CN103374353B

CN103374353B - The manufacture method of crystal aligning agent, liquid crystal orienting film, liquid crystal display device and liquid crystal display device

Info

Publication number: CN103374353B
Application number: CN201310120851.5A
Authority: CN
Inventors: 林英治; 秋池利之; 清水成夫
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2012-04-20
Filing date: 2013-04-09
Publication date: 2016-01-20
Anticipated expiration: 2033-04-09
Also published as: CN103374353A; TW201343792A; KR20130118765A; JP5884618B2; KR102038394B1; JP2013224989A; TWI558771B

Abstract

The invention provides the manufacture method of a kind of crystal aligning agent, liquid crystal orienting film, liquid crystal display device and liquid crystal display device, this crystal aligning agent with fewer rayed amount to the tilt angle characteristic desired by film imparting, and can obtain the liquid crystal display device of excellent heat resistance.A kind of crystal aligning agent, it comprises the polymkeric substance of the base had represented by following formula (1). in formula (1), X is hydrogen atom or methyl.L to be singly-bound or carbon number be 1 ~ 20 alkane two base, this alkane two base can interrupt 1 time ~ 10 times under the non-conterminous condition of Sauerstoffatom by Sauerstoffatom.Y is singly-bound ,-O-,-COO-,-OCO-or-OCOO-.Ring A is naphthalene nucleus.

Description

The manufacture method of crystal aligning agent, liquid crystal orienting film, liquid crystal display device and liquid crystal display device

Technical field

The present invention relates to the manufacture method of a kind of crystal aligning agent, liquid crystal orienting film, liquid crystal display device and liquid crystal display device, particularly relate to a kind of crystal aligning agent etc. being suitably used for the manufacture of the liquid crystal display device of vertical orientation type.

Background technology

Before, as liquid crystal display device, the various type of drive that electrode structure or physical property of liquid crystal molecule of using etc. are different are developed, such as there will be a known twisted nematic (TwistedNematic, TN) type or STN Super TN (SuperTwistedNematic) type, vertical orientation (VerticalAlignment, VA) the various liquid crystal display device of type, coplanar switching (In-PlaneSwitching, IPS) type etc.These liquid crystal display device have to make liquid crystal molecule carry out the liquid crystal orienting film of orientation.As the material of liquid crystal orienting film, such as, there will be a known polyamic acid or polyimide, polyester, organopolysiloxane etc.

In addition, in recent years, in liquid crystal display device, as the new technology of the orientation in order to control liquid crystal molecule, propose there is polymer-stabilized alignment (PolymerSustainedAlignment, PSA) technology (for example, referring to patent documentation 1).This PSA technology is following technology: be first mixed into in the liquid crystal layer of liquid crystal cells by the polymerizable component being undertaken by rayed being polymerized, under the state making liquid crystal molecules tilt by applying voltage, rayed is carried out to liquid crystal cells, make polymerizable component carry out being polymerized and control the molecule orientation of liquid crystal molecule thus.

But, when controlling the orientation of liquid crystal molecule by PSA technology, rayed must be carried out with higher irradiation dose, therefore, detrimentally affect being brought to liquid crystal molecule or film, the possibility that the display quality that there is liquid crystal display device thus declines.On the other hand, if reduce rayed amount, then in obtained liquid crystal display device, produce liquid crystal molecule sometimes for unfavorable conditions such as the response speed of voltage change are slack-off.Therefore, propose to obtain the tilt angle characteristic desired by giving film with fewer rayed amount, and liquid crystal molecule is for the technology (for example, referring to patent documentation 2) of the enough fast liquid crystal display device of the response speed of voltage change.In this patent documentation 2; announcement have use to comprise to have (methyl) acryl organopolysiloxane, with polyamic acid or the polyimide crystal aligning agent as component of polymer; substrate forms liquid crystal orienting film; and form liquid crystal cells; under the state being applied with voltage between to substrate, rayed is carried out to liquid crystal cells, manufacture liquid crystal display device thus.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2003-149647 publication

Patent documentation 2: Japanese Patent Laid-Open 2011-118358 publication

In recent years, liquid crystal display device not only as before for display terminals such as PC, and for the multiple use such as such as liquid crystal TV set or auto-navigation system, mobile phone, smart mobile phone, information display.With this kind of multi-usage, requirement for the high performance of liquid crystal display device improves further, as crystal aligning agent, need following crystal aligning agent, namely come by rayed to give in the technology of tilt angle characteristic to film, even if rayed amount is less, the crystal aligning agent of the enough fast liquid crystal display device of the response speed of liquid crystal molecule also can be obtained.

Summary of the invention

The present invention is the invention completed in view of described problem, its main purpose is to provide a kind of crystal aligning agent, this crystal aligning agent is when coming by rayed to give tilt angle characteristic to film, even if rayed amount is few, the liquid crystal display device that the response speed of liquid crystal molecule is enough fast also can be obtained.

The people such as the present inventor in order to reach prior art as above problem and make great efforts study result, finding the polymkeric substance by making crystal aligning agent comprise with ad hoc structure, described problem can be solved, thus complete the present invention.Specifically, the manufacture method of following crystal aligning agent, liquid crystal orienting film, liquid crystal display device and liquid crystal display device is provided by the present invention.

The present invention in one form, provides a kind of crystal aligning agent, it is characterized in that: the polymkeric substance (P) comprising the base had represented by following formula (1).

[changing 1]

In formula (1), X is hydrogen atom or methyl.L to be singly-bound or carbon number be 1 ~ 20 alkane two base, this alkane two base can difference, and also under the non-conterminous condition of Sauerstoffatom, can be interrupted 1 time ~ 10 times by Sauerstoffatom.Y is singly-bound ,-O-, * ¹-COO-, * ¹-OCO-or-OCOO-(wherein, " * ¹" represent the associative key with L).Ring A is naphthalene nucleus." * " represents associative key.

According to crystal aligning agent of the present invention, comprise the polymkeric substance (P) of the base had represented by described formula (1) as component of polymer, thus when by use the film that formed of this crystal aligning agent carry out rayed tilt angle characteristic is manifested time, even if less rayed amount, the liquid crystal display device that the response speed of liquid crystal molecule is enough fast also can be obtained.

The present invention is in another form, and provide a kind of manufacture method of liquid crystal display device, it comprises: the 1st step, is coated on respectively by crystal aligning agent of the present invention on this conducting film of a pair substrate with conducting film, then heats it and form film; 2nd step, in the described film of the layer mode in opposite directions across liquid crystal molecule, constructs liquid crystal cells by a pair substrate subtend configuration being formed with this film; And the 3rd step, under the state being applied with voltage between the conducting film had a pair substrate, rayed is carried out to liquid crystal cells.

When using crystal aligning agent of the present invention to manufacture liquid crystal display device, by adopting described method, even if less rayed amount, the tilt angle characteristic desired by also can giving film, and the liquid crystal display device that the response speed that can manufacture liquid crystal molecule is enough fast.

The present invention in one form, provides a kind of liquid crystal orienting film using crystal aligning agent of the present invention to be formed and the liquid crystal display device possessing described liquid crystal orienting film.Such as, and then the present invention, in another form, provides one to have the polymkeric substance (P) of the base represented by described formula (1), has the organopolysiloxane of the base represented by described formula (1).

Accompanying drawing explanation

Fig. 1 is the orthographic plan of the pattern representing the transparency electrode being patterned to slit-shaped.

The explanation of symbol

A, B: substrate

Embodiment

Below, each composition contained in crystal aligning agent of the present invention and other compositions of optionally and at random allocating are described.

< polymkeric substance (P) >

Crystal aligning agent of the present invention comprises component of polymer, and the polymkeric substance (P) at least comprising the base had represented by following formula (1) is as this component of polymer.

[changing 2]

About the L of described formula (1), as alkane two base that carbon number is 1 ~ 20, it can be straight-chain, also can be branch-like, include, for example: methylene radical, ethylidene, propane-1, 2-bis-base, propane-1, 3-bis-base, butane-1, 2-bis-base, butane-1, 4-bis-base, pentane-1, 5-bis-base, hexane-1, 6-bis-base, heptane-1, 7-bis-base, octane-1, 8-bis-base, nonane-1, 9-bis-base, decane-1, 10-bis-base, dodecyl-1, 12-bis-base, tetradecyl-1, 14-bis-base, hexadecyl-1, 16-bis-base, octadecyl-1, 18-bis-base, petrosilane-1, 20-bis-base etc.This alkane two base can not adjoin as condition with Sauerstoffatom, is interrupted 1 time ~ 10 times by Sauerstoffatom, specifically, include, for example by "-(CH ₂) _a-O-(CH ₂) _b-" (wherein, a, b be meet a+b≤20 more than 1 integer), "-(CH ₂) _c-O-(CH ₂) _d-O-(CH ₂) _e-" (wherein, c, d, e for meet c+d+e≤20 more than 1 integer) represented by base etc.

As L, among described, with regard to can accelerating the viewpoint of the response speed of liquid crystal molecule further, preferred carbon number is 4 ~ 20, and more preferably carbon number is 6 ~ 20, and then more preferably carbon number is 8 ~ 20.

The binding site of the Y in naphthalene nucleus (ring A) and other bases (in formula, the base represented by associative key) is not particularly limited, and specifically, can enumerate: 1,3-position, Isosorbide-5-Nitrae-position, 1,5-position, 1,6-position, 1,7-position, 2,6-positions, 2,7-positions etc.Wherein, preferred 2,6-positions.

As the concrete example of the base represented by described formula (1), include, for example following base.

[changing 3]

In formula, X represents hydrogen atom or methyl, and " * " represents associative key.

The main chain backbone of polymkeric substance (P) is not particularly limited, and include, for example: organopolysiloxane skeleton, polyester backbone, polyamic acid skeleton, polyimide backbone etc.Among these skeletons, just easily the base represented by described formula (1) is directed into regard to the viewpoint on main polymer chain, preferred organopolysiloxane skeleton.That is, crystal aligning agent of the present invention preferably comprises the organopolysiloxane (hereinafter also referred to as specific organopolysiloxane) of the base had represented by described formula (1) as component of polymer.

The specific organopolysiloxane > of <

Specific organopolysiloxane in the present invention is by manufacturing vitochemical ordinary method proper combination.Such as, as a kind of wherein method, the method that can be listed below: (i) makes following polymkeric substance react with the carboxylic acid (C-1) of base had represented by described formula (1), above-mentioned polymkeric substance is that the mixture of the water-disintegrable silane compound (si-1) containing epoxy group(ing) or this silane compound (si-1) and other silane compounds is hydrolyzed condensation and the polymkeric substance (organopolysiloxane containing epoxy group(ing)) that obtains.

[silane compound (si-1)]

Silane compound (si-1) is as long as have epoxy group(ing), then its structure is not particularly limited, but preferably has the compound of the base represented by following formula (ep-1) or formula (ep-2).

[changing 4]

In formula (ep-1), Z is singly-bound or Sauerstoffatom, and h is the integer of 1 ~ 3, and i is the integer of 0 ~ 6.Wherein, when i is 0, Z is singly-bound.In formula (ep-2), j is the integer of 1 ~ 6." * " represents the associative key with Siliciumatom.

As the preferred concrete example of silane compound (si-1), include, for example: 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl dimethyl methoxy silane, 3-glycidoxypropyl dimethylethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane etc.Among these silane compounds, can particularly preferably use in 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane and 3-glycidoxypropyltrimewasxysilane at least any one.Moreover as silane compound (si-1), can be used alone a kind of described silane compound or two or more combinationally used.

[other silane compounds]

As the concrete example of other silane compounds of synthesis that can be used for specific organopolysiloxane, include, for example: tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-acryloxypropyl Trimethoxy silane etc.These silane compounds can be used alone a kind or two or more combinationally used.

[hydrolysis-condensation reaction of silane compound]

When the synthesis of specific organopolysiloxane, the hydrolysis-condensation reaction of silane compound is undertaken by such as under type: preferably under the existence of suitable catalyzer and organic solvent, the one kind or two or more of silane compound as above and water are reacted.

When synthesizing specific organopolysiloxane by described method (i) coming, relative to the total amount of the silane compound used in reaction, for the synthesis of the usage ratio of silane compound (si-1) be preferably set to more than 70 % by mole, more preferably be set to more than 80 % by mole, and then be more preferably set to more than 90 % by mole.

When hydrolysis-condensation reaction, relative to silane compound (total amount) 1 mole, the usage ratio of water preferably 0.5 mole ~ 100 moles, more preferably 1 mole ~ 30 moles.

As described catalyzer, include, for example: acid, alkali metal compound, organic bases, titanium compound, zirconium compounds etc.Concrete example as these catalyzer: as acid, include, for example hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoracetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resin, various Lewis acids etc.;

As alkali metal compound, include, for example sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc.;

As organic bases, include, for example the one-level organic amine ~ secondary organic amine as ethamine, diethylamine, piperazine, piperidines, Pyrrolizidine, pyrroles; Three grades of organic amines as triethylamine, three-Tri N-Propyl Amine, three-n-Butyl Amine 99, pyridine, DMAP, diazabicycloundecene; Level Four organic amine etc. as tetramethyl ammonium hydroxide.As organic bases, among these, preferably three grades of organic amines or level Four organic amine.

As described catalyzer, just can suppress the viewpoint of the side reactions such as the open loop of epoxy group(ing), maybe can accelerate with regard to the viewpoint of hydrolytic condensation speed, the viewpoint of excellent storage stability etc., among these catalyzer, preferred as alkali compound or organic bases, particularly preferably organic bases.

The usage quantity of organic bases is different according to reaction conditions such as kind, temperature of organic bases etc., should set aptly, such as, relative to all silane compounds, and preferably 0.01 times mole ~ 3 times moles, more preferably 0.05 times mole ~ 1 times mole.

As the organic solvent that can use when hydrolysis-condensation reaction, include, for example: hydrocarbon, ketone, ester, ether, alcohol etc.

As its concrete example: as hydrocarbon, include, for example toluene, dimethylbenzene etc.;

As ketone, include, for example methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, metacetone, pimelinketone etc.;

As ester, include, for example vinyl acetic monomer, n-butyl acetate, isoamyl acetate, propylene glycol methyl ether acetate, 3-methoxybutyl acetic ester, ethyl lactate etc.;

As ether, include, for example glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), dioxan etc.;

As alcohol, include, for example 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol list-positive propyl ether, ethylene glycol list-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list-positive propyl ether etc.Among these organic solvents, preferably use non-water-soluble organic solvent.Moreover these organic solvents can be used alone a kind or two or more is used in combination.

Relative to all silane compound 100 weight parts, usage ratio preferably 10 weight part ~ 10 of the organic solvent in hydrolysis-condensation reaction, 000 weight part, more preferably 50 weight part ~ 1,000 weight part.

Hydrolysis-condensation reaction is implemented preferably by such as under type: silane compound as above is dissolved in organic solvent, after being mixed by this solution, utilizes such as oil bath etc. to heat with organic bases and water.

When hydrolysis-condensation reaction, preferably Heating temperature is set to less than 130 DEG C, is more preferably set to 40 DEG C ~ 100 DEG C.Preferably be set to 0.5 hour ~ 12 hours heat-up time, be more preferably set to 1 hour ~ 8 hours.Hanker adding, can stir mixed solution, under also can being placed in backflow.

After reaction terminates, water is preferably utilized to clean the organic solvent layer being separated taking-up from reaction solution.When this cleaning, by using the water containing a small amount of salt (such as, the aqueous ammonium nitrate solution etc. of 0.2wt% (weight percent) left and right) to clean, become preferred with regard to easy viewpoint with regard to cleaning operation.Till water layer after cleaning proceeds to cleaning becomes neutrality, thereafter, after optionally utilizing the siccative such as anhydrous calciumsulphate, molecular sieve to carry out drying to organic solvent layer, by removal of solvents, the organopolysiloxane (being the organopolysiloxane containing epoxy group(ing) when method (i)) as target can be obtained thus.

[carboxylic acid (C-1)]

With the carboxylic acid (C-1) used in the reaction of the organopolysiloxane containing epoxy group(ing) for having the compound containing carboxyl of the base represented by described formula (1), specifically, represented by following formula (c1).

[changing 5]

In formula (c1), the implication of X, L, Y and A is identical with described formula (1).

Carboxyl in naphthalene nucleus (ring A) and the binding site of Y are not particularly limited, but preferred 2,6-positions.

As the preferred concrete example of carboxylic acid (C-1), include, for example the compound etc. respectively represented by following formula (c1-1) ~ formula (c1-4).

[changing 6]

In formula, X is hydrogen atom or methyl.

[reaction of the organopolysiloxane containing epoxy group(ing) and carboxylic acid (C-1)]

The reaction of the organopolysiloxane containing epoxy group(ing) and carboxylic acid (C-1) can preferably be carried out under the existence of catalyzer and organic solvent.

When the reaction of the organopolysiloxane containing epoxy group(ing) and carboxylic acid (C-1), as carboxylic acid, the carboxylic acid that can be used alone (C-1) or carboxylic acid (C-1) is used with other carboxylic acids.As other carboxylic acids spendable herein, include, for example: formic acid, acetic acid, propionic acid, phenylformic acid, tolyl acid, there is the carboxylic acid etc. of vertical orientation base described later.

Relative to the total amount of the carboxylic acid used in reaction, the usage ratio of carboxylic acid (C-1) preferably more than 30 % by mole, more preferably more than 35 % by mole.

In addition, relative to the epoxy group(ing) that the organopolysiloxane containing epoxy group(ing) has, the usage ratio of carboxylic acid (total amount) preferably more than 5 % by mole, more preferably 10 % by mole ~ 90 % by mole, and then more preferably 15 % by mole ~ 80 % by mole.Moreover the epoxy group(ing) being less than the organopolysiloxane containing epoxy group(ing) by making the usage ratio of carboxylic acid and having, can obtain the organopolysiloxane of base and the epoxy group(ing) had represented by described formula (1).

As the catalyzer that uses in reaction, such as, can use organic bases, the known compound etc. as the so-called hardening accelerator of the reaction of promotion epoxy compounds.

Herein, as described organic bases, include, for example: the one-level organic amine ~ secondary organic amine as ethamine, diethylamine, piperazine, piperidines, Pyrrolizidine, pyrroles; Three grades of organic amines as triethylamine, three-Tri N-Propyl Amine, three-n-Butyl Amine 99, pyridine, DMAP, diazabicycloundecene; Level Four organic amine etc. as tetramethyl ammonium hydroxide.As organic bases, among these, preferably three grades of organic amines or level Four organic amine.

In addition, as described hardening accelerator, include, for example: as the tertiary amine as benzyldimethylamine, 2,4,6-tri-(dimethylamino methyl) phenol;

As the imidazolium compounds as glyoxal ethyline, 2-n-heptyl imidazoles, 2-n-undecane base imidazoles, 2-phenylimidazole;

As the organo phosphorous compounds as diphenylphosphine, triphenylphosphine;

As the Si Ji phosphonium salt as zephiran chloride triphenyl phosphonium, bromination four-Zheng Ding Ji Phosphonium, Diethylaminoethyl triphenyl phosphonium, bromination Yi base triphenyl phosphonium;

As the diazabicyclo alkene as 1,8-diazabicyclo [5.4.0] hendecene-7 or its organic acid salt; As the organometallic compound as zinc octoate, stannous octoate, aluminium acetylacetonate misfit thing;

As the quarternary ammonium salt as tetraethylammonium bromide, bromination four-normal-butyl ammonium, etamon chloride, tetran-butylphosphonium chloride ammonium;

As the boron compound as boron trifluoride, triphenyl borate;

As the metal halogen compound as zinc chloride, tin chloride;

The high-melting-point decentralized potentiality hardening accelerators such as amine add-on type promotor such as the affixture of dicyandiamide or amine and epoxy resin; Utilize the microcapsule-type potentiality hardening accelerator on the surface of the hardening accelerators such as imidazolium compounds described in polymer overmold, organo phosphorous compounds or Si Ji phosphonium salt; Amine salt type potentiality hardening accelerator; The potentiality hardening accelerators etc. such as the hot cationic polymerization type potentiality hardening accelerator of the thermal dissociation types such as Lewis acid (LewisAcid) salt, Bronsted acid (BronstedAcid) salt.Among these hardening accelerators, preferred quarternary ammonium salt.

Relative to organopolysiloxane 100 weight part containing epoxy group(ing), described catalyzer with below preferred 100 weight parts, more preferably 0.01 weight part ~ 100 weight part, and then the ratio of more preferably 0.1 weight part ~ 20 weight part uses.

As the organic solvent of the reaction of the organopolysiloxane that can be used for containing epoxy group(ing) and carboxylic acid (C-1), include, for example: hydrocarbon compound, ether compound, ester cpds, ketone compound, amide compound, alkylol cpd etc.Among these organic solvents, with regard to the viewpoint of the easiness of the solvability of raw material and product and the refining of product, preferred ether compound, ester cpds, ketone compound, as the concrete example of solvent particularly preferably, can enumerate: 2-butanone, methyl-n-butyl ketone, methyl iso-butyl ketone (MIBK) and N-BUTYL ACETATE etc.

The ratio that organic solvent preferably becomes more than 0.1wt% with solid component concentration (ratio that the total weight of the composition beyond desolventizing in reaction soln is shared in the gross weight of solution) uses, and the ratio more preferably becoming 5wt% ~ 50wt% with solid component concentration uses.

Temperature of reaction preferably 0 DEG C ~ 200 DEG C, more preferably 50 DEG C ~ 150 DEG C.Preferably 0.1 hour ~ 50 hours reaction times, more preferably 0.5 hour ~ 20 hours.

As the method for the specific organopolysiloxane manufactured in the present invention, except described method (i), (ii) can be enumerated and make to have the water-disintegrable silane compound (si-2) of at least 1 base represented by described formula (1) or this silane compound (si-2) and the mixture of other silane compounds and to be hydrolyzed the method for condensation.The silane compound (si-2) used when utilizing the synthesis of the method (ii) is such as by obtaining as under type: make to have the silane compound (si-1) of epoxy group(ing), with have by as described in the carboxylic acid (C-1) of base represented by formula (1) react.In addition, as other silane compounds, can be used in the explanation of described method (i), as the compound etc. illustrated in " other silane compounds ".

Relative to the total amount of the silane compound used in reaction, the usage ratio of the silane compound (si-2) in hydrolysis-condensation reaction is preferably set to more than 5 % by mole, more preferably be set to 10 % by mole ~ 70 % by mole, and then be more preferably set to 20 % by mole ~ 50 % by mole.Moreover the kind of the usage ratio of the water in hydrolysis-condensation reaction or catalyzer and organic solvent and amount, various reaction conditions can the explanations of the direct hydrolysis-condensation reaction of using said method (i).

[vertical orientation base]

When crystal aligning agent of the present invention being used for the manufacture of liquid crystal display device of vertical orientation type, specific organopolysiloxane can have the vertical orientation base in order to give good vertical orientation to film.As this vertical orientation base, include, for example: the fluoroalkyl that the alkyl that carbon number is 4 ~ 40, carbon number are 4 ~ 40, carbon number be 4 ~ 40 alkoxyl group, carbon number be 17 ~ 51 there is the base of steroid skeleton, there is the base etc. of polynuclear plane.

Herein, as described alkyl, include, for example normal-butyl, n-pentyl, n-hexyl, n-octyl, positive decyl, dodecyl, n-hexadecyl, Octadecane base etc.; As described fluoroalkyl, include, for example trifluoromethylpropyl, trifluoromethylbutyl, trifluoromethyl hexyl, trifluoromethyl decyl, pentafluoroethyl group propyl group, pentafluoroethyl group butyl, pentafluoroethyl group octyl group etc.; As described alkoxyl group, include, for example butoxy, pentyloxy, hexyloxy, octyloxy etc.;

As the base with steroid skeleton, include, for example cholestane base, cholesteryl, lanostane base etc.; As the base with polynuclear plane, include, for example 4,4 '-biphenylene, 4,4 '-Ya bi(cyclohexan)yl and having is selected from by following formula

[changing 7]

The base etc. of at least one in the group formed.

As manufacturing, there is the method for the specific organopolysiloxane of vertical orientation base, include, for example as inferior method: (I) make the organopolysiloxane containing epoxy group(ing), and carboxylic acid (C-1) and the carboxylic acid with vertical orientation base carry out the method for reacting; (II) make to have the organopolysiloxane of base represented by described formula (1) and epoxy group(ing), carry out the method for reacting with the carboxylic acid with vertical orientation base; (III) make to have the organopolysiloxane of polymerizability unsaturated link(age), carry out the method for reacting with the nucleophilic compound (mercaptan compound or amine compound) with vertical orientation base.

When utilizing described method (I) and method (II), as the concrete example of carboxylic acid with vertical orientation base, include, for example: the longer chain fatty acids such as caproic acid, n-caprylic acid, n-capric acid, dodecanoic acid, Palmiticacid, stearic acid, 4-positive hexyl phenenyl formic acid, 4-n-octyl formic acid, the positive decyl phenylformic acid of 4-, 4-n-dodecane yl benzoic acid, 4-n-hexadecane yl benzoic acid, 4-stearyl phenylformic acid etc. have the phenylformic acid of chain alkyl, the stearic aminobenzoic acid of the positive hexyloxybenzoate of 4-, 4-n-octyloxy phenylformic acid, 4-n-decyloxy phenylformic acid, 4-n-dodecane aminobenzoic acid, 4-n-hexadecane aminobenzoic acid, 4-etc. has the phenylformic acid of long-chain alkoxy base, cholestane aminobenzoic acid, cholestene aminobenzoic acid, lanostane aminobenzoic acid, cholestane oxygen base carbonyl benzoic acid, cholestene oxygen base carbonyl benzoic acid, lanostane oxygen base carbonyl benzoic acid, succinic acid-5 ξ-cholestane-3-base, succinic acid-5 ξ-cholestene-3-base, succinic acid-5 ξ-lanostane-3-base etc. have the phenylformic acid of steroid skeleton, 4-(4-amyl group-cyclohexyl) phenylformic acid, 4-(4-hexyl-cyclohexyl) phenylformic acid, 4-(4-heptyl-cyclohexyl) phenylformic acid, 4 '-amyl group-dicyclohexyl-4-carboxylic acid, 4 '-hexyl-dicyclohexyl-4-carboxylic acid, 4 '-heptyl-dicyclohexyl-4-carboxylic acid, 4 '-amyl group-biphenyl-4-carboxylic acid, 4 '-hexyl-biphenyl-4-carboxylic acid, 4 '-heptyl-biphenyl-4-carboxylic acid, 4-(4-amyl group-dicyclohexyl-4-base) phenylformic acid, 4-(4-hexyl-dicyclohexyl-4-base) phenylformic acid, 4-(4-heptyl-dicyclohexyl-4-base) phenylformic acid, the phenylformic acid containing polynuclear plane such as 6-(4 '-cyanobiphenyl-4-oxygen base) caproic acid, the carboxylic acid etc. containing fluoroalkyl such as 6,6,6-trifluoro caproic acid, 4-(4,4,4-triRuorobutyl) phenylformic acid.These acid can be used alone a kind or two or more combinationally used.

On the other hand, when utilizing described method (III), the concrete example of nucleophilic compound as having vertical orientation base: as amine compound, include, for example: the primary amines such as amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, heptadecyl-amine, n-Laurylamine, tridecyl amine, tetradecylamine, pentadecyl amine, cetylamine, heptadecylamine (HDA), octadecylamine, nonadecane amine, 4-(4-pentylcyclohexyl)-aniline, 4-octyloxy aniline; The secondary amine etc. such as dibutylamine, diamylamine, dihexylamine, two heptyl amices, Di-Octyl amine, nonyl amine, didecylamine, two-heptadecyl-amine, two-n-Laurylamine, two-tridecyl amine, two-tetradecylamine, two-pentadecyl amine, two-cetylamine, two-heptadecylamine (HDA), two-octadecylamine, two-nonadecane amine.In addition, as mercaptan compound, include, for example: butyl sulfhydryl, pentan-thiol, hexylmercaptan, heptanthiol, spicy thioalcohol, the ninth of the ten Heavenly Stems mercaptan, decyl mercaptan, undecane thiol, dodecyl mercaptans, tridecane thiol, tetradecane mercaptan, pentadecane mercaptan, hexadecanethiol, heptadecane mercaptan, octadecanethiol, nonadecane mercaptan, 4-butylbenzene mercaptan, 4-amylbenzene mercaptan, 4-hexyl benzene mercaptan, 4-heptyl benzene mercaptan, 4-octyl group benzenethiol, 4-decyl benzenethiol, 4-dodecyl benzenethiol, 4-tetradecyl benzenethiol, 4-hexadecyl benzenethiol, 4-butyl phenyl ether mercaptan, 4-hexyloxy benzenethiol, 4-octyloxy benzenethiol, 4-dodecyloxy benzenethiol, 4-(4 '-butylcyclohexyl) benzenethiol, 4-(4 '-hexyl cyclohexyl) benzenethiol etc.

Specific organopolysiloxane of the present invention preferably utilizes gel permeation chromatography (GelPermeationChromatography, the weight average molecular weight of the polystyrene conversion GPC) measured is 500 ~ 100,000, and more preferably weight average molecular weight is 1,000 ~ 10,000.

Using in the liquid crystal display device manufactured by this crystal aligning agent, with regard to can accelerating the viewpoint of the response speed of liquid crystal molecule fully, relative to the total amount of component of polymer contained in crystal aligning agent, preferred more than the 1wt% of amount of specific organopolysiloxane contained in crystal aligning agent of the present invention, more preferably more than 5wt%.

< polymkeric substance (Q) >

When polymkeric substance (P) is for specific organopolysiloxane, can contain in the lump specific organopolysiloxane, with at least one polymkeric substance (Q) be selected from the group that is made up of polyamic acid and polyimide.By containing polymkeric substance (Q), with regard to can promoting the viewpoint of the various characteristic points such as the LCD alignment of the film using this crystal aligning agent to be formed or voltage preserving property, thermotolerance, physical strength preferably.

When containing specific organopolysiloxane and polymkeric substance (Q) as component of polymer time, relative to the total amount of component of polymer contained in crystal aligning agent, preferred 1wt% ~ the 99wt% of content of polymkeric substance (Q), more preferably 10wt% ~ 95wt%.By the content of polymkeric substance (Q) is set to more than 1wt%, the improvement effect of LCD alignment or voltage preserving property, thermotolerance, physical strength etc. can be obtained aptly, by the content of polymkeric substance (Q) is set to below 99wt%, the improvement effect of the response speed of the liquid crystal molecule produced by specific organopolysiloxane can be obtained aptly.

< polyamic acid >

Polyamic acid contained in crystal aligning agent of the present invention is such as by making tetracarboxylic dianhydride and diamines carry out reacting synthesizing.

[tetracarboxylic dianhydride]

As the tetracarboxylic dianhydride for the synthesis of the polyamic acid in the present invention, include, for example: aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.Concrete example as these tetracarboxylic dianhydrides:

As aliphatics tetracarboxylic dianhydride, include, for example 1,2,3,4-butane tetracarboxylic acid dianhydride etc.;

As ester ring type tetracarboxylic dianhydride, include, for example 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl norbornane-2:3, 5:6-dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, cyclopentanetetracarboxylic's dianhydride etc.,

As aromatic tetracarboxylic acid's dianhydride, include, for example pyromellitic acid anhydride etc.;

In addition, tetracarboxylic dianhydride etc. described in Japanese Patent Laid-Open 2010-97188 publication can be used.Moreover described tetracarboxylic dianhydride can be used alone a kind or two or more combinationally used.

As the tetracarboxylic dianhydride for the synthesis of polyamic acid, be preferably used alone the mixture of ester ring type tetracarboxylic dianhydride or use ester ring type tetracarboxylic dianhydride and aromatic tetracarboxylic acid's dianhydride.In the latter case, relative to the total amount of the tetracarboxylic dianhydride used in synthesis, preferably containing the ester ring type tetracarboxylic dianhydride of more than 20 % by mole, more preferably containing the ester ring type tetracarboxylic dianhydride of more than 40 % by mole.

[diamines]

As the diamines for the synthesis of the polyamic acid in the present invention, include, for example: aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.Concrete example as these diamines: as aliphatie diamine, include, for example 1,3-m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine etc.;

As ester ring type diamines, include, for example Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (hexahydroaniline), 1,3-two (amino methyl) hexanaphthenes etc.;

As aromatic diamine, include, for example Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4，4′-diaminodipohenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenylenediisopropylidene) dianiline, 4,4 '-(metaphenylene two isopropylidene) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethylammonium-1H-indenes-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethylammonium-1H-indenes-6-amine, 3,5-diaminobenzoic acid, cholestane oxygen base-3,5-diaminobenzene, cholestene oxygen base-3,5-diaminobenzene, cholestane oxygen base-2,4-diaminobenzene, cholestene oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, two (the 4-aminobenzoic acyl-oxygen base) cholestane of 3,6-, 3-(3,5-diaminobenzene methanoyl) cholestane, two (4-amino-benzene oxygen) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3,5-diaminobenzoic acid ester, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthene of 1,1-, 2,4-diamino-N, N-diallyl aniline, 4-amino-benzylamine, 3-amino-benzylamine, and the compound etc. represented by following formula (A-1),

[changing 8]

In formula, X ⁱand X ^iIbe independently singly-bound ,-O-,-COO-or-OCO-, R ⁱfor alkane two base that carbon number is 1 ~ 3, a be 0 or 1, b be the integer of 0 ~ 2, c is the integer of 1 ~ 20, and n is 0 or 1.Wherein, 0 is become when a and b is different.

As diamino organo-siloxane, such as, can enumerate two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc. respectively, in addition, diamines described in Japanese Patent Laid-Open 2010-97188 publication can be used.As diamines, can be used alone a kind of described diamines or two or more combinationally used.

As in described formula (A-1) by "-X ⁱ-(R ⁱ-X ^iI) _n-" represented by the base of divalence, preferred carbon number is alkane two base, *-O-, *-COO-or the *-O-C of 1 ~ 3 ₂h ₄-O-(wherein, with associative key and the diamino-phenyl bond of " * ").As base "-C _ch _2c+1" concrete example, include, for example: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.Relative to other bases, 2 amino in diamino-phenyl are preferably in 2,4-position or 3,5-position.

As the concrete example of the compound represented by described formula (A-1), include, for example the compound etc. respectively represented by following formula (A-1-1) ~ formula (A-1-3).

[changing 9]

[molecular weight regulator]

When synthesizing polyamides acid, also tetracarboxylic dianhydride as above and diamines and suitable molecular weight regulator together can be made the polymkeric substance for synthesizing terminal-modified type.By making the polymkeric substance of this terminal-modified type, effect of the present invention can be can't harm and improve the coating (printing) of crystal aligning agent further.

As molecular weight regulator, include, for example: sour single acid anhydride, monoamine compound, monoisocyanate compound etc.Concrete example as them: as acid list acid anhydride, include, for example MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.; As monoamine compound, include, for example aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine etc.; As monoisocyanate compound, include, for example phenylcarbimide, naphthyl isocyanate etc.

Relative to total 100 weight part of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight regulator is preferably set to below 20 weight parts, is more preferably set to below 10 weight parts.

The synthesis > of < polyamic acid

For the tetracarboxylic dianhydride of the building-up reactions of the polyamic acid in the present invention and the usage ratio of diamines preferably relative to amino 1 equivalent of diamines, the anhydride group of tetracarboxylic dianhydride becomes the ratio of 0.2 equivalent ~ 2 equivalent, and more preferably the anhydride group of tetracarboxylic dianhydride becomes the ratio of 0.3 equivalent ~ 1.2 equivalent.

The building-up reactions of polyamic acid is preferably carried out in organic solvent.Temperature of reaction now preferably-20 DEG C ~ 150 DEG C, more preferably 0 DEG C ~ 100 DEG C.In addition, preferably 0.1 hour ~ 24 hours reaction times, more preferably 0.5 hour ~ 12 hours.

Herein, as the organic solvent used in reaction, include, for example: aprotic polar solvent, phenol and derivative thereof, alcohol, ketone, ester, ether, halon, hydrocarbon etc.

Concrete example as these organic solvents: as described aprotic polar solvent, include, for example METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolidone, N-ethyl-2-pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc.; As described amphyl, include, for example meta-cresol, xylenol, halogenation phenol etc.;

As described alcohol, include, for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triethylene glycol, ethylene glycol monomethyl ether etc.; As described ketone, include, for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.;

As described ester, include, for example ethyl lactate, n-Butyl lactate, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, methoxy methyl propionate, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate etc.;

As described ether, include, for example diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF) etc.;

As described halon, include, for example methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.; As described hydrocarbon, include, for example hexane, heptane, octane, benzene,toluene,xylene, isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.

Among these organic solvents, preferred use be selected from the group's (organic solvent of the first group) be made up of aprotic polar solvent and phenol and derivative thereof more than one, or be selected from the organic solvent of the first group more than a kind with more than one the mixture be selected from group's (organic solvent of the second group) of being made up of alcohol, ketone, ester, ether, halon and hydrocarbon.In the latter case, relative to the total amount of the organic solvent of the first group and the organic solvent of the second group, preferred below the 50wt% of usage ratio of the organic solvent of the second group, more preferably below 40wt%, and then more preferably below 30wt%.

The usage quantity (a) of organic solvent is preferably set to following amount, and namely relative to the total amount (a+b) of reaction soln, the total amount (b) of tetracarboxylic dianhydride and diamines becomes 0.1wt% ~ 50wt%.

Obtain the reaction soln that polyamic acid is dissolved in this way.This reaction soln can directly for the preparation of crystal aligning agent, also can for the preparation of crystal aligning agent or also can to the preparation for crystal aligning agent after carrying out through the polyamic acid of segregation refining after making polyamic acid segregation contained in reaction soln.When making polyimide when carrying out dehydration closed-loop to polyamic acid, can by described reaction soln directly for dehydration closed-loop reaction, also can for dehydration closed-loop reaction or also can react for dehydration closed-loop after carrying out through the polyamic acid of segregation refining after making in reaction soln contained polyamic acid segregation.The segregation of polyamic acid and refiningly can to carry out according to known method.

< polyimide >

Polyimide contained in crystal aligning agent of the present invention is such as by addition imidization and obtaining after carrying out dehydration closed-loop to the polyamic acid synthesized as described.

Described polyimide can be the whole complete imide compounds of carrying out dehydration closed-loop to the amido acid structure that the polyamic acid as its precursor has, and also can be only to carry out dehydration closed-loop to a part for amido acid structure and amido acid structure and imide ring structure the part imide compound of depositing.The imide rate of the polyimide in the present invention preferably more than 30%, more preferably 50% ~ 99%, and then more preferably 60% ~ 99%.This imide rate represents that imide ring structure number is relative to the ratio shared by the amido acid structure number of polyimide and the total of imide ring structure number with per-cent.Herein, a part for imide ring also can be different imide ring.

The dehydration closed-loop of polyamic acid carries out preferably by following method: the method heated polyamic acid; Or polyamic acid is dissolved in organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer and optionally carry out the method that heats.Wherein, the method for the latter is preferably utilized.

Add in the method for dewatering agent and dehydration closed-loop catalyzer in the solution to described polyamic acid, as dewatering agent, such as, can use the acid anhydrides such as acetic anhydride, propionic anhydride, trifluoro-acetic anhydride.Relative to 1 mole, the amido acid structure of polyamic acid, the usage quantity of dewatering agent is preferably set to 0.01 mole ~ 20 moles.As dehydration closed-loop catalyzer, such as, can use the tertiary amine such as pyridine, collidine, two picolins, triethylamine.Relative to used dewatering agent 1 mole, the usage quantity of dehydration closed-loop catalyzer is preferably set to 0.01 mole ~ 10 moles.As the organic solvent used in dehydration closed-loop reaction, the organic solvent and illustrative organic solvent that use in the synthesis as polyamic acid can be enumerated.The temperature of reaction preferably 0 DEG C ~ 180 DEG C of dehydration closed-loop reaction, more preferably 10 DEG C ~ 150 DEG C.Preferably 1.0 hours ~ 120 hours reaction times, more preferably 2.0 hours ~ 30 hours.

Obtain the reaction soln containing polyimide in this way.This reaction soln can directly for the preparation of crystal aligning agent, also can for the preparation of crystal aligning agent after remove dewatering agent and dehydration closed-loop catalyzer from reaction soln, also can for the preparation of crystal aligning agent or also can to the preparation for crystal aligning agent after carrying out through the polyimide of segregation refining after making polyimide emanate.These purification operations can be carried out according to known method.

Other compositions of < >

Crystal aligning agent of the present invention optionally also can contain other compositions.As these other compositions, include, for example: the compound (hereinafter referred to as " compound containing epoxy group(ing) "), functional silanes compound etc. in other polymkeric substance beyond described, molecule with at least one epoxy group(ing).

[other polymkeric substance]

Other polymkeric substance described can be used for improving solution properties or electrical characteristic.As these other polymkeric substance, include, for example: other organopolysiloxane beyond described specific organopolysiloxane, poly amic acid ester, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate etc.

When other polymkeric substance are added in crystal aligning agent, relative to the total polymer amount in said composition, its allotment ratio preferably below 50 quality %, more preferably 0.1 quality % ~ 40 quality %, and then more preferably 0.1 quality % ~ 30 quality %.

[compound containing epoxy group(ing)]

Compound containing epoxy group(ing) can be used for promoting liquid crystal orienting film with the cohesiveness of substrate surface or electrical characteristic.Herein, as the compound containing epoxy group(ing), include, 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, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-hexahydroaniline etc. are as preference.In addition, as the compound containing epoxy group(ing), the organopolysiloxane containing epoxy group(ing) that No. 2009/096598th, International Publication can be used to record.

When being added in crystal aligning agent by these epoxy compoundss, relative to total 100 weight part of polymkeric substance contained in crystal aligning agent, its allotment ratio is preferably below 40 weight parts, more preferably 0.1 weight part ~ 30 weight part.

[functional silanes compound]

Described functional silanes compound can use for the purpose of the printing promoting crystal aligning agent.As this kind of functional silanes compound, include, for example: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-triethoxysilylpropyltetrasulfide diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-trimethoxysilyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidoxypropyl methyltrimethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 3-glycidoxypropyltrimewasxysilane etc.

When being added in crystal aligning agent by these functional silanes compounds, relative to total 100 weight part of polymkeric substance, its allotment ratio is preferably below 2 weight parts, more preferably 0.02 weight part ~ 0.2 weight part.

As other compositions, except described, the compound or antioxidant etc. with at least one oxetanylmethoxy can be used in molecule.

< solvent >

Crystal aligning agent of the present invention is that component of polymer and other composition preferred dissolutions of optionally and at random allocating are formed in organic solvent.

Herein, the solvent used in preparation as crystal aligning agent of the present invention, include, for example: METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, N-BUTYL ACETATE, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (ethylene glycol butyl ether), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, dipropylene glycol monomethyl ether (DipropyleneGlycolMonomethylEther, DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, Texacar PC etc.These solvents can be used alone or two or more is used in combination.

Solid component concentration in crystal aligning agent of the present invention (ratio that the total weight of the composition beyond the desolventizing of crystal aligning agent is shared in the gross weight of crystal aligning agent) considers viscosity, volatility etc. and suitablely to select, but the scope of preferred 1wt% ~ 10wt%.Namely, as aftermentioned, crystal aligning agent of the present invention is coated on substrate surface, preferably heat, formed thus as liquid crystal orienting film film or become the film of liquid crystal orienting film, but now, when solid component concentration is less than 1wt%, the thickness of this film becomes too small and is difficult to obtain good liquid crystal orienting film.On the other hand, when solid component concentration is more than 10wt%, the thickness of film becomes excessive and is difficult to obtain good liquid crystal orienting film, and in addition, the viscosity of crystal aligning agent increases and forms the liquid crystal orienting film of coating characteristics difference.

The scope of solid component concentration is particularly preferably different according to the method used when being coated on substrate by crystal aligning agent.Such as when utilizing turner method, particularly preferably solid component concentration is set to the scope of 1.5wt% ~ 4.5wt%.When utilizing print process, particularly preferably solid component concentration being set to the scope of 3wt% ~ 9wt%, making soltion viscosity become the scope of 12mPas ~ 50mPas thus.When utilizing ink jet method, particularly preferably solid component concentration being set to the scope of 1wt% ~ 5wt%, making soltion viscosity become the scope of 3mPas ~ 15mPas thus.

Prepare the temperature preferably 10 DEG C ~ 50 DEG C during crystal aligning agent of the present invention, more preferably 20 DEG C ~ 30 DEG C.

< liquid crystal orienting film and liquid crystal display device >

Liquid crystal orienting film of the present invention is formed by the crystal aligning agent prepared as described.In addition, liquid crystal display device of the present invention possesses the liquid crystal orienting film using this crystal aligning agent to be formed.The pattern of this liquid crystal display device is not particularly limited, but particularly preferably vertical orientation type.Below, the manufacture method of liquid crystal orienting film of the present invention and liquid crystal display device is described.Moreover the manufacture method below enumerating the liquid crystal display device of vertical orientation type is described as an example.

[the 1st step: the formation of film]

First, substrate is coated with crystal aligning agent of the present invention, secondly coated face is heated, on substrate, form film thus.

First, substrate two panels being provided with patterned nesa coating is set to a pair, in the forming surface of the nesa coating in these substrates, hectograph (offset) print process, spin-coating method, roller coating machine method or ink jet printing method is preferably utilized to be coated with crystal aligning agent of the present invention respectively.Herein, as substrate, such as, can use the glass such as float glass, soda glass; Comprise the transparency carrier of the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(alicyclic olefin).As the nesa coating be arranged in the one side of substrate, can use and comprise stannic oxide (SnO ₂) NESA film (registered trademark of PPG company of the U.S.), comprise indium oxide-tin oxide (In ₂o ₃-SnO ₂) tin indium oxide (IndiumTinOxide, ITO) film etc.When patterned nesa coating will be obtained, such as, can utilize following method etc.: after the patternless nesa coating of formation, formed the method for pattern by photoetch; The method with the shade of desired pattern is used when forming nesa coating.When coating of liquid crystalline orientation agent, in order to make the cohesiveness of substrate surface and nesa coating and film become better, also the pre-treatment being coated with functional silanes compound, functionality titanium compound etc. in advance can be implemented to the face that should form film in substrate surface.

After coating of liquid crystalline orientation agent, in order to prevent the sagging etc. of be coated with crystal aligning agent, preferably implement to preheat (prebake conditions).Prebake conditions temperature preferably 30 DEG C ~ 200 DEG C, more preferably 40 DEG C ~ 150 DEG C, particularly preferably 40 DEG C ~ 100 DEG C.Preferably 0.25 minute ~ 10 minutes prebake conditions time, more preferably 0.5 minute ~ 5 minutes.Thereafter, solvent is removed completely, optionally to carry out amido acid structure existing in polymkeric substance implementing calcining (toasting afterwards) step for the purpose of hot-imide.Rear storing temperature preferably 80 DEG C ~ 300 DEG C, more preferably 120 DEG C ~ 250 DEG C.Post-bake times preferably 5 minutes ~ 200 minutes, more preferably 10 minutes ~ 100 minutes.The thickness of the film formed in this way preferably 0.001 μm ~ 1 μm, more preferably 0.005 μm ~ 0.5 μm.

Remove organic solvent by the heating after coating of liquid crystalline orientation agent, be formed into the film of alignment film thus.Now, polymkeric substance contained in crystal aligning agent of the present invention be polyamic acid or the imide amination polymer with imide ring structure and amido acid structure, also can heat further after formation film, carry out dehydration closed-loop reaction thus, and make the film through further imidization.

It directly can be used as liquid crystal orienting film by the film formed in this way, but optionally also can carry out friction treatment.

[the 2nd step: constructing of liquid crystal cells]

Prepare the substrate that 2 are formed with liquid crystal orienting film as described, and configure liquid crystal between 2 plate bases of subtend configuration, manufacture liquid crystal cells thus.Herein, when having carried out friction treatment to film, be each the angle of regulation with the frictional direction of each film, such as orthogonal or antiparallel mode, by 2 plate base subtend configurations.

When liquid crystal cells will be manufactured, include, for example 2 kinds of following methods.

First method has been from method (vacuum injection mode) known since before.First, 2 plate base subtends are configured across gap (cell gap) in the mode of each liquid crystal orienting film subtend, sealing agent is used to be fitted by the periphery of 2 plate bases, to inject in the cell gap that divided by substrate surface and sealing agent and after filling liquid crystal, filling orifice is sealed, manufactures liquid crystal cells thus.

Second method is the method being called as instillation (OneDropFill, ODF) mode.The position of the regulation on a substrate in 2 plate bases being formed with liquid crystal orienting film, be coated with the sealing material of such as ultraviolet light photopolymerization, and then behind several positions liquid crystal drop being added to the regulation on LCD alignment face, to fit another substrate in the mode of liquid crystal orienting film subtend, and make liquid crystal diffuse on whole of substrate, then whole irradiating ultraviolet light of substrate is cured the sealant, manufacture liquid crystal cells thus.

When utilizing any one method, it is desirable to the liquid crystal cells for manufacturing in this way, be heated to all further till used liquid crystal becomes the temperature of isotropic phase, till then slowly cooling to room temperature, remove flowing orientation during filling liquid crystal thus.

As sealing agent, such as, can use the epoxy resin etc. containing stiffening agent and the alumina balls as spacer.

As liquid crystal, nematic liquid crystal and smectic liquid crystal can be enumerated, wherein preferred nematic liquid crystal, such as can use that schiff bases (schiffbase) is liquid crystal, azoxy (azoxy) is liquid crystal, biphenyl system liquid crystal, Santosol 360 system liquid crystal, ester system liquid crystal, terphenyl system liquid crystal, cyclohexyl biphenyl hexane system liquid crystal, pyrimidine system liquid crystal, dioxan system liquid crystal, double-octane system liquid crystal, cube methane series liquid crystal etc.In addition, can use by the compound added in these liquid crystal such as: the cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate; As trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) the chiral agent of selling; To oxygen base benzylidene-to Ferroelectric liquid Crystals etc. such as amino-2-methyl butyl laurates in the last of the ten Heavenly stems.

The thickness of the layer of liquid crystal molecule is preferably set to 1 μm ~ 5 μm.

[the 3rd step: light irradiation step]

After the constructing of liquid crystal cells, under the state being applied with voltage between the conducting film had a pair substrate, rayed is carried out to liquid crystal cells.

The voltage that this place applies such as can be set to direct current or the interchange of 5V ~ 50V.

As irradiated light, such as, can use ultraviolet and the visible rays of the light of the wavelength containing 150nm ~ 800nm, but preferably contain the ultraviolet of the light of the wavelength of 300nm ~ 400nm.As the light source irradiating light, such as, can use: Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.Moreover the ultraviolet of described preferred wavelength region may is by obtaining light source and method also such as such as strainer, diffraction grating etc. etc.

As the irradiation dose of light, preferably 1,000J/m ²above, less than 100,000J/m ², more preferably 1,000J/m ²~ 50,000J/m ².Such as in the manufacture of the liquid crystal display device of PSA pattern known before, 100,000J/m must be irradiated ²the light of left and right, but in the manufacture method of liquid crystal display device of the present invention, even if rayed amount is being set to 50,000J/m ²below, and then be set to 10,000J/m ²when following, also can obtain the liquid crystal display device with desired tilt angle characteristic, and contribute to the reduction of the manufacturing cost of liquid crystal display device.In addition, the decline of the electrical characteristic caused by the irradiation of high light or liquid crystal molecule can be suppressed for the decline of the responsiveness of voltage change.

Then, Polarizer is fitted in the outer surface of liquid crystal cells, liquid crystal display device of the present invention can be obtained thus.

As the Polarizer of outside surface being fitted in liquid crystal cells; can enumerate and utilize the clamping of cellulose acetate protective membrane be called as the Polarizer of the light polarizing film of " H film " or comprise the Polarizer of H film itself, described H film is that one side makes polyvinyl alcohol extend the light polarizing film of orientation one side absorption iodine.

Liquid crystal display device of the present invention can be effectively applied to various device, such as can be used for the various display unit such as clock, portable game machine, word processor, notes type PC, auto-navigation system, video camera (camcorder), personal digital assistant (PersonalDigitalAssistant, PDA), digital camera, mobile phone, smart mobile phone, various watch-dog, liquid crystal TV set, information display.

[embodiment]

Below, further illustrate the present invention by embodiment, but the present invention does not limit by these embodiments.

The weight average molecular weight of each polymkeric substance in synthesis example, epoxy equivalent (weight), the soltion viscosity of each polymers soln and the imide rate of polyimide are measured by following method.

[weight average molecular weight of polymkeric substance]

The weight average molecular weight Mw of polymkeric substance is the polystyrene conversion value measured by the gel permeation chromatography under following condition.

Tubing string: eastern Cao (Tosoh) (share) manufactures, TSKgelGRCXLII

Solvent: tetrahydrofuran (THF)

Temperature: 40 DEG C

Pressure: 68kgf/cm ²

[epoxy equivalent (weight)]

The value that epoxy equivalent (weight) measures according to JISC2105 " hydrochloric acid-methyl ethyl ketone method ".

[soltion viscosity of polymers soln]

The soltion viscosity [mPas] of polymers soln is the solution for using the solvent of regulation polymer concentration to be prepared into 10wt%, utilizes E type rotational viscosimeter to measure at 25 DEG C.

[the imide rate of polyimide]

The solution of polyimide is fed in pure water, after at room temperature fully drying under reduced pressure being carried out to obtained throw out, is dissolved in deuterodimethylsulfoxide, tetramethylsilane is also at room temperature measured as primary standard ¹h-NMR.According to obtained ¹h-NMR spectrum, utilizes the formula represented by following mathematical expression (1x) to obtain imide rate [%].

Imide rate [%]=(1-A ¹/ A ²× α) × 100... (1x)

In mathematical expression (1x), A ¹for the peak area being derived from the proton of NH base occurred near chemical shift 10ppm, A ²for being derived from the peak area of other protons, α is the number ratios of other protons for 1 proton of the NH base in the precursor (polyamic acid) of polymkeric substance.

The synthesis > of < organopolysiloxane

[synthesis example 1]

2-(3 is added in the reaction vessel possessing stirrer, thermometer, dropping funnel and reflux cooling pipe, 4-epoxycyclohexyl) ethyl trimethoxy silane (ECETS) 98.6g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10g, and at room temperature mix.Then, after utilizing dropping funnel to last 30 minutes dropping deionized water 100g, mix under reflux, and at 60 DEG C, carry out reaction in 6 hours.After reaction terminates, take out organic layer, utilize 0.2wt% aqueous ammonium nitrate solution to clean, till the water after cleaning becomes neutrality.Thereafter, under reduced pressure solvent and water are heated up in a steamer, obtain the organopolysiloxane containing epoxy group(ing) of the transparent liquid as thickness thus.The organopolysiloxane that this contains epoxy group(ing) is carried out ¹the result that H-NMR analyzes, obtains the crest based on epoxy group(ing), has confirmed the side reaction not producing epoxy group(ing) in the reaction near chemical shift (δ)=3.2ppm as theoretical strength.

Then, the organopolysiloxane containing epoxy group(ing) obtained in this way is added in the there-necked flask of 200mL, as the methyl iso-butyl ketone (MIBK) 30.0g of solvent, as 4-(4-n-pentyl-cyclohexyl) phenylformic acid (PCHBA) 54.9g of carboxylic acid (relative to the epoxy group(ing) that the described organopolysiloxane containing epoxy group(ing) has, be equivalent to 20 % by mole), and compound (1) 178g that the X in compound represented by described formula (c1-1) is methyl is (relative to the epoxy group(ing) that the described organopolysiloxane containing epoxy group(ing) has, be equivalent to 50 % by mole), and as trade(brand)name " UCAT18X " (Sanya general sieve (San-Apro) (share) manufacture) 0.10g of catalyzer, one side stirs 48 hours one sides and reacts at 100 DEG C.After reaction terminates, add vinyl acetic monomer in subtend reaction mixture and the organic layer that obtains carries out 3 washings, after using magnesium sulfate to carry out drying, solvent is heated up in a steamer, obtains organopolysiloxane (PS-1) thus.The weight average molecular weight Mw of gel permeation chromatography (GPC) to the polystyrene conversion that this organopolysiloxane (PS-1) measures is utilized to be 8,400.

[synthesis example 2 ~ synthesis example 6]

Each compound of following table 1 is changed to by with the compound (1) in the carboxylic acid that uses in the reaction of the organopolysiloxane containing epoxy group(ing), in addition, organopolysiloxane (PS-2) ~ organopolysiloxane (PS-6) is obtained respectively by the method identical with described synthesis example 1.The Mw of these organopolysiloxane is shown in following table 1 in the lump.Moreover organopolysiloxane (PS-1) ~ organopolysiloxane (PS-4) is equivalent to specific organopolysiloxane respectively.

[table 1]

In table 1, the amount of the carboxylic acid allotment amount (% by mole) of epoxy group(ing) for having relative to the organopolysiloxane containing epoxy group(ing).The abbreviation of each compound is respectively following implication.

Compound (2): among the compound represented by described formula (c1-2), X is the compound of hydrogen atom

Compound (3): among the compound represented by described formula (c1-3), X is the compound of methyl

Compound (4): among the compound represented by described formula (c1-4), X is the compound of hydrogen atom

Compound (5): by the compound represented by following formula (d-1)

Compound (6): by the compound represented by following formula (d-2)

[changing 10]

The synthesis > of < polyimide

[synthesis example 7]

Make 2 as tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride (TCA) 110g (0.50 mole), as Ursol D (PDA) 46g (0.425 mole) of diamines and 3-(3,5-diaminobenzene methanoyl) cholestane (HCDA) 39g (0.075 mole) is dissolved in METHYLPYRROLIDONE (NMP) 830g, and at 60 DEG C, carry out reaction in 6 hours.Be separated and take out a small amount of obtained polyamic acid solution, add NMP and make the solution that polyamic acid concentration is 10wt%, the soltion viscosity determined is 60mPas.

Then, in obtained polyamic acid solution, add NMP1,900g, and add pyridine 40g and acetic anhydride 51g, at 110 DEG C, then carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, new NMP is utilized to carry out solvent exchange (by this operation to intrasystem solvent, the pyridine and acetic anhydride that are used for dehydration closed-loop reaction are removed to system outer), the imide rate obtained thus containing the 15wt% that has an appointment is about the solution of the polyimide (PI-1) of 50%.Be separated and take out a small amount of obtained polyimide solution, add NMP and make the solution that polyimide concentration is 10wt%, the soltion viscosity determined is 47mPas.

[embodiment 1]

The preparation > of < crystal aligning agent

To containing polyimide (PI-1) as the NMP added in the solution of polymkeric substance as organic solvent and ethylene glycol butyl ether (BC), and then becoming polyimide (PI-1) with polymkeric substance composition: the mode of organopolysiloxane (PS-1)=90: 10 (weight ratio) adds organopolysiloxane (PS-1), and makes that solvent composition is NMP: BC=50: 50 (weight ratios), solid component concentration is the solution of 6.0wt%.Use aperture is that the strainer of 1 μm filters this solution, prepares crystal aligning agent thus.

The manufacture of < liquid crystal display device and evaluation >

Use the crystal aligning agent prepared in this way, and change having that it's too late ultraviolet irradiation amount (3 levels) manufacturing 4 liquid crystal display device altogether of the pattern of transparency electrode.In addition, the liquid crystal display device manufactured by these is carried out to the evaluation of various characteristic.

[there is the manufacture of the liquid crystal display device of patternless transparency electrode]

Use liquid crystal orienting film printing press (Japan's description printing (Nissha) (share) manufactures), the crystal aligning agent prepared in this way is coated on the transparent electrical pole-face of the glass substrate with the transparency electrode comprising ito film, the hot-plate of 80 DEG C carries out 1 minute heating (prebake conditions) by removal of solvents after, the hot-plate of 150 DEG C carries out heating (afterwards toast) in 10 minutes, and forms average film thickness and be film.

Utilize and there is the rubbing machine of the roller being wound with artificial silk cloth, with the hair press-in length of the platform movement speed of the roller rotating speed of 400rpm, 3cm/ second, 0.1mm, friction treatment is carried out to this film.Thereafter, in ultrapure water, carry out 1 minute ultrasonic cleaning, in the cleaning oven of 100 DEG C, then carry out drying in 10 minutes, obtain the substrate with liquid crystal orienting film thus.Repeat this operation, obtain the substrate that a pair (2) have liquid crystal orienting film.

Secondly, in the respective outer rim with liquid crystal orienting film of described a pair substrate, it is after the epoxy adhesive of the alumina balls of 5.5 μm that coating is placed with diameter, crimps, and binding agent is hardened in the mode that LCD alignment face is relative after superposing.Then, fill nematic liquid crystal (Merck manufacture, MLC-6608) between from liquid crystal injecting port towards a pair substrate, then utilize acrylic acid series photo-hardening binding agent to be sealed by liquid crystal injecting port, manufacture liquid crystal cells thus.

Then, for the liquid crystal cells obtained in this way, towards between electrode, apply the interchange 10V that frequency is 60Hz, under the state that liquid crystal has driven, use UV irradiation equipment metal halide lamp being used for light source, with 10,000J/m ²irradiation dose irradiation ultraviolet radiation.Moreover this irradiation dose uses the value measured for quantorecorder that benchmark carries out measuring with wavelength 365nm.

[evaluation of voltage retention]

Use the liquid crystal display device that manufactures in this way, apply the voltage of 5V with the application time of 60 microseconds, the interval of 167 milliseconds at 23 DEG C after, measure remove apply after voltage retention (VHR) after 167 milliseconds.Measurement result is shown in following table 2.Moreover the VHR-1 that use Dongyang technology (TOYOCorporation) (share) manufactures is as determinator.

[there is the manufacture of the liquid crystal display device of patterned transparency electrode]

There is slit-shaped respectively that be patterned to as shown in Figure 1 and be divided on the substrate A of the glass of the ITO electrode in multiple region and each electrode surface of substrate B, liquid crystal orienting film printing press (Japan's description printing (share) manufactures) is used to be coated with the crystal aligning agent of the embodiment 1 prepared in this way, the hot-plate of 80 DEG C carries out 1 minute heating (prebake conditions) by removal of solvents after, the hot-plate of 150 DEG C carries out heating (afterwards toast) in 10 minutes, and forms average film thickness and be film.After 1 minute ultrasonic cleaning being carried out to this film in ultrapure water, in the cleaning oven of 100 DEG C, carry out drying in 10 minutes, obtain the substrate with liquid crystal orienting film thus.Repeat this operation, obtain the substrate that a pair (2) have liquid crystal orienting film.Moreover the pattern of the electrode used is the pattern with the electrode pattern identical type in PSA pattern.

Repeat described operation, manufacture the liquid crystal cells that 3 have patterned transparency electrode.1 liquid crystal cells is wherein directly for the evaluation of the response speed of liquid crystal molecule described later.For 2 remaining liquid crystal cells, by with manufacture there is the liquid crystal display device of patternless transparency electrode time identical method, under the state being applied with voltage between to conducting film, with 5,000J/m ²or 10,000J/m ²irradiation dose carry out rayed respectively after, for the evaluation of the response speed of liquid crystal molecule.

[evaluation of the response speed of liquid crystal molecule]

For each liquid crystal display device manufactured in this way, first, do not apply voltage and irradiate visible ray, and utilizing optical universal meter mensuration through the brightness of the light of liquid crystal display device, this value is set to relative permeability 0%.Secondly, measure the transmitance during interchange 5 seconds being applied with 60V between the electrode to liquid crystal display device in the same manner as described, this value is set to relative permeability 100%.When being applied with the interchange of 60V to each liquid crystal display device, measuring relative permeability and be transformed into time till 90% from 10%, is response speed by this timing definition, and evaluates liquid crystal molecule for the responsiveness of change being disconnected to Voltage On state from voltage.

Be 5,000J/m by liquid crystal display device, the irradiation dose of not irradiating light ²liquid crystal display device and irradiation dose be 10,000J/m ²the measurement result of respective response speed of liquid crystal display device be shown in following table 2.

[embodiment 2 ~ embodiment 4 and comparative example 1, comparative example 2]

Change the amount of polyimide of the preparation being used for crystal aligning agent, the kind of organopolysiloxane and amount as described in Table 2 respectively, in addition, prepare crystal aligning agent in the same manner as example 1.In addition, use these crystal aligning agents respectively, manufacture liquid crystal display device in the same manner as example 1, and manufactured liquid crystal display device is evaluated.Their evaluation result is shown in table 2.

[table 2]

As shown in table 2, in the liquid crystal display device of embodiment 1 ~ embodiment 4, liquid crystal molecule for the response speed of voltage change all faster than comparative example 1, comparative example 2, and excellent especially in embodiment 1, embodiment 3, embodiment 4.

Claims

1. a crystal aligning agent, is characterized in that: comprising the base had represented by following formula (1) is the organopolysiloxane of side chain,

[changing 1]

In formula (1), X is hydrogen atom or methyl; L to be singly-bound or carbon number be 1 ~ 20 alkane two base, described alkane two base can be branch-like, also under the non-conterminous condition of Sauerstoffatom, can be interrupted 1 time ~ 10 times by Sauerstoffatom; Y is singly-bound ,-O-, * ¹-COO-, * ¹-OCO-or-OCOO-, wherein, " * ¹" represent the associative key with L; Ring A is naphthalene nucleus; " * " represents associative key.

2. crystal aligning agent according to claim 1, is characterized in that: described L to be carbon number be 4 ~ 20 alkane two base.

3. crystal aligning agent according to claim 1, is characterized in that: also comprise at least one polymkeric substance (Q) in the group being selected from and being made up of polyamic acid and polyimide.

4. a manufacture method for liquid crystal display device, is characterized in that comprising:

1st step, is coated on crystal aligning agent according to any one of claim 1 to 3 respectively on the described conducting film of a pair substrate with conducting film, then heats it and form film;

2nd step, to make described film across the layer mode in opposite directions of liquid crystal molecule, constructs liquid crystal cells by a pair substrate subtend configuration being formed with described film; And

3rd step, to described liquid crystal cells carries out rayed under the state being applied with voltage between the conducting film had described a pair substrate.

5. a liquid crystal orienting film, is characterized in that: use crystal aligning agent according to any one of claim 1 to 3 and formed.

6. a liquid crystal display device, is characterized in that: comprise liquid crystal orienting film according to claim 5.