiloxane, and the major part of other organopolysiloxane can be used as independent with [A] compound and the material that exists and existing, and its part also can be used as with the condenses of [A] compound and exists.

X in above-mentioned formula (5) ¹And Y ¹In,

As the alkyl of carbonatoms 1～20, for example enumerate out methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive lauryl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, NSC 172782 base, Octadecane base, NSC 77136 base, NSC 62789 base etc.;

As the alkoxyl group of carbonatoms 1～16, for example enumerate out methoxyl group, oxyethyl group etc.;

As the aryl of carbonatoms 6～20, for example enumerate out phenyl etc.

With regard to other organopolysiloxane; At least a silane compound that for example can be through selecting in the group that will form by alkoxysilane compound containing trialkylsilyl group in molecular structure and halogenated silanes compound (below; Be sometimes referred to as " raw silicon hydride compounds "); Preferably in suitable organic solvent, thereby hydrolysis or hydrolytic condensation are synthetic in the presence of water and catalyzer.

As spendable raw silicon hydride compounds here, for example enumerate out tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec.-butoxy silane, four tert.-butoxy silane, tetrachloro silicane; Methyltrimethoxy silane; Union carbide A-162; Methyl three positive propoxy silane; Methyl three isopropoxy silane; Methyl three n-butoxy silane; Methyl three sec.-butoxy silane; Methyl three tert.-butoxy silane; Methyl triple phenoxyl silane; METHYL TRICHLORO SILANE; Ethyl trimethoxy silane; Ethyl triethoxysilane; Ethyl three positive propoxy silane; Ethyl three isopropoxy silane; Ethyl three n-butoxy silane; Ethyl three sec.-butoxy silane; Ethyl three tert.-butoxy silane; Ethyl trichlorosilane; Phenyltrimethoxysila,e; Phenyl triethoxysilane; Phenyl-trichloro-silicane; Dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyldichlorosilane(DMCS); Trimethylammonium methoxy silane, trimethylethoxysilane, trimethylchlorosilane etc.Among them, preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylammonium methoxy silane, trimethylethoxysilane.

When synthetic other organopolysiloxane,, for example enumerate out alkylol cpd, ketone compound, amide compound or ester cpds or other aprotic compound as can arbitrarily used organic solvent.They can use or use two or more separately.

As alkylol cpd, for example enumerate out:

Methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, 2-methyl butanol, sec.-amyl alcohol, tertiary amyl alcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl amyl alcohol, secondary hexyl alcohol, 2-ethyl butanol, secondary enanthol, heptan-3-alcohol, n-Octanol, 2-Ethylhexyl Alcohol, secondary octanol, nonanol-, 2; 6-dimethyl-enanthol-4, nonylcarbinol, secondary hendecanol, Exxal 12, secondary tetradecanol, secondary heptadecanol, phenol, hexalin, methyl ring hexalin, 3; 3, monohydroxy-alcohol compounds such as 5-cyclonol, benzylalcohol, diacetone alcohol;

Terepthaloyl moietie, 1,2-Ucar 35,1,3 butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-pinakon, 2,4-heptanediol, 2-ethyl-1, polyol compounds such as 3-pinakon, Diethylene Glycol, dipropylene glycol, triglycol, tripropylene glycol;

Ethylene glycol monomethyl ether; Ethylene glycol monoethyl ether; Ethylene glycol ether; Ethylene glycol monobutyl ether; Ethylene glycol ether; The glycol monomethyl phenyl ether; Glycol monomethyl-2-ethyl-butyl ether; Diethylene glycol monomethyl ether; Diethylene glycol monoethyl ether; Diethylene glycol monopropyl ether; Diethylene glycol monobutyl ether; The Diethylene Glycol monohexyl ether; Propylene glycol monomethyl ether; Dihydroxypropane single-ether; Propylene glycol monopropyl ether; Propylene glycol monobutyl ether; Dipropylene glycol monomethyl ether; Dipropylene glycol list ether; The part ether of polyol compounds such as dipropylene glycol list propyl ether etc.These alkylol cpds can use or use two or more separately.

As ketone compound, for example enumerate out:

Acetone, methylethylketone, methyl n-propyl ketone, methyl n-butyl ketone, metacetone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl normal-butyl ketone, methyl n hexyl ketone, DIBK, trimethylammonium nonanone, pimelinketone, methyl-n-butyl ketone, methylcyclohexanone, 2; Single ketones compounds such as 4-pentane diketone, acetonyl-acetone, methyl phenyl ketone, fenchone

Acetopyruvic acid, 2,4-hexane diketone, 2,4-heptane diketone, 3,5-heptane diketone, 2,4-octane diketone, 3; 5-octane diketone, 2,4-nonane diketone, 3,5-nonane diketone, 5-methyl-2,4-hexane diketone, 2,2; 6,6-tetramethyl--3,5-heptane diketone, 1,1,1; 5,5,5-hexafluoro-2, beta-diketone compounds such as 4-heptane diketone etc.These ketone compounds can use or use two or more separately.

As above-mentioned amide compound; For example enumerate out methane amide, N-NMF, N; Dinethylformamide, N-ethyl-formamide, N; N-DEF, ethanamide, N-methylacetamide, DMAC N,N, N-ethyl acetamide, N, N-diethyl acetamide, N-methyl propanamide, N-Methyl pyrrolidone, N-formyl morpholine, N-formyl piperidine, N-carbonyl pyrrolidine, N-ethanoyl morpholine, N-ethanoyl piperidines, N-acetyl-pyrrolidine etc.These amide compounds can use or use two or more separately.

As ester cpds, for example enumerate out diethyl carbonate, ethylene carbonate, Texacar PC, diethyl carbonate, methyl acetate, ETHYLE ACETATE, gamma-butyrolactone, γ-Wu Neizhi, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, acetate 3-methoxyl group butyl ester, methyl amyl acetate, acetate 2-ethyl butyl ester, acetate 2-ethylhexyl, jasmal, hexalin acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, methyl aceto acetate, acetate ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, acetate diethylene glycol monomethyl ether, acetate diethylene glycol monoethyl ether, acetate Diethylene Glycol list n-butyl ether, acetate propylene glycol monomethyl ether, acetate dihydroxypropane single-ether, acetate propylene glycol monopropyl ether, acetate propylene glycol monobutyl ether, acetate dipropylene glycol monomethyl ether, acetate dipropylene glycol list ether, diacetate glycol ester, acetate methoxyl group triglycol ester, ethyl propionate, n-butyl propionate, isopentyl pyruvate, diethyl oxalate, oxalic acid di-n-butyl, methyl lactate, ethyl lactate, n-butyl lactate, lactic acid n-pentyl ester, ethyl malonate, dimethyl phthalate, diethyl phthalate etc.These ester cpds can use or use two or more separately.

As other aprotic compound; For example enumerate out acetonitrile, DMSO 99.8MIN., N; N; N ', N '-tetraethyl-sulphamide, HPT, N-methylmorpholine ketone, N-methylpyrrole, N-N-ethyl pyrrole N-, N-methyl-Δ 3-pyrroline, N-methyl piperidine, N-ethylpiperidine, N, N-lupetazin, N-Methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-N-methyl-2-2-pyrrolidone N-, 1; 3-dimethyl--2-imidazolidone, 1,3-dimethyl tetrahydro-2 (1H)-pyrimidone etc.Among these solvents, the part ether or the ester cpds of special preferred polyol compound, polyol compound.

Amount as the water that uses when other organopolysiloxane synthetic; The alkoxyl group that is had with respect to the raw silicon hydride compounds and the total amount of halogen atom 1 mole; Be preferably 0.01～100 mole, more preferably 0.1～30 mole, further be preferably 1～1.5 mole.

As spendable catalyzer when other organopolysiloxane synthetic, for example enumerate out metallo-chelate, organic acid, mineral acid, organic bases, ammoniacal liquor, alkali metal cpd etc.

As above-mentioned metallo-chelate; For example enumerate out: tri-alkoxy list (acetopyruvic acid) titaniums such as triethoxy list (acetopyruvic acid) titanium; Two (acetopyruvic acid) titaniums of dialkoxy such as two (acetopyruvic acid) titaniums of diethoxy; Monoalkoxy three (acetopyruvic acid) titaniums such as monosubstituted ethoxy three (acetopyruvic acid) titanium; Four (acetopyruvic acid) titanium; Tri-alkoxy list (ethyl acetoacetic acid) titaniums such as triethoxy list (ethyl acetoacetic acid) titanium, two (ethyl acetoacetic acid) titaniums of dialkoxy such as two (ethyl acetoacetic acid) titaniums of diethoxy, monoalkoxy three (ethyl acetoacetic acid) titaniums such as monosubstituted ethoxy three (ethyl acetoacetic acid) titanium; Four (ethyl acetoacetic acid) titanium, single (acetopyruvic acid) three (ethyl acetoacetic acid) titanium, two (acetopyruvic acids) two (ethyl acetoacetic acid) titanium, single (ethyl acetoacetic acid) titanium etc. of three (acetopyruvic acids) comprise the titanium chelates such as titanium compound of two or more chelating ligands;

Tri-alkoxy list (acetopyruvic acid) zirconiums such as triethoxy list (acetopyruvic acid) zirconium; Two (acetopyruvic acid) zirconiums of dialkoxy such as two (acetopyruvic acid) zirconiums of diethoxy; Monoalkoxy three (acetopyruvic acid) zirconiums such as monosubstituted ethoxy three (acetopyruvic acid) zirconium; Four (acetopyruvic acid) zirconium; Tri-alkoxy list (ethyl acetoacetic acid) zirconiums such as triethoxy list (ethyl acetoacetic acid) zirconium; Two (ethyl acetoacetic acid) zirconiums of dialkoxy such as two (ethyl acetoacetic acid) zirconiums of diethoxy; Monoalkoxy three (ethyl acetoacetic acid) zirconiums such as monosubstituted ethoxy three (ethyl acetoacetic acid) zirconium, four (ethyl acetoacetic acid) zirconium, single (acetopyruvic acid) three (ethyl acetoacetic acid) zirconium, two (acetopyruvic acids) two (ethyl acetoacetic acid) zirconium, single (ethyl acetoacetic acid) zirconium etc. of three (acetopyruvic acids) comprise the zirconium chelates such as zirconium compounds of two or more chelating ligands;

Aluminum chelates such as three (acetopyruvic acid) aluminium, three (ethyl acetoacetic acid) aluminium etc.

As above-mentioned organic acid; For example enumerate out aliphatics saturated carboxylic acids such as formic acid, acetate, propionic acid; Aliphatics such as propanedioic acid, fumaric acid unsaturated carboxylic acid, aromatic carboxylic acids such as Whitfield's ointment, phenylformic acid, phthalic acid, aromatic sulphonic acids such as tosic acid, Phenylsulfonic acid; Halogen-containing carboxylic acids such as Monochloro Acetic Acid, trichoroacetic acid(TCA), trifluoroacetic acid, Hydrocerol A, tartrate etc.

As above-mentioned mineral acid, for example enumerate out hydrochloric acid, nitric acid, sulfuric acid, hydrogen fluoride, phosphoric acid etc.

As above-mentioned organic bases; For example enumerate out pyridine, pyrroles, piperazine, tetramethyleneimine, piperidines, picoline, Trimethylamine 99, triethylamine, monoethanolamine, diethylolamine, dimethyl-monoethanolamine, monomethyl diethylolamine, trolamine, diazabicyclo octane, diazabicyclo nonane, diazabicyclo undecylene, TMAH etc.

As above-mentioned alkali metal cpd, for example enumerate out sodium hydroxide, Pottasium Hydroxide, hydrated barta, calcium hydroxide etc.These catalyzer can use or use two or more separately.

Among these catalyzer, preferable alloy inner complex, organic acid, mineral acid.As metallo-chelate, titanium chelate more preferably.

With regard to catalyst consumption, be preferably 0.001～10 mass parts with respect to raw silicon hydride compounds 100 mass parts, more preferably 0.001～1 mass parts.

Catalyzer can make an addition to as being dissolved in organic solvent and in the solution that obtains in the silane compound of raw material or with silane compound in advance, perhaps also solubilized or be scattered in the water that is added.

The water that when other organopolysiloxane synthetic, adds can be intermittently or make an addition to continuously as being dissolved in organic solvent and in the solution that obtains in the silane compound of raw material or with silane compound.

Temperature of reaction during as other organopolysiloxane synthetic is preferably 0～100 ℃, more preferably 15～80 ℃.Reaction times is preferably 0.5～24 hour, more preferably 1～8 hour.

This liquid crystal aligning agent contains when containing [A] compound under other the situation of polymkeric substance, and the content of polymkeric substance as other is preferably below 10,000 mass parts with respect to [A] compound 100 mass parts.The preferred content of other polymkeric substance is different because of the kind of other polymkeric substance.

This liquid crystal aligning agent is under the situation that contains [A] compound and [B] polymkeric substance; With regard to both preferred usage ratios, the total amount of [B] polymkeric substance is preferably 100～5,000 mass parts with respect to [A] compound 100 mass parts; 200～3,000 mass parts more preferably.

On the other hand; This liquid crystal aligning agent contains under the situation of [A] compound and other organopolysiloxane; With regard to both preferred usage ratios, be 100～2,000 mass parts with respect to other the amount of organopolysiloxane of [A] compound 100 mass parts.

This liquid crystal aligning agent contains when containing [A] compound under other the situation of polymkeric substance, as other polymkeric substance, and preferred [B] polymkeric substance or other organopolysiloxane.

[solidifying agent, curing catalysts and curing catalyst]

The more firm purpose of crosslinking reaction from making [A] compound can make solidifying agent and curing catalysts be contained in this liquid crystal aligning agent.Purpose from promoting the curing reaction that solidifying agent is administered can make curing catalyst be contained in this liquid crystal aligning agent.

As solidifying agent, can use: have the solidified nature compound of epoxy group(ing) or contain normally used solidifying agent in the curing of solidification compound of compound with epoxy group(ing).As such solidifying agent, for example enumerate out polyamine, polybasic acid anhydride, polycarboxylic acid.

As polybasic acid anhydride, for example enumerate out tricarboxylic acid anhydrides of hexanaphthene and other polybasic acid anhydride.

As the hexanaphthene tricarboxylic acid anhydride, for example enumerate out hexanaphthene-1,3,4-tricarboxylic acid-3,4-acid anhydrides, hexanaphthene-1,3,5-tricarboxylic acid-3,5-acid anhydrides, hexanaphthene-1,2,3-tricarboxylic acid-2,3-acid anhydrides etc.As other polybasic acid anhydride; For example enumerate out 4-methyl tetrahydrophthalic anhydride, methyl carbic anhydride, dodecenylsuccinic anhydride, succinyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, by normally used tetracarboxylic dianhydride in the compound of following formula (6) expression, polyamic acid synthetic, enumerate out α-terpinene, alloocimene etc. in addition and have the ester ring type compound of conjugated double bond and diels-alder reaction product of maleic anhydride (Diels-Alder reaction product) and their hydrogenation thing etc.

In the formula (6), x is 1～20 integer.

As curing catalysts, for example can use antimony hexafluoride compound, phosphorus hexafluoride compound, praseodynium acid aluminium etc.These catalyzer can carry out catalysis by the cationoid polymerisation to epoxy group(ing) under the effect of heating.

As above-mentioned curing catalyst, for example enumerate out imidazolium compounds, the quaternary phosphonium compound; Quaternary ammonium compound; 1, Diazabicycloalkenes such as 8-diazabicyclo [5.4.0] 11 carbon-7-alkene, its organic acid salt, organometallic compounds such as zinc octoate, stannous octoate, acetopyruvic acid aluminium coordination compound; Boron cpd such as boron trifluoride, triphenyl borate; Metal halide such as zinc chloride, tin chloride compound, HMP decentralized potentiality curing catalysts such as amine add-on type promotor such as the affixture of Dyhard RU 100, amine and epoxy resin are by the surface coverage microcapsule-type potentiality curing catalyst that obtain of polymkeric substance with season squama salt etc.; Amine salt type potentiality curing catalyst, the hot cationic polymerization type potentiality curing catalyst of high temperature dissociative types such as lewis acid, Bronsted hydrochlorate etc.

[epoxy compounds]

Consider for the viewpoint of the cementability of the substrate surface of formed liquid crystal orientation film from raising, can make above-mentioned epoxy compounds be contained in this liquid crystal aligning agent.

As epoxy compounds, preferred ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibrominated neopentylglycol diglycidyl ether, 1; 3,5,6-four glycidyl group-2; 4-pinakon, N, N, N '; N '-four glycidyl group m-xylene diamine, 1, two (N, the N-diglycidyl amino methyl) hexanaphthenes of 3-, N; N, N ', N '-four glycidyl group-4; 4 '-diaminodiphenyl-methane, N, N-diglycidyl benzylamine, N, N-diglycidyl-amino methyl hexanaphthene.

This liquid crystal aligning agent contains under the situation of epoxy compounds; With regard to its contain proportional with regard to; With respect to above-mentioned [A] polyorganosiloxane compounds and arbitrarily used other total 100 mass parts of polymkeric substance, be preferably below 0.01～40 mass parts, more preferably 0.1～30 mass parts.

Again, this liquid crystal aligning agent contains under the situation of epoxy compounds, also can share alkaline catalystss such as 1 benzyl 2 methyl imidazole from the purpose that efficiently causes its crosslinking reaction.

[functional silanes compound]

Can use the functional silanes compound with the purpose of the cementability of the substrate of the liquid crystal orientation film that is obtained from raising.As the functional silanes compound; For example enumerate out 3-TSL 8330,3-aminopropyltriethoxywerene werene, 2-TSL 8330,2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1; 4; 7-three azepine decane, 10-triethoxysilyl-1; 4; 7-three azepine decane, 9-trimethoxysilyl-3; 6-diaza nonyl acetic ester, 9-triethoxysilyl-3; 6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, two (oxo the ethylidene)-3-TSL 8330s of N-, two (oxo the ethylidene)-3-aminopropyltriethoxywerene werene of N-, 3-glycidyl ether oxygen base propyl trimethoxy silicane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane etc. is further enumerated out tetracarboxylic dianhydride who is put down in writing in the japanese kokai publication sho 63-291922 communique and the reactant with amino silane compound etc.

This liquid crystal aligning agent contains under the situation of functional silanes compound, with regard to its contain proportional with regard to, be preferably below 50 mass parts with respect to above-mentioned [A] compound and arbitrarily used other total 100 mass parts of polymkeric substance, more preferably below 20 mass parts.

[tensio-active agent]

As tensio-active agent, for example enumerate out nonionogenic tenside, AS, cats product, amphoterics, (gathering) silicone surfactant, polyalkylene oxide tensio-active agent, fluorochemical surfactant etc.

This liquid crystal aligning agent contains under the situation of tensio-active agent, with regard to its contain proportional with regard to, all 100 mass parts with respect to liquid crystal aligning agent are preferably below 10 mass parts, more preferably below 1 mass parts.

< preparation method of liquid crystal aligning agent >

As stated, this liquid crystal aligning agent serves as to contain by composition with [A] compound, can contain other optional member as required, but preferably is dissolved in organic solvent with each composition and the mode of the compsn of the solution shape that obtains prepares.

As the organic solvent that can be used to prepare this liquid crystal aligning agent, preferred solubilized [A] compound and arbitrarily used other composition and not with the organic solvent of their reactions.The organic solvent that can be preferred for this liquid crystal aligning agent is different because of other the kind of polymkeric substance of adding arbitrarily.

This liquid crystal aligning agent contains under the situation of [A] compound and [B] polymkeric substance, as preferred organic, enumerates out: illustrative organic solvent as the organic solvent that uses in polyamic acid synthetic and in above-mentioned.At this moment, also can share as the poor solvent that uses in polyamic acid of the present invention synthetic and illustrative poor solvent.These organic solvents can use or use two or more separately.

On the other hand; This liquid crystal aligning agent only contains under the situation of [A] compound as polymkeric substance; Or contain under [A] compound and the situation of other organopolysiloxane as polymkeric substance; As preferred organic, for example enumerate out 1-oxyethyl group-2-propyl alcohol, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Ucar 35 monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether (ethylene glycol butyl ether), glycol monomethyl amyl ether, ethylene glycol ether, Diethylene Glycol, methylcellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetic ester, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl group Trivalin SF, diethylene glycol monobutyl ether, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, acetate 3-methoxyl group butyl ester, methyl amyl acetate, acetate 2-ethyl butyl ester, acetate 2-ethylhexyl, jasmal, n-hexyl acetate, hexalin acetate, octyl acetate, pentyl acetate, Isoamyl Acetate FCC etc.Among them, be preferably n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate.

Can be used for preparing the preferred solvent of this liquid crystal aligning agent, can according to other polymkeric substance use have or not with and kind, make up above-mentioned organic solvent more than one and obtain.Such solvent is that under following preferred solid component concentration, not separating out each contained in liquid crystal aligning agent composition and making the surface tension of liquid crystal aligning agent is the solvent of the scope of 25～40mN/m.

The solid component concentration of this liquid crystal aligning agent, be the weight of the whole compositions except solvent in the liquid crystal aligning agent shared ratio in the gross weight of liquid crystal aligning agent; Select though consider viscosity, volatility etc., be preferably the scope of 1～10 quality %.This liquid crystal aligning agent is coated substrate surface, and formation will become filming of liquid crystal orientation film, but solid component concentration is that this thickness of filming is difficult for becoming too small and can obtains good liquid crystal orientation film under the above situation of 1 quality %.On the other hand, solid component concentration is under the situation below the 10 quality %, and the thickness that suppresses to film becomes excessive and can obtain good liquid crystal orientation film, and in addition, it is good preventing the viscosity increase of liquid crystal aligning agent and making coating characteristics.The method that adopts when especially preferably the scope of solid component concentration is because of coating of liquid crystalline alignment agent on substrate is different.For example, based on the scope that is preferably 1.5～4.5 quality % under the situation of rotational method especially.Under the situation based on print process, especially preferably solid component concentration is made as the scope of 3～9 quality %, soltion viscosity is made as the scope of 12～50mPas thus.Under the situation based on ink jet method, especially preferably solid component concentration is made as the scope of 1～5 quality %, soltion viscosity is made as the scope of 3～15mPas thus.Temperature when preparing this liquid crystal aligning agent is preferably 0 ℃～200 ℃, more preferably 0 ℃～40 ℃.

< liquid crystal display device >

Liquid crystal display device of the present invention is the liquid crystal display device that possesses the PSA mode of the liquid crystal orientation film that is formed by this liquid crystal aligning agent.According to this liquid crystal display device, through forming liquid crystal orientation film, thereby make liquid crystal aligning property high, and can bring into play excellent high-speed response property by above-mentioned liquid crystal aligning agent.Below, see figures.1.and.2, the embodiment of liquid crystal display device is described.

[first embodiment]

The liquid crystal display device 1 of Fig. 1 is: possess a pair of substrate 2 of subtend configuration, respectively be laminated in the inner surface side of this a pair of substrate 2 a pair of liquid crystal orientation film 3, be filled in 3 of above-mentioned liquid crystal orientation films and the liquid crystal display device of the PSA mode of the liquid crystal layer 4 that forms by polymerizable liquid crystal compound.

As a pair of substrate 2, for example can use glass such as float glass, soda glass, the transparency carrier that forms by plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefine.

Internal surface at above-mentioned a pair of substrate 2 is provided with transparency electrode 5a and 5b.Transparency electrode 5a becomes common electrode (common electrode), and transparency electrode 5b becomes pixel electrode.As this transparency electrode 5, for example can use to comprise White tin oxide (SnO ₂) NESA film (U.S. PPG register of company trade mark), comprise Indium sesquioxide-White tin oxide (In ₂O ₃-SnO ₂) ITO film etc.Again, this transparency electrode and known liquid crystal display device are same, are connected with not shown TFT, bus (busline) etc.

On the surface of two transparency electrode 5a and 5b (the face side of subtend), be formed with wire projection (works is used in the control of dykes and dams shape orientation) 6.As the size of this wire projection, for example highly be that 1.5 μ m, width are 10 μ m; As the interval for example is 25 μ m.Through this wire projection 6 liquid crystal molecule being orientated cuts apart.

In the inner surface side of a pair of substrate 2, being situated between is formed with liquid crystal orientation film 3 by transparency electrode 5a, 5b and wire projection 6.This liquid crystal orientation film 3 is a vertical alignment layer, forms through this above-mentioned liquid crystal aligning agent.Can implement processing such as friction treatment, light orientation process to the surface of this liquid crystal orientation film 3, also can not implement.According to this liquid crystal display device, through forming liquid crystal orientation film, thereby make that liquid crystal aligning property is excellent and can bring into play excellent high-speed response property by above-mentioned liquid crystal aligning agent.

Be filled with the liquid crystal layer 4 that forms by polymerizable liquid crystal compound 3 of this liquid crystal orientation films.This liquid crystal layer 4 possesses negative dielectric constant anisotropy is arranged.As such liquid crystal, for example can use dicyano benzene series liquid crystal, pyridazine is that liquid crystal, Schiff's base are that liquid crystal, azoxy are that liquid crystal, biphenyl are that liquid crystal, Santosol 360 are liquid crystal etc.In addition; As above-mentioned polymerizable liquid crystal compound; Not special the qualification can not used known thing, for example can use the monomer that will have acryl and liquid crystal skeleton and polymerization starter together to make an addition to negative (dielectric constant anisotropy of bearing) type liquid crystal and the material that obtains.As above-mentioned monomeric addition, for example below the above 1 quality % of 0.1 quality %.As the thickness of liquid crystal layer 4, for example be about about 4 μ m.

In this liquid crystal display device 1, owing to form liquid crystal layer 4 by polymerizable liquid crystal compound, thus in the liquid crystal layer 4, be formed with polymer layer 7 at interface with liquid crystal orientation film 3.This polymer layer 7 is given liquid crystal molecule 4a in the liquid crystal layer 4 with tilt angle with the angle θ p of regulation.

In this liquid crystal display device 1, same with known liquid crystal display device, at the range upon range of not shown Polarizer of two outside surfaces of substrate 2.As this Polarizer; Not special the qualification; But enumerate out: the light polarizing film that is known as " H film " that obtains while make the PVA (PVOH) FILM stretch orientation absorb iodine clips the Polarizer that forms via the rhodia protective membrane, or the Polarizer that forms by H film itself etc.

According to this liquid crystal display device 1, through forming liquid crystal orientation film 3, thereby make the raising of liquid crystal aligning property, and can bring into play excellent high-speed response property by above-mentioned liquid crystal aligning agent.

[second embodiment]

The liquid crystal display device 11 of Fig. 2 (a) is: possess a pair of substrate 2 of subtend configuration, respectively be laminated in the inner surface side of this a pair of substrate 2 a pair of liquid crystal orientation film 3, be filled in 3 of above-mentioned liquid crystal orientation films and the liquid crystal display device of the PSA mode of the liquid crystal layer 4 that forms by polymerizable liquid crystal compound.In this liquid crystal display device 11, also same with liquid crystal display device 1, at the range upon range of not shown Polarizer of two outside surfaces of substrate 2.

Liquid crystal display device 11 does, the liquid crystal display device that the orientation that the transparency electrode 15 through patterning replaces the wire projection 6 of liquid crystal display device 1 to carry out liquid crystal molecule is cut apart.The transparency electrode 5a (common electrode) of the substrate 2 in the liquid crystal display device 11, liquid crystal orientation film 3, liquid crystal layer 4 and a side is owing to be with the same material of the liquid crystal display device of Fig. 11 thereby omit explanation.

At the internal surface of a side of aforesaid substrate 2, be equipped with the transparency electrode 15 (pixel electrode) of herring-bone form ground patterning.Use the transparency electrode 15 of such patterning, thereby the liquid crystal molecule 4a in the liquid crystal layer 4 is orientated along this transparency electrode 15, just can realize being orientated and cut apart (with reference to Fig. 2 (b)).Again, this transparency electrode and known liquid crystal display device are same, are connected with not shown TFT, bus etc.

In this liquid crystal display device 11, also through under the state that has applied voltage, making curable liquid crystal layer, thereby can remember the vergence direction of the liquid crystal molecule in the liquid crystal layer, as the liquid crystal display device of PSA mode and work.

Even through this liquid crystal display device 11, also pass through to form liquid crystal orientation film, thereby make that liquid crystal aligning property is excellent and can bring into play excellent high-speed response property by above-mentioned liquid crystal aligning agent.

[other embodiment]

Again, for this liquid crystal display device, in liquid crystal layer, the cured portion that manifests PSA can the mode with polymer layer 4 form as the liquid crystal display device 1 of Fig. 1, also can part property or formation universally in liquid crystal layer.In addition, also can be orientated and cut apart through the electrode that slit (slit), partition wall wait to substitute above-mentioned wire projection or patterning.In any embodiment; Also according to this liquid crystal display device; For example supported under the state of liquid crystal molecule after tilting with respect to substrate interface minimumly; Therefore liquid crystal orientation film is formed by this liquid crystal aligning agent, when applying voltage, can make liquid crystal molecule positively swing to this vergence direction and can improve the responsiveness of this moment.

< method of manufacture of liquid crystal display device >

With the situation of the liquid crystal display device 1 of Fig. 1 is an example of example method of manufacture that this liquid crystal display device is described.

As the method for manufacture of liquid crystal display device 1, can enumerate out method with following operation:

Form the operation of liquid crystal orientation film 3 at each internal surface of a pair of substrate 2 with transparency electrode 5a or 5b and wire projection 6 through above-mentioned liquid crystal aligning agent,

Above-mentioned a pair of substrate 2 according to the mode subtend configuration that internal surface faces each other, is filled the operation of polymerizable liquid crystal compound between this substrate, and

Under the state that has applied voltage, make above-mentioned polymerizable liquid crystal compound solidified operation.

With regard to the formation of above-mentioned liquid crystal orientation film, can be through behind the coating of liquid crystalline alignment agent, thus solidify formation down in the effect of heating.

As the curing of above-mentioned polymerizable liquid crystal compound, can enumerate out: the thermofixation of using the photocuring of ultraviolet ray etc., giving based on heat.As the irradiation dose under the situation of photocuring, not special the qualification for example is 1,000～5 as ultraviolet irradiation amount still, 000mJ/cm ²About.In addition, the voltage that applies during polymerization does not limit especially yet, but is about 0～20V.

Through solidifying (polymerization) while applying voltage in this wise, form liquid crystal layer, thereby under the state after the inclination, support liquid crystal molecule, can control the orientation of liquid crystal molecule effectively.In addition, according to this method of manufacture, through forming liquid crystal orientation film, thereby can make the liquid crystal display device that liquid crystal aligning property is high and have the PSA mode of excellent high-speed response property by above-mentioned liquid crystal aligning agent.

Embodiment

Below, come further explain the present invention through synthetic example and embodiment, but the present invention is not subject to these embodiment.

The polystyrene conversion value that the weight-average molecular weight (Mw) of the organopolysiloxane with epoxy group(ing) that in following embodiment, obtains and [A] compound is measured for the GPC by following specification.

Chromatographic column: eastern ソ one commercial firm, TSKgelGRCXLII

Solvent: THF

Temperature: 40 ℃

Pressure: 68kgf/cm ²

Again, the starting compound that in following embodiment, uses and the necessary amounts of polymkeric substance are guaranteed through the starting compound and the synthetic of polymkeric substance that carry out repeatedly as required under the synthetic route shown in the following synthetic example.

< organopolysiloxane synthetic>with epoxy group(ing)

[synthetic example 1]

To possessing whisking appliance arranged, in the reaction vessel of TM, tap funnel and reflux condensing tube, add 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (ECETS) 100.0g, MIBK 500g and triethylamine 10.0g, at room temperature mix.Then, spend 30 minutes behind tap funnel dropping deionized water 100g, reacted 6 hours while under refluxing, mix at 80 ℃.Behind the reaction terminating, take out organic layer, wash after the water after the washing becomes neutrality, under reduced pressure solvent and water are distillated, thereby obtained to have the organopolysiloxane of epoxy group(ing) with the mode of heavy-gravity transparent liquid through 0.2 quality % aqueous ammonium nitrate solution.

This organopolysiloxane with epoxy group(ing) has been carried out ¹H-NMR analyzes, and has confirmed: near chemical shift (δ)=3.2ppm, can equally obtain the peak based on epoxy group(ing) as theoretical strength, in reaction, not cause the side reaction of epoxy group(ing).

[synthetic example 2～3]

Shown in below table 1, will add raw material and set, in addition, the organopolysiloxane that has obtained to have epoxy group(ing) respectively with the mode of heavy-gravity transparent liquid with the operation likewise of synthetic example 1.To be shown in table 1 in the lump by the Mw and the epoxy equivalent (weight) of the organopolysiloxane that synthesizes example 1～3 acquisition with epoxy group(ing).Again, the abbreviation of the raw silicon hydride compounds in the table 1 is represented following meaning.

ECETS:2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane

MTMS: methyltrimethoxy silane

PTMS: phenyltrimethoxysila,e

Table 1

< synthesizing of specific carboxylic acid >

[synthesizing of specific carboxylic acid 1]

Synthesized specific carboxylic acid 1 according to the reactions route.

[synthetic example 4]

In the there-necked flask that possesses the 500mL that prolong is arranged, add 4-cyanic acid-4 '-xenol 6.3g, 11-bromo undecanoic acid methyl esters 10g, salt of wormwood 14.2g, N, dinethylformamide 200mL, 160 ℃ of heated and stirred 5 hours.After utilizing TLC to confirm that reaction finishes, reaction soln is cooled to room temperature.Reaction soln is devoted water 500mL, carried out mixing and stirred.With the white solid filtering separation of having separated out, water further washs.Through 80 ℃ with the solid vacuum-drying that is obtained, thereby obtained 11g compound 1.

[synthetic example 5]

Then, in the there-necked flask that possesses the 200mL that prolong is arranged, add 10g compound 1,1.6g lithium hydroxide monohydrate, 30mL methyl alcohol, 15mL water, 80 ℃ of heated and stirred 4 hours.After utilizing TLC to confirm that reaction finishes, reaction soln is cooled to room temperature.Under the state that has stirred reaction soln, Hydrogen chloride is slowly dripped in reaction soln.To separate out solid filtering, wash in proper order by water, alcoholic acid.Through 80 ℃ with the solid vacuum-drying that is obtained, thereby obtained the specific carboxylic acid 1 of 8g.

[synthesizing of specific carboxylic acid 2]

Synthesized specific carboxylic acid 2 according to the reactions route.

[synthetic example 6]

In the there-necked flask that possesses the 500mL that prolong is arranged, add 4-cyanic acid-4 '-xenol 15g, ethylene carbonate 13.5g, Tetrabutyl amonium bromide (TBAB) 2.5g, N, dinethylformamide 300mL, 150 ℃ of heated and stirred 9 hours.After utilizing TLC to confirm that reaction finishes, reaction soln is cooled to room temperature.Mixing solutions separatory with ETHYLE ACETATE 300mL, 1N-aqueous sodium hydroxide solution 100mL has washed reaction soln.Extracted organic layer, further carried out the separatory washing then according to the order of 1N-aqueous sodium hydroxide solution 100mL, water 100mL.With sal epsom with the organic layer drying after, organic solvent is distillated.After the solid vacuum-drying that is obtained, 250mL carries out recrystallize with ethanol 100mL/ hexane, thereby has obtained 13.1g compound 2.

[synthetic example 7]

To possessing prolong arranged, add 4-chlorobenzene sulfonyl chloride, the 60mL dehydration methylene dichloride of 12g compound 2,12.7g in the there-necked flask of the 200mL of tap funnel and mix.Cooling off with ice bath under the state of reaction soln, spending 10 minutes and drip the dehydration methylene dichloride 10mL solution of triethylamine 6.6g.Under the ice bath state, stirred 30 minutes, turn back to room temperature and further stirred 6 hours.In reaction soln, add chloroform 150mL, water 100mL has carried out 4 separatory washings.With the organic layer that dried over mgso extracted, organic solvent is distillated.Thereby the solids wash that is obtained has been obtained 16.1g compound 3 with ethanol.

[synthetic example 8]

In the there-necked flask that possesses the 300mL that prolong is arranged, add 4-methyl hydroxybenzoate, the 12.5g salt of wormwood of 15g compound 3,11g, the N of 180mL, dinethylformamide, 80 ℃ of heated and stirred 9 hours.After utilizing TLC to confirm that reaction finishes, reaction soln is cooled to room temperature.Reaction soln is devoted 500mL water, carried out mixing and stirred.With the white solid filtering separation of having separated out, further wash with ethanol.Through 80 ℃ with the solid vacuum-drying that is obtained, thereby obtained 10g compound 4.

[synthetic example 9]

In the there-necked flask that possesses the 100mL that prolong is arranged, add 9.5g compound 4,1.6g lithium hydroxide monohydrate, 30mL methyl alcohol, 15mL THF, 15mL water, 80 ℃ of heated and stirred 4 hours.After utilizing TLC to confirm that reaction finishes, reaction soln is cooled to room temperature.Under the state that has stirred reaction soln, Hydrogen chloride is slowly dripped in reaction soln.To separate out solid filtering, wash in proper order by water, alcoholic acid.Through 80 ℃ with the solid vacuum-drying that is obtained, thereby obtained the specific carboxylic acid 2 of 9g.

[synthesizing of specific carboxylic acid 3]

Synthesized specific carboxylic acid 3 according to the reactions route.

[synthetic example 10]

In synthetic example 4, use 2,3,5 of 10.7g, 6-tetrafluoro-4-(pentafluorophenyl group) thus phenol substitutes 4-cyanic acid-4 '-xenol has obtained 13.7g compound 5.

[synthetic example 11]

In synthetic example 5, use 13.5g compound 5 to come alternative compounds 1, thereby obtained the specific carboxylic acid 3 of 11.2g.

[synthesizing of specific carboxylic acid 4]

Synthesized specific carboxylic acid 4 according to the reactions route.

[synthetic example 12]

In synthetic example 6, use 2,3,5 of 25.5g, 6-tetrafluoro-4-(pentafluorophenyl group) phenol substitutes 4-cyanic acid-4 '-xenol, thereby has obtained 23.1g compound 6.

[synthetic example 13]

In synthetic example 7, use 18.9g compound 6 to come alternative compounds 2, thereby obtained 24.1g compound 7.

[synthetic example 14]

In synthetic example 8, use 20g compound 7 to come alternative compounds 3, thereby obtained 15.4g compound 8.

[synthetic example 15]

In synthetic example 9, use 13g compound 8 to come alternative compounds 4, thereby obtained the specific carboxylic acid 4 of 11.4g.

[synthesizing of specific carboxylic acid 5]

Synthesized specific carboxylic acid 5 according to the reactions route.

[synthetic example 16]

With the synthetic operation likewise of specific carboxylic acid 1, obtained 15g the number of methylene radical has been changed to 5 and the specific carboxylic acid 5 that obtains from 10.

[synthesizing of specific carboxylic acid 6]

Synthesized specific carboxylic acid 6 according to the reactions route.

[synthetic example 17]

In the there-necked flask that possesses the 500mL that prolong is arranged, add 2; 2 ', 3,3 '-tetrafluoro-4 '-propyl group-4-xenol 10.1g, 11-bromo undecanoic acid methyl esters 10g, salt of wormwood 14.2g, N; Dinethylformamide 200mL, 160 ℃ of heated and stirred 5 hours.After utilizing TLC to confirm that reaction finishes, reaction soln is cooled to room temperature.Reaction soln is devoted water 500mL, carried out mixing and stirred.With the white solid filtering separation of having separated out, water further washs.Through 80 ℃ with the solid vacuum-drying that is obtained, thereby obtained 10.8g compound 9.

[synthetic example 18]

Then, in the there-necked flask that possesses the 200mL that prolong is arranged, add 10g compound 9,1.6g lithium hydroxide monohydrate, 30mL methyl alcohol, 15mL water, 80 ℃ of heated and stirred 4 hours.After utilizing TLC to confirm that reaction finishes, reaction soln is cooled to room temperature.Under the state that has stirred reaction soln, Hydrogen chloride is slowly dripped in reaction soln.To separate out solid filtering, wash in proper order by water, alcoholic acid.Through 80 ℃ with the solid vacuum-drying that is obtained, thereby obtained the specific carboxylic acid 6 of 6g.

[synthesizing of specific carboxylic acid 7]

Synthesized specific carboxylic acid 7 according to the reactions route.

[synthetic example 19]

With initial compounds (2; 2 ', 3,3 '-tetrafluoro-4 '-propyl group-4-xenol) 10.1g becomes the compound of putting down in writing in the above-mentioned reaction scheme (2; 3-two fluoro-4-(4-propyl group-cyclohexyl) phenol) 9.1g; In addition, the synthetic operation likewise with above-mentioned specific carboxylic acid 6 has obtained the specific carboxylic acid 7 of 5.9g.

[synthesizing of specific carboxylic acid 8]

Synthesized specific carboxylic acid 8 according to the reactions route.

[synthetic example 20]

With initial compounds (2,2 ', 3; 3 '-tetrafluoro-4 '-propyl group-4-xenol) 10.1g becomes the compound of putting down in writing in the above-mentioned reaction scheme (2,2 ', 3; 3 '-tetrafluoro-4-propyl group-4 "-the hydroxyl terphenyl) 12.9g; in addition, the synthetic operation likewise with above-mentioned specific carboxylic acid 6 has obtained the specific carboxylic acid 8 of 7.1g.

[synthesizing of specific carboxylic acid 9]

Synthesized specific carboxylic acid 9 according to the reactions route.

[synthetic example 21]

With initial compounds (2; 2 ', 3,3 '-tetrafluoro-4 '-propyl group-4-xenol) 10.1g becomes the compound of putting down in writing in the above-mentioned reaction scheme (2; 3-two fluoro-4-(4-propyl group cyclohexyl methoxyl group) phenol) 10.2g; In addition, the synthetic operation likewise with above-mentioned specific carboxylic acid 6 has obtained the specific carboxylic acid 9 of 6.5g.

[synthesizing of specific carboxylic acid 10]

Synthesized specific carboxylic acid 10 according to the reactions route.

[synthetic example 22]

With initial compounds (2; 2 ', 3,3 '-tetrafluoro-4 '-propyl group-4-xenol) 10.1g becomes the compound of putting down in writing in the above-mentioned reaction scheme (2; 3-two fluoro-4 '-(4-propyl group phenylethyl) biphenyl) 12.6g; In addition, the synthetic operation likewise with above-mentioned specific carboxylic acid 6 has obtained the specific carboxylic acid 10 of 7.2g.

[synthesizing of specific carboxylic acid 11]

Synthesized specific carboxylic acid 11 according to the reactions route.

[synthetic example 23]

10.1g becomes the compound 14.2g that puts down in writing in the above-mentioned reaction scheme with initial compounds (2,2 ', 3,3 '-tetrafluoro-4 '-propyl group-4-xenol), and in addition, the synthetic operation likewise with above-mentioned specific carboxylic acid 6 has obtained the specific carboxylic acid 11 of 7.6g.

[synthesizing of specific carboxylic acid 12]

According to the reactions route, synthesized specific carboxylic acid 12.

[synthetic example 24]

In the there-necked flask that possesses the 500mL that prolong is arranged; Add 4-[difluoro (4-amyl group cyclohexyl) methoxyl group]-2; 3-difluorophenol 12.5g, 11-bromo undecanoic acid methyl esters 10g, salt of wormwood 14.2g, N, dinethylformamide 200mL, 160 ℃ of heated and stirred 5 hours.After utilizing TLC to confirm that reaction finishes, reaction soln is cooled to room temperature.Reaction soln is devoted 500mL water, carried out mixing and stirred.With the white solid filtering separation of having separated out, water further washs.Through 80 ℃ with the solid vacuum-drying that is obtained, thereby obtained 14.8g compound 10.

[synthetic example 25]

Then, in the there-necked flask that possesses the 200mL that prolong is arranged, add 10g compound 10,1.6g lithium hydroxide monohydrate, 30mL methyl alcohol, 15mL water, 80 ℃ of heated and stirred 4 hours.After utilizing TLC to confirm that reaction finishes, reaction soln is cooled to room temperature.Under the state that has stirred reaction soln, Hydrogen chloride is slowly dripped in reaction soln.To separate out solid filtering, wash in proper order by water, alcoholic acid.Through 80 ℃ with the solid vacuum-drying that is obtained, thereby obtained the specific carboxylic acid 12 of 6g.

< synthesizing of [A] compound >

[synthetic example 26]

In the there-necked flask of 100mL; Add 9.8g by above-mentioned synthetic routine 1 organopolysiloxane with epoxy group(ing), 28g MIBK, 5.0g that obtain by the above-mentioned synthetic routine 5 specific carboxylic acids 1,3.3g that obtain as represented 4-octyloxy phenylformic acid of illustrative formula (4-11) and the UCAT 18X (quaternary amine of サ Application ア プ ロ commercial firm) of 0.20g by one of compound of above-mentioned formula (4) expression, stirred 12 hours at 80 ℃.Behind the reaction terminating, carry out redeposition, throw out is dissolved in ETHYLE ACETATE and obtains solution, this solution is carried out 3 washings, then solvent is distillated, thereby obtained [A] compd A-1 of 14.5g with the white powder mode with methyl alcohol.The Mw of [A] compd A-1 is 6,500.

[synthetic example 27]

Use 4g to substitute specific carboxylic acid 1, likewise operate with synthetic example 26 in addition, thereby obtained the white powder of [A] compd A-2 of 12.8g by the specific carboxylic acid 2 that synthetic example 9 obtains.The Mw of [A] compd A-2 is 6,000.

[synthetic example 28]

Use 6.8/g to substitute specific carboxylic acid 1, likewise operate with synthetic example 26 in addition, thereby obtained the white powder of [A] compd A-3 of 14.7g by the specific carboxylic acid 3 that synthetic example 11 obtains.The Mw of [A] compd A-3 is 8,100.

[synthetic example 29]

Use 5.6g to substitute specific carboxylic acid 1, likewise carried out the synthetic of [A] compound with synthetic example 26 in addition by the specific carboxylic acid 4 that synthetic example 15 obtains.Its result has obtained the white powder of [A] compd A-4 of 15.0g.The Mw of [A] compd A-4 is 7,500.

[synthetic example 30]

In the there-necked flask of 100mL; Add 9.8g by above-mentioned synthetic routine 1 organopolysiloxane with epoxy group(ing), 28g MIBK, 10g that obtain by the above-mentioned synthetic routine 5 specific carboxylic acids 1 that obtain and the UCAT 18X (quaternary amine of サ Application ア プ ロ commercial firm) of 0.20g, stirred 12 hours at 80 ℃.Behind the reaction terminating, carry out redeposition, throw out is dissolved in ETHYLE ACETATE, this solution is carried out 3 washings, then solvent is distillated, thereby obtained [A] compd A-5 of 16.0g with the white powder mode with methyl alcohol.The Mw of [A] compd A-5 is 8,500.

[synthetic example 31]

Use 4.1g to substitute specific carboxylic acid 1, likewise operate with synthetic routine 26 in addition and obtained the white powder of [A] compd A-6 of 12.4g by the specific carboxylic acid 5 that synthetic example 16 obtains.The Mw of [A] compd A-6 is 6,200.

[synthetic example 32]

Use 3.6g as represented 4-(the 4-amyl group cyclohexyl) phenylformic acid of illustrative formula (4-13) substitutes 4-octyloxy phenylformic acid by one of compound of above-mentioned formula (4) expression; In addition with the operation likewise of synthetic example 26, thereby obtained the white powder of [A] compd A-7 of 13.4g.The Mw of [A] compd A-7 is 7,900.

[synthetic example 33]

In the there-necked flask of 100mL; Add 9.8g by above-mentioned synthetic routine 1 organopolysiloxane with epoxy group(ing), 28g MIBK, 8.0g that obtain by the above-mentioned synthetic routine 5 specific carboxylic acids 1,1.4g that obtain by 4-(the 4-amyl group cyclohexyl) phenylformic acid of above-mentioned formula (4-13) expression and the UCAT 18X (quaternary amine of サ Application ア プ ロ commercial firm) of 0.20g, stirred 12 hours at 80 ℃.Behind the reaction terminating, carry out redeposition, throw out is dissolved in ETHYLE ACETATE, this solution is carried out 3 washings, then solvent is distillated, thereby obtained [A] compd A-8 of 13.9g with the white powder mode with methyl alcohol.The Mw of [A] compd A-8 is 8,900.

[synthetic example 34]

In the there-necked flask of 100mL; Add 9.8g by above-mentioned synthetic routine 1 organopolysiloxane with epoxy group(ing), 28g MIBK, 2.0g that obtain by the above-mentioned synthetic routine 5 specific carboxylic acids 1,5.8g that obtain by 4-(the 4-amyl group cyclohexyl) phenylformic acid of above-mentioned formula (4-13) expression and the UCAT 18X (quaternary amine of サ Application ア プ ロ commercial firm) of 0.20g, stirred 12 hours at 80 ℃.Behind the reaction terminating, carry out redeposition, throw out is dissolved in ETHYLE ACETATE and obtains solution, this solution is carried out 3 washings, then solvent is distillated, thereby obtained [A] compd A-9 of 13.4g with the white powder mode with methyl alcohol.The Mw of [A] compd A-9 is 7,600.

[synthetic example 35]

In the there-necked flask of 100mL; Add 9.8g by above-mentioned synthetic routine 1 organopolysiloxane with epoxy group(ing), 28g MIBK, 8.0g that obtain by the above-mentioned synthetic routine 5 specific carboxylic acids 1,2.6g that obtain by the carboxylic acid derivative of above-mentioned formula (4-12) expression and the UCAT 18X (quaternary amine of サ Application ア プ ロ commercial firm) of 0.20g, stirred 12 hours at 80 ℃.Behind the reaction terminating, carry out redeposition, throw out is dissolved in ETHYLE ACETATE, this solution is carried out 3 washings, then solvent is distillated, thereby obtained [A] compd A-10 of 15.5g with the white powder mode with methyl alcohol.The Mw of [A] compd A-10 is 9,200.

[synthetic example 36]

Use 6.1g to substitute specific carboxylic acid 1, likewise operate with synthetic routine 26 in addition and obtained the white powder of [A] compd A-11 of 18.4g by the specific carboxylic acid 6 that synthetic example 18 obtains.The Mw of [A] compd A-11 is 7,300.

[synthetic example 37]

Use 5.7g to substitute specific carboxylic acid 1, likewise operate with synthetic routine 26 in addition and obtained the white powder of [A] compd A-12 of 17.5g by the specific carboxylic acid 7 that synthetic example 19 obtains.The Mw of [A] compd A-12 is 7,600.

[synthetic example 38]

Use 7.2g to substitute specific carboxylic acid 1, likewise operate with synthetic routine 26 in addition and obtained the white powder of [A] compd A-13 of 19.1g by the specific carboxylic acid 8 that synthetic example 20 obtains.The Mw of [A] compd A-13 is 7,000.

[synthetic example 39]

Use 6.2g to substitute specific carboxylic acid 1, likewise operate with synthetic routine 26 in addition and obtained the white powder of [A] compd A-14 of 18.1g by the specific carboxylic acid 9 that synthetic example 21 obtains.The Mw of [A] compd A-14 is 6,900.

[synthetic example 40]

Use 7.0g to substitute specific carboxylic acid 1, likewise operate with synthetic routine 26 in addition and obtained the white powder of [A] compd A-15 of 19.4g by the specific carboxylic acid 10 that synthetic example 22 obtains.The Mw of [A] compd A-15 is 7,500.

[synthetic example 41]

Use 8.4g to substitute specific carboxylic acid 1, likewise operate with synthetic routine 26 in addition and obtained the white powder of [A] compd A-16 of 20.1g by the specific carboxylic acid 11 that synthetic example 23 obtains.The Mw of [A] compd A-16 is 7,300.

[synthetic example 42]

Use 7.2g to substitute specific carboxylic acid 1, likewise operate with synthetic routine 26 in addition and obtained the white powder of [A] compd A-17 of 19.5g by the specific carboxylic acid 12 that synthetic example 25 obtains.The Mw of [A] compd A-17 is 7,300.

[relatively more synthetic example 1]

In the there-necked flask of 100mL; Add organopolysiloxane with epoxy group(ing), 28g MIBK, the 4-octyloxy phenylformic acid of 3.3g and the UCAT 18X (quaternary amine of サ Application ア プ ロ commercial firm) of 0.10g of 9.8g, stirred 12 hours at 80 ℃ by above-mentioned synthetic routine 1 acquisition.Behind the reaction terminating, carry out redeposition, throw out is dissolved in ETHYLE ACETATE, this solution is carried out 3 washings, then solvent is distillated, thereby obtained [A] Compound C A-1 of 9.6g with the white powder mode with methyl alcohol.The Mw of Compound C A-1 is 6,000.

< synthesizing of polyamic acid >

[synthetic example 43]

With 1,2,3,4-tetramethylene tetracarboxylic acid dianhydride 19.61g (0.1 mole) and 4,4 '-diamino--2,2 '-dimethyl diphenyl 21.23g (0.1 mole) is dissolved in N-N-methyl-2-2-pyrrolidone N-367.6g, has at room temperature reacted 6 hours.Then, reaction mixture is injected excessive methyl alcohol, make the reaction product deposition.Use the methanol wash throw out, through under reduced pressure 40 ℃ of dryings 15 hours, thereby obtained 35g polyamic acid PA-1.

[synthetic example 44]

With 2,3, two (methylamine) 14.23g (0.1 mole) of 5-tricarboxylic basic ring amyl group acetate dianhydride 22.4g (0.1 mole) and hexanaphthene are dissolved in N-N-methyl-2-2-pyrrolidone N-329.3g, have reacted 6 hours at 60 ℃.Then, reactant is injected excessive methyl alcohol, make the reaction product deposition.Use the methanol wash throw out,, thereby obtained 32g polyamic acid PA-2 under reduced pressure 40 ℃ of dryings 15 hours.

< synthesizing of polyimide >

[synthetic example 45]

Take the polyamic acid PA-2 of 17.5g,, carried out imidization 120 ℃ of reactions 4 hours to wherein adding N-N-methyl-2-2-pyrrolidone N-232.5g, pyridine 3.8g and diacetyl oxide 4.9g by above-mentioned synthetic routine 44 acquisitions.Then, reaction mixture is injected excessive methyl alcohol, make the reaction product deposition.Use the methanol wash throw out, drying under reduced pressure 15 hours, thus obtained 15g polyimide PI-1.

[synthetic example 46]

Will be as tetracarboxylic dianhydride's 2; 3; 5-tricarboxylic basic ring amyl group acetate dianhydride 19.88g; Be dissolved among the N-N-methyl-2-2-pyrrolidone N-140g as Ursol D 6.83g, the diaminodiphenyl-methane 3.58g of diamine compound and the diamines 4.72g that representes by above-mentioned formula (G-4), reacted 4 hours at 60 ℃.Then, reaction soln is flow in the excessive methyl alcohol and make the reaction product deposition., use methanol wash, under reduced pressure obtained polyamic acid 32.8g 40 ℃ of dryings 24 hours thereafter.The polyamic acid 30g that is obtained is dissolved among the N-N-methyl-2-2-pyrrolidone N-400g; Add pyridine 12.0g and diacetyl oxide 15.5g and 110 ℃ of dehydration closed-loops 4 hours; With above-mentioned operation likewise; Precipitate, washing, drying under reduced pressure, obtained the Mw=92 of 25g, 000, the polyimide PI-2 of Mw/Mn=4.19, imidization rate 79%.

< preparation of liquid crystal aligning agent >

[embodiment 1]

Take to contain the solution of the polyamic acid PA-1 that obtains by synthetic example 43; The amount of taking is to be scaled wherein contained polyamic acid PA-1 to be equivalent to 1; The amount of 000 mass parts; Add [A] compd A-1 (100 mass parts), further add N-N-methyl-2-2-pyrrolidone N-and ethylene glycol butyl ether, be the N-N-methyl-2-2-pyrrolidone N-thereby process solvent composition: ethylene glycol butyl ether=50: 50 (mass ratio), solid component concentration are the solution of 3.0 quality %.Strainer by aperture 10.2 μ m filters this solution, thereby has prepared liquid crystal aligning agent S-1.

[embodiment 2～21 and comparative example 1]

The combination of the polyorganosiloxane compounds of polyamic acid of setting conduct [B] polymkeric substance or polyimide, conduct [A] composition as record in the table 2; In addition; Likewise operate with embodiment 1, thereby prepared liquid crystal aligning agent S-2～S-21 and CS-1.

[comparative example 2]

In polyimide PI-2 by above-mentioned synthetic routine 46 acquisitions; According to solvent composition is the N-N-methyl-2-2-pyrrolidone N-: the mode of ethylene glycol butyl ether=70: 30 (mass ratio) adds N-N-methyl-2-2-pyrrolidone N-and ethylene glycol butyl ether respectively, thereby processes the solution that solid component concentration is 3.0 quality %.Strainer by aperture 0.2 μ m filters this solution and has prepared liquid crystal aligning agent CS-2.Again, corresponding composition is not used in the expression of "-" in the table.

< manufacturing of liquid crystal display device >

As the liquid crystal display device of the liquid crystal aligning agent S-1 that has used embodiment 1, made 15 type XGA panels (pel spacing: 297 μ m, pixel count: 1024 * 768).The mode chart of one pixel of panel for this reason shown in Figure 3 (liquid crystal display device).On the substrate of a side, formed the transparency electrode 21 of patterning.Further, on this substrate, be provided with TFT22 and bus 23 for transparency electrode 21 is worked as pixel electrode.The transparency electrode 21 of patterning as shown in Figure 3 is extended to 4 orientation (upper right, bottom right, upper left, down left) from the pixel central part.Here, the electrode width of the transparency electrode 21 of boundary portion (spine) patterning nearby is 2 μ m, the width of (space) is 4 μ m at interval, away from the electrode width in the zone of boundary portion be 4 μ m, wide at interval be 2 μ m.Is 5 μ m from the boundary portion end to the pattern width change section apart from x.At the substrate of other side, formed transparency electrode (common electrode).Baseplate material has used the glass substrate OA-2 (NEG corporate system) of thickness of slab 0.7mm.

On these substrates, use liquid crystal aligning agent S-1 to form liquid crystal orientation film through print process, 180 ℃ of thermal treatments of having carried out 60 minutes.Further, Jie with these baseplate-laminatings, has made the sylphon that does not inject liquid crystal by the sept (ponding Off ア イ Application ケ ミ カ Le commercial firm system) of diameter 4 μ m.In this box, inject the micro-dielectric constant anisotropy that has added photopolymerization monomer (big Japanese ink corporate system) and be negative liquid crystal (メ Le Network commercial firm system).The addition of photopolymerization monomer is 2.4 quality %.Then, this groove is applied voltage and irradiation ultraviolet radiation, with monomer polymerization and the polymerization materialization.Further,, Polarizer is fitted according to the mutually orthogonal mode of the polarization direction of 2 Polarizers, thereby made the liquid crystal display device of embodiment 1 on the two sides, the outside of substrate.The voltage that applies during polymerization is that 10V, UV irradiation dose are 2,000mJ/cm ²(λ=365nm).

Use substitutes liquid crystal aligning agent S-1 by the liquid crystal aligning agent of table 2 expression, in addition, carries out and above-mentioned same operation, has used the liquid crystal display device of embodiment 2～20 with the liquid crystal aligning agent of comparative example 1 and 2 thereby process.

< evaluation >

Evaluation below the liquid crystal display device of having made carried out.The result is shown in table 2 in the lump.

[orientation]

For liquid crystal display device by above-mentioned manufacturing; The light that under the backlight irradiation, does not apply under the voltage status through visual observation leaks at random the having or not of orientation; Do not have light to leak orientation situation at random and be " zero "; Exist light to leak orientation situation at random in a part and be " △ ", the situation that can't obtain vertical orientated state fully is " * ".

[response speed (the electrooptics responsiveness during beginning)]

Utilization comprises the time that device that polarizing microscope, photodetector and pulse produce machine has been measured the beginning of liquid crystal response.Liquid crystal response speed is meant here: when not applying voltage status to the voltage of 5V that applies maximum 1 second from the liquid crystal display device to made, be changed to the 90% needed time of transsmissivity (msec.) from transsmissivity 10%.

Table 2

	Liquid crystal aligning agent	[A] composition	[B] composition	Orientation	Response speed (msec.)
						Embodiment 1	S-1	A-1	PA-1	○	30
Embodiment 2	S-2	A-2	PA-1	○	32
						Embodiment 3	S-3	A-3	PA-1	○	28
Embodiment 4	S-4	A-4	PA-1	○	31
						Embodiment 5	S-5	A-5	PI-2	○	38
Embodiment 6	S-6	A-6	PA-1	○	27
						Embodiment 7	S-7	A-7	PA-1	○	27
Embodiment 8	S-8	A-8	PA-1	△	30
						Embodiment 9	S-9	A-9	PA-1	○	32
Embodiment 10	S-10	A-10	PA-1	○	33
						Embodiment 11	S-11	A-7	PA-2	○	32
Embodiment 12	S-12	A-7	PI-1	○	31
						Embodiment 13	S-13	A-7	PI-2	○	38
Embodiment 14	S-14	A-8	PI-2	○	34
						Embodiment 15	S-15	A-11	PA-1	○	27
Embodiment 16	S-16	A-12	PA-1	○	27
						Embodiment 17	S-17	A-13	PA-1	○	27
Embodiment 18	S-18	A-14	PA-1	○	27
						Embodiment 19	S-19	A-15	PA-1	○	27
Embodiment 20	S-20	A-16	PA-1	○	27
						Embodiment 21	S-21	A-17	PA-1	○	27
Comparative example 1	CS-1	CA-1	PA-1	○	53
						Comparative example 2	CS-2	-	PI-2	○	56

Result according to table 2 can know; The orientation of liquid crystal display device that possesses the liquid crystal orientation film that the liquid crystal aligning agent that uses embodiment 1～21 makes is excellent; And aspect response speed of liquid crystal, compare high speed with the liquid crystal display device of comparative example and reach about more than about 2/3.

Utilizability on the industry

Liquid crystal aligning agent of the present invention can be preferred for making the liquid crystal display device of the excellent PSA mode of high-speed response property.

Description of reference numerals

1,11 liquid crystal display device

2 substrates

3 liquid crystal orientation films

4 liquid crystal layers

The 4a liquid crystal molecule

5,5a, 5b transparency electrode

6 wire projections

The transparency electrode of 15 patternings

21 transparency electrodes

22TFT

23 buses

Claims (7)

1. a liquid crystal aligning agent is characterized in that, it is the liquid crystal aligning agent that the liquid crystal orientation film in the liquid crystal display device that forms the PSA mode is used, contain [A] and have compound by the group of following formula (1) expression,

In the formula (1), R ¹For having the group of two single ring architectures, R at least ²For comprising the binding group of two keys, triple bond, ehter bond, ester bond or Sauerstoffatom, a is 0～1 integer.

2. liquid crystal aligning agent according to claim 1, wherein, [A] compound has: be derived from the organopolysiloxane with epoxy group(ing) part, be derived from part by the compound of following formula (2) expression,

In the formula (2), R ¹, R ²And a and the same definition of above-mentioned formula (1), R ³Be alkylidene group, phenylene or the cyclohexylidene of methylene radical, carbonatoms 2～30, these groups can further have substituting group.

3. liquid crystal aligning agent according to claim 1 and 2, wherein, above-mentioned R ¹Be group by following formula (3) expression,

In the formula (3), R ⁴Be Wasserstoffatoms, cyanic acid, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxyl group, trifluoromethoxy or alkyl-carbonyl oxygen base, R ⁵For remove the group of (b+1) valency that (b+1) individual Wasserstoffatoms obtains from benzene, biphenyl, naphthalene, hexanaphthene, bis cyclohexane, phenylcyclohexane or heterogeneous ring compound, these groups can further have substituting group, R ⁶Be any the binding group in the alkylidene group that comprises methylene radical, carbonatoms 2～10, two key, triple bond, ehter bond, ester bond and the heterocycle, these groups can further have substituting group, R ⁷Be phenylene, biphenylene, naphthyl, cyclohexylidene, two cyclohexylidene, cyclohexylidene phenylene or heterocycle independently of one another, these groups can further have substituting group, and b is 1～9 integer, and b is under the situation more than 2, a plurality of R ⁴Can be identical also can be different, c is 0～1 integer, d is 1～2 integer, d is under 2 the situation, a plurality of R ⁶, R ⁷And c can be the same or different separately.

4. liquid crystal aligning agent according to claim 2, wherein, above-mentioned epoxy group(ing) is by following formula (X ¹-1) or (X ¹-2) group of expression,

Formula (X ¹-1) in, A is Sauerstoffatom or singly-bound, and h is 1～3 integer, and i is 0～6 integer, and wherein, i is that A is a singly-bound under 0 the situation,

Formula (X ¹-2) in, j is 0～6 integer.

5. liquid crystal aligning agent according to claim 1 and 2, it further contains at least a polymkeric substance of selecting in the group that [B] be made up of polyamic acid and polyimide.

6. the liquid crystal display device of a PSA mode, it possesses the liquid crystal orientation film that is formed by each described liquid crystal aligning agent in claim 1～claim 5.

7. the method for manufacture of the liquid crystal display device of a PSA mode, it has following operation:

Form the operation of liquid crystal orientation film at each internal surface of a pair of substrate with transparency electrode through each described liquid crystal aligning agent in claim 1～claim 5,

Above-mentioned a pair of substrate according to the mode subtend configuration that internal surface faces each other, is filled the operation of polymerizable liquid crystal compound between this substrate, and

Under the state that has applied voltage, make above-mentioned polymerizable liquid crystal compound solidified operation.

Images