CN101735825B - Liquid crystal aligning agent, polyorganosiloxane, liquid crystal aligning film, forming method thereof and liquid crystal display element - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent, polyorganosiloxane, a liquid crystal aligning film, a forming method thereof and a liquid crystal display element. The present invention provides the liquid crystal aligning agent which can form the liquid crystal aligning film that can generate a pretilt angle with long time stability through an optical aligning method. The liquid crystal aligning agent comprises radiation-sensitive linear polyorganosiloxane which is prepared through the reaction of the following components: specific polyorgansiloxane with epoxy radical; (A) cinnamic acid derivative; and (B) a specific compound with a radiation-sensitive structure that is preferably selected from: acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitro-aryl structure, fluorenes structure, naphthalene structure, anthracene structure, acridine structure and indole structure.

Description

Liquid crystal aligning agent, organopolysiloxane, liquid crystal orientation film and forming method thereof and liquid crystal display device

Technical field

The present invention relates to liquid crystal aligning agent, organopolysiloxane, liquid crystal orientation film and forming method thereof and liquid crystal display device.

Background technology

So far, known have the nematic liquid crystal with positive dielectric anisotropy is being formed to sandwich structure in having the substrate of transparency electrode of liquid crystal orientation film, and the liquid crystal display device (referring to Patent Document 1～4) of the various liquid crystal cells such as IPS (switching face in) type that are orientated in the horizontal direction with respect to substrate of the major axis that makes as required the major axis of liquid crystal molecule reverse continuously the TN type (twisted-nematic) of 0～360 ° and STN (supertwist is to row) type, liquid crystal molecule between substrate.

In this liquid crystal cell, as the means that make liquid crystal aligning, the existing organic membrane that forms on substrate surface, then by making it produce liquid crystal aligning energy to this organic membrane surface with certain orientation friction with clothes such as regenerated fibers, the method using it as liquid crystal orientation film (carrying out the method for grinding process), to the method for substrate surface oblique evaporation silicon oxide or there is the method etc. of the unimolecular film of chain alkyl by Langmuir-Blodgett method (LB method) formation.Wherein, from the angle of substrate size, liquid crystal aligning homogeneity, treatment time and processing cost, consider, conventionally by grinding process, produce liquid crystal aligning energy.

But, if carry out the orientation of liquid crystal by grinding process, exist owing to easily producing dust, static in operation, thereby cause alignment layer surface to adhere to dust and become the problem of the reason that shows bad generation.Particularly in the situation that use has the substrate of TFT (thin film transistor) element, also exist the static producing to cause TFT element circuitry to be damaged and become the problem of the reason of decrease in yield.And from now on day by day in the liquid crystal display device of height precise densification, along with the densification of pixel, substrate surface produces uneven unavoidably, so make to carry out equably the grinding process difficulty that day by day gradually becomes.

As other method that makes the liquid crystal orientation film generation liquid crystal aligning energy in liquid crystal cell, the known optical alignment method that makes its generation liquid crystal aligning energy by the photosensitive films such as the polyvinyl cinnamate forming on substrate surface, polyimide being irradiated to the ray of polarisation or non-polarisation.If employing the method, can not produce static and dust, can realize the liquid crystal aligning (referring to Patent Document 6～16 and 19～21) of homogeneous.

But, in the liquid crystal cell of TN type (twisted-nematic), STN (supertwist is to row) type etc., liquid crystal orientation film must make liquid crystal molecule with respect to real estate angle (tilt angle) tilted alignment (referring to Patent Document 2) to be scheduled to.In the situation that adopting optical alignment method to form liquid crystal orientation film, tilt angle is conventionally by producing (referring to Patent Document 6) by incident direction from the radiation exposure real estate of substrate normal run-off the straight.

In addition, as the operating mode of the liquid crystal display device beyond above-mentioned, the known liquid crystal molecule that makes to have negative dielectric anisotropic vertical orientated vertical (homeotrophic) alignment mode between substrate also.In this operating mode, when applying voltage between substrate liquid crystal molecule is tilted to the direction parallel with substrate, must make the direction of liquid crystal molecule in from substrate normal direction to real estate tilt.As the means that reach this object, proposed such as the method that projection is set on substrate surface, make to arrange in transparency electrode band method, adopt polishing alignment films to make tilt the slightly in advance method etc. (refer to Patent Document 5 and non-patent literature 1～3) of (making its pre-tilt) of the direction of liquid crystal molecule in from substrate normal direction to real estate.

Above-mentioned optical alignment method, known be also (referring to Patent Document 15～21) of great use as the method for controlling liquid crystal molecules tilt direction in the liquid crystal display device of vertical alignment mode.

Like this, the liquid crystal orientation film that adopts above-mentioned optical alignment method to manufacture, can be effectively applied to liquid crystal display device.But, the liquid crystal orientation film that in the past adopted optical alignment method to manufacture, its tilt angle is unstable, that is to say, although can demonstrate good tilt angle performance when liquid crystal orientation film has just formed, has tilt angle performance As time goes on and the problem of decline.

[patent documentation]

[patent documentation 1] Japanese kokai publication hei 4-153622 communique

[patent documentation 2] Japanese kokai publication sho 60-107020 communique

[patent documentation 3] Japanese kokai publication sho 56-91277 communique

No. 5928733 specification sheets of [patent documentation 4] United States Patent (USP)

[patent documentation 5] Japanese kokai publication hei 11-258605 communique

[patent documentation 6] Japanese kokai publication hei 9-222605 communique

[patent documentation 7] Japanese kokai publication hei 6-287453 communique

[patent documentation 8] Japanese kokai publication hei 10-251646 communique

[patent documentation 9] Japanese kokai publication hei 11-2815 communique

[patent documentation 10] Japanese kokai publication hei 11-152475 communique

[patent documentation 11] TOHKEMY 2000-144136 communique

[patent documentation 12] TOHKEMY 2000-319510 communique

[patent documentation 13] TOHKEMY 2000-281724 communique

[patent documentation 14] Japanese kokai publication hei 9-297313 communique

[patent documentation 15] TOHKEMY 2003-307736 communique

[patent documentation 16] TOHKEMY 2004-163646 communique

[patent documentation 17] Japanese kokai publication hei 9-211468 communique

[patent documentation 18] TOHKEMY 2003-114437 communique

[patent documentation 19] TOHKEMY 2006-171304 communique

[patent documentation 20] TOHKEMY 2007-224273 communique

[patent documentation 21] TOHKEMY 2007-256484 communique

[patent documentation 22] TOHKEMY 2007-191447 communique

[patent documentation 23] Japanese kokai publication sho 63-291922 communique

[non-patent literature]

[non-patent literature 1] " liquid crystal ", the 3rd volume, the 2nd phase, p117 (1999)

[non-patent literature 2] " liquid crystal ", the 3rd volume, the 4th phase, p272 (1999)

[non-patent literature 3] " Jpn Appl.phys. ", the 36th volume, p428 (1997)

[non-patent literature 4] Chemical Reviews, the 95th volume, p1409 (nineteen ninety-five)

[non-patent literature 5] T.J.Scheffer etc., J.Appl.Phys., the 19th volume, p2013 (1980)

Summary of the invention

The present invention In view of the foregoing makes, its objective is to provide can form and can produce tilt angle by optical alignment method, and the liquid crystal aligning agent of the liquid crystal orientation film of the tilt angle producing excellent in stability in time.

Another object of the present invention is to provide the method that is formed liquid crystal orientation film by above-mentioned liquid crystal aligning agent.

Another object of the present invention is to provide the good liquid crystal orientation film of long-term reliability and liquid crystal display device.

The present invention is other object and advantage further, can be learned by the following description.

According to the present invention, above object and advantages of the present invention, first, by a kind of liquid crystal aligning agent, reached, at least one in the group that its condenses that contains the organopolysiloxane, its hydrolyzate and the hydrolyzate that make to be selected from the repeating unit with following formula (1) expression forms, has and is selected from carboxyl, hydroxyl ,-SH ,-NCO ,-NHR (wherein R is that hydrogen atom or carbonatoms are 1～6 alkyl) ,-CH=CH with (A) ₂with-SO ₂the cinnamic acid derivative of at least one group in the group that Cl forms and (B) have and be selected from carboxyl, hydroxyl ,-SH ,-NCO ,-NHR (wherein R is that hydrogen atom or carbonatoms are 1～6 alkyl) ,-CH=CH ₂with-SO ₂at least one group in the group that Cl forms and the reaction of the compound of light enhanced sensitivity structure and the radiation sensitive linear organopolysiloxane that makes,

In formula (1), X ¹for thering is any monovalent organic radical group of epoxy group(ing), Y ¹for hydroxyl, the carbonatoms alkoxyl group that is 1～10, alkyl that carbonatoms is 1～20 or the carbonatoms aryl that is 6～20.

Above object and advantages of the present invention, the second, by a kind of method that forms of liquid crystal orientation film, to be reached, it applies above-mentioned liquid crystal aligning agent and forms and film on substrate, and this is filmed and irradiates the ray of polarisation or non-polarisation.

Above object and advantages of the present invention, the 3rd, the liquid crystal orientation film being formed by above-mentioned liquid crystal aligning agent is reached, and the 4th, by the liquid crystal display device with above-mentioned liquid crystal orientation film, reached.

If adopt liquid crystal aligning agent of the present invention, can form by optical alignment method the liquid crystal orientation film of tilt angle excellent in stability in time.The liquid crystal orientation film of the present invention being formed by liquid crystal aligning agent of the present invention, applicable to various liquid crystal display device.The liquid crystal display device of the present invention with this liquid crystal orientation film, even through life-time service in the situation that, display performance can variation yet.Therefore, liquid crystal display device of the present invention can be effectively applied to various devices, for example,, applicable to the display unit of clock and watch, portable game machine, word processor, subnotebook PC, automobile navigation instrument, pick up camera, portable data assistance, digital camera, mobile telephone, various watch-dog, liquid crystal TV set etc.

Accompanying drawing explanation

The graphic representation that Fig. 1 distributes for the existence on film thickness direction of the fragment that shows the m/z=231 being observed by ToF-SIMS in embodiment T-1.

Fig. 2 is for showing the graphic representation of the aggregate-value that the fragment of the m/z=231 being observed by ToF-SIMS in embodiment T-1 distributes on film thickness direction.

Embodiment

Below, the present invention is described in detail.

Liquid crystal aligning agent of the present invention, at least one (hereinafter referred to as " organopolysiloxane with epoxy group(ing) ") in the group that the condenses that contains the organopolysiloxane, its hydrolyzate and the hydrolyzate that make to be selected from the repeating unit with above-mentioned formula (1) expression forms, has and is selected from carboxyl, hydroxyl ,-SH ,-NCO ,-NHR (wherein R is that hydrogen atom or carbonatoms are 1～6 alkyl) ,-CH=CH with (A) ₂with-SO ₂the cinnamic acid derivative (hereinafter referred to as " cinnamic acid derivative (A) ") of at least one group in the group that Cl forms and (B) have and be selected from carboxyl, hydroxyl ,-SH ,-NCO ,-NHR (wherein R is that hydrogen atom or carbonatoms are 1～6 alkyl) ,-CH=CH ₂with-SO ₂at least one group in the group that Cl forms and the reaction of the compound (hereinafter referred to as " light enhanced sensitivity compound (B) ") of light enhanced sensitivity structure and the radiation sensitive linear organopolysiloxane that makes.Here, in not damaging the scope of effect of the present invention, the compound that a part for above-mentioned cinnamic acid derivative (A) can also be represented by following formula (5) is replaced,

R ¹⁵-R ¹⁶-R ¹⁷ (5)

In formula (5), R ¹⁵for the carbonatoms that the contains ester ring type group any monovalent organic radical group that is 3～40, or be carbonatoms be 4～20 alkyl or alkoxyl group, wherein the part or all of hydrogen atom of abovementioned alkyl or alkoxyl group optionally can be replaced by fluorine atom, R ¹⁶for singly-bound or phenylene, but work as R ¹⁵during for alkoxyl group, R ¹⁶for phenylene, R ¹⁷for being selected from carboxyl, hydroxyl ,-SH ,-NCO ,-NHR (wherein R is that hydrogen atom or carbonatoms are 1～6 alkyl) ,-CH=CH ₂with-SO ₂at least one group in the group that Cl forms.

<radiation sensitive linear organopolysiloxane>

[organopolysiloxane with epoxy group(ing)]

As the X in above-mentioned formula (1) ¹group, is preferably following formula (X ¹-1) or (X ¹-2) group representing,

In above-mentioned formula, " * " is expressed as connecting key.

As Y ¹the carbonatoms alkoxyl group that is 1～10, can enumerate such as methoxyl group, oxyethyl group etc.; The alkyl that is 1～20 as carbonatoms, can enumerate such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.; The aryl that is 6～20 as carbonatoms, can enumerate such as phenyl etc.;

The organopolysiloxane with epoxy group(ing), weight-average molecular weight of the polystyrene conversion that it is measured by gel permeation chromatography (GPC) is preferably 500～100000, and more preferably 1000～10000, more preferably 1000～5000.

This organopolysiloxane with epoxy group(ing), can be by will preferably thering is the silane compound of epoxy group(ing) or there is the silane compound of epoxy group(ing) and the mixture of other silane compound, preferably under the existence of suitable organic solvent, water and catalyzer, be hydrolyzed or hydrolysis, condensation and synthesize.

As the above-mentioned silane compound with epoxy group(ing), can enumerate for example 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-dimethyl methoxy silane, 3-glycidoxy propyl-dimethyl Ethoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl triethoxysilane etc.

As above-mentioned other silane compound, can enumerate for example tetrachloro silicane, tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, trichlorosilane, Trimethoxy silane, triethoxyl silane, three positive propoxy silane, three isopropoxy silane, three n-butoxy silane, three sec-butoxy silane, fluoro trichlorosilane, fluoro Trimethoxy silane, fluoro triethoxyl silane, fluoro three positive propoxy silane, fluoro three isopropoxy silane, fluoro three n-butoxy silane, fluoro three sec-butoxy silane, METHYL TRICHLORO SILANE, 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, 2-(trifluoromethyl) ethyl trichlorosilane, 2-(trifluoromethyl) ethyl trimethoxy silane, 2-(trifluoromethyl) ethyl triethoxysilane, 2-(trifluoromethyl) ethyl three positive propoxy silane, 2-(trifluoromethyl) ethyl three isopropoxy silane, 2-(trifluoromethyl) ethyl three n-butoxy silane, 2-(trifluoromethyl) ethyl three sec-butoxy silane, 2-(perfluor n-hexyl) ethyl trichlorosilane, 2-(perfluor n-hexyl) ethyl trimethoxy silane, 2-(perfluor n-hexyl) ethyl triethoxysilane, 2-(perfluor n-hexyl) ethyl three positive propoxy silane, 2-(perfluor n-hexyl) ethyl three isopropoxy silane, 2-(perfluor n-hexyl) ethyl three n-butoxy silane, 2-(perfluor n-hexyl) ethyl three sec-butoxy silane, 2-(perfluor n-octyl) ethyl trichlorosilane, 2-(perfluor n-octyl) ethyl trimethoxy silane, 2-(perfluor n-octyl) ethyl triethoxysilane, 2-(perfluor n-octyl) ethyl three positive propoxy silane, 2-(perfluor n-octyl) ethyl three isopropoxy silane, 2-(perfluor n-octyl) ethyl three n-butoxy silane, 2-(perfluor n-octyl) ethyl three sec-butoxy silane, methylol trichlorosilane, methylol Trimethoxy silane, hydroxyethyl Trimethoxy silane, methylol three positive propoxy silane, methylol three isopropoxy silane, methylol three n-butoxy silane, methylol three sec-butoxy silane, 3-(methyl) acryloxy propyltrichlorosilan, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-(methyl) acryloxy propyl group three positive propoxy silane, 3-(methyl) acryloxy propyl group three isopropoxy silane, 3-(methyl) acryloxy propyl group three n-butoxy silane, 3-(methyl) acryloxy propyl group three sec-butoxy silane, 3-sulfydryl propyltrichlorosilan, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-sulfydryl propyl group three positive propoxy silane, 3-sulfydryl propyl group three isopropoxy silane, 3-sulfydryl propyl group three n-butoxy silane, 3-sulfydryl propyl group three sec-butoxy silane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three positive propoxy silane, vinyl silane triisopropoxide, vinyl three n-butoxy silane, vinyl three sec-butoxy silane, allyltrichlorosilane, allyltrimethoxysilanis, allyltriethoxysilane, allyl group three positive propoxy silane, allyl group three isopropoxy silane, allyl group three n-butoxy silane, allyl group three sec-butoxy silane, phenyl-trichloro-silicane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl three positive propoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, phenyl three sec-butoxy silane, dimethyl dichlorosilane (DMCS), methyl dimethoxysilane, methyldiethoxysilane, methyl two positive propoxy silane, methyl diisopropoxy silane, methyl two n-butoxy silane, methyl di-secondary butoxy silane, dimethyldichlorosilane(DMCS), dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl two positive propoxy silane, dimethyl diisopropoxy silane, dimethyl two n-butoxy silane, dimethyl di-secondary butoxy silane, (methyl) [2-(perfluor n-octyl) ethyl] dichlorosilane, (methyl) [2-(perfluor n-octyl) ethyl] dimethoxy silane, (methyl) [2-(perfluor n-octyl) ethyl] diethoxy silane, (methyl) [2-(perfluor n-octyl) ethyl] two positive propoxy silane, (methyl) [2-(perfluor n-octyl) ethyl] diisopropoxy silane, (methyl) [2-(perfluor n-octyl) ethyl] two n-butoxy silane, (methyl) [2-(perfluor n-octyl) ethyl] di-secondary butoxy silane, (methyl) (3-sulfydryl propyl group) dichlorosilane, (methyl) (3-sulfydryl propyl group) dimethoxy silane, (methyl) (3-sulfydryl propyl group) diethoxy silane, (methyl) (3-sulfydryl propyl group) two positive propoxy silane, (methyl) (3-sulfydryl propyl group) diisopropoxy silane, (methyl) (3-sulfydryl propyl group) two n-butoxy silane, (methyl) (3-sulfydryl propyl group) di-secondary butoxy silane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxy silane, (methyl) (vinyl) diethoxy silane, (methyl) (vinyl) two positive propoxy silane, (methyl) (vinyl) diisopropoxy silane, (methyl) (vinyl) two n-butoxy silane, (methyl) (vinyl) di-secondary butoxy silane, divinyl dichlorosilane, divinyl dimethoxy silane, divinyl diethoxy silane, divinyl two positive propoxy silane, divinyl diisopropoxy silane, divinyl two n-butoxy silane, divinyl di-secondary butoxy silane, diphenyl dichlorosilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenylbenzene two positive propoxy silane, phenylbenzene diisopropoxy silane, phenylbenzene two n-butoxy silane, phenylbenzene di-secondary butoxy silane, chloro dimethylsilane, methoxyl group dimethylsilane, oxyethyl group dimethylsilane, trimethysilyl chloride, bromo trimethyl silane, iodo trimethyl silane, methoxytrimethylsilane, ethoxytrimethylsilane, positive propoxy trimethyl silane, IPOTMS isopropyloxy trimethylsilane, n-butoxy trimethyl silane, sec-butoxy trimethyl silane, tert.-butoxy trimethyl silane, (chlorine) (vinyl) dimethylsilane, (methoxyl group) (vinyl) dimethylsilane, (oxyethyl group) (vinyl) dimethylsilane, (chlorine) (methyl) diphenyl silane, (methoxyl group) (methyl) diphenyl silane, (oxyethyl group) (methyl) diphenyl silane etc. has the silane compound of 1 Siliciumatom, in addition, can also enumerate commodity for example KC-89 by name, 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 (being produced by SHIN-ETSU HANTOTAI's chemical industry (strain) above), グ ラ ス レ ジ Application (being produced by clear and Electricity work (strain)), SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (the Shang You East of Yi レ ダ ウ コ mono-ニ Application グ (strain) produces), FZ3711, FZ3722 (more than, by Japanese ユ ニ カ mono-(strain) produce), 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 (being produced by チ Star ソ (strain) above), メ チ Le シ リ ケ mono-ト MS 51, メ チ Le シ リ ケ mono-ト MS56 (by Mitsubishi Chemical's (strain), being produced above), エ チ Le シ リ ケ mono-ト 28, エ チ Le シ リ ケ mono-ト 40, エ チ Le シ リ ケ mono-ト 48 (being produced by コ Le コ mono-ト (strain) above), the partial condensate of GR100, GR650, GR908, GR950 (being produced by clear and Electricity work (strain) above) etc.

In these other silane compounds, 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 or dimethyldiethoxysilane.

The organopolysiloxane with epoxy group(ing) using in the present invention, its epoxide equivalent is preferably 100～10000g/ mole, and more preferably 150～1000g/ mole, is particularly preferably 150～300g/ mole.Therefore, synthetic, while thering is the organopolysiloxane of epoxy group(ing), there is the silane compound of epoxy group(ing) and the usage rate of other silane compound, be preferably set to the epoxide equivalent of gained organopolysiloxane is adjusted in above-mentioned scope.In synthetic the present invention, use there is the organopolysiloxane of epoxy group(ing) time, preferably only use and there is the silane compound of epoxy group(ing), and do not use other silane compound.

Operable organic solvent during as the synthetic organopolysiloxane with epoxy group(ing), can enumerate such as hydro carbons, ketone, ester class, ethers, alcohols etc.

As above-mentioned hydro carbons, can enumerate such as toluene, dimethylbenzene etc., as above-mentioned ketone, can enumerate such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, metacetone, pimelinketone etc.; As above-mentioned ester class, can enumerate such as vinyl acetic monomer, n-butyl acetate, isoamyl acetate, propylene glycol methyl ether acetate, 3-methoxyl group butylacetic acid ester, ethyl lactate etc., as above-mentioned ethers, can enumerate such as glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), dioxane etc., as above-mentioned alcohols, can enumerate such as 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether etc.Preferred water-insoluble solvent wherein.

These organic solvents can independent or two or more mixing uses.

The consumption of organic solvent, with respect to the whole silane compounds of 100 weight part, is preferably 10～10000 weight parts, more preferably 50～1000 weight parts.

While preparing the organopolysiloxane with epoxy group(ing), the consumption of water, with respect to whole silane compounds, is preferably 0.5～100 times mole, more preferably 1～30 times mole.

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

As above-mentioned alkali metal compound, can enumerate such as sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc.

As above-mentioned organic bases, can enumerate organic primary, secondary amine such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles; Organic quaternary ammoniums such as trimethylamine, tetramethyl ammonium hydroxide such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene etc.In these organic basess, organic quaternary ammoniums such as trimethylamine, tetramethyl ammonium hydroxide such as preferred triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine.

Catalyzer while thering is the organopolysiloxane of epoxy group(ing) as preparation, preferred as alkali compound or organic bases.Due to by using alkali metal compound or organic bases as catalyzer, can not there is the side reactions such as open loop of epoxy group(ing), can make object organopolysiloxane with very fast hydrolysis, condensation rates, therefore production stability is good, because of but preferably.In addition, contain and adopt alkali metal compound or organic bases as catalyzer and the liquid crystal aligning agent of the present invention of the reaction product of the synthetic organopolysiloxane with epoxy group(ing) and cinnamic acid derivative, because storage stability is very excellent, therefore easily.Its reason, by inference perhaps as non-patent literature 4 (Chemical Reviews, the 95th volume, p1409 (nineteen ninety-five)) described in, if be owing to using alkali metal compound or organic bases as catalyzer in hydrolysis, condensation reaction, can form random structure, ladder structure or cage structure, thereby obtain the cause that silanol groups contains the organopolysiloxane that ratio is little.That is to say, by inference, this organopolysiloxane is because silanol groups content ratio is little, thereby can suppress the condensation reaction between silanol groups, and when liquid crystal aligning agent of the present invention also contains other following polymkeric substance, can suppress the condensation reaction of silanol groups and other polymkeric substance, thereby obtain the good result of storage stability.

As catalyzer, organic bases particularly preferably.The consumption of organic bases, according to reaction conditionss such as the kind of organic bases, temperature etc. and different, should suitably set, for example, with respect to whole silane compounds, be preferably 0.01～3 times mole, more preferably 0.05～1 times mole.

Hydrolysis while preparing the organopolysiloxane with epoxy group(ing) or hydrolysis, condensation reaction, preferably by thering is the silane compound of epoxy group(ing) and other silane compound is as required dissolved in organic solvent, this solution is mixed with organic bases and water, by carrying out such as heating such as oil baths.

In hydrolysis, during condensation reaction, Heating temperature is preferably below 130 ℃, more preferably 40～100 ℃, preferably heat 0.5～12 hour, more preferably 1～8 hour better.In heat-processed, can be uniformly mixed liquid, also can under refluxing, carry out.

After reaction finishes, preferably the organic solvent layer separating from reaction solution is washed with water.When this washs, from the angle that washing operation easily carries out is considered, preferably adopt the water that contains a small amount of salt, such as the aqueous solution of the ammonium nitrate that contains 0.2 % by weight left and right etc., wash.It is neutrality that washing proceeds to the water layer making after washing, after then organic solvent layer being dried with suitable siccative such as anhydrous calciumsulphate, molecular sieves as required, except desolventizing, can obtain the organopolysiloxane with epoxy group(ing) as target compound.

In the present invention, as the organopolysiloxane with epoxy group(ing), also can use commercially available product.As this commercially available product, can enumerate such as DMS-E01, DMS-E12, DMS-E21, EMS-32 (being produced by チ Star ソ (strain) above) etc.

[cinnamic acid derivative (A)]

In the present invention, operable cinnamic acid derivative (A) is to have to be selected from carboxyl, hydroxyl ,-SH ,-NCO ,-NHR (wherein R is that hydrogen atom or carbonatoms are 1～6 alkyl) ,-CH=CH ₂with-SO ₂the cinnamic acid derivative of at least one group in the group that Cl forms.

As cinnamic acid derivative (A), be preferably the compound of following formula (2) expression or the compound that following formula (3) represents,

(in formula (2), R ¹for the carbonatoms that the contains ester ring type group any monovalent organic radical group that is 3～40, or be the carbonatoms alkyl that is 1～40, wherein the part or all of hydrogen atom of abovementioned alkyl optionally can be replaced by fluorine atom, R ²for singly-bound, Sauerstoffatom ,-COO-or-OCO-, R ³for the aromatic group of divalence, the heterocyclic group of the ester ring type group of divalence, divalence or the condensed ring group of divalence, R ⁴for singly-bound, Sauerstoffatom ,-COO-or-OCO-, R ⁵for singly-bound, Sauerstoffatom, sulphur atom, methylene radical, the carbonatoms alkylidene group that is 2～10 or the aromatic group of divalence, work as R ⁵during for singly-bound, t is 1, and R ⁶for hydrogen atom, work as R ⁵during for the aromatic group of methylene radical, alkylidene group or divalence, t is 0 or 1, and R ⁶for carboxyl, hydroxyl ,-SH ,-NCO ,-NHR ,-CH=CH ₂or-SO ₂cl, wherein above-mentioned R is the alkyl that hydrogen atom or carbonatoms are 1～6, R ⁷for fluorine atom or cyano group, the integer that a is 0～3, the integer that b is 0～4),

(in formula (3), R ⁸for the carbonatoms that the contains ester ring type group any monovalent organic radical group that is 3～40, or be the carbonatoms alkyl that is 1～40, wherein the part or all of hydrogen atom of abovementioned alkyl optionally can be replaced by fluorine atom, R ⁹for the aromatic group of Sauerstoffatom or divalence, R ¹⁰for Sauerstoffatom ,-COO-or-OCO-, R ¹¹for the condensed ring group of the aromatic group of divalence, the heterocyclic group of divalence or divalence, R ¹²for singly-bound ,-OCO-(CH ₂) _e-* or-O-(CH ₂) _g-*, above-mentioned e and g 1～10 the integer of respectively doing for oneself wherein, " * " represents separately with its connecting key and R ¹³connect R ¹³for carboxyl, hydroxyl ,-SH ,-NCO ,-NHR ,-CH=CH ₂or-SO ₂cl, wherein above-mentioned R is the alkyl that hydrogen atom or carbonatoms are 1～6, R ¹⁴for fluorine atom or cyano group, the integer that c is 0～3, the integer that d is 0～4).

As the R in above-mentioned formula (2) ¹the carbonatoms that the contains ester ring type group any monovalent organic radical group that is 3～40, can enumerate such as cholest-, cholestane base, adamantyl etc.As R ¹the carbonatoms alkyl that is 1～40, be preferably the alkyl that for example carbonatoms is 1～20, wherein the part or all of hydrogen atom of this alkyl optionally can be replaced by fluorine atom.Example as this alkyl, can enumerate for example n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base, 4, 4, 4-trifluoro butyl, 4, 4, 5, 5, 5-five fluorine amyl groups, 4, 4, 5, 5, 6, 6, 6-seven fluorine hexyls, 3, 3, 4, 4, 5, 5, 5-seven fluorine amyl groups, 2, 2, 2-trifluoroethyl, 2, 2, 3, 3, 3-five fluoropropyls, 2-(perfluoro butyl) ethyl, 2-(perfluoro capryl) ethyl, 2-(perfluor decyl) ethyl etc.

As R ³and R ⁵divalence aromatic group, can enumerate for example Isosorbide-5-Nitrae-phenylene, the fluoro-Isosorbide-5-Nitrae-phenylene of 2-, the fluoro-Isosorbide-5-Nitrae-phenylene of 3-, 2,3,5,6-tetrafluoro-Isosorbide-5-Nitrae-phenylene etc.; As R ³divalent heterocyclic group, can enumerate for example Isosorbide-5-Nitrae-pyridylidene, 2,5-pyridylidene, Isosorbide-5-Nitrae-furylidene etc.; As R ³divalence condensed ring group, can enumerate such as naphthylidene etc.

As R ³ester ring type group, can enumerate such as Isosorbide-5-Nitrae-cyclohexylidene etc.

The compound representing as above-mentioned formula (2), is preferably R in above-mentioned formula (2) ⁵for singly-bound, t is 1, and R ⁶for the compound of hydrogen atom, or R ⁵for the aromatic group of methylene radical, alkylidene group or divalence, t is 0 or 1, and R ⁶compound for carboxyl.

The preferred example of the compound representing as above-mentioned formula (2), can enumerate the compound of following formula (2-1) for example～(2-35) represent separately,

In formula, R ¹identical with the definition in above-mentioned formula (2) separately, respectively do for oneself 1～10 integer of f.

As the R in above-mentioned formula (3) ⁸the carbonatoms that the contains ester ring type group any monovalent organic radical group that is 3～40, can enumerate such as cholest-, cholestane base, adamantyl etc.As R ⁸the carbonatoms alkyl that is 1～40, be preferably the alkyl that for example carbonatoms is 1～20, wherein the part or all of hydrogen atom of alkyl optionally can be replaced by fluorine atom.As the example of this alkyl, can enumerate for example as the R in above-mentioned formula (2) ¹alkyl and illustrative group.

As R ⁹and R ¹¹divalence aromatic group, heterocyclic group or condensed ring group, can enumerate for example as the R in above-mentioned formula (2) ³and R ⁵divalence aromatic group, heterocyclic group or condensed ring group and the group enumerated respectively.

As R ¹³, preferred carboxyl.

The preferred example of the compound representing as above-mentioned formula (3), can enumerate the compound of following formula (3-1) for example～(3-11) represent separately,

In formula, R ⁸identical with the definition in above-mentioned formula (3) separately, respectively do for oneself 1～10 integer of u.

This cinnamic acid derivative (A) can be by suitably combining the information of organic synthesis to synthesize.Its synthetic route and reaction conditions, the general knowledge by technician and a small amount of trial test are easy to set.

[light enhanced sensitivity compound (B)]

Light enhanced sensitivity compound (B) in the present invention is to have to be selected from carboxyl, hydroxyl ,-SH ,-NCO ,-NHR (wherein R is that hydrogen atom or carbonatoms are 1～6 alkyl) ,-CH=CH ₂with-SO ₂at least one group in the group that Cl forms and the compound of light enhanced sensitivity structure.By the above-mentioned organopolysiloxane with epoxy group(ing) is reacted with the mixture of cinnamic acid derivative (A) and light enhanced sensitivity compound (B), radiation sensitive linear organopolysiloxane contained in liquid crystal aligning agent of the present invention is had derive from the photosensitive structure (styracin structure) of cinnamic acid derivative (A) and derive from concurrently the light enhanced sensitivity structure of light enhanced sensitivity compound (B), this light enhanced sensitivity structure has by useful to irradiation of rays and excites and give the function of photosensitive structure contiguous in polymkeric substance with this excitation energy.This excited state, can be one heavily to excite, and can be also triple exciting, and long and shift efficiently the angle of energy from the life-span, is preferably triple exciting.The ray that above-mentioned smooth enhanced sensitivity structure absorbs, is preferably ultraviolet ray or visible rays that wavelength is 150～600nm scope.Its shorter ray of wavelength ratio, owing to not processing by common optical system, thereby can not be applicable to optical alignment method.On the other hand, its longer ray of wavelength ratio, is difficult to cause the excited state of above-mentioned smooth enhanced sensitivity structure because energy is little.

As this smooth enhanced sensitivity structure, can enumerate such as methyl phenyl ketone structure, benzophenone structure, anthraquinone ring, biphenyl structural, carbazole structure, nitro aryl structure, fluorene structured, naphthalene structure, anthracene structure, acridine structure, indole structure etc., can be at least one in the middle of them.These structures refer to respectively the structure consisting of the structure of removing 1～4 hydrogen atom gained from benzophenone, methyl phenyl ketone, anthraquinone, biphenyl, carbazole, oil of mirbane or dinitrobenzene, naphthalene, fluorenes, anthracene, acridine or indoles.Here, methyl phenyl ketone structure, carbazole structure and indole structure are preferably respectively 1～4 in the hydrogen atom being had by the phenyl ring of removing methyl phenyl ketone, carbazole or indoles and structure that the group that obtains forms.

As light enhanced sensitivity structure, in the middle of them, be preferably at least one in the group that is selected from methyl phenyl ketone structure, benzophenone structure, anthraquinone ring, biphenyl structural, carbazole structure, nitro aryl structure and naphthalene structure formation, be particularly preferably at least one in the group that is selected from methyl phenyl ketone structure, benzophenone structure and nitro aryl structure formation.

As light enhanced sensitivity compound (B), be preferably the compound with carboxyl and light enhanced sensitivity structure, as preferred compound, can enumerate the compound of following formula (B-1) for example～(B-42) represent separately,

In above-mentioned formula, respectively do for oneself 1～6 integer of p, q, r and s.

The radiation sensitive linear organopolysiloxane using in the present invention, can be by making organopolysiloxane and cinnamic acid derivative (A) and the light enhanced sensitivity compound (B) with epoxy group(ing) as above, preferably, under the existence of catalyzer, preferably in organic solvent, react and synthesize.

Here, cinnamic acid derivative (A), with respect to 1 mole of Siliciumatom with the organopolysiloxane of epoxy group(ing), preferably with 0.001～1 mole, more preferably 0.1～1 mole, further preferably the scope of 0.2～0.9 mole is used.Light enhanced sensitivity compound (B), with respect to 1 mole of Siliciumatom with the organopolysiloxane of epoxy group(ing), preferably with 0.0001～0.5 mole, more preferably 0.0005～0.2 mole, further preferably the scope of 0.001～0.1 mole is used.

In the present invention, in not damaging the scope of effect of the present invention, the compound that a part for above-mentioned cinnamic acid derivative can also be represented by above-mentioned formula (5) is replaced and is used.Now, radiation sensitive linear organopolysiloxane synthetic, can react and carry out by making to have the organopolysiloxane of epoxy group(ing) and the compound of cinnamic acid derivative (A) and above-mentioned formula (5) expression and light enhanced sensitivity compound (B).

As the R in above-mentioned formula (5) ¹⁵, be preferably carbonatoms and be 8～20 alkyl or alkoxyl group, or carbonatoms be 4～21 fluoro-alkyl or fluoroalkyl, as R ¹⁶, be preferably singly-bound, Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, as R ¹⁷, be preferably carboxyl.

The preferred example of the compound representing as above-mentioned formula (5), can enumerate the compound of following formula (5-1) for example～(5-4) represent separately,

C _hF _2h+1-C _iH _2i-COOH (5-1)

(in above-mentioned formula, h is 1～3 integer, i is 3～18 integer, j is 5～20 integer, k is 1～3 integer, the integer that m is 0～18, the integer that n is 1～18), as preferred example, can enumerate the compound of following formula (5-3-1) in above-mentioned formula～(5-3-3) represent separately.

The compound that above-mentioned formula (5) represents, make to react with the organopolysiloxane with epoxy group(ing) together with above-mentioned cinnamic acid derivative (A) and light enhanced sensitivity compound (B), and import, make gained liquid crystal orientation film produce the compound at the position of tilt angle expression power.In this manual, the compound that above-mentioned formula (5) represents is called as " other tilt angle expression power compound " below.

In the present invention, when a part for above-mentioned cinnamic acid derivative (A) is used by other tilt angle expression power compound replacement, the total usage rate of cinnamic acid derivative (A), light enhanced sensitivity compound (B) and other tilt angle expression power compound, with respect to 1 mole of Siliciumatom with the organopolysiloxane of epoxy group(ing), be preferably 0.001～1 mole, more preferably 0.1～1 mole, further preferably 0.2～0.9 mole.Now, other tilt angle expression power compound, with respect to the total amount with cinnamic acid derivative (A), preferably with 50 % by mole of following, more preferably 25 % by mole of following scopes uses.If the usage rate of other tilt angle expression power compound surpasses 50 % by mole, there will be at liquid crystal display device during in ON, produce the situation of the trouble that occurs abnormal area.

As catalyzer, can use organic bases or promote epoxy compounds and the so-called curing catalyst of conduct of anhydride reaction and known compound.

As above-mentioned organic bases, can enumerate organic primary, secondary amine such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles; The trimethylamines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene; Organic quaternary ammonium such as tetramethyl ammonium hydroxide etc.In these organic basess, the trimethylamines such as preferred triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; Organic quaternary ammonium such as tetramethyl ammonium hydroxide.

As above-mentioned curing catalyst, can enumerate for example benzyl dimethyl amine, 2,4, the tertiary amines such as 6-tri-(dimethylamino methyl) phenol, cyclohexyl dimethyl amine, trolamine;

Glyoxal ethyline, 2-n-heptyl imidazoles, 2-undecyl imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyano ethyl)-glyoxal ethyline, 1-(2-cyano ethyl)-2-n-undecane base imidazoles, 1-(2-cyano ethyl)-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2-phenyl-4,5-bis-(methylol) imidazoles, 1-(2-cyano ethyl)-2-phenyl-4,5-bis-[(2 '-cyano group oxyethyl group) methyl] imidazoles, 1-(2-cyano ethyl)-2-n-undecane base imidazoles trimellitate, 1-(2-cyano ethyl)-2-phenylimidazole trimellitate, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole trimellitate, 2,4-diamino-6-[2 '-Methylimidazole-(1 ')] ethyl-s-triazine, 2,4-diamino-6-(2 '-n-undecane base imidazoles) ethyl-s-triazine, 2,4-diamino-6-[2 '-ethyl-4 '-Methylimidazole-(1 ')] ethyl-s-triazine, the tricarbimide affixture of glyoxal ethyline, the tricarbimide affixture of 2-phenylimidazole, 2,4-diamino-6-[2 '-Methylimidazole (1 ')] imidazolium compoundss such as tricarbimide affixture of ethyl-s-triazine, the organo phosphorous compoundss such as diphenylphosphine, triphenylphosphine, tricresyl phosphite phenylester,

Benzyl base triphenyl phosphonium chloride, four normal-butyl bromination Phosphonium, first base three phenyl phosphonium bromides, ethyl triphenyl phosphonium bromide, normal-butyl three phenyl phosphonium bromides, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, second base triphenyl phosphonium acetate, 4-butyl-phosphonium, O, the quaternary alkylphosphonium salts such as O-diethyl phosphorothioate, four positive fourth base Phosphonium benzotriazoles, four positive fourth base Phosphonium a tetrafluoro borates, four positive fourth base Phosphonium tetraphenyl borate salts, tetraphenylphosphoniphenolate tetraphenyl borate salts;

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

The organometallic compounds such as zinc octoate, stannous octoate, methyl ethyl diketone aluminum complex;

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

The boron compounds such as boron trifluoride, boric acid triphenyl ester;

The metal halide such as zinc chloride, tin chloride;

The high-melting-point decentralized potentiality curing catalysts such as amine add-on type promotor such as the affixture of dicyanodiamide or amine and epoxy resin;

The minigel type potentiality curing catalyst of polymkeric substance coating for the surface of the curing catalysts such as above-mentioned imidazolium compounds, organic phosphine compound, quaternary alkylphosphonium salt; Amine salt type potentiality curing catalyst;

The potentiality curing catalysts such as lewis acid, the contour temperature drop solution of Bronsted hydrochlorate cationic polymerization type potentiality hot in nature curing catalyst etc.

In the middle of them, be preferably the quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride.

Catalyzer, has the organopolysiloxane of epoxy group(ing) with respect to 100 weight parts, preferably following with 100 weight parts, more preferably 0.01～100 weight part, more preferably the ratio of 0.1～20 weight part is used.

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.

Operable organic solvent during as radiation sensitive linear organopolysiloxane synthetic, can enumerate such as hydrocarbon compound, ether compound, ester cpds, ketone compound, amide compound, alkylol cpd etc.Wherein, from the solvability of raw material and product and the easily refining property angle of product, preferably ether compound, ester cpds, ketone compound.Solvent is so that solids content concn (the total weight of the composition beyond desolventizing in reaction soln accounts for the ratio of total solution weight) is preferably the amount use above, more preferably 5～50 % by weight of 0.1 % by weight.

Contained radiation sensitive linear organopolysiloxane in liquid crystal aligning agent of the present invention, use has the organopolysiloxane of epoxy group(ing) as raw material, and the open loop addition by its epoxy group(ing) imports the structure that derives from cinnamic acid derivative (A) and light enhanced sensitivity compound (B).This preparation method is very easy.And, particularly in the method that can improve the importing rate of the styracin structure that derives from cinnamic acid derivative (A), be most suitable method.In addition, due to the light enhanced sensitivity structure that derives from light enhanced sensitivity compound (B) bonding chemically on radiation sensitive linear organopolysiloxane, thereby can be efficiently near the styracin structure that derives from cinnamic acid derivative (A) being present in, supply with the excitation energy being produced by useful to irradiation of rays when the optical alignment method in radiation sensitive linear organopolysiloxane, thereby can obtain enough good liquid crystal aligning and show tilt angle by a small amount of radiation exposure.In addition, due to light enhanced sensitivity structure bonding chemically in matrix polymer, thereby when forming as the filming of liquid crystal orientation film, the distillation while curing after can preventing.

[other composition]

Liquid crystal aligning agent of the present invention contains radiation sensitive linear organopolysiloxane as above.

Liquid crystal aligning agent of the present invention, except radiation sensitive linear organopolysiloxane as above, in the situation that not damaging effect of the present invention, can also further contain other composition.As this other composition, can enumerate such as the compound (hereinafter referred to as " epoxy compounds ") in the polymkeric substance (hereinafter referred to as " other polymkeric substance ") beyond radiation sensitive linear organopolysiloxane, solidifying agent, curing catalysts, curing catalyst, molecule with at least one epoxy group(ing), functional silanes compound, tensio-active agent, photosensitizing agent etc.

[other polymkeric substance]

Above-mentioned other polymkeric substance can be in order further to improve the solution property of liquid crystal aligning agent of the present invention and the electric property of gained liquid crystal orientation film is used.As this other polymkeric substance, can enumerate such as being selected from least one polymkeric substance in the group that polyamic acid and polyimide form, be selected from least one (hereinafter referred to as " other organopolysiloxane "), poly amic acid ester in the group that the condenses of organopolysiloxane, its hydrolyzate and hydrolyzate that following formula (4) represents forms, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.

(in formula (4), X ²for hydroxyl, halogen atom, the carbonatoms alkyl that is 1～20, alkoxyl group that carbonatoms is 1～6 or carbonatoms be 6～20 aryl, Y ²for hydroxyl or the carbonatoms alkoxyl group that is 1～10).

[polyamic acid]

Above-mentioned polyamic acid can be by making tetracarboxylic dianhydride react and make with diamine compound.

As operable tetracarboxylic dianhydride in polyamic acid synthetic, for example can enumerate 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 3,5,6-, tri-carboxyl norbornane-2-acetic acid dianhydrides, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-8-methyl-naphthalene [1,2-c]-furans-1,3-diketone, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride, the aliphatics tetracarboxylic dianhydrides such as tetracarboxylic dianhydride and ester ring type tetracarboxylic dianhydride that following formula (T-1)～(T-14) represents separately,

Pyromellitic acid dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dianhydride, to phenylene-bis-(triphenyl phthalic acid) dianhydride, metaphenylene-bis-(triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, aromatic tetracarboxylic acid's dianhydrides such as tetracarboxylic dianhydride that following formula (T-15)～(T-18) represents separately etc.

As preferred tetracarboxylic dianhydride in the middle of them, can enumerate 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-8-methyl-naphthalene [1, 2-c]-furans-1, 3-diketone, 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride, butane tetracarboxylic acid dianhydride, 1, 3-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, pyromellitic acid dianhydride, 3, 3 ', 4, 4 '-sulfobenzide tetracarboxylic dianhydride, 1, 4, 5, 8-naphthalene tetracarboxylic acid dianhydride, 2, 3, 6, 7-naphthalene tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 '-diphenyl ether tetracarboxylic dianhydride or above-mentioned formula (T-1), (T-2) and (T-15)～tetracarboxylic dianhydride of (T-18) representing separately.

These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

As operable diamine compound in polyamic acid synthetic, can enumerate for example Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formylaniline, 4,4 '-diaminodiphenyl oxide, 1,5-diaminonaphthalene, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 2,2-bis-(4-amino-benzene oxygen) propane, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] sulfone, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(3-amino-benzene oxygen) benzene, 9,9-bis-(4-aminophenyl)-10-hydrogen anthracene, 2,7 diamin of luorene, 9,9-bis-(4-aminophenyl) fluorenes, 4,4 '-methylene radical-bis-(2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-bis-is chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to phenylene isopropylidene) pentanoic, 4,4 '-(metaphenylene isopropylidene) pentanoic, 2,2-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 4,4 '-bis-[(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, 6-(4-phenyl styryl ketone oxygen base) hexyloxy (2,4-diaminobenzene), 6-(4 '-fluoro-4-phenyl styryl ketone oxygen base) hexyloxy (2,4-diaminobenzene), 8-(4-phenyl styryl ketone oxygen base) octyloxy (2,4-diaminobenzene), 8-(4 '-fluoro-4-phenyl styryl ketone oxygen base) octyloxy (2,4-diaminobenzene), 1-oxygen in last of the ten Heavenly stems base-2,4-diaminobenzene, 1-tetradecyloxyaniline-2,4-diaminobenzene, 1-pentadecane oxygen base-2,4-diaminobenzene, 1-n-Hexadecane oxygen base-2,4-diaminobenzene, 1-octadecane oxygen base-2,4-diaminobenzene, 1-cholest-oxygen base-2,4-diaminobenzene, 1-cholestane oxygen base-2,4-diaminobenzene, dodecyloxy (3,5-diaminobenzene formyl), tetradecyloxyaniline (3,5-diaminobenzene formyl), pentadecane oxygen base (3,5-diaminobenzene formyl), n-Hexadecane oxygen base (3,5-diaminobenzene formyl), octadecane oxygen base (3,5-diaminobenzene formyl), cholest-oxygen base (3,5-diaminobenzene formyl), cholestane oxygen base (3,5-diaminobenzene formyl), (2,4-diamino phenoxy) cetylate, (2,4-diamino phenoxy) stearate, (2,4-diamino phenoxy)-4-trifluoro methyl benzoate, the aromatic diamines such as diamine compound that following formula (D-1)～(D-5) represents separately,

Diamino 4-phenyl-thiophene etc. has heteroatomic aromatic diamine;

M-xylene diamine, 1,3-propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0 ^2,7]-Ya undecyl dimethyl diamines, 4, aliphatie diamine and the ester ring type diamines such as 4 '-methylene radical two (hexahydroaniline);

The diamino organo-siloxanes such as diamino hexamethyldisiloxane etc.

As preferred diamines in the middle of them, can enumerate Ursol D, 4,4 '-diaminodiphenyl-methane, 1,5-diaminonaphthalene, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 4,4 '-(to phenylene isopropylidene) pentanoic, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 2,2-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 4,4 '-bis-[(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, 1-n-Hexadecane oxygen base-2,4-diaminobenzene, 1-octadecane oxygen base-2,4-diaminobenzene, 1-cholest-oxygen base-2,4-diaminobenzene, 1-cholestane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base (3,5-diaminobenzene formyl), octadecane oxygen base (3,5-diaminobenzene formyl), cholest-oxygen base (3,5-diaminobenzene formyl), the diamine compound that cholestane oxygen base (3,5-diaminobenzene formyl) and above-mentioned formula (D-1)～(D-5) represent separately.

These diamine compounds can be used alone or in combination of two or more.

Supply with the tetracarboxylic dianhydride of polyamic acid building-up reactions and the usage rate of diamine compound, preferably 1 equivalent contained with respect to diamine compound is amino, the anhydride group that makes tetracarboxylic dianhydride is the ratio of 0.2～2 equivalent, is more preferably the ratio of 0.3～1.2 equivalent.

The building-up reactions of polyamic acid, preferably in organic solvent, is preferable over-20～150 ℃, more preferably under the temperature condition of 0～100 ℃, preferably carries out 0.5～24 hour, more preferably carries out 2～10 hours.Here, as organic solvent, so long as can dissolve the solvent of synthetic polyamic acid, it is had no particular limits, can enumerate for example METHYLPYRROLIDONE, N, N-N,N-DIMETHYLACETAMIDE, DMF, N, the non-proton property polar solvents such as N-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; Between the phenol solvent such as sylvan, xylenol, phenol, halogenated phenol.The consumption of organic solvent (a) is: the total amount (b) that makes tetracarboxylic dianhydride and diamine compound is preferably 0.1～50 % by weight, the amount of 5～30 % by weight more preferably with respect to the total amount (a+b) of reaction soln.

As mentioned above, obtained dissolving the reaction soln of polyamic acid.This reaction soln, can directly supply with the modulation of liquid crystal aligning agent, also polyamic acid contained in reaction soln can be separated to the modulation of rear supply liquid crystal aligning agent, or after also isolated polyamic acid can being refined, resupply the modulation of liquid crystal aligning agent.When polyamic acid dehydration closed-loop is become to polyimide, above-mentioned reaction soln can directly be supplied with dehydration closed-loop reaction, also after polyamic acid contained in reaction soln can being separated, resupply dehydration closed-loop reaction, or resupply dehydration closed-loop reaction after also separated polyamic acid can being refined.

The separation of polyamic acid, can be by above-mentioned reaction soln be put in a large amount of poor solvents, obtain precipitate, then the method for this precipitate of drying under reduced pressure, or the organic solvent in reaction soln is distillated to the method for removing and carries out with vaporizer decompression.In addition, by this polyamic acid is dissolved in organic solvent again, then with poor solvent, make its method of separating out, or carry out once or several times the method for the operation that distillates with vaporizer decompression, can refine polyamic acid.

[polyimide]

Above-mentioned polyimide can be prepared by the amido acid structure dehydration closed-loop imidization that the polyamic acid making is as mentioned above had.Now, can be the complete imidization of amido acid structure fully dehydrating closed loop, or can be also only a part of amido acid structure dehydration closed-loop, amido acid structure and imide structure the part imide compound of depositing.The imide rate of the polyimide in the present invention, is preferably more than 30%, and more preferably 40～95%.

The dehydration closed-loop of polyamic acid, can (i) pass through the method for heating polyamic acid, or (ii) by polyamic acid is dissolved in organic solvent, in this solution, add the method for dewatering agent and dehydration closed-loop catalyzer heating as required to carry out.

Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i), is preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, there will be the situation of the molecular weight and molecular weight of gained imide amination polymer.In the reaction times of the method for heating polyamic acid, be preferably 0.5～48 hour, more preferably 2～20 hours.

On the other hand, in the method for adding dewatering agent and dehydration closed-loop catalyzer in polyamic acid solution of above-mentioned (ii), as dewatering agent, can use acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride.The usage rate of dewatering agent is preferably 0.01～20 mole with respect to 1 mole of polyamic acid structural unit.In addition, as dehydration closed-loop catalyzer, can use tertiary amines such as pyridine, collidine, two picolins, triethylamine.But, be not limited to these.The usage rate of dehydration closed-loop catalyzer is preferably 0.01～10 mole with respect to 1 mole of dewatering agent used.As organic solvent used in dehydration closed-loop reaction, can enumerate the organic solvent of enumerating as organic solvent used in polyamic acid synthetic.The temperature of reaction of dehydration closed-loop reaction, is preferably 0～180 ℃, and more preferably 10～150 ℃, the reaction times is preferably 0.5～20 hour, more preferably 1～8 hour.

The polyimide making in aforesaid method (i), can directly supply with the modulation of liquid crystal aligning agent by it, or after also can being refined, resupplies the modulation of liquid crystal aligning agent.On the other hand, in aforesaid method (ii), obtain the reaction soln containing polyimide.This reaction soln, it directly can be supplied with to the modulation of liquid crystal aligning agent, also can from reaction soln, remove dewatering agent and dehydration closed-loop catalyzer and supply with the modulation of liquid crystal aligning agent afterwards, polyimide can also be separated to the modulation of rear supply liquid crystal aligning agent, or after also separated polyimide can being refined, resupply the modulation of liquid crystal aligning agent.From reaction soln, remove dewatering agent and dehydration closed-loop catalyzer, can adopt such as methods such as solvent exchanges.The separation of polyimide, refining, can implement and as separated, the described same operation of process for purification of polyamic acid, carry out above.

[other organopolysiloxane]

Other organopolysiloxane in the present invention is at least one being selected from the group that the condenses of organopolysiloxane, its hydrolyzate and hydrolyzate that above-mentioned formula (4) represents forms.For other organopolysiloxane, the weight-average molecular weight of the polystyrene conversion that it is measured by GPC is preferably 500～100000, and more preferably 500～10000.

This other organopolysiloxane, can be by for example will being selected from least one silane compound (below also referred to as " raw silicon hydride compounds ") in the group that alkoxysilane compound containing trialkylsilyl group in molecular structure and halogenated silanes compound form preferably in suitable organic solvent, under the existence of water and catalyzer, be hydrolyzed or hydrolysis, condensation and synthesize.

As operable raw silicon hydride compounds here, can enumerate such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, four tert.-butoxy silane, tetrachloro silicane etc.;

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.

Preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylammonium methoxy silane or trimethylethoxysilane in the middle of them.

When other polysiloxane synthetic, as the organic solvent that can optionally use, can enumerate for example alkylol cpd, ketone compound, amide compound or ester cpds or other non-proton property compound.They can be used alone or in combination of two or more.

As above-mentioned alkylol cpd, can enumerate for example 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, 3-enanthol, n-Octanol, 2-Ethylhexyl Alcohol, secondary octanol, nonanol-, 2, 6-2,6-dimethyl-4-heptanol, nonylcarbinol, secondary hendecanol, Exxal 12, secondary tetradecanol, secondary heptadecanol, phenol, hexalin, methyl-cyclohexanol, 3, 3, 5-cyclonol, benzylalcohol, the monohydroxy-alcohol compounds such as Pyranton,

Ethylene glycol, 1,2-PD, 1,3 butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexylene glycol, 2,4-heptanediol, 2-ethyl-1, the polyol compounds such as 3-hexylene glycol, glycol ether, dipropylene glycol, triglycol, tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol mono hexyl ether, ethylene glycol list phenyl ether, ethylene glycol list-2-ethyl-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary propyl ether, diglycol monotertiary butyl ether, diglycol monotertiary hexyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol single-butyl ether, dipropylene glycol monomethyl ether, DPE, the part ether of the polyol compounds such as dipropylene glycol list propyl ether etc.These alkylol cpds can one kind or two or morely be used in combination.

As above-mentioned ketone compound, can enumerate for example acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, metacetone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, ethyl normal-butyl ketone, methyl n hexyl ketone, diisobutyl ketone, trimethylammonium nonanone, pimelinketone, methyl-n-butyl ketone, methylcyclohexanone, 2, the single ketones compounds such as 4-diacetylmethane, acetonyl-acetone, methyl phenyl ketone, fenchone;

Methyl ethyl diketone, 2,4-hexanedione, 2,4-heptadione, 3,5-heptadione, 2,4-acetyl caproyl, 3,5-acetyl caproyl, 2,4-diketone in the ninth of the ten Heavenly Stems, 3,5-diketone in the ninth of the ten Heavenly Stems, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl--3,5-heptadione, 1,1,1,5,5,5-hexafluoro-2, the beta-diketone compounds such as 4-heptadione etc.These ketone compounds can a kind or two or more be used in combination.

As above-mentioned amide compound; can enumerate for example methane amide, N-METHYLFORMAMIDE, N; dinethylformamide, N-ethyl-formamide, N; N-diethylformamide, ethanamide, N-methylacetamide, N; N-N,N-DIMETHYLACETAMIDE, 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 a kind or two or more be used in combination.

As above-mentioned ester cpds, can enumerate for example diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, ritalin, vinyl acetic monomer, gamma-butyrolactone, γ-valerolactone, n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxyl group butyl ester, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-ethylhexyl, Benzyl Acetate, cyclohexyl acetate, methyl cyclohexanol acetate, acetic acid n-nonyl ester, methyl acetoacetate, methyl aceto acetate, acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diglycol monotertiary n-butyl ether, acetic acid propylene glycol monomethyl ether, acetic acid dihydroxypropane single-ether, acetic acid propylene glycol monopropyl ether, acetic acid propylene glycol single-butyl ether, acetic acid dipropylene glycol monomethyl ether, acetic acid DPE, ethylene diacetate, methoxyl group triglycol acetic ester, ethyl propionate, n-butyl propionate, isoamyl propionate, oxalic acid diethyl ester, dibutyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, lactic acid n-pentyl ester, diethyl malonate, dimethyl phthalate, diethyl phthalate etc.These ester cpds can a kind or two or more be used in combination.

As other non-proton property compound, can enumerate for example acetonitrile, dimethyl sulfoxide (DMSO), N, N, N ' N '-tetraethyl-sulphonamide, hexamethyl phosphoric triamide, N-methylmorpholine, 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, METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolinone, 1,3-dimethyl tetrahydro-2 (1H)-pyrimidone etc.

In these solvents, particularly preferably part ether or the ester cpds of polyol compound or polyol compound.

The amount of the water using during as other organopolysiloxane synthetic, 1 mole of the alkoxyl group having with respect to raw silicon hydride compounds and the total amount of halogen atom, be preferably 0.01～100 mole, more preferably 0.1～30 mole, more preferably 1～1.5 mole.

Operable catalyzer during as other organopolysiloxane synthetic, can enumerate such as metal complex, organic acid, mineral acid, organic bases, ammonia, alkali metal compound, alkaline earth metal compound etc.

As above-mentioned metal complex, can enumerate for example triethoxy list (methyl ethyl diketone) titanium, three positive propoxy list (methyl ethyl diketone) titaniums, three isopropoxy list (methyl ethyl diketone) titaniums, three n-butoxy list (methyl ethyl diketone) titaniums, three sec-butoxy list (methyl ethyl diketone) titaniums, three tert.-butoxy list (methyl ethyl diketone) titaniums, diethoxy bis(acetylacetonate) titanium, two positive propoxy bis(acetylacetonate) titaniums, diisopropoxy bis(acetylacetonate) titanium, two n-butoxy bis(acetylacetonate) titaniums, two sec-butoxy bis(acetylacetonate) titaniums, two tert.-butoxy bis(acetylacetonate) titaniums, monosubstituted ethoxy tri acetylacetonato titanium, single positive propoxy tri acetylacetonato titanium, single isopropoxy tri acetylacetonato titanium, single n-butoxy tri acetylacetonato titanium, single sec-butoxy tri acetylacetonato titanium, single tert.-butoxy tri acetylacetonato titanium, four (methyl ethyl diketone) titanium, triethoxy list (methyl aceto acetate) titanium, three positive propoxy list (methyl aceto acetate) titaniums, three isopropoxy list (methyl aceto acetate) titaniums, three n-butoxy list (methyl aceto acetate) titaniums, three sec-butoxy list (methyl aceto acetate) titaniums, three tert.-butoxy list (methyl aceto acetate) titaniums, diethoxy two (methyl aceto acetate) titanium, two positive propoxy two (methyl aceto acetate) titaniums, diisopropoxy two (methyl aceto acetate) titanium, two n-butoxy two (methyl aceto acetate) titaniums, two sec-butoxy two (methyl aceto acetate) titaniums, two tert.-butoxy two (methyl aceto acetate) titaniums, monosubstituted ethoxy three (methyl aceto acetate) titanium, single positive propoxy three (methyl aceto acetate) titanium, single isopropoxy three (methyl aceto acetate) titanium, single n-butoxy three (methyl aceto acetate) titanium, single sec-butoxy three (methyl aceto acetate) titanium, single tert.-butoxy three (methyl aceto acetate) titanium, four (methyl aceto acetate) titanium, single (methyl ethyl diketone) three (methyl aceto acetate) titanium, two (methyl ethyl diketone) two (methyl aceto acetate) titaniums, the titanium coordination compoundes such as tri acetylacetonato list (methyl aceto acetate) titanium,

Triethoxy list (methyl ethyl diketone) zirconium, three positive propoxy list (methyl ethyl diketone) zirconiums, three isopropoxy list (methyl ethyl diketone) zirconiums, three n-butoxy list (methyl ethyl diketone) zirconiums, three sec-butoxy list (methyl ethyl diketone) zirconiums, three tert.-butoxy list (methyl ethyl diketone) zirconiums, diethoxy two (methyl ethyl diketone) zirconium, two positive propoxy two (methyl ethyl diketone) zirconiums, diisopropoxy two (methyl ethyl diketone) zirconium, two n-butoxy two (methyl ethyl diketone) zirconiums, two sec-butoxy two (methyl ethyl diketone) zirconiums, two tert.-butoxy two (methyl ethyl diketone) zirconiums, monosubstituted ethoxy tri acetylacetonato zirconium, single positive propoxy tri acetylacetonato zirconium, single isopropoxy tri acetylacetonato zirconium, single n-butoxy tri acetylacetonato zirconium, single sec-butoxy tri acetylacetonato zirconium, single tert.-butoxy tri acetylacetonato zirconium, four (methyl ethyl diketone) zirconium, triethoxy list (methyl aceto acetate) zirconium, three positive propoxy list (methyl aceto acetate) zirconiums, three isopropoxy list (methyl aceto acetate) zirconiums, three n-butoxy list (methyl aceto acetate) zirconiums, three sec-butoxy list (methyl aceto acetate) zirconiums, three tert.-butoxy list (methyl aceto acetate) zirconiums, diethoxy two (methyl aceto acetate) zirconium, two positive propoxy two (methyl aceto acetate) zirconiums, diisopropoxy two (methyl aceto acetate) zirconium, two n-butoxy two (methyl aceto acetate) zirconiums, two sec-butoxy two (methyl aceto acetate) zirconiums, two tert.-butoxy two (methyl aceto acetate) zirconiums, monosubstituted ethoxy three (methyl aceto acetate) zirconium, single positive propoxy three (methyl aceto acetate) zirconium, single isopropoxy three (methyl aceto acetate) zirconium, single n-butoxy three (methyl aceto acetate) zirconium, single sec-butoxy three (methyl aceto acetate) zirconium, single tert.-butoxy three (methyl aceto acetate) zirconium, four (methyl aceto acetate) zirconium, single (methyl ethyl diketone) three (methyl aceto acetate) zirconium, two (methyl ethyl diketone) two (methyl aceto acetate) zirconiums, the zirconium coordination compoundes such as tri acetylacetonato list (methyl aceto acetate) zirconium,

The aluminium coordination compoundes such as aluminium tris(acetylacetonate), three (methyl aceto acetate) aluminium etc.

As above-mentioned organic acid, can enumerate for example acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, oxalic acid, toxilic acid, Methylpropanedioic acid, hexanodioic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2 ethyl hexanoic acid, oleic acid, stearic acid, linolic acid, linolenic acid (acid of リ ノ レ イ Application), Whitfield's ointment, M-nitro benzoic acid, para-aminobenzoic acid, tosic acid, Phenylsulfonic acid, Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, formic acid, propanedioic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartrate etc.

As above-mentioned mineral acid, can enumerate such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid etc.

As above-mentioned organic bases, can enumerate such as pyridine, pyrroles, piperazine, tetramethyleneimine, piperidines, picoline, Trimethylamine 99, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, trolamine, diazabicyclooctane (ジ ア ザ PVC シ Network ロ オ Network ラ Application), diazabicyclononane, diazabicylo undecylene, tetramethyl ammonium hydroxide etc.

As above-mentioned alkali metal compound, can enumerate such as sodium hydroxide, potassium hydroxide etc.; As above-mentioned alkaline earth metal compound, can enumerate such as hydrated barta, calcium hydroxide etc.

These catalyzer can a kind or two or more use together.

In these catalyzer, preferable alloy coordination compound, organic acid or mineral acid, more preferably titanium coordination compound or organic acid.

The usage rate of catalyzer, with respect to 100 weight part raw silicon hydride compounds, is preferably 0.001～10 weight part, more preferably 0.001～1 weight part.

The water adding during other organopolysiloxane synthetic, can intermittently or be added in raw silicon hydride compounds continuously or silane compound is dissolved in the solvent of organic solvent gained.Catalyzer can join in raw silicon hydride compounds in advance or silane compound is dissolved in the solvent of organic solvent gained, or also can be dissolved in or be scattered in added water.

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

[usage rate of other polymkeric substance]

Liquid crystal aligning agent of the present invention when containing above-mentioned radiation sensitive linear organopolysiloxane and other polymkeric substance simultaneously, and the usage rate of other polymkeric substance, with respect to 100 weight part radiation sensitive linear organopolysiloxane, is preferably below 10000 weight parts.The preferred usage rate of other polymkeric substance, according to the kind of other polymkeric substance and difference.

Liquid crystal aligning agent of the present invention is when containing above-mentioned radiation sensitive linear organopolysiloxane and be selected from least one polymkeric substance in the group that polyamic acid and polyimide form, both preferred usage rates, with respect to 100 weight part radiation sensitive linear organopolysiloxane, the total amount of polyamic acid and polyimide is 100～5000 weight parts, and more preferably this value is 200～2000 weight parts.

In addition, liquid crystal aligning agent of the present invention is when containing radiation sensitive linear organopolysiloxane and other organopolysiloxane, both preferred usage rates, with respect to 100 weight part radiation sensitive linear organopolysiloxane, other organopolysiloxane is 100～2000 weight parts.

Liquid crystal aligning agent of the present invention, when containing radiation sensitive linear organopolysiloxane and other polymkeric substance simultaneously, as the kind of other polymkeric substance, be preferably at least one polymkeric substance in the group that is selected from polyamic acid and polyimide formation, or other organopolysiloxane.

[solidifying agent and curing catalysts and curing catalyst]

Above-mentioned solidifying agent and curing catalysts, can be to be contained in liquid crystal aligning agent for the object of the further crosslinking reaction of strengthening radiation sensitive linear organopolysiloxane, above-mentioned curing catalyst can be to be contained in liquid crystal aligning agent of the present invention in order to promote the object of the curing reaction that solidifying agent participates in.

As above-mentioned solidifying agent, curing and the normally used solidifying agent of the solidification compound that there is the solidified nature compound of epoxy group(ing) or contain the compound with epoxy group(ing) can be used as, such as polyamine, polybasic acid anhydride, polycarboxylic acid etc. can be enumerated.

As above-mentioned polybasic acid anhydride, can enumerate for example tricarboxylic acid anhydrides of hexanaphthene and other polybasic acid anhydride.

Object lesson as the tricarboxylic acid anhydrides of hexanaphthene, can enumerate for example 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, can enumerate for example 4-methyl tetrahydrophthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, succinyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, normally used tetracarboxylic dianhydride in the compound that following formula (6) represents and polyamic acid synthetic,

(in formula (6), the integer that p is 1～20), in addition, can also enumerate α-terpinene, alloocimene etc. and have the ester ring type compound of conjugated diolefine key and the diels-Alder reaction product of maleic anhydride and hydrogenated products thereof etc.

As above-mentioned curing catalysts, can use such as antimony hexafluoride compound, phosphorus hexafluoride compound, aluminium acetylacetonate etc.These catalyzer can pass through heating and the cationoid polymerisation of catalysis epoxy group(ing).

As above-mentioned curing catalyst, can enumerate for example imidazolium compounds;

Quaternary phosphonium compound;

Quaternary ammonium compound;

The Diazabicycloalkenes such as 1,8-diazabicylo [5.4.0], 11 carbon-7-alkene and organic salt thereof;

The organometallic compounds such as zinc octoate, stannous octoate, methyl ethyl diketone aluminum complex;

The boron compounds such as boron trifluoride, boric acid triphenyl ester; The metal halide such as zinc chloride, tin chloride;

The high-melting-point decentralized potentiality curing catalysts such as amine add-on type promotor such as the affixture of dicyanodiamide, amine and epoxy;

The minigel type potentiality curing catalyst of polymkeric substance coating for the surface of quaternary alkylphosphonium salt etc.; Amine salt type potentiality curing catalyst;

Lewis acid, the contour temperature drop solution of Bronsted hydrochlorate cationic polymerization type potentiality hot in nature curing catalyst etc.

The usage rate of the solidifying agent in the present invention, with respect to 100 weight part radiation sensitive linear organopolysiloxane, is preferably below 100 weight parts.The usage rate of curing catalysts, with respect to 100 weight part radiation sensitive linear organopolysiloxane, is preferably below 2 weight parts.The usage rate of curing catalyst, with respect to 100 weight part radiation sensitive linear organopolysiloxane, is preferably below 10 weight parts.

[epoxy compounds]

Above-mentioned epoxy compounds can be from the formed liquid crystal orientation film of further raising, the fusible angle of substrate surface to be contained in liquid crystal aligning agent of the present invention.

As this epoxy compounds, preferably can enumerate for example 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-dibromoneopentyl glycol diglycidylether, 1, 3, 5, 6-four glycidyl group-2, 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, 3-bis-(N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl hexanaphthene etc.

When liquid crystal aligning agent of the present invention contains epoxy compounds, as it, contain ratio, total amount with respect to the above-mentioned radiation sensitive linear organopolysiloxane of 100 weight part and optional other polymkeric substance using, is preferably below 40 weight parts, more preferably 0.1～30 weight part.

In addition, when liquid crystal aligning agent of the present invention contains epoxy compounds, for the object that its crosslinking reaction high-level efficiency is carried out, can also with the basic catalyst couplings such as 1 benzyl 2 methyl imidazole.Now, the usage rate of basic catalyst, with respect to 100 weight part epoxy compounds, is preferably below 10 weight parts, more preferably 0～2 weight part.

[functional silanes compound]

Above-mentioned functional silanes compound can be to use in order to improve the fusible object of gained liquid crystal orientation film and substrate.As functional silanes compound, can enumerate for example 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-APTES, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilicane alkyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, N-bis-(oxyethylene group)-3-TSL 8330, N-bis-(oxyethylene group)-APTES, 3-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane etc., and can enumerate tetracarboxylic dianhydride described in patent documentation 23 (Japanese kokai publication sho 63-291922 communique) and the reaction product etc. with amino silane compound.

When liquid crystal aligning agent of the present invention contains functional silanes compound, as it, contain ratio, total amount with respect to the above-mentioned radiation sensitive linear organopolysiloxane of 100 weight part and optional other polymkeric substance using, is preferably below 50 weight parts, more preferably below 20 weight parts.

[tensio-active agent]

As above-mentioned tensio-active agent, can enumerate such as nonionogenic tenside, anion surfactant, cats product, amphoterics, silicone tensio-active agent, polyalkylene oxide tensio-active agent, fluorochemical surfactant etc.

When liquid crystal aligning agent of the present invention contains tensio-active agent, as it, contain ratio, with respect to 100 weight part liquid crystal aligning agent total amounts, be preferably below 10 weight parts, more preferably below 1 weight part.

[photosensitizing agent]

As above-mentioned photosensitizing agent, can enumerate for example tetramethyl-benzene, benzonitrile, phenyl propyl ketone, Propiophenone, methyl phenyl ketone, xanthone, 4-methoxyacetophenone, 3-methoxyacetophenone, anthrone, phenyl aldehyde, 4,4 '-dimethoxy benzophenone, benzophenone, fluorenes, 9,10-benzophenanthrene, biphenyl, thioxanthone, anthraquinone, 4,4 '-bis-(diethylamino) benzophenone, phenanthrene, naphthalene, 4-phenyl methyl phenyl ketone, 4-phenyl benzophenone, 2-iodine naphthalene, acenaphthene, 2-naphthyl cyanide, 1-iodine naphthalene, 1-naphthyl cyanide,

, coronene, benzil, fluoranthene, pyrene, 1,2-benzanthrene, acridine, anthracene, naphthacene, 2-methoxynaphthalene, Isosorbide-5-Nitrae-dicyano naphthalene, 9-cyano group anthracene, 9,10-dicyano anthracene, 2,6,9,10-four cyano anthracene etc.

When liquid crystal aligning agent of the present invention contains photosensitizing agent, as it, contain ratio, with respect to 100 weight part radiation sensitive linear organopolysiloxane, be preferably below 20 weight parts, more preferably below 10 weight parts.

<liquid crystal aligning agent>

Liquid crystal aligning agent of the present invention, as mentioned above, contains radiation sensitive linear organopolysiloxane as essential composition, in addition, also contains as required other composition, is preferably modulated into each composition and is dissolved in the molten liquid composition in organic solvent.

Operable organic solvent in modulation as liquid crystal aligning agent of the present invention, preferably can dissolve radiation sensitive linear organopolysiloxane and optional other composition using, and the solvent not reacting with them.

The organic solvent that can preferably use in liquid crystal aligning agent of the present invention, according to the kind of other polymkeric substance of optional interpolation and difference.

When liquid crystal aligning agent of the present invention contains radiation sensitive linear organopolysiloxane and be selected from least one polymkeric substance in the group that polyamic acid and polyimide form, as preferred organic solvent, can enumerate as solvent used in polyamic acid synthetic and illustrative solvent.These organic solvents can be used alone or in combination of two or more.

In addition, when liquid crystal aligning agent of the present invention only contains radiation sensitive linear organopolysiloxane as polymkeric substance, or while containing radiation sensitive linear organopolysiloxane and other organopolysiloxane, as preferred organic solvent, can enumerate for example 1-oxyethyl group-2-propyl alcohol, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol propyl ether, dipropylene glycol dme, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether (ethylene glycol butyl ether), ethylene glycol monopentyl ether, ethylene glycol ether, glycol ether, 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, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxyl group butyl ester, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-ethylhexyl, Benzyl Acetate, the just own ester of acetic acid, cyclohexyl acetate, octyl acetate, amyl acetate-n, isoamyl acetate etc.Wherein, preferably can enumerate n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid etc.

Operable preferred solvent in the modulation of liquid crystal aligning agent of the present invention, whether basis uses other polymkeric substance and kind thereof, by the solvent of a kind of above-mentioned organic solvent or two or more combination gained, under following preferred solids content concn, each composition contained in liquid crystal aligning agent can not separated out, and makes the surface tension of liquid crystal aligning agent drop on the solvent of 25～40mN/m scope.

Solids content concn in liquid crystal aligning agent of the present invention, in liquid crystal aligning agent, the weight of all the components beyond solvent accounts for the ratio of liquid crystal aligning agent gross weight, considers viscosity, volatility etc. and selects, and is preferably the scope of 1～10 % by weight.Liquid crystal aligning agent of the present invention, is coated on substrate surface, forms as the filming of liquid crystal orientation film, and when solids content concn less than 1 % by weight, the thickness that there will be this to film is too small and be difficult to obtain the situation of good liquid crystal orientation film.On the other hand, when solids content concn surpasses 10 % by weight, there will be coating thickness blocked up and be difficult to obtain good liquid crystal orientation film, and the viscosity of liquid crystal aligning agent increase the imperfect situation of screening characteristics that causes.Particularly preferred solids content concn scope, the method adopting when liquid crystal aligning agent is coated on to substrate and difference.For example, when adopting spin-coating method, the scope of 1.5～4.5 % by weight particularly preferably.When adopting print process, particularly preferably making solids content concn is the scope of 3～9 % by weight, like this, can make soltion viscosity drop on the scope of 12～50mPas.When adopting ink jet method, particularly preferably making solids content concn is the scope of 1～5 % by weight, like this, can make soltion viscosity drop on the scope of 3～15mPas.

Temperature during modulation liquid crystal aligning agent of the present invention, is preferably 0～200 ℃, more preferably 10～60 ℃.

The formation method of<liquid crystal orientation film>

Liquid crystal aligning agent of the present invention, applicable to forming liquid crystal orientation film by optical alignment method.

As the method that forms liquid crystal orientation film, can enumerate for example on substrate, applying liquid crystal aligning agent of the present invention and form and film, then by this is filmed, irradiate polarisation or non-polarisation ray make its produce liquid crystal aligning can method.

First, adopt suitable coating methods such as rolling method, spin-coating method, print process, ink jet method, liquid crystal aligning agent of the present invention is coated on to nesa coating one side of the substrate that is provided with pattern-like nesa coating.Then, by this applicator surface is preheated to (prebake), then burn till (curing afterwards), form and film.Prebake condition is for for example carrying out at 40～120 ℃ 0.1～5 minute, rear baking conditions for preferably at 120～300 ℃, more preferably at 150～250 ℃, preferably carry out 5～200 minutes, more preferably carry out 10～100 minutes.After the thickness of filming after curing, be preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.

As aforesaid substrate, can use glass such as float glass, soda-lime glass; The plastics transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate etc.

As above-mentioned nesa coating, can use SnO ₂nESA film, the In of system ₂o ₃-SnO ₂the ITO film of system etc.The formation of the pattern of these nesa coatings, can adopt photoetch method or when nesa coating forms, use method of mask etc.

When the coating of liquid crystal aligning agent, for the binding property of further improving substrate or nesa coating and filming, can also on substrate and nesa coating, apply in advance functional silanes compound, titanate compound etc.

Then,, by above-mentioned filming irradiated to ray or the non-polarisation ray of linear polarization or part polarisation, make it produce liquid crystal aligning energy.Here, as ray, can use the ultraviolet ray and the visible rays that for example contain the light of 150～800nm wavelength, and preferably contain the ultraviolet ray of the light of 300～400nm wavelength.When ray used is linear polarization or part polarisation, irradiation can be carried out from the direction perpendicular to real estate, also can from oblique direction, carry out in order to produce pre-tilt angle, and, they combinations can also be carried out.When irradiating non-polarisation ray, direction of illumination must be tilted direction.

As light source used, can use such as low pressure mercury lamp, high voltage mercury lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.The ultraviolet ray of above-mentioned preferred wavelength range can be by obtaining the means of above-mentioned light source and couplings such as spectral filter, diffraction grating etc.

Irradiation dose as ray, is preferably 1J/m ²above, and not enough 10000J/m ², 10～3000J/m more preferably ².In addition, when the liquid crystal orientation film that makes by optical alignment method to be formed by previously known liquid crystal aligning agent produces liquid crystal aligning energy, need 10000J/m ²above radiation exposure.But, if use liquid crystal aligning agent of the present invention, even if the radiation exposure while adopting optical alignment method is 3000J/m ²1000J/m even below, ²when following, also can produce good liquid crystal aligning energy, be conducive to reduce the manufacturing cost of liquid crystal display device.

In addition, so-called in the present invention " tilt angle ", refers to the angle that liquid crystal molecule tilts from the direction parallel with real estate.

<liquid crystal orientation film>

The liquid crystal orientation film of the present invention being formed by liquid crystal aligning agent of the present invention, its tilt angle excellent in stability in time.The reason that shows this unforeseeable excellent results in order to disclose it, the present inventors have carried out careful research, and result learns, and liquid crystal orientation film of the present invention is compared with previously known liquid crystal orientation film, has special membrane structure.

That is to say, to liquid crystal orientation film of the present invention, from the group of above-mentioned (A) cinnamic acid derivative, the existence on thickness direction distributes in investigation, beat all discovery, in liquid crystal orientation film of the present invention, derive from the group of (A) cinnamic acid derivative, be partially distributed in 30% scope of from film surface thickness, or even in 25% scope, particularly in 20% scope.And, derive from the concentration of the group of (A) cinnamic acid derivative, on the surface of liquid crystal orientation film, there is maximum value.By inference, this photosensitivity group cloth partially in the narrow range of film near surface, is to produce with few exposure one of the reason of the tilt angle of excellent in stability in time.

And learn that this special membrane structure particularly, when liquid crystal aligning agent of the present invention contains above-mentioned radiation sensitive linear organopolysiloxane and other polymkeric substance with above-mentioned preferred content ratio simultaneously, can positively obtain.

The existence of the group of deriving from liquid crystal orientation film (A) cinnamic acid derivative on film thickness direction distributes, and can analyze (flight time secondary ion mass spectrometry) by for example ToF-SIMS and know.

More particularly, to thering is the liquid crystal orientation film forming on the nesa coating of substrate of nesa coating, adopt ToF-SIMS determinator, the Bi that is 25kV with acceleration voltage ₃ ⁺⁺ion cluster is as primary ion, is 0.05pA, to measure visual field be under 100 μ m, the quality measurement scope condition that is 0～1850amu, and liquid crystal orientation film is repeated to C at ionic current ₆₀sputter and ToF-SIMS analyze, for example, till mensuration proceeds to the atomic species (indium ion) detecting from the nesa coating of ITO.Owing to thinking, at the time point that the atomic species that derives from nesa coating detected, reached position, Mo deep, so will measure start the mensuration of the thickness scope to this time point as liquid crystal orientation film, the distribution of the count number of fragment of group that investigation is equivalent to derive from (A) cinnamic acid derivative on film thickness direction.And, in order to eliminate the impact of measuring mouth, the count number of each degree of depth of film (degree of depth from film surface) is proofreaied and correct divided by the minimum value (mensuration is chewed level) of thickness scope inside counting quantity, and so the existence of the group of known deriving from (A) cinnamic acid derivative on film thickness direction distributes.

In addition, the group that derives from (A) cinnamic acid derivative is distributed in 30% scope of from film surface thickness partially, refer in the distribution of above-mentioned correction, from the surface of liquid crystal orientation film to the concentration that derives from the group of (A) cinnamic acid derivative in 30% scope be the more than 95% of the whole concentration of thickness scope.

The manufacture method of<liquid crystal display device>

Liquid crystal display device of the present invention has the liquid crystal orientation film being formed by liquid crystal aligning agent of the present invention.Liquid crystal display device of the present invention can for example be manufactured as follows.

Prepare two substrates that as above form liquid crystal orientation film, by arrange liquid crystal between these two substrates, manufacture liquid crystal cell.The manufacture of liquid crystal cell, can enumerate two kinds of for example following methods.

First method is previously known method.First, two substrates are oppositely arranged by gap (box gap), make liquid crystal orientation film separately relatively to, with sealing agent, fitted in the periphery position of two substrates, in the box gap being surrounded by substrate surface and sealing agent, note after topping up crystalline substance, sealing filling orifice, can make liquid crystal cell.

Second method is the method that is called ODF (One Drop Fill) mode.Regulation position on a substrate in two substrates that form liquid crystal orientation film, coating is ultra-violet solidified sealant material for example, on liquid crystal aligning face, drip after liquid crystal again, another piece substrate of fitting, make liquid crystal orientation film relatively to, then to whole irradiation ultraviolet radiation of substrate, make sealant cures, can make liquid crystal cell.

When adopting either method, all need then liquid crystal cell to be heated to, after temperature that liquid crystal used is isotropic phase, slowly cool to room temperature the flow orientation when eliminating liquid crystal and filling.

Then, by the polaroid of fitting, can make liquid crystal display device of the present invention on the outer surface of liquid crystal cell.Here, when liquid crystal orientation film is horizontal alignment, the polarization direction angulation of linear polarization ray and the angle of each substrate and polaroid that by adjustment, have formed the irradiation in two substrates of liquid crystal orientation film, can obtain the liquid crystal display device with TN type or STN type liquid crystal cell.On the other hand, when liquid crystal orientation film is vertical orientated property, by making to have formed, the direction of easy axis of orientation of two substrates of liquid crystal orientation film is parallel forms liquid crystal cell, and make polaroid become miter angle and fit thereon with easy axis of orientation with its polarization direction, can make the liquid crystal display device with vertical alignment-type liquid crystal box.

As above-mentioned sealing agent, can use such as containing as the alumina balls of separator and the epoxy resin of solidifying agent etc.

As above-mentioned liquid crystal, preferably use such as nematic liquid crystal, dish shape type liquid crystal etc.

When being TN type liquid crystal cell or STN type liquid crystal cell, the nematic liquid crystal preferably with positive dielectric anisotropy, can be used such as biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.And can also further add cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in above-mentioned liquid crystal; The chirality agent of selling with trade(brand)name " C-15 ", " CB-15 " (production of メル Network society); To oxygen base α-tolylene-to ferroelectric liquid crystals such as amino-2-methyl butyl laurate etc. and using in the last of the ten Heavenly stems.

On the other hand, when being vertical alignment-type liquid crystal box, the nematic liquid crystal preferably with negative dielectric anisotropic, can be used such as diaminobenzene class liquid crystal, pyridazine class liquid crystal, schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.

The polaroid using as liquid crystal cell outside, can enumerate polyvinyl alcohol is extended to the light polarizing film that is referred to as " H film " that orientation absorbs iodine is simultaneously clipped in cellulose acetate protective membrane and polaroid, or the polaroid self made of H film etc.

The liquid crystal display device of the present invention of so manufacturing, the various excellent propertys such as display performance, long-term reliability.

[embodiment]

Below, by embodiment, the present invention is carried out to more specific description, but the present invention is not limited to these embodiment.

Weight-average molecular weight Mw in following examples is the value of passing through the polystyrene conversion of gel permeation chromatography (GPC) mensuration under following condition.

Pillar: East ソ mono-(strain) manufactures, TSK gel GRCXL II

Solvent: tetrahydrofuran (THF)

Temperature: 40 ℃

Pressure: 68kg f/cm ²

Epoxide equivalent is measured according to JIS C 2105 " hydrochloric acid-methyl ethyl ketone method ".

The soltion viscosity of polymers soln is the value that adopts E type viscometer to measure at 25 ℃ to the polymers soln described in each synthesis example.

In addition, in the middle of following, the synthetic of starting compound and polymkeric substance repeats according to following synthetic route as required, with the necessary amounts of guaranteeing to be used in ensuing synthesizing.

<there is organopolysiloxane synthetic of epoxy group(ing)>

Synthesis example E-1

To being equipped with in the reaction vessel of agitator, thermometer, addition funnel and reflux condensing tube, add 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, at room temperature mix.Then, by addition funnel, through 30 minutes, drip after 100g deionized water, under refluxing, mix, at 80 ℃, make its reaction 6 hours simultaneously.After reaction finishes, take out organic layer, after adopting the aqueous ammonium nitrate solution of 0.2 % by weight wash to be neutrality to the water after washing, under reduced pressure distillate except desolventizing and water, obtain having the thickness transparent liquid of the organopolysiloxane (EPS-1) of epoxy group(ing).

The organopolysiloxane (EPS-1) that this is had to epoxy group(ing) carries out ¹h-NMR analyzes, and obtains the peak based on epoxy group(ing) of theoretical strength near chemical shift (δ)=3.2ppm, confirms not occur in reaction the side reaction of epoxy group(ing).

This weight-average molecular weight Mw with the organopolysiloxane (EPS-1) of epoxy group(ing) is 2200, and epoxide equivalent is 186g/ mole.

Synthesizing of<cinnamic acid derivative (A)>

Synthesis example C-1

According to following route 1, synthesized cinnamic acid derivative (2-4-1).

Synthetic route 1

In the eggplant type flask of 1L, add 91.3g 4-Para Hydroxy Benzoic Acid methyl esters, 182.4g salt of wormwood and 320ml METHYLPYRROLIDONE, after at room temperature carrying out stirring for 1 hour, add 99.7g 1-bromo pentane silane, at 100 ℃, stir 5 hours.After reaction finishes, water carries out redeposition.Then, in this precipitation, add 48g sodium hydroxide and 400ml water, the reaction that is hydrolyzed for 3 hours refluxes.After reaction finishes, with hydrochloric acid, neutralize, the precipitation of generation is carried out to recrystallization with ethanol, obtain the white crystal of 102g compound (2-4-1-1).

Get 10.41g in this compound (2-4-1-1) to reaction vessel, add wherein 100ml thionyl chloride and 77 μ L DMFs, at 80 ℃, stir 1 hour.Then, under reduced pressure distillate and remove thionyl chloride, add methylene dichloride, with sodium bicarbonate aqueous solution, wash, and by dried over mgso, after concentrating, add tetrahydrofuran (THF) wiring solution-forming.

Then, in above-mentioned 500mL three-necked flask in addition, add 7.39g 4-hydroxycinnamic acid, 13.82g salt of wormwood, 0.48g Tetrabutyl amonium bromide, 50ml tetrahydrofuran (THF) and 100ml water.This aqueous solution, with ice-cooled, is slowly dripped to above-mentioned tetrahydrofuran solution, further under agitation carry out reaction in 2 hours.After reaction finishes, add hydrochloric acid to neutralize, after extracting by ethyl acetate, by dried over mgso, after concentrating, with ethanol, carry out recrystallization, obtain the white crystal of 9.0g cinnamic acid derivative (2-4-1).

Synthesis example C-2

In above-mentioned synthesis example C-1, except iodo-4,4 with 110.9g 1-, 4-trifluoro butane replaces beyond 1-bromo pentane silane, similarly carry out with synthesis example C-1, obtain the white crystal of the compound (cinnamic acid derivative (2-4-2)) of the following formula of 9.2g (2-4-2) expression.

Synthesis example C-3

In above-mentioned synthesis example C-1, except replace compound (2-4-1-1) synthetic, that use as 9.91g 4-amyl group-trans cyclohexane carboxylic acid for intermediate, similarly carry out with synthesis example C-1, obtain the white crystal of the compound (cinnamic acid derivative (2-23-1)) of the following formula of 13g (2-23-1) expression.

Synthesis example C-4

According to following route 2, synthesized cinnamic acid derivative (2-31-1).

Synthetic route 2

To being equipped with in the three-necked flask of 500ml of return line, thermometer and nitrogen ingress pipe, add 31g compound (2-31-1-1), 0.23g palladium, 1.2g tri-(o-tolyl) phosphine, 56ml triethylamine, 8.2ml vinylformic acid and 200ml N, N-N,N-DIMETHYLACETAMIDE stirs and carries out reaction in 3 hours at 120 ℃.After reaction finishes, filter reaction mixture, in gained filtrate, add 1L ethyl acetate, the organic layer of gained is washed 2 times with dilute hydrochloric acid successively, wash with water 3 times, then with after dried over mgso, under reduced pressure except desolventizing, by gained solid recrystallization from the mixed solvent of ethyl acetate and tetrahydrofuran (THF), obtain the crystal of 15g cinnamic acid derivative (2-31-1).

Synthesis example C-5

In above-mentioned synthesis example C-4, except the compound representing by the following formula of 36g (2-32-1-1) replaces compound (2-31-1-1), C-4 similarly operates with synthesis example, obtains the compound (cinnamic acid derivative (2-32-1)) that the following formula of 16g (2-32-1) represents.

Synthesis example C-6

According to following route 3, synthesized cinnamic acid derivative (2-35-1).

Synthetic route 3

To being equipped with in the eggplant type flask of 300ml of return line and nitrogen ingress pipe, add 21g compound (2-35-1-1), 80ml thionyl chloride and 0.1mL DMF, at 80 ℃, stir and react for 1 hour.After reaction finishes, from reaction mixture, distillate and remove thionyl chloride, then add 150ml methylene dichloride, gained organic layer is washed with water 3 times.This organic layer, with after dried over mgso, under reduced pressure, except desolventizing, is added to 400ml tetrahydrofuran (THF) (using it as A solution) in the solid (compound (1-35-1-2)) of gained.

In addition, to being equipped with in the three-necked flask of 1L of addition funnel and thermometer, add 16gp-hydroxycinnamic acid, 24g salt of wormwood, 0.87g Tetrabutyl amonium bromide, 200ml water and 100ml tetrahydrofuran (THF), with ice-cooled to below 5 ℃.Through 3 hours, drip wherein above-mentioned A solution, further under agitation carry out reaction in 1 hour.After reaction finishes, to add in reaction mixture dilute hydrochloric acid make pH be below 4 after, add 3L toluene and 1L tetrahydrofuran (THF), the organic layer of gained is washed with water 3 times.This organic layer, with after dried over mgso, under reduced pressure, except desolventizing, by the solid of gained recrystallization from the mixed solvent of ethanol and tetrahydrofuran (THF), is obtained to 21g cinnamic acid derivative (2-35-1).

Synthesizing of<radiation sensitive linear organopolysiloxane>

Embodiment S-1

In the three-necked flask of 200ml, add compound (the 2-4-1) (Siliciumatom having with respect to EPS-1 making in the organopolysiloxane with epoxy group(ing) (EPS-1) that makes in the above-mentioned synthesis example E-1 of 5.0g, 46.4g methyl iso-butyl ketone (MIBK), the above-mentioned synthesis example C-1 of 4.76g as cinnamic acid derivative (A), be equivalent to 50 % by mole), the compound (Siliciumatom having with respect to EPS-1 is equivalent to 20 % by mole) that represents as the following formula (B-1-1) of light enhanced sensitivity compound (B) of 1.08g,

With 0.10g Tetrabutylammonium bromide, at 80 ℃, stir and react for 12 hours.After reaction finishes, with methyl alcohol, carry out redeposition, throw out is dissolved in ethyl acetate and obtains solution, by after this solution with water washing 3 times, distillate except desolventizing, obtain the white powder of 2.8g radiation sensitive linear organopolysiloxane (S-1).The weight-average molecular weight Mw of radiation sensitive linear organopolysiloxane (S-1) is 12500.

Embodiment S-2～S-55

In above-described embodiment S-1, except the kind of cinnamic acid derivative (A) and light enhanced sensitivity compound (B) and consumption are as shown in table 1 respectively, similarly operate with embodiment S-1, synthesized respectively radiation sensitive linear organopolysiloxane (S-2)～(S-55).The weight-average molecular weight of each radiation sensitive linear organopolysiloxane of gained is shown in table 1 in the lump.

In addition, in embodiment S-49 and S-54, as cinnamic acid derivative (A), respectively by two kinds of compound couplings, in embodiment S-31, S-48, S-51 and S-52, with other tilt angle expression power compound, substitute a part for cinnamic acid derivative (A) respectively and use.

Table 1

Table 1 is continuous

Table 1 is continuous

The abbreviation of the cinnamic acid derivative in table 1 (A), light enhanced sensitivity compound (B) and other tilt angle expression power compound, is respectively following implication.

<cinnamic acid derivative (A)>

2-4-1: the cinnamic acid derivative making in above-mentioned synthesis example C-1 (2-4-1)

2-4-2: the cinnamic acid derivative making in above-mentioned synthesis example C-2 (2-4-2)

2-23-1: the cinnamic acid derivative making in above-mentioned synthesis example C-3 (2-23-1)

2-31-1: the cinnamic acid derivative making in above-mentioned synthesis example C-4 (2-31-1)

2-32-1: the cinnamic acid derivative making in above-mentioned synthesis example C-5 (2-32-1)

2-35-1: the cinnamic acid derivative making in above-mentioned synthesis example C-6 (2-35-1)

<light enhanced sensitivity compound (B)>

B-1-1: the compound that above-mentioned formula (B-1-1) represents

B-2: the compound that above-mentioned formula (B-2) represents

B-3: the compound that above-mentioned formula (B-3) represents

B-5: the compound that above-mentioned formula (B-5) represents

B-11: the compound that above-mentioned formula (B-11) represents

B-28-1: the compound that following formula (B-28-1) represents

B-39-1: the compound that following formula (B-39-1) represents

B-42-1: the compound that following formula (B-42-1) represents

B-42-2: the compound that following formula (B-42-2) represents

<other tilt angle expression power compound>

5-3-1: the compound that following formula (5-3-1) represents

Synthesizing of<other polymkeric substance>

[synthesizing of polyamic acid]

Synthesis example PA-1

Using the pyromellitic acid dianhydride 109g as tetracarboxylic dianhydride (0.50 mole) and 1,2,3,4-tetramethylene tetracarboxylic dianhydride 98g (0.50 mole), as 4 of diamine compound, 4-diamino-diphenyl ether 200g (1.0 moles) is dissolved in 2290g METHYLPYRROLIDONE, makes it at 40 ℃, react after 3 hours, append 1350g METHYLPYRROLIDONE, obtain the about 3590g of solution containing 10 % by weight polyamic acids (PA-1).The soltion viscosity of this polyamic acid solution is 210mPas.

Synthesis example PA-2

Using as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride 98g (0.50 mole) and pyromellitic acid dianhydride 109g (0.50 mole), and as 4 of diamine compound, 4 '-diaminodiphenyl-methane 198g (1.0 moles) is dissolved in 2290g METHYLPYRROLIDONE, and it is reacted 3 hours at 40 ℃, append 1350g METHYLPYRROLIDONE, obtain the solution containing 10 % by weight polyamic acids (PA-2).The soltion viscosity of this polyamic acid solution is 135mPas.

Synthesis example PA-3

Using as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride 196g (1.0 moles), and as 4 of diamine compound, 4 '-diamino-diphenyl ether 200g (1.0 moles) is dissolved in 2246g METHYLPYRROLIDONE, and it is reacted 4 hours at 40 ℃, append 1321g METHYLPYRROLIDONE, obtain the solution containing 10 % by weight polyamic acids (PA-3).The soltion viscosity of this polyamic acid solution is 220mPas.

Synthesis example PA-4

Using as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride 196g (1.0 moles), and as 2 of diamine compound, 2 '-dimethyl-4,4 '-benzidine 212g (1.0 moles) is dissolved in 3670g METHYLPYRROLIDONE, it is reacted 3 hours at 40 ℃, obtain the solution containing 10 % by weight polyamic acids (PA-4).The soltion viscosity of this polyamic acid solution is 170mPas.

Synthesis example PA-5

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224g (1.0 moles), and as 4 of diamine compound, 4 '-diamino-diphenyl ether 200g (1.0 moles) is dissolved in 2404g METHYLPYRROLIDONE, it is reacted 4 hours at 40 ℃, obtain the solution containing polyamic acid (PA-5).This polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 190mPas.

[synthesizing of polyimide]

Synthesis example PI-1

Using as tetracarboxylic dianhydride's 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride 112g (0.50 mole) and 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone 157g (0.50 mole), and as the Ursol D 95g (0.88 mole) of diamine compound, 2, 2-bis-(trifluoromethyl)-4, 4-benzidine 32g (0.10 mole), 3, 6-bis-(4-aminobenzoic acyl-oxygen base) cholestane 6.4g (0.010 mole) and octadecane oxygen base-2, 5-diaminobenzene 4.0g (0.015 mole) is dissolved in 960g METHYLPYRROLIDONE, it is reacted 9 hours at 60 ℃.The gained polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 58mPas.

In gained polyamic acid solution, add 2740g METHYLPYRROLIDONE, 396g pyridine and 409g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by being carried out to solvent exchange with new METHYLPYRROLIDONE, the solvent in system (by this solvent exchange, operates, the pyridine and the acetic anhydride that in dehydration closed-loop reaction, use are removed to system, lower with), obtain about 2500g and contain the solution that 15 % by weight imide rates are about 95% polyimide (PI-1).

This polyimide solution that takes a morsel, under reduced pressure, except after desolventizing, is dissolved in gamma-butyrolactone, is made into the solution that polymer concentration is 8.0 % by weight, and the soltion viscosity of mensuration is 33mPas.

Synthesis example PI-2

Using as tetracarboxylic dianhydride's 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride 112g (0.50 mole) and 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone 157g (0.50 mole), Ursol D 96g (0.89 mole) as diamine compound, diamino propyl group tetramethyl disiloxane 25g (0.10 mole) and 3, 6-bis-(4-aminobenzoic acyl-oxygen base) cholestane 13g (0.020 mole), and be dissolved in 960g METHYLPYRROLIDONE as the N-octadecylamine 8.1g (0.030 mole) of monoamine, it is reacted 6 hours at 60 ℃.The gained polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 60mPas.

In gained polyamic acid solution, append 2700g METHYLPYRROLIDONE, then add 396g pyridine and 409g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new METHYLPYRROLIDONE, obtain containing the solution that 15 % by weight imide rates are about 95% polyimide (PI-2).This polyimide solution that takes a morsel, adds METHYLPYRROLIDONE, is diluted to the solution that concentration is 6.0 % by weight, and the soltion viscosity of mensuration is 18mPas.

Synthesis example PI-3

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224g (1.0 moles), Ursol D 107g (0.99 mole) and 3 as diamine compound, 6-bis-(4-aminobenzoic acyl-oxygen base) cholestane 6.43g (0.010 mole) is dissolved in 3039g METHYLPYRROLIDONE, it is reacted 6 hours at 60 ℃, obtain the polyamic acid solution that soltion viscosity is about 260mPas.

In gained polyamic acid solution, append 2700g METHYLPYRROLIDONE, then add 396g pyridine and 306g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new METHYLPYRROLIDONE, obtain containing the solution that 9.0 % by weight imide rates are about 89% polyimide (PI-3).This polyimide solution that takes a morsel, adds METHYLPYRROLIDONE, is diluted to the solution that concentration is 5.0 % by weight, and the soltion viscosity of mensuration is 74mPas.

Synthesis example PI-4

Using as tetracarboxylic dianhydride's 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride 112g (0.50 mole) and 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone 157g (0.50 mole), Ursol D 89g (0.82 mole) as diamine compound, 2, 2 '-bis-(trifluoromethyl)-4, 4 '-benzidine 32g (0.10 mole), 1-(3, 5-diaminobenzene methanoyl)-4-(4-trifluoromethyl benzoyloxy)-hexanaphthene 25g (0.059 mole) and octadecane oxygen base-2, 5-diaminobenzene 4.0g (0.011 mole) is dissolved in 2175g METHYLPYRROLIDONE, it is reacted 6 hours at 60 ℃.The gained polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 110mPas.

Get the 1500g in gained polyamic acid solution, append wherein 3000g METHYLPYRROLIDONE, then add 221g pyridine and 228g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new METHYLPYRROLIDONE, obtain containing the solution that 10 % by weight imide rates are about 92% polyimide (PI-4).This polyimide solution that takes a morsel, adds METHYLPYRROLIDONE, is diluted to the solution that concentration is 4.5 % by weight, and the soltion viscosity of mensuration is 26mPas.

Synthesis example PI-5

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 19.9g (0.089 mole), Ursol D 6.8g (0.063 mole), 4 as diamine compound, the compound 4.7g (0.009 mole) that 4 '-diaminodiphenyl-methane 3.6g (0.018 mole) and above-mentioned formula (D-4) represent is dissolved in 140g METHYLPYRROLIDONE, and it is reacted 4 hours at 60 ℃.The gained polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that solid component concentration is 10 % by weight, and the soltion viscosity of mensuration is 115mPas.

In gained polyamic acid solution, append 325g METHYLPYRROLIDONE, then add 14g pyridine and 18g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new METHYLPYRROLIDONE, obtain containing the solution that 15.4 % by weight imide rates are about 77% polyimide (PI-5).This polyimide solution that takes a morsel, adds METHYLPYRROLIDONE, is diluted to the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 84mPas.

Synthesis example PI-6

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 20.9g (0.093 mole), as the Ursol D 9.2g (0.085 mole) of diamine compound and the compound 4.9g (0.009 mole) of above-mentioned formula (D-4) expression, be dissolved in 140g METHYLPYRROLIDONE, it is reacted 4 hours at 60 ℃.The gained polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 126mPas.

In gained polyamic acid solution, append 325g METHYLPYRROLIDONE, then add 7.4g pyridine and 9.5g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new METHYLPYRROLIDONE, obtain containing the solution that 16.1 % by weight imide rates are about 54% polyimide (PI-6).This polyimide solution that takes a morsel, adds METHYLPYRROLIDONE, is diluted to the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 75mPas.

Synthesis example PI-7

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 18.8g (0.084 mole), as the Ursol D 7.4g (0.068 mole) of diamine compound and the compound 8.9g (0.017 mole) of above-mentioned formula (D-4) expression, be dissolved in 140g METHYLPYRROLIDONE, it is reacted 4 hours at 60 ℃.The gained polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 126mPas.

In gained polyamic acid solution, append 325g METHYLPYRROLIDONE, then add 6.6g pyridine and 8.5g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new METHYLPYRROLIDONE, obtain containing the solution that 15.9 % by weight imide rates are about 55% polyimide (PI-7).This polyimide solution that takes a morsel, adds METHYLPYRROLIDONE, is diluted to the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 75mPas.

Synthesis example PI-8

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 19.1g (0.085 mole), as Ursol D 7.4g (0.069 mole) and the following formula (D-6) of diamine compound

The compound 8.5g (0.017 mole) representing is dissolved in 140g METHYLPYRROLIDONE, and it is reacted 4 hours at 60 ℃.The gained polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 206mPas.

In gained polyamic acid solution, append 325g METHYLPYRROLIDONE, then add 6.7g pyridine and 8.7g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new METHYLPYRROLIDONE, obtain containing the solution that 15.8 % by weight imide rates are about 52% polyimide (PI-8).This polyimide solution that takes a morsel, adds METHYLPYRROLIDONE, is diluted to the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 105mPas.

Synthesis example PI-9

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 17.3g (0.077 mole), as the Ursol D 5.9g (0.054 mole) of diamine compound,, the compound 7.7g (0.016 mole) of the compound 4.1g (0.008 mole) that above-mentioned formula (D-4) represents and above-mentioned formula (D-6) expression is dissolved in 140g METHYLPYRROLIDONE, it is reacted 4 hours at 60 ℃.The gained polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 117mPas.

In gained polyamic acid solution, append 325g METHYLPYRROLIDONE, then add 6.1g pyridine and 7.9g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new METHYLPYRROLIDONE, obtain containing the solution that 15.4 % by weight imide rates are about 55% polyimide (PI-9).This polyimide solution that takes a morsel, adds METHYLPYRROLIDONE, is diluted to the solution that concentration is 10 % by weight, and the soltion viscosity of mensuration is 109mPas.

[synthesizing of other organopolysiloxane]

Synthesis example OE-1

To being equipped with in the 200ml three-necked flask of prolong, add 20.8g tetraethoxysilane and 28.2g 1-oxyethyl group-2-propyl alcohol, at 60 ℃, carry out heated and stirred.The capacity that is added in is wherein that the 0.26g maleic anhydride of modulating in another flask of 20ml is dissolved in the maleic anhydride aqueous solution in 10.8g water, further heats, stirs and react for 4 hours at 60 ℃.From gained reaction mixture, distillate except desolventizing, then add 1-oxyethyl group-2-propyl alcohol, again concentrate, obtain the polymers soln containing other organopolysiloxane of 10 % by weight (PS-1).Measuring the weight-average molecular weight Mw of other organopolysiloxane (PS-1), is 5100.

The modulation of<liquid crystal aligning agent and the evaluation of storage stability>

Embodiment A-1

[modulation of liquid crystal aligning agent]

The radiation sensitive linear organopolysiloxane (S-1) making in 100 weight part above-described embodiment S-1 is mixed with the solution containing polyamic acid (PA-1) making in the above-mentioned synthesis example PA-1 of amount that polyamic acid (PA-1) is equivalent to 2000 weight parts that is converted into as other polymkeric substance, add wherein METHYLPYRROLIDONE and ethylene glycol butyl ether, being made into solvent composition is METHYLPYRROLIDONE: ethylene glycol butyl ether=50: 50 (weight ratios), solids content concn are the solution of 3.0 % by weight.This solution is filtered with the filter that aperture is 1 μ m, modulate liquid crystal aligning agent (A-1).

[evaluation of storage stability]

This liquid crystal aligning agent (A-1) is preserved 6 months at-15 ℃.Before preservation and after preserving, with E type viscometer, at 25 ℃, measure viscosity.During velocity of variation less than 10% before and after soltion viscosity is preserved, storage stability is evaluated as " well ", is 10% when above, and storage stability is evaluated as " bad ", and now the storage stability of liquid crystal aligning agent (A-1) is " well ".

Embodiment A-2～A-16, A-18～A-68, A-70～A-89 and A-91～A-109

Except the kind of radiation sensitive linear organopolysiloxane and the kind of other polymkeric substance and consumption are as shown in table 2 respectively, similarly operate with embodiment A-1, modulate respectively liquid crystal aligning agent (A-2)～(A-16), (A-18)～(A-68), (A-70)～(A-89) and (A-91)～(A-109).

To these liquid crystal aligning agent, similarly evaluate storage stability with embodiment A-1 respectively.Evaluation result is shown in table 2.

Embodiment A-17

Take and be counted as the solution containing other organopolysiloxane (PS-1) making in the above-mentioned synthesis example OE-1 of amount that other organopolysiloxane (PS-1) is equivalent to 2000 weight parts, add wherein the radiation sensitive linear organopolysiloxane (S-3) making in 100 weight part above-described embodiment S-3, add again 1-oxyethyl group-2-propyl alcohol, be made into the solution that solids content concn is 4.0 % by weight.This solution is filtered with the filter that aperture is 1 μ m, modulate liquid crystal aligning agent (A-17).

To this liquid crystal aligning agent (A-17), similarly evaluate storage stability with embodiment A-1, evaluation result is shown in table 2.

Embodiment A-69 and A-90

Except the kind of used radiation sensitive linear organopolysiloxane is as shown in table 2, similarly operate with embodiment A-17, modulate respectively liquid crystal aligning agent (A-69) and (A-90).

To these liquid crystal aligning agent, similarly evaluate storage stability with embodiment A-1 respectively, evaluation result is shown in table 2.

Table 2

Table 2 is continuous

Table 2 is continuous

Table 2 is continuous

The manufacture of<liquid crystal display device and evaluation>

Embodiment D-1

[formation of liquid crystal orientation film and the manufacture of liquid crystal display device]

Adopt spin coater, the liquid crystal aligning agent of modulating in above-described embodiment A-1 (A-1) is coated on the transparent electrical pole-face with the glass substrate of the transparency electrode of ITO film system, on the hot-plate of 80 ℃, carry out after 1 minute prebake, in chamber, carried out at 200 ℃, heating 1 hour in the baking oven of nitrogen ventilation, forming thickness is filming of 0.1 μ m.Then by this film coated surface being irradiated to 200J/m with the direction of 40 ° of tilting from substrate normal with Hg-Xe lamp and Glan-Taylor prism ²the polarisation ultraviolet ray containing 313nm bright line, make liquid crystal orientation film.Repeat same operation, produce the substrate that a pair of (two) have liquid crystal orientation film.

On the periphery of the face with liquid crystal orientation film of a substrate in aforesaid substrate, after applying and added diameter to be the epoxy resin binder of alumina balls of 5.5 μ m by silk screen printing, the liquid crystal aligning face that makes a pair of substrate relatively to, and the projecting direction mutual antiparallel of the ultraviolet optical axis that makes each substrate on real estate and carry out pressing, then through 1 hour, make tackiness agent carry out thermofixation at 150 ℃.Then, fill in from liquid crystal injecting port to the gap between substrate negative type liquid crystal (メル Network society produces, MLC-6608) after, with epoxy base class adhesive closure liquid crystal injecting port.And the flow orientation when eliminating Liquid crystal pour, after it is heated at 150 ℃, slowly cools to room temperature.Then the polaroid of fitting on substrate Wai Ce two sides, makes its polarization direction mutually vertical, and with the ultraviolet optical axis of liquid crystal orientation film the angle at 45 ° of the projecting direction on real estate, produce liquid crystal display device.

To this liquid crystal display device, according to following method, evaluate.Evaluation result is shown in table 3.

(1) evaluation of liquid crystal aligning

Liquid crystal display device to above manufacture, has or not abnormal area in the variation of light and shade while at room temperature opening cut-out (applying releasing) 5V voltage by observation by light microscope, is not evaluated as " well " while there is no abnormal area.

(2) evaluation of tilt angle

According to the method for recording in non-patent literature 5 (T.J.Scheffer etc., J.Appl.Phys., the 19th volume, 2013 (1980)), by using the crystallization rotational method of He-Ne laser, the liquid crystal display device of above manufacture is carried out to the mensuration of tilt angle.

(3) evaluation of voltage retention

Under the envrionment temperature of 60 ℃, in the time span of 167 milliseconds, the liquid crystal cell of above manufacture is applied to the voltage of 5V, application time is 60 microseconds, then measures from voltage and removes to the voltage retention 167 milliseconds.Determinator adopts " VHR-1 " type of (strain) bundle Yang テ Network ニ カ system.

(4) evaluation of tilt angle stability

The liquid crystal display device of manufacturing was above preserved after 30 days at 23 ℃, again measured tilt angle.When 1 ° of the variable quantity less than from initial value, tilt angle estimation of stability is " well ".

Embodiment D-2～D-109

Except the kind of liquid crystal aligning agent used is as shown in table 3, similarly form liquid crystal orientation film with embodiment D-1, produce liquid crystal display device, and evaluate.

The results are shown in table 3.

Table 3

Table 3 is continuous

Table 3 is continuous

Table 3 is continuous

Embodiment T-1

Adopt spin coater, the liquid crystal aligning agent of modulating in above-described embodiment A-46 (A-46) is coated on the transparent electrical pole-face with the glass substrate of the transparency electrode of ITO film system, on the hot-plate of 80 ℃, carry out after 1 minute prebake, in chamber, carried out at 210 ℃, heating 20 minutes in the baking oven of nitrogen ventilation, what to form thickness be 80nm films.

The ToF-SIMS determinator that adopts ULVAC-PHI society to manufacture, the Bi that is 25kV with acceleration voltage ₃ ⁺⁺ion cluster, as primary ion, is 0.05pA at ionic current, under the condition that to measure visual field and be 100 μ m, quality measurement scope be 0～1850amu, the coated surface of above formation is repeated to C ₆₀sputter and ToF-SIMS analyze, till mensuration proceeds to the indium ion detecting from ITO.The time point that indium ion detected is considered as from film coated surface, reaching the degree of depth of 80nm, and the composition in investigation coating thickness direction distributes.Now, the curve that the fragment of demonstration m/z=231 distributes is shown in Fig. 1 (exist and distribute) and Fig. 2 (aggregate-value).In addition, the curve shown in these figure, is that the count number of each this fragment of depth is distributed to the curve of measuring mouth level and having proofreaied and correct.

The fragment of above-mentioned m/z=231, is considered to be equivalent to derive from the fragment that the following formula of cinnamic acid derivative (2-4-2) represents.

Therefore, result by Fig. 1 can effectively be known by inference, what at the present embodiment, form films, and the group that derives from (A) cinnamic acid derivative is sentenced the highest concentration in film coated surface and existed, and is partially distributed in from surface to the scope (30% scope at the most) of 20% left and right of thickness.

Claims (11)

1. a liquid crystal aligning agent, it is characterized in that containing: make to be selected from least one in the group that the condenses of organopolysiloxane, its hydrolyzate and the hydrolyzate with the repeating unit that following formula (1) represents forms, with (A) have the carboxyl of being selected from, hydroxyl ,-SH ,-NCO ,-NHR and-SO ₂the cinnamic acid derivative of at least one group in the group that Cl forms and (B) there is the carboxyl of being selected from, hydroxyl ,-SH ,-NCO ,-NHR ,-CH=CH ₂with-SO ₂at least one group in the group that Cl forms and the reaction of the compound of light enhanced sensitivity structure and the radiation sensitive linear organopolysiloxane that makes, wherein R is that hydrogen atom or carbonatoms are 1～6 alkyl,

(1)

In formula (1), X ¹for thering is any monovalent organic radical group of epoxy group(ing), Y ¹for hydroxyl, the carbonatoms alkoxyl group that is 1～10, alkyl that carbonatoms is 1～20 or the carbonatoms aryl that is 6～20.

2. liquid crystal aligning agent claimed in claim 1, wherein above-mentioned (A) cinnamic acid derivative is the compound that the compound that represents of following formula (2) or following formula (3) represent,

(2)

In formula (2), R ¹for the carbonatoms that the contains ester ring type group any monovalent organic radical group that is 3～40, or be the carbonatoms alkyl that is 1～40, wherein the part or all of hydrogen atom of abovementioned alkyl optionally can be replaced by fluorine atom, R ²for singly-bound, Sauerstoffatom ,-COO-or-OCO-, R ³for the aromatic group of divalence, the heterocyclic group of the ester ring type group of divalence, divalence or the condensed ring group of divalence, R ⁴for singly-bound, Sauerstoffatom ,-COO-or-OCO-, R ⁵for singly-bound, methylene radical, the carbonatoms alkylidene group that is 2～10 or the aromatic group of divalence, work as R ⁵during for singly-bound, t is 1, and R ⁶for hydrogen atom, work as R ⁵during for the aromatic group of methylene radical, alkylidene group or divalence, t is 0 or 1, and R ⁶for carboxyl, hydroxyl ,-SH ,-NCO ,-NHR or-SO ₂cl, wherein above-mentioned R is the alkyl that hydrogen atom or carbonatoms are 1～6, R ⁷for fluorine atom or cyano group, the integer that a is 0～3, the integer that b is 0～4,

(3)

In formula (3), R ⁸for the carbonatoms that the contains ester ring type group any monovalent organic radical group that is 3～40, or be the carbonatoms alkyl that is 1～40, wherein the part or all of hydrogen atom of abovementioned alkyl optionally can be replaced by fluorine atom, R ⁹for the aromatic group of Sauerstoffatom or divalence, R ¹⁰for Sauerstoffatom ,-COO-or-OCO-, R ¹¹for the condensed ring group of the aromatic group of divalence, the heterocyclic group of divalence or divalence, R ¹²for singly-bound ,-OCO-(CH ₂) _e-* or-O-(CH ₂) _g-*, above-mentioned e and g 1～10 the integer of respectively doing for oneself wherein, " * " represents separately with its connecting key and R ¹³connect R ¹³for carboxyl, hydroxyl ,-SH ,-NCO ,-NHR or-SO ₂cl, wherein above-mentioned R is the alkyl that hydrogen atom or carbonatoms are 1～6, R ¹⁴for fluorine atom or cyano group, the integer that c is 0～3, the integer that d is 0～4.

3. liquid crystal aligning agent claimed in claim 1, the wherein X in above-mentioned formula (1) ¹group is following formula (X ¹-1) or (X ¹-2) group representing,

(X ¹-1)

(X ¹-2)

In above-mentioned formula, " * " is expressed as connecting key.

4. liquid crystal aligning agent claimed in claim 1, wherein (B) to have the light enhanced sensitivity structure in the compound of light enhanced sensitivity structure be at least one being selected from the group that methyl phenyl ketone structure, benzophenone structure, anthraquinone ring, biphenyl structural, carbazole structure, nitro aryl structure, fluorene structured, naphthalene structure, anthracene structure, acridine structure and indole structure form.

5. the liquid crystal aligning agent described in claim 1～4 any one, it further contains at least one polymkeric substance being selected from the group that polyamic acid and polyimide form.

6. the liquid crystal aligning agent described in claim 1～4 any one, it further contains at least one being selected from the group that condenses of organopolysiloxane, its hydrolyzate and hydrolyzate that following formula (4) represents forms,

(4)

In formula (4), X ²for hydroxyl, halogen atom, the carbonatoms alkyl that is 1～20, alkoxyl group that carbonatoms is 1～6 or carbonatoms be 6～20 aryl, Y ²for hydroxyl or the carbonatoms alkoxyl group that is 1～10.

7. a formation method for liquid crystal orientation film, is characterized in that: on substrate, applies the liquid crystal aligning agent described in claim 1～6 any one and forms and film, and to this useful to irradiation of rays of filming.

8. a liquid crystal orientation film, is characterized in that being formed by the liquid crystal aligning agent described in claim 1～6 any one.

9. liquid crystal orientation film claimed in claim 8, the group that it is characterized in that deriving from (A) cinnamic acid derivative described in claim 1～6 any one is distributed in 30% scope of from liquid crystal orientation film surface thickness partially.

10. a liquid crystal display device, is characterized in that having the liquid crystal orientation film being formed by the liquid crystal aligning agent described in claim 1～6 any one.

11. 1 kinds of radiation sensitive linear organopolysiloxane, it is characterized in that by making to be selected from least one in the group that the condenses of organopolysiloxane, its hydrolyzate and the hydrolyzate of the repeating unit that the formula (1) that has described in claim 1 or 3 represents forms, with (A) have the carboxyl of being selected from, hydroxyl ,-SH ,-NCO ,-NHR and-SO ₂the cinnamic acid derivative of at least one group in the group that Cl forms, and (B) there is the carboxyl of being selected from, hydroxyl ,-SH ,-NCO ,-NHR ,-CH=CH ₂with-SO ₂at least one group in the group that Cl forms and the reaction of the compound of light enhanced sensitivity structure make, and wherein R is that hydrogen atom or carbonatoms are 1～6 alkyl.

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