CN107111190A

CN107111190A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element

Info

Publication number: CN107111190A
Application number: CN201580059292.9A
Authority: CN
Inventors: 国见奈穗
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2014-10-28
Filing date: 2015-10-26
Publication date: 2017-08-29
Also published as: KR102488715B1; KR20170077144A; TW201630978A; JP6776897B2; JPWO2016068085A1; CN115746874A; WO2016068085A1; TWI780023B

Abstract

There is provided and represent element for obtaining aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal of the alignment films for being suitable for light orientation purposes, the alignment films will not also produce bright spot in the case of negative type liquid crystal, result in good after image characteristic.A kind of aligning agent for liquid crystal, it contains at least one kind of polymer (A) in the group being made up of the imide amination polymer of polyimide precursor and the polyimide precursor, and the polyimide precursor has the construction unit shown in construction unit and formula (2) shown in formula (1).(X₁、X₂：Formula (X1 1) or (X1 2)；R₁、R₂、R₃、R₄And R₆It is each independently the alkyl of hydrogen atom or carbon number 1~4.R₅For the alkyl of carbon number 1~4.N is 1~6 integer.)

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element

Technical field

The present invention relates to the aligning agent for liquid crystal for being suitable for optical alignment method processing, the liquid crystal aligning obtained by the aligning agent for liquid crystal Film and the liquid crystal of the liquid crystal orientation film has been used to represent element.

Background technology

The liquid crystal used in liquid crystal TV set, liquid crystal display etc. represents that element is generally provided with element for controlling The liquid crystal orientation film of liquid crystal arrangement state.As liquid crystal orientation film, main use will be with polyamides such as polyamic acids (poly- AMIC acid) Imines precursor, the solution of soluble polyimide are applied to glass substrate etc. as the aligning agent for liquid crystal of main component, and burn till Obtained from polyimides system liquid crystal orientation film.Now, according to industrial most popular method, the liquid crystal orientation film by using The surface for the polyimides system liquid crystal orientation film that the cloth such as cotton, nylon, polyester are formed on the electrode substrate along a direction friction, So-called brushing processing is carried out to make.

Optical alignment method is as the method for orientation treatment without brushing, with can industrially be entered using easy manufacturing process The advantage of row production.

For IPS (In Plane Switching) type of drive, FFS (Fringe Field switching) driving side The liquid crystal of formula is represented for element, compared with taking the liquid crystal orientation film that brushing facture is obtained, by using taking light orientation The liquid crystal orientation film that method is obtained, can expect that liquid crystal represents the contrast of element, raising of angle of visibility characteristic etc., it is possible to increase liquid Crystalline substance represents the performance of element, therefore is attracted attention as desirable liquid crystal aligning processing method.

But, compared with handling obtained liquid crystal orientation film by brushing, the liquid crystal orientation film obtained by optical alignment method Exist polymeric membrane the anisotropy for differently- oriented directivity it is small the problem of.If anisotropy is small, sufficient liquid can not be obtained , when liquid crystal is made representing element, there is the problem of after image etc. occur in brilliant orientation.The liquid obtained as raising by optical alignment method The anisotropic method of brilliant alignment films, it is proposed that：After light irradiation, removal causes the master of foregoing polyimides because of light irradiation Chain is cut off so as to the low molecular weight compositions of generation.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 9-297313 publications

Patent document 2：Japanese Unexamined Patent Publication 2011-107266 publications

Non-patent literature

Non-patent literature 1：" liquid crystal photo-alignment film ", functional material, in November, 1997 number, 13-22 pages of Vol.17, No.11

The content of the invention

Problems to be solved by the invention

Represent to use positive type liquid crystal in the past in element in the liquid crystal of IPS type of drive, FFS type of drive, by using negative Type liquid crystal, can reduce the transmission loss of electrode upper, it is possible to increase contrast.If the liquid crystal obtained by optical alignment method is taken It is used to represent element using the IPS type of drive of negative type liquid crystal material, the liquid crystal of FFS type of drive to film, then can expects have The higher expression performance of element is represented than conventional liquid crystal.

But, present inventor has performed research, as a result understand：Element is represented having used the liquid crystal of negative type liquid crystal material In the case of, there is the incidence height for representing bad (bright spot), generation and represent bad in the liquid crystal orientation film obtained by optical alignment method The problem of.

The problem of the present invention is that there is provided the optical alignment method for being adapted for use in the liquid crystal orientation film for obtaining optical alignment method purposes The aligning agent for liquid crystal of processing, the liquid crystal orientation film obtained by the aligning agent for liquid crystal and the liquid crystal watch for possessing the aligning agent for liquid crystal Show element, the liquid crystal orientation film will not also produce bright spot in the case of negative type liquid crystal is used, and can obtain good After image characteristic.

The solution used to solve the problem

Found when the present inventor is furtherd investigate：Liquid crystal comprising the polyimides based polymer with specific structure takes For realizing above-mentioned purpose it is effective to agent, so as to complete the present invention.

The present invention is a kind of aligning agent for liquid crystal, it is characterised in that it contains selected from sub- by polyimide precursor and the polyamides At least one kind of polymer (A) in the group of the imide amination polymer composition of amine precursor, the polyimide precursor has following formula And the construction unit shown in following formula (2) (1).

(in formula (1), formula (2), X₁And X₂It is each independently selected from the structure group as shown in following formula (X1-1) and (X1-2) Into group in it is at least one kind of.R₁、R₂、R₃、R₄And R₆It is each independently the alkyl of hydrogen atom or carbon number 1~4.R₅For carbon The alkyl of atomicity 1~4.N is 1~6 integer.)

The effect of invention

According to the present invention, it is possible to provide be suitable for the aligning agent for liquid crystal of optical alignment method processing, the aligning agent for liquid crystal can obtain energy The bright spot and illumination sensitivity that enough suppress to observe in conventional light orientation position logos are high, the liquid crystal with good after image characteristic Alignment films.By possessing the liquid crystal orientation film obtained by the aligning agent for liquid crystal, using the teaching of the invention it is possible to provide do not represent bad and reliability High liquid crystal represents element.

Embodiment

The aligning agent for liquid crystal of the present invention is as described above, containing selected from by polyimide precursor and the acyl of the polyimide precursor At least one kind of polymer (present invention in, also referred to as particular polymers (A)) in the group of imines fluidized polymer composition, the polyamides Imines precursor has following formula (1) and the construction unit shown in following formula (2).In the present invention, construction unit shown in formula (1) and Construction unit shown in following formula (2) may reside in same polyimide precursor, in addition, the construction unit shown in formula (1) It can also be present in different polyimide precursors with the construction unit shown in following formula (2).

X in above-mentioned formula (1), formula (2)₁、X₂、R₁、R₂It is each as defined above.Wherein, from high-sensitivity and liquid crystal From the viewpoint of orientation, X₁、X₂It is preferred that with previously described formula (X1-2).From the sight by heating the easness for carrying out imidizate Point sets out, R₁、R₂Preferably hydrogen atom or methyl, ethyl.From the viewpoint of liquid crystal aligning, R₃、R₄、R₆Preferably hydrogen is former Son.From the viewpoint of liquid crystal aligning, R₅Preferably methyl.In addition, from the viewpoint of liquid crystal aligning, n is preferably 1~ 3 integer, particularly preferably 2.

There is the polyimide precursor of construction unit shown in construction unit shown in formula (1) and formula (2), gather in the present invention Amic acid is manufactured by following methods.It should illustrate, in the present invention, before the polyimides of construction unit shown in formula (1) Body and polyimide precursor with construction unit shown in formula (2) can be manufactured respectively, can also be made by the way that both are mixed Make.

In addition, as carrying out the diamines of polycondensation with tetrabasic carboxylic acid or its dianhydride, it is preferred that assign structure shown in formula (1) The diamines of construction unit respectively uses more than a kind shown in the diamines and imparting formula (2) of unit, and manufacture has structure shown in formula (1) The polyimide precursor of construction unit shown in unit and formula (2).

Now, by making the X in the above-mentioned formula of imparting (1)₁Tetrabasic carboxylic acid or its dianhydride and assign the X in above-mentioned formula (2)₂'s Tetrabasic carboxylic acid or its dianhydride are with assigning Y₁Diamines and assign Y₂Diamines in the presence of the solvent with -20~150 DEG C, preferably with 0~ 50 DEG C carry out 30 minutes~24 hours, preferably carry out the polycondensation reaction of 1~12 hour to manufacture.

The reaction of diamines and tetrabasic carboxylic acid is generally carried out in a solvent.As the solvent now used, as long as generated The solvent that polyimide precursor can dissolve just is not particularly limited.The concrete example of solvent used in reaction is exemplified below out, but It is not limited to these examples.

For example, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones or gamma-butyrolacton, N, N- diformazans can be included Base formamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) or 1,3- methylimidazole alkanones.In addition, polyimide precursor When solvent solubility is high, MEK, cyclohexanone, cyclopentanone, 4- hydroxy-4-methyl-2-pentanones or following formula can be used Solvent shown in [D-1]~formula [D-3].

(in formula [D-1], D¹Represent the alkyl of carbon number 1~3；In formula [D-2], D²Represent the alkane of carbon number 1~3 Base；In formula [D-3], D³Represent the alkyl of carbon number 1~4).

These solvents can be used alone, and can also be used in mixed way.And then, even insoluble polyimide precursor is molten Agent, in the range of the polyimide precursor generated will not be separated out, can also mix and be used into aforementioned solvents.In addition, molten Moisture in agent can hinder polymerisation, and then cause generated polyimide precursor to hydrolyze, therefore, and solvent preferably takes off Water is used after drying.

In addition, in order to obtain polyamic acid Arrcostab, following methods can be used：Make to have carried out dialkyl ester to carboxylic acid group The method that the tetrabasic carboxylic acid of change carries out polycondensation with primary diamines compound or secondary diamine compounds；Make to have carried out dialkyl ester to carboxylic acid group The method that the carboxylic acid halides of tetrabasic carboxylic acid two of change carries out polycondensation with primary diamines compound or secondary diamine compounds；Or by the carboxylic of polyamic acid The method that base is converted into ester.

When diamine component and the tetrabasic carboxylic acid composition is reacted in a solvent, following methods can be included：To make diamines into Solution obtained from being dispersed or dissolved in solvent is stirred, and is directly added tetrabasic carboxylic acid composition or is made tetrabasic carboxylic acid composition point Dissipate or be dissolved in after solvent the method for row addition again；Conversely, to make tetrabasic carboxylic acid composition obtained from being dispersed or dissolved in solvent it is molten The method that diamine component is added in liquid；Alternately method etc. of addition diamine component and tetrabasic carboxylic acid composition, can use these it In any means.In addition, diamine component or tetrabasic carboxylic acid composition can be pre-mixed respectively using a variety of and when reacting it In the state of reacted, can also successively react respectively, can also make to react obtained low-molecular weight respectively and mix Reaction is so as to be made polymer.

Polymerization temperature now can select -20~150 DEG C of arbitrary temp, be preferably -5~100 DEG C of scope.This Outside, reaction can be carried out under arbitrary concentration, but concentration it is too low when, it is difficult to obtain the polymer of HMW, excessive concentration When, the viscosity of reaction solution becomes too high and is difficult to uniform stirring.It is therefore preferable that being 1~50 mass %, more preferably 5~30 matter Measure %.Initial reaction stage can be carried out in higher concentrations, add solvent again thereafter.

In the polymerisation of polyimide precursor, total mole of total molal quantity of diamine component and tetrabasic carboxylic acid composition The ratio between number is preferably 0.8~1.2, particularly preferably 0.9~1.0.In the same manner as common polycondensation reaction, the mol ratio closer to 1.0, then the molecular weight of the polyimide precursor generated becomes bigger.

The polyimides of the present invention is to make polyimides obtained from foregoing polyimide precursor closed loop, is gathered to obtain this Acid imide, the method that foregoing polyamides acid or polyamic acid Arrcostab can be used to carry out closed loop and polyimides is made.

The acid amides acidic group closed loop rate (also referred to as acid imide rate) of the polyimides of the present invention is not necessarily required to as 100%, Can be according to purposes, purpose come any adjustment, preferably 50~80%.

As the method for making polyimide precursor carry out imidizate, it can include the solution of polyimide precursor is direct The hot-imide of heating or the catalysis imidizate that catalyst is added into the solution of polyimide precursor.Make polyamides sub- Temperature when amine precursor carries out hot-imide in the solution is 100~400 DEG C, is preferably 120~250 DEG C, preferably while will The water generated by imidization reaction is removed to outside system, while carrying out hot-imide.Reaction time is preferably 30 minutes ~4 hours.

The catalysis imidizate of polyimide precursor can be by adding base catalyst in the solution to polyimide precursor And acid anhydrides, and -20~250 DEG C, preferably stir and carry out at 0~180 DEG C.Reaction time is preferably 30 minutes~4 hours.

The amount of base catalyst is 0.5~30 mole times, preferably 2~20 moles times of acid amides acidic group, and the amount of acid anhydrides is 1~50 mole of acid amides acidic group times, it is preferably 3~30 moles times.As base catalyst, pyridine, triethylamine, three can be included Methylamine, tri-n-butylamine or trioctylamine.Wherein, pyridine has the alkalescence for being suitable to promote reaction, so it is preferred that.

As acid anhydrides, acetic anhydride, trimellitic anhydride or pyromellitic dianhydride can be included.Wherein, if using acetic anhydride, Reaction is easily refined after terminating, so it is preferred that.Based on catalysis imidizate acid imide rate can by adjust catalytic amount and Reaction temperature, reaction time control.

The generated polyimide precursor of recovery or polyamides are sub- from the reaction solution of polyimide precursor or polyimides During amine, can put into reaction solution to solvent precipitates it.As the solvent for precipitation, can include methanol, ethanol, Isopropanol, acetone, hexane, butyl cellosolve, heptane, MEK, methyl iso-butyl ketone (MIBK), toluene, benzene, water etc..Put into solvent And make the polymer that it is precipitated after being recovered by filtration, air drying or heat drying can be carried out under normal or reduced pressure.In addition, By make precipitation reclaim polymer be dissolved in solvent again and precipitate again recovery operation repeat 2~10 times when, can reduce Impurity in polymer.As solvent now, it can include such as alcohols, ketone, hydrocarbon, if using among these More than 3 kinds solvents, then purification efficiency further improve, so it is preferred that.

The particular polymers (A) of the present invention preferably use polyamic acid Arrcostab.Manufacture the preferred of polyamic acid Arrcostab Specific method is shown in following (1)~(3).

(1) method manufactured by the esterification of polyamic acid

By diamine component and tetrabasic carboxylic acid composition manufacture polyamic acid, its carboxyl (COOH yls) is set to be chemically reacted, i.e. ester Change reaction, so as to manufacture the method for polyamic acid Arrcostab.

On esterification, specifically, make polyamic acid with esterifying agent in the presence of the solvent preferably with -20~150 DEG C, more preferably with 0~50 DEG C of preferred reaction 30 minutes~24 hours, more preferably react 1~4 hour.

As foregoing esterifying agent, the esterifying agent that can preferably easily remove after esterification can include N, N- diformazans Base formamide dimethylacetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N, N- Dimethylformamide di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1- methyl -3- p-methylphenyls three Nitrence, 1- ethyl -3- p-methylphenyls triazenes, 1- propyl group -3- p-methylphenyls triazenes, 4- (4,6- dimethoxys -1,3,5- three Piperazine -2- bases) -4- methyl morpholine hydrochlorides etc..The consumption of esterifying agent is preferably 2 relative to 1 mole of the repeat unit of polyamic acid ~6 molar equivalents.Wherein, preferably 2~4 molar equivalents.

, can as the solvent used in foregoing esterification from the viewpoint of the dissolubility of polyamic acid in a solvent Include foregoing diamine component and the solvent used in the reaction of tetrabasic carboxylic acid composition.Wherein, preferably DMF, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones or gamma-butyrolacton.Solvent can use a kind or be used in mixed way 2 kinds More than.

In foregoing esterification, the concentration of polyamic acid in a solvent is difficult from the viewpoint of separating out preferably from polyamic acid For 1~30 mass %.Wherein, preferably 5~20 mass %.

(2) method manufactured by the reaction of diamine component and tetracarboxylic acid acid diesters dichloride

The reaction of diamine component and tetracarboxylic acid acid diesters dichloride specifically makes diamine component and tetracarboxylic acid acid diesters two Chloride in the presence of alkali and solvent preferably with -20~150 DEG C, more preferably with 0~50 DEG C of preferred reaction 30 minutes~24 it is small When, more preferably react the method for 1~4 hour.

Aforementioned bases can use pyridine, triethylamine, DMAP etc..Wherein, in order that reaction is leniently promoted, Preferably pyridine.The consumption of alkali is preferably the amount that can be easily removed after previous reaction, relative to tetracarboxylic acid acid diesters dichloride, Preferably 2~4 times moles.Wherein, more preferably 2~3 times moles.

From the viewpoint of resulting polymers, the i.e. dissolubility of polyamic acid Arrcostab in a solvent, make in previous reaction Solvent can include foregoing diamine component and the solvent used in the reaction of tetrabasic carboxylic acid composition.Wherein, preferably N, N- bis- NMF, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones or gamma-butyrolacton.These solvents can use a kind Or be mixed with two or more.

In previous reaction, the viewpoint that the concentration of polyamic acid Arrcostab in a solvent is difficult to separate out from polyamic acid Arrcostab Set out preferably 1~30 mass %.Wherein, preferably 5~20 mass %.In addition, in order to prevent tetracarboxylic acid acid diesters dichloride Hydrolysis, the solvent for making polyamic acid Arrcostab is preferably dehydrated as far as possible.And then, previous reaction is preferably in nitrogen Carried out in gas atmosphere, to prevent outer gas to be mixed into.

(3) method manufactured by the reaction of diamine component and tetracarboxylic acid acid diesters

It is the method manufactured by the polycondensation reaction of diamine component and tetracarboxylic acid acid diesters, is to make diamines specifically Composition and tetracarboxylic acid acid diesters in the presence of condensing agent, alkali and solvent preferably with 0~150 DEG C, more preferably with 0~100 DEG C preferably Reaction 30 minutes~24 hours, the method for more preferably reacting 3~15 hours.

Aforementioned condensation agent can use triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyls -3- (3- dimethylaminos Propyl group) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, O- (benzos three Azoles -1- bases)-N, N, N ', N '-tetramethylurea tetrafluoroborate, O- (BTA -1- bases)-N, N, N ', N '-tetramethylurea six Fluorophosphate, (thio -3- benzoxazolyls of 2,3- dihydros -2-) phosphonic acid diphenyl ester etc..The consumption of condensing agent is relative to tetrabasic carboxylic acid Diester is preferably 2~3 times moles, particularly preferably 2~2.5 times moles.

Aforementioned bases can use the tertiary amines such as pyridine, triethylamine.The consumption of alkali is preferably that can easily go after foregoing polycondensation reaction The amount removed, relative to diamine component, preferably 2~4 times moles, particularly preferably 2~3 times moles.

From the viewpoint of resulting polymers, the i.e. dissolubility of polyamic acid Arrcostab in a solvent, make in polycondensation reaction Solvent can include foregoing diamine component and the solvent used in the reaction of tetrabasic carboxylic acid composition.Particularly preferably N, N- diformazan Base formamide, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones or gamma-butyrolacton.Solvent can be used in mixed way 2 kinds with On.

In addition, in above-mentioned polycondensation reaction, being used as additive by adding lewis acid, reaction can be carried out effectively.As The halo lithium such as lewis acid, preferably lithium chloride, lithium bromide.Lewis acidic consumption relative to diamine component be preferably 0.1~ 10 times moles, particularly preferably 2.0~3.0 times moles.

Polyamic acid alkyl is reclaimed in the solution of the polyamic acid Arrcostab obtained by the method by above-mentioned (1)~(3) During ester, reaction solution can be put into solvent and precipitate it.As the solvent used in precipitation, can enumerate water outlet, methanol, Ethanol, 2- propyl alcohol, hexane, butyl cellosolve, acetone, toluene etc..Put into solvent and make the polymer that it is precipitated for removal The purpose of the foregoing additive/catalyst class used is preferably carried out that operation is cleaned multiple times with above-mentioned solvent., can be with after being recovered by filtration Air drying or heat drying are carried out under normal or reduced pressure.In addition, the polymer for reclaiming precipitation is dissolved in into solvent again And precipitate again recovery operation repeat 2~10 times when, the impurity in polymer can be reduced.As solvent now, it can arrange The solvent of polymer can be dissolved by enumerating.

The polyamic acid Arrcostab of the present invention is preferably the method for (1) or (2) among the method for foregoing (1)~(3).

Aligning agent for liquid crystal is the coating solution for being used to be formed liquid crystal orientation film (also referred to as resin coating), is containing specific poly- The coating solution for being used to form liquid crystal orientation film of compound (A) and solvent.The content of particular polymers (A) in aligning agent for liquid crystal Can suitably it be changed according to the coating method of aligning agent for liquid crystal, the target film thickness of liquid crystal orientation film, preferably 2~10 mass %, Particularly preferably 3~7 mass %.On the other hand, the content of solvent is preferably 70~99.9 mass %, more preferably 90~98 matter Measure %.

The solvent used in the aligning agent for liquid crystal of the present invention is (also referred to as good for dissolving the solvent of particular polymers (A) Solvent), particularly preferably organic solvent.The concrete example of good solvent is exemplified below out, but is not limited to these examples.

Such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N- second can be included Base -2-Pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolacton, 1,3- dimethyl-imidazols alkanone, MEK, cyclohexanone, cyclopentanone, 4- hydroxy-4-methyl-2-pentanones etc..Wherein, preferably use METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones or γ- Butyrolactone.

And then, when the dissolubility of particular polymers (A) in a solvent is high, preferably use previously described formula [D-1]~formula [D-3] institute The solvent shown.

Good solvent in aligning agent for liquid crystal is preferably 20~99 overall mass % of solvent, more preferably 20~90 matter Measure %, particularly preferably 30~80 mass %.

Aligning agent for liquid crystal can contain liquid crystal when making coating of liquid crystalline alignment agent in the range of effect of the present invention is not damaged The solvent (also referred to as poor solvent) that the film of alignment films, surface smoothness are improved.These poor solvents are preferably that liquid crystal takes 1~80 mass % of the solvent entirety included into agent.Wherein, preferably 10~80 mass %.More preferably 20~70 matter Measure %.

The concrete example of poor solvent is exemplified below out, but is not limited to these examples.Such as ethanol, isopropyl can be included Alcohol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohols, 2- amylalcohols, 3- amylalcohols, 2-methyl-1-butene alcohol, isoamyl alcohol, uncle penta Alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanols, 2- methyl-1-pentenes alcohol, 2- methyl -2- amylalcohols, 2- ethyls-n-butyl alcohol, 1- heptan Alcohol, 2- enanthol, 3- enanthol, 1- octanols, sec-n-octyl alcohol, 2- ethyl -1- hexanols, cyclohexanol, 1 methyl cyclohexanol, 2- methyl cyclohexanes Alcohol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,4- fourths Glycol, 2,3- butanediols, 1,5- pentanediols, 2- methyl -2,4-PD, 2- ethyl -1,3- hexylene glycols, dipropyl ether, butyl oxide, Two hexyl ether, dioxanes, glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, 1,2- butoxy ethane, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ether, dibutyl ethylene glycol ether, 2 pentanone, propione, methyl-n-butyl ketone, 2- Heptanone, 4- heptanone, 3- ethoxybutyls acetic acid esters, 1- methyl amyls acetic acid esters, 2- ethyl-butyls acetic acid esters, 2- ethylhexyl second Acid esters, ethylene glycol acetate, ethylene acetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) second Alcohol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl ether, ethylene glycol monohexylether, 2- (hexyl epoxide) ethanol, furfuryl alcohol, diethylene glycol, third Glycol, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propyl alcohol, propylene glycol methyl ether acetate, DPG, DPG list Methyl ether, DPE, dimethyl ether, Tripropylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol list Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol acetate, ethylene acetate, diethylene glycol monoethyl ether second Acid esters, butyl carbitol acetate, 2- (2- ethoxy ethoxies) ethylhexoate, diethylene glycol acetic acid esters, three second two The positive fourth of alcohol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid Ester, propyleneglycolmethyletheracetate list ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionates, 3- ethoxy-c acid methyl second Ester, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxypropionic acid fourths Ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, previously described formula [D-1]~formula [D-3] institute Solvent shown etc..

Wherein, 1- hexanols, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, ethylene glycol are preferably used Monobutyl ether or dimethyl ether.

It is preferred that importing following cross-linked compounds into the aligning agent for liquid crystal of the present invention：With epoxy radicals, NCO, The cross-linked compound of oxetanylmethoxy or cyclocarbonate radical；With selecting free hydroxyl, hydroxy alkyl and low-grade alkoxy alkyl The cross-linked compound of at least one kind of substituent in the group of composition；Or, the bridging property chemical combination with polymerism unsaturated bond Thing.These substituents, polymerism unsaturated bond must have more than 2 in cross-linked compound.

As the cross-linked compound with epoxy radicals or NCO, such as bisphenol acetone glycidol can be included Ether, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl group isocyanuric acid ester, four shrink sweet Oil base aminobphenyl, four glycidyl group m-xylene diamine, four glycidyl group -1,3- double (amino-ethyl) hexamethylene, four benzene Base glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl ether, 1,3- pairs (1- (2, 3- glycidoxies) -1- trifluoromethyl -2,2,2- trifluoromethyls) benzene, 4,4- double (2,3- glycidoxies) octafluorobiphenyl, three Glycidyl para-aminophenol, four glycidyl group m-xylene diamine, 2- (4- (2,3- glycidoxies) phenyl) -2- (4- (1,1- double (4- (2,3- glycidoxies) phenyl) ethyls) phenyl) propane, the double (4- (1- (4- (2,3- glycidoxies) of 1,3- Phenyl) -1- (4- (1- (4- (2,3- glycidoxies) phenyl) -1- Methylethyls) phenyl) ethyl) phenoxy group) -2- propyl alcohol etc..

Cross-linked compound with oxetanylmethoxy is with the oxetanylmethoxy shown at least two following formula [4A] Compound.

Specifically, the 58~59 of International Publication publication No. WO2011/132751 (2011.10.27 is disclosed) can be included The cross-linked compound shown in formula [4a]~formula [4k] described in page.

It is with the ring carbon acid shown at least two following formula [5A] as the cross-linked compound with cyclocarbonate radical The cross-linked compound of ester group.

Specifically, page 76~82 of International Publication publication No. WO2012/014898 (2012.2.2 is disclosed) can be included Described in formula [5-1]~formula [5-42] shown in cross-linked compound.

, can as the cross-linked compound with least one kind of substituent in the group for selecting free hydroxyl and alkoxy to constitute Include the amino resins for example with hydroxyl or alkoxy, such as melamine resin, carbamide resin, guanamine resin, glycoluril-formaidehyde tree Fat, succinamide-formaldehyde resin, ethylene urea-formaldehyde resins etc..Specifically, the hydrogen atom of amino can be used by methylol Or alkoxy methyl or melamine derivative, benzoguanamine derivative or the glycoluril of both substitution.The melamine derivative Or benzoguanamine derivative can exist in the form of dimer or tripolymer.Their preferably every 1 triazine rings have average 3 Above and the methylol or alkoxy methyl of less than 6.

As above-mentioned melamine derivative or the example of benzoguanamine derivative, every 1 triazine ring of commercially available product can be included Substitution has the MX-750 of average 3.7 methoxies, the substitution of every 1 triazine ring to have the MW-30 of average 5.8 methoxies (being above Sanwa Chemical Co., Ltd's system), the first such as CYMEL 300,301,303,350,370,771,325,327,703,712 Epoxide methylates melamine；The methoxymethylated butoxymethyl melamine such as CYMEL 235,236,238,212,253,254； The butoxymethyl melamines such as CYMEL 506,508；CYMEL 1141 etc the isobutoxy first of methyl containing Carboxvmethoxv Base melamine；CYMEL 1123 etc methoxymethylated ethoxyl methyl benzoguanamine；CYMEL 1123-10's etc Methoxymethylated butoxymethyl benzoguanamine；CYMEL 1128 etc butoxymethyl benzoguanamine；CYMEL 1125-80 etc the ethoxyl methyl of methyl containing Carboxvmethoxv benzoguanamine (is above three well サイア Na ミ De companies System).In addition, as the example of glycoluril, can include CYMEL 1170 etc butoxymethyl glycoluril, CYMEL 1172 it The methylolation glycoluril of class, Powder link 1174 etc methoxyl group methylolation glycoluril etc..

As the benzene with hydroxyl or alkoxy or benzene phenoloid, such as 1,3,5- tri- (methoxy methyls can be included Base) benzene, 1,2,4- tri- (i-propoxymethyl) benzene, double (sec-butoxymethyl) benzene of 1,4- or 2,6- bishydroxymethyls be to the tert-butyl group Phenol.

More specifically, can include International Publication publication No. WO2011/132751 (2011.10.27 is disclosed) 62~ The cross-linked compound of formula [6-1]~formula [6-48] described in page 66.

As the cross-linked compound with polymerism unsaturated bond, such as trimethylolpropane tris (methyl) can be included Acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyl-oxies There are 3 polymerisms not in poly- (methyl) the acrylate equimolecular of base oxethyl trimethylolpropane, glycerine polyglycidyl ether The cross-linked compound of saturation base；Ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol Two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane bisphenol-A Type two (methyl) acrylate, expoxy propane bisphenol type two (methyl) acrylate, 1,6-HD two (methyl) acrylate, Glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) propylene Acid esters, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) propylene There is the bridging property of 2 polymerism unsaturated groups in acid esters, (methyl) acrylate of 3-hydroxypivalic acid neopentyl glycol two equimolecular Compound；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, 2- phenoxy group -2- hydroxypropyls (methyl) acrylate, 2- (methyl) acryloxy -2- hydroxypropyl phthalates, 3- chlorine-2-hydroxyls propyl group (methyl) acrylate, glycerine list (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl phosphoric acid There is cross-linked compound of 1 polymerism unsaturated group etc. in ester, N- methylols (methyl) acrylamide equimolecular.

And then, the compound shown in following formula [7A] can also be used.

(in formula [7A], E₁Represent be selected from by cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, Group in the group of fluorenes ring, anthracene nucleus and phenanthrene ring composition, E₂Representing the group being selected from following formula [7a] and formula [7b], n represents 1~ 4 integer.)

Above-mentioned one for cross-linked compound, but it is not limited to them.In addition, being used in the aligning agent for liquid crystal of the present invention Cross-linked compound can be a kind, two or more can also be combined.

The content of cross-linked compound in the aligning agent for liquid crystal of the present invention is relative to whole mass parts of component of polymer 100 Preferably 0.1~150 mass parts.Wherein, show target effect to promote cross-linking reaction, relative to whole polymer into Divide 100 mass parts, preferably 0.1~100 mass parts.More preferably 1~50 mass parts.

In the range of effect of the present invention is not damaged, aligning agent for liquid crystal of the invention can use coating of liquid crystalline alignment agent When the film thickness uniformity of liquid crystal orientation film, the compound that improves of surface smoothness.

As the compound for improving the film thickness uniformity of liquid crystal orientation film, surface smoothness, fluorine system surface can be included Activating agent, silicone based surfactants, nonionic surfactants etc..

More specifically, it (is Tohkem above that can include such as Eftop EF301, EF303, EF352 Products Corporation systems)；Megafac F171, F173, R-30 (being above DIC Corporation systems)； Fluorad FC430, FC431 (being above Sumitomo 3M Limited systems)；AsahiGuard AG710、Surflon S- 382nd, SC101, SC102, SC103, SC104, SC105, SC106 (being above Asahi Glass Co., Ltd's system) etc..

The consumption of surfactant is preferably relative to the mass parts of whole component of polymer 100 contained in aligning agent for liquid crystal 0.01~2 mass parts, more preferably 0.01~1 mass parts.

And then, the compound for moving to promote element to take off electric charge as the electric charge promoted in liquid crystal orientation film can also be to Described in page 69~73 that International Publication publication No. WO2011/132751 (2011.10.27 is disclosed) is added in aligning agent for liquid crystal Nitrogen heterocyclic ring amines shown in formula [M1]~formula [M156].The amines can be added directly in aligning agent for liquid crystal, It is row addition again after 0.1~10 mass %, preferably 1~7 mass % solution to be preferably made concentration.As long as solvent dissolving is special Determine polymer (A) to be just not particularly limited.

In the aligning agent for liquid crystal of the present invention, except add above-mentioned poor solvent, cross-linked compound, resin coating or Make compound that the film thickness uniformity and/or surface smoothness of liquid crystal orientation film are improved and promote de- electric charge compound it Outside, if in the range of effect of the present invention is not damaged, can also add for change liquid crystal orientation film dielectric constant, conduction Dielectric substance, the conductive materials of the electrical characteristics such as property.

Liquid crystal orientation film is film obtained from above-mentioned aligning agent for liquid crystal is applied to substrate and drying, burnt till.As applying The substrate of cloth aligning agent for liquid crystal of the present invention, as long as the high substrate of the transparency is just not particularly limited, can use glass base While plate, silicon nitride board, plastic bases such as acrylic compounds substrate, polycarbonate substrate etc. are used.Now, conform to the principle of simplicity chemical industry skill From the viewpoint of, preferably use the substrate for being formed with ITO electrode for driving liquid crystal etc..In addition, for the liquid crystal of reflection-type Represent for element, if being only unilateral substrate, the opaque material such as silicon wafer can be used, electrode now can also make With the material of the meeting reflected light such as aluminium.

The coating method of aligning agent for liquid crystal is not particularly limited, and industrial is usually to utilize silk-screen printing, intaglio printing, soft The method of the progress such as version printing, ink-jet method.As other coating methods, there are infusion process, rolling method, slot coated method, spin coating Method, spraying process etc., can use them according to purpose.

After aligning agent for liquid crystal is coated on substrate, it is possible to use hot plate, thermal cycle type baking oven, IR (infrared ray) type baking oven Deng heater meanses, make solvent evaporation that liquid crystal orientation film is made.It is coated with the drying after the aligning agent for liquid crystal of the present invention, burns till step Arbitrary temperature and time can be selected.Contained solvent is removed generally for abundant, can be included：50~120 DEG C, it is excellent It is selected at 60~100 DEG C and dries 1~10 minute, preferably dries 1~5 minute, thereafter at 150~300 DEG C, preferably 180~250 5~120 minutes are burnt till at DEG C, the condition of 10~60 minutes is preferably burnt till.When the thickness of liquid crystal orientation film after burning till is excessively thin, liquid Crystalline substance represents that the reliability of element is reduced sometimes, therefore preferably 5~300nm, more preferably 10~200nm.

The method that orientation process is carried out to the liquid crystal orientation film that the aligning agent for liquid crystal by the present invention is obtained can be brushing Logos, is suitably for light orientation position logos.As the preference of light orientation position logos, it can include：To foregoing liquid crystal alignment films The radioactive ray that surface irradiation is polarized along certain orientation, are according to circumstances preferably carried out at heating at a temperature of 150~250 DEG C Reason, so as to assign the method for liquid crystal aligning (also referred to as liquid crystal aligning ability).As radioactive ray, can use with 100~ The ultraviolet or luminous ray of 800nm wavelength.Wherein, it is however preferred to have 100~400nm, more preferably have 200~400nm The ultraviolet of wavelength.

In addition, in order to improve liquid crystal aligning, the substrate of liquid crystal orientation film can be coated with while entering with 50~250 DEG C Row heating, while irradiation radioactive ray.

The exposure of foregoing radioactive ray is preferably 1~10,000mJ/cm².Wherein, preferably 100~5,000mJ/cm².This The liquid crystal orientation film that sample is operated and made can be such that liquid crystal molecule is stably orientated along certain direction.

And then, water, solvent can also be used to carry out the liquid crystal orientation film for having irradiated polarization radioactive ray using preceding method Contact is handled.

The solvent used in being handled as above-mentioned contact, as long as dissolving is because radioactive ray irradiate and are generated by liquid crystal orientation film Analyte solvent, be just not particularly limited.As concrete example, water outlet, methanol, ethanol, 2- propyl alcohol, acetone, first can be enumerated Ethyl ketone, 1- methoxy-2-propanols, 1- methoxy-2-propanols acetic acid esters, butyl cellosolve, ethyl lactate, methyl lactate, dipropyl Keto-alcohol, 3- methoxy methyl propionates, 3- ethoxyl ethyl propionates, propyl acetate, butyl acetate, cyclohexyl acetate etc..Wherein, from From the viewpoint of versatility, solvent security, preferably water, 2- propyl alcohol, 1- methoxy-2-propanols or ethyl lactate.More preferably For water, 1- methoxy-2-propanols or ethyl lactate.Solvent can be a kind, can also combine two or more.

Handled as above-mentioned contact, impregnation process, spraying treatment (also referred to as spray treatment) can be included.From effectively Dissolve from the viewpoint of the analyte generated by radioactive ray by liquid crystal orientation film, the processing time in these processing is preferably 10 Second~1 hour.Wherein, the impregnation process of 1~30 minute is preferably carried out.In addition, solvent during aforementioned contact processing can be normal Temperature, can also be heated, preferably 10~80 DEG C.Wherein, preferably 20~50 DEG C.In addition, from the dissolubility of analyte From the viewpoint of, ultrasonication etc. can also be carried out as needed.

It is molten preferably by low boilings such as water, methanol, ethanol, 2- propyl alcohol, acetone, MEKs after aforementioned contact processing Agent is rinsed (also referred to as rinse), carries out burning till for liquid crystal orientation film.At this time it is also possible to any in carrying out rinse and burning till Person, or carry out both.The temperature burnt till is preferably 150~300 DEG C.Wherein, preferably 180~250 DEG C.More preferably 200 ~230 DEG C.In addition, the time burnt till is preferably 10 seconds~30 minutes.Wherein, preferably 1~10 minute.

The liquid crystal that the liquid crystal orientation film of the present invention is suitable as the Transverse electric-field types such as IPS modes, FFS modes represents element Liquid crystal orientation film, especially as FFS modes liquid crystal represent the liquid crystal orientation film of element for be useful.Liquid crystal is represented After the substrate that element can be by obtaining the subsidiary liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention, known method is utilized Liquid crystal cells are made, and are obtained using the liquid crystal cells.

As one of liquid crystal cells preparation method, illustrated so that the liquid crystal of passive-matrix structure represents element as an example. It should illustrate, or each pixel portion for constituting graphical representation is provided with TFT (Thin Film Transistor, film Transistor) etc. the liquid crystal of the active matrix structure of conversion element represent element.

Specifically, prepare transparent glass substrate of electrode, common electrode is set on one substrate, on another substrate Segment electrode (segment electrode) is set.ITO electrode can be for example made in these electrodes, and being patterned to can be real Existing desired graphical representation.Then, dielectric film is set to cover common electrode and segment electrode on each substrate.Insulating film such as may be used The SiO formed by sol-gel process is included to be made₂-TiO₂Film.

Then, liquid crystal orientation film is formed on each substrate, it is face-to-face with mutual liquid crystal aligning film surface on one substrate Another overlapping substrate of mode, be around bonded with sealant.For control base board gap, generally mixed in advance in sealant Sept is entered, has also been spread in advance for control base board gap moreover it is preferred that being not provided with part in the face of sealant Sept.A part for sealant is pre-set can be from the opening portion of outside filling liquid crystal.Then, by being set in sealant Opening portion, to by two plate bases and sealant encirclement space in inject liquid crystal material, thereafter, by the opening portion bonding agent Sealed.Injection can use vacuum impregnation, can also use the method for utilizing capillarity in an atmosphere.Liquid crystal material Material can use any one of positive type liquid crystal material, negative type liquid crystal material, preferably negative type liquid crystal material.Then, carry out inclined Shake the setting of piece.Specifically, a pair of polarizers are pasted on the surface with liquid crystal layer opposite side of two plate bases.

Operate as above, by using the aligning agent for liquid crystal of the present invention, the after image caused by exchange driving can be suppressed, And can obtain taking into account the liquid crystal orientation film of the adaptation of sealant and basal substrate.Especially, for irradiation polarization radioactive ray Obtained from be useful for light orientation position logos liquid crystal orientation film.

Embodiment

It is exemplified below embodiment and the present invention is described in more detail, but the present invention is not limited to them.Used below The abbreviation of compound and the assay method of each characteristic are as follows.

NMP：METHYLPYRROLIDONE

BCS：Butyl cellosolve

DA-1：Double (4- amino-benzene oxygens) ethane of 1,2-

DA-2：4- (2- (methylamino) ethyl) aniline

DA-3：P-phenylenediamine

DA-4：4- (2- amino-ethyls) aniline

DA-5：With reference to following formula (DA-5)

[viscosity]

The viscosity of poly amic acid ester and polyamic acid solution etc. uses E type viscosimeter TVE-22H (Toki Sangyo Co., Ltd. System), it is that 1.1mL, cone rotor are that TE-1 (1 ° 34 ', R24), temperature are to be measured under conditions of 25 DEG C in sample size.

[molecular weight]

The molecular weight of poly amic acid ester etc. is measured by GPC (normal temperature gel permeation chromatography) device, with polyethylene glycol Number-average molecular weight (Mn) and weight average molecular weight (Mw) are calculated with the form of PEO scaled value.

GPC devices：Shodex company systems (GPC-101), post：Shodex company systems (KD803, KD805 series connection), post Temperature：50 DEG C, eluent：DMF (is used as additive, lithium bromide monohydrate (LiBrH₂O) it is 30mmol/ L, phosphoric acid anhydrous crystal (orthophosphoric acid) are that 30mmol/L, tetrahydrofuran (THF) are 10ml/L), flow velocity：1.0ml/ minute

Standard curve making standard sample：The TSK standard PEO (weight average molecular weight of TOSOH Co., Ltd's manufacture (Mw) it is about 900,000,150,000,100,000,30,000) and Polymer Laboratories Ltd. manufactures is poly- Ethylene glycol (peak molecular weight (Mp) is about 12,000,4,000,1,000).It is overlapping in order to avoid peak, determine respectively following Two kinds of samples：By 900,000,100,000,12,000,1,000 this 4 kinds samples that mix；And, by 150,000, 30,000th, 4,000 this 3 kinds samples that mix.

[anisotropy of alignment films]

Liquid crystal orientation film evaluation system " the LAYSCAN LABO H " manufactured using MORITEX Corporation (LYS-LH30S-1A) it is measured.The polyimide film irradiation extinction ratio for being 100nm to thickness across polarizer is 10:1 with On the wavelength 254nm through linear polarization ultraviolet, determine gained alignment films for the anisotropic big of differently- oriented directivity It is small.

[making of liquid crystal cells]

Making possesses fringe field switching (Fringe Field Switching：FFS) mode liquid crystal represents the composition of element Liquid crystal cells.

Prepare electroded substrate first.Substrate is the glass substrate that size is 30mm × 50mm and thickness is 0.7mm. On substrate, as the 1st layer, form for constituting counter electrode and possessing the ITO electrode of solid shape pattern.In the 1st layer of pair To on electrode, as the 2nd layer, SiN (silicon nitride) film of the film forming using CVD is formd.It is used as the film of the 2nd layer of SiN film Thickness is 500nm, its function as interlayer dielectric.On the SiN film as the 2nd layer, as the 3rd layer, configure ITO Comb teeth-shaped pixel electrode formed by film figure, so as to form the 1st pixel and the 2nd pixel the two pixels.The chi of each pixel It is very little to be：Vertical 10mm and horizontal about 5mm.Now, the 1st layer of counter electrode and the 3rd layer of pixel electrode are because of the 2nd layer of SiN film Act on and be in electric insulation.

3rd layer of pixel electrode has what " ＜ " shape electrode key element that middle body bends was constituted through multiple arrangements Comb teeth-shaped shape.The width of the width of each electrode key element is 3 μm, between electrode key element at intervals of 6 μm.Form each pixel The multiple arrangements of " ＜ " shape electrode key element that pixel electrode is bent by middle body and constitute, therefore the shape of each pixel is not Oblong-shaped, but possess the shape of " ＜ " similar to runic that bent in the same manner as electrode key element in middle body. Also, each pixel is split up and down using the central bent portion as boundary, with the 1st region on the upside of bent portion and downside 2nd region.

When contrasting the 1st region and 2 region of each pixel, the formation direction of the electrode key element of their pixel electrode is constituted It is different.That is, during using the brushing direction of aftermentioned liquid crystal orientation film as benchmark, in the 1st region of pixel, so that+10 ° of angle is presented The mode of degree (clockwise) forms the electrode key element of pixel electrode, in the 2nd region of pixel, (suitable with the angle for being presented -10 ° Hour hands) mode form the electrode key element of pixel electrode.That is, the 1st region of each pixel is constituted as follows with the 2nd region：By The side for the spinning movement (plane switching) liquid crystal, in real estate for applying voltage between pixel electrode and counter electrode and inducing To opposite direction each other.

Then, what is prepared with after 1.0 μm of filter filtering aligning agent for liquid crystal, being coated on by spin coating is above-mentioned powered The substrate of pole and the back side are formed with ito film and with glass substrate of the height for 4 μm of column spacer.In 80 DEG C of heating plate After upper drying 5 minutes, with 230 DEG C of heated air circulation type baking oven burn till within 20 minutes, form the film that thickness is 100nm.Every It is 10 to coated surface irradiation extinction ratio polarizer:More than 1 ultraviolet for being 254nm through linear polarization and wavelength.Make this Substrate impregnates 3 minutes at least one kind of solvent in water and organic solvent, it is impregnated in pure water 1 minute, Heated 5 minutes on 150 DEG C~300 DEG C of hot plate, obtain the substrate with liquid crystal orientation film.Using above-mentioned two plate base as one group, The printing and sealing agent on substrate, by another plate base by liquid crystal aligning film surface face-to-face and differently- oriented directivity pasted in the way of 0 ° After conjunction, make sealant cures, so as to make dummy cell.By depressurizing injection liquid crystal MLC-7026- in the injection normal direction dummy cell 100 (MERCK CORPORATION systems), seal inlet, obtain FFS driving liquid crystal cells.Thereafter, by gained liquid crystal cells with 110 DEG C are heated 1 hour, are placed after a night, are evaluated for each.

[the after image evaluation caused by long-term exchange driving]

It is mutually isostructural liquid crystal cells to prepare the liquid crystal cells with being used in above-mentioned after image evaluation.

Using the liquid crystal cells, the alternating voltage 120 of the frequency application ± 5V under 60 DEG C of isoperibol with 60Hz is small When.Thereafter, make short-circuit condition is presented between the pixel electrode of liquid crystal cells and counter electrode, directly place one day at room temperature.

After placement, liquid crystal cells are arranged between 2 polarizers configured in the vertical mode of polarization axle, not applied Backlight is lighted in the state of voltage, the arrangement angles of liquid crystal cells are adjusted, so that the brightness of transmitted light reaches minimum.Then, will Liquid crystal cells are made to be rotated from the 2nd region of the 1st pixel most dark angle to anglec of rotation conduct during the most dark angle of the 1st region Angle delta and calculate.Similarly, the 2nd region and the 1st region are compared for 2nd pixel, calculate same angle delta.And And, the average value of the 1st pixel and the angle delta value of the 2nd pixel is calculated as the angle delta of liquid crystal cells, passes through the value Size evaluates liquid crystal aligning.That is, the value of angle △ is smaller, then liquid crystal aligning is better.

[evaluation (contrast) of the bright spot of liquid crystal cells]

Evaluation for carrying out bright spot with the liquid crystal cells that above-mentioned (making of liquid crystal cells) equally make.

Observe liquid crystal cells to carry out by petrographic microscope (ECLIPSE E600WPOL) (NIKON's system).It is specific and Liquid crystal cells are set in speech, crossed nicols (crossed nicols), 5 times of polarized light microscope observing liquid crystal is set to using multiplying power Unit, and the bright spot number having confirmed that is counted, bright spot number is denoted as " good " less than 10, is more than 10 by bright spot number It is denoted as " bad ".

DA-1 1.03g are measured into the 50mL four-neck flasks of subsidiary agitating device and subsidiary nitrogen ingress pipe (4.20mmol), DA-2 0.421g (2.80mmol), DA-3 0.76g (7.00mmol), and NMP 33.60g are added, it is defeated on one side Nitrogen is sent while stirring and dissolving it.While the diamine solution is stirred, while addition 1,3- dimethyl -1,2,3,4- cyclobutane Tetracarboxylic dianhydride 2.95g (13.16mmol), and then add NMP 3.73g in the way of solid component concentration reaches 12 mass %. Thereafter, it is stirred at room temperature 24 hours, so as to obtain polyamic acid solution (A).At 25 DEG C of the temperature of the polyamic acid solution Viscosity is 316mPas.In addition, the molecular weight of the polyamic acid is Mn=13530, Mw=29850.

DA-1 0.95g are measured into the 50mL four-neck flasks of subsidiary agitating device and subsidiary nitrogen ingress pipe (3.90mmol), DA-2 0.98g (6.5mmol), DA-4 0.35g (2.60mmol), and NMP33.15g is added, while conveying Nitrogen is while stirring and dissolving it.While the diamine solution is stirred, while addition 1,3- dimethyl -1,2,3,4- cyclobutane four Carboxylic acid dianhydride 2.74g (12.22mmol), and then add NMP 3.73g in the way of solid component concentration reaches 12 mass %.Its Afterwards, it is stirred at room temperature 24 hours, so as to obtain polyamic acid solution (B).It is viscous at 25 DEG C of the temperature of the polyamic acid solution Spend for 483mPas.In addition, the molecular weight of the polyamic acid is Mn=14260, Mw=30050.

DA-1 1.47g are measured into the 50mL four-neck flasks of subsidiary agitating device and subsidiary nitrogen ingress pipe (6.00mmol), DA-2 0.90g (6.00mmol), and NMP 31.96g, one side supplying nitrogen are added while stirring and making its molten Solution.While the diamine solution is stirred, while addition 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride 2.60g (11.58mmol), and then add NMP 3.55g in the way of solid component concentration reaches 12 mass %.Thereafter, stir at room temperature Mix 24 hours, so as to obtain polyamic acid solution (C).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 423mPas. In addition, the molecular weight of the polyamic acid is Mn=14010, Mw=29540.

DA-1 1.59g are measured into the 50mL four-neck flasks of subsidiary agitating device and subsidiary nitrogen ingress pipe (6.50mmol), DA-3 0.70g (6.50mmol), and NMP 33.01g, one side supplying nitrogen are added while stirring and making its molten Solution.While the diamine solution is stirred, while addition 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride 2.78g (12.42mmol), and then add NMP 3.66g in the way of solid component concentration reaches 12 mass %.Thereafter, stir at room temperature Mix 24 hours, so as to obtain polyamic acid solution (D).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 360mPas. In addition, the molecular weight of the polyamic acid is Mn=13810, Mw=28400.

DA-1 1.03g are measured into the 50mL four-neck flasks of subsidiary agitating device and subsidiary nitrogen ingress pipe (4.20mmol), DA-3 0.76g (7.00mmol), DA-4 0.38g (2.80mmol), and NMP 34.38g are added, it is defeated on one side Nitrogen is sent while stirring and dissolving it.While the diamine solution is stirred, while addition 1,3- dimethyl -1,2,3,4- cyclobutane Tetracarboxylic dianhydride 3.04g (13.58mmol), and then add NMP 3.82g in the way of solid component concentration reaches 12 mass %. Thereafter, it is stirred at room temperature 24 hours, so as to obtain polyamic acid solution (E).At 25 DEG C of the temperature of the polyamic acid solution Viscosity is 428mPas.In addition, the molecular weight of the polyamic acid is Mn=14080, Mw=29960.

DA-2 1.13g are measured into the 50mL four-neck flasks of subsidiary agitating device and subsidiary nitrogen ingress pipe (7.50mmol), DA-3 0.81g (7.50mmol), and NMP 33.87g, one side supplying nitrogen are added while stirring and making its molten Solution.While the diamine solution is stirred, while addition 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride 3.39g (14.85mmol), and then add NMP 3.76g in the way of solid component concentration reaches 12 mass %.Thereafter, stir at room temperature Mix 24 hours, so as to obtain polyamic acid solution (F).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 280mPas. In addition, the molecular weight of the polyamic acid is Mn=12250, Mw=26550.

1,3- dimethyl -1,2,3,4- is measured into the 50mL four-neck flasks of subsidiary agitating device and subsidiary nitrogen ingress pipe Cyclobutane tetracarboxylic dianhydride 3.36g (15.00mmol), and NMP 3.73g, one side supplying nitrogen are added while stirring and making its molten Solution.While the acid dianhydride solution is stirred, while addition DA-3 1.13g (12.68mmol), DA-5 0.81g (1.50mmol), enter And add NMP 7.46g in the way of solid component concentration reaches 10 mass %.Thereafter, it is stirred at room temperature 24 hours, so that Obtain polyamic acid solution (G).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 460mPas.In addition, the polyamide The molecular weight of acid is Mn=15020, Mw=33320.

12 mass % polyamic acid solution (A) 15.00g is measured into 100ml conical flasks, addition NMP9.00g and BCS 6.00g, are mixed 8 hours at 25 DEG C, so as to obtain aligning agent for liquid crystal (1).The aligning agent for liquid crystal does not observe muddy, analysis Go out etc. abnormal, confirm as uniform solution.

In addition to using 12 mass % polyamic acid solution (B) 15.00g, implement similarly to Example 1, so that To aligning agent for liquid crystal (2).The aligning agent for liquid crystal does not observe the exceptions such as muddy, precipitation, confirms as uniform solution.

In addition to using 12 mass % polyamic acid solution (C) 15.00g, implement similarly to Example 1, so that To aligning agent for liquid crystal (3).The aligning agent for liquid crystal does not observe the exceptions such as muddy, precipitation, confirms as uniform solution.

In addition to using 12 mass % polyamic acid solution (D) 15.00g, implement similarly to Example 1, so that To aligning agent for liquid crystal (4).The aligning agent for liquid crystal does not observe the exceptions such as muddy, precipitation, confirms as uniform solution.

In addition to using 12 mass % polyamic acid solution (E) 15.00g, implement similarly to Example 1, so that To aligning agent for liquid crystal (5).The aligning agent for liquid crystal does not observe the exceptions such as muddy, precipitation, confirms as uniform solution.

In addition to using 12 mass % polyamic acid solution (F) 15.00g, implement similarly to Example 1, so that To aligning agent for liquid crystal (6).The aligning agent for liquid crystal does not observe the exceptions such as muddy, precipitation, confirms as uniform solution.

In addition to using 12 mass % polyamic acid solution (G) 15.00g, implement similarly to Example 1, so that To aligning agent for liquid crystal (7).The aligning agent for liquid crystal does not observe the exceptions such as muddy, precipitation, confirms as uniform solution.

(embodiment 5)

After above-mentioned aligning agent for liquid crystal (1) is filtered with 1.0 μm of filter, the ITO bases of rotary coating to 30mm × 40mm On plate.After making it dry 2 minutes on 80 DEG C of hot plate, with 230 DEG C of heated air circulation type baking oven burn till within 14 minutes, so that Form the film that thickness is 100nm.It is 26 to coated surface irradiation extinction ratio across polarizer:1 wavelength through linear polarization For 254nm ultraviolet, so as to obtain liquid crystal orientation film.

Determine the anisotropic height for differently- oriented directivity of gained liquid crystal orientation film.Above-mentioned ultraviolet irradiation amount is 200mJ/cm²When anisotropy value be 3.39, be 300mJ/cm²When anisotropy value be 4.10, be 400mJ/cm²When Anisotropy value is 3.26.Above-mentioned ultraviolet irradiation amount when anisotropy is changed into highest is 300mJ/cm², it is set at light orientation Optimal irradiation condition under reason.

(embodiment 6)

In addition to using above-mentioned aligning agent for liquid crystal (2), implement to obtain liquid crystal orientation film similarly to Example 5.Determine The anisotropic size for differently- oriented directivity of gained liquid crystal orientation film.Above-mentioned ultraviolet irradiation amount is 50mJ/cm²When Anisotropy value is 0.05, is 100mJ/cm²When anisotropy value be 0.61, be 200mJ/cm²When anisotropy value be 0.06.Above-mentioned ultraviolet irradiation amount when anisotropy is changed into highest is 100mJ/cm², it is set to the optimal photograph under light orientation processing Penetrate condition.

(embodiment 7)

In addition to using above-mentioned aligning agent for liquid crystal (3), implement to obtain liquid crystal orientation film similarly to Example 5.Determine The anisotropic size for differently- oriented directivity of gained liquid crystal orientation film.Above-mentioned ultraviolet irradiation amount is 50mJ/cm²When Anisotropy value is 0.10, is 100mJ/cm²When anisotropy value be 0.92, be 200mJ/cm²When anisotropy value be 0.15.Above-mentioned ultraviolet irradiation amount when anisotropy is changed into highest is 100mJ/cm², it is set to the optimal photograph under light orientation processing Penetrate condition.

(comparative example 5)

In addition to using above-mentioned aligning agent for liquid crystal (4), implement to obtain liquid crystal orientation film similarly to Example 5.Determine The anisotropic size for differently- oriented directivity of gained liquid crystal orientation film.Above-mentioned ultraviolet irradiation amount is 100mJ/cm²When Anisotropy value be 3.02, be 200mJ/cm²When anisotropy value be 5.37, be 300mJ/cm²When anisotropy value be 3.40.Above-mentioned ultraviolet irradiation amount when anisotropy is changed into highest is 200mJ/cm², it is set to the optimal photograph under light orientation processing Penetrate condition.

(comparative example 6)

In addition to using above-mentioned aligning agent for liquid crystal (5), implement to obtain liquid crystal orientation film similarly to Example 5.Determine The anisotropic size for differently- oriented directivity of gained liquid crystal orientation film.Above-mentioned ultraviolet irradiation amount is 200mJ/cm²When Anisotropy value be 4.28, be 300mJ/cm²When anisotropy value be 4.57, be 400mJ/cm²When anisotropy value be 3.03.Above-mentioned ultraviolet irradiation amount when anisotropy is changed into highest is 300mJ/cm², it is set to the optimal photograph under light orientation processing Penetrate condition.

(comparative example 7)

In addition to using above-mentioned aligning agent for liquid crystal (6), implement to obtain liquid crystal orientation film similarly to Example 5.Determine The anisotropic size for differently- oriented directivity of gained liquid crystal orientation film.Above-mentioned ultraviolet irradiation amount is 300mJ/cm²When Anisotropy value be 0.54, be 400mJ/cm²When anisotropy value be 0.65, be 500mJ/cm²When anisotropy value be 0.60.Above-mentioned ultraviolet irradiation amount when anisotropy is changed into highest is 400mJ/cm², it is set to the optimal photograph under light orientation processing Penetrate condition.

(comparative example 8)

In addition to using above-mentioned aligning agent for liquid crystal (7), implement to obtain liquid crystal orientation film similarly to Example 5.Determine The anisotropic size for differently- oriented directivity of gained liquid crystal orientation film.Above-mentioned ultraviolet irradiation amount is 400mJ/cm²When Anisotropy value be 1.61, be 600mJ/cm²When anisotropy value be 1.71, be 800mJ/cm²When anisotropy value be 1.59.Above-mentioned ultraviolet irradiation amount when anisotropy is changed into highest is 600mJ/cm², it is set to the optimal photograph under light orientation processing Penetrate condition.

By the anisotropy for differently- oriented directivity of the liquid crystal orientation film obtained by embodiment 5~7 and comparative example 5~8 Size measurement result summarize be shown in table 1.

[table 1]

(embodiment 8)

By above-mentioned aligning agent for liquid crystal (1) with after 1.0 μm of filter filtering, it is coated on what is prepared by rotary coating Above-mentioned attached electroded substrate and back side film forming have ito film and with the glass substrate highly for 4 μm of column spacer.Make After it is dried 5 minutes on 80 DEG C of hot plate, with 230 DEG C of heated air circulation type baking oven burn till within 20 minutes, so as to form film Thickness is 100nm film.It is 26 to coated surface irradiation extinction ratio across polarizer:1 wavelength through linear polarization is 254nm Ultraviolet 0.3J/cm².Thereafter, heated 14 minutes on 230 DEG C of hot plate, so as to obtain the substrate of subsidiary liquid crystal orientation film. Using above-mentioned 2 plate base as one group, the printing and sealing agent on substrate, with liquid crystal aligning film surface face-to-face and differently- oriented directivity reaches 0 ° Mode paste after another 1 plate base, make sealant cures to make dummy cell.Injected by depressurizing in the injection normal direction dummy cell Liquid crystal MLC-7026-100 (MERCK CORPORATION systems), seals inlet, obtains FFS driving liquid crystal cells.Thereafter, will After gained liquid crystal cells are heated 1 hour at 110 DEG C, place a night, and implement the after image evaluation caused by long-term exchange driving. The angle delta value of the liquid crystal cells after long-term exchange driving is 0.04 degree.In addition, the bright spot observation in unit is carried out, it is as a result bright Point number is less than 10, is good.

(embodiment 9)

It is 100nm using method formation thickness same as Example 8 in addition to using above-mentioned aligning agent for liquid crystal (2) Film.It is 26 to coated surface irradiation extinction ratio across polarizer:1 wavelength through linear polarization is 254nm ultraviolet 0.1J/cm²Afterwards, heated 14 minutes on 230 DEG C of hot plate, so as to obtain the substrate of subsidiary liquid crystal orientation film.Should except using Outside the substrate of subsidiary liquid crystal orientation film, FFS driving liquid crystal cells are made using method same as Example 8, for gained Unit implements the after image evaluation caused by long-term exchange driving.The angle delta value of the liquid crystal cells after long-term exchange driving is 0.10 degree.In addition, carrying out the bright spot observation in unit, as a result bright spot number is less than 10, is good.

(embodiment 10)

Irradiate after polarized UV rays, it is impregnated in 2- propyl alcohol 3 minutes, then, impregnated 1 minute in pure water, except this Outside, make FFS driving liquid crystal cells using method same as Example 9.For the FFS drive liquid crystal cells, implement by After image evaluation caused by long-term exchange driving.The angle delta value of the liquid crystal cells after long-term exchange driving is 0.08 degree.In addition, The bright spot observation in unit is carried out, as a result bright spot number is less than 10, is good.

(embodiment 11)

It is 100nm using method formation thickness same as Example 8 in addition to using above-mentioned aligning agent for liquid crystal (3) Film.It is 26 to coated surface irradiation extinction ratio across polarizer:1 wavelength through linear polarization is 254nm ultraviolet 0.1J/cm²Afterwards, it is impregnated in 2- propyl alcohol 3 minutes, then, impregnated 1 minute in pure water.Thereafter, in 230 DEG C of hot plate Upper heating 14 minutes, obtains the substrate of subsidiary liquid crystal orientation film.In addition to using the substrate of the subsidiary liquid crystal orientation film, utilize Method same as Example 8 makes FFS driving liquid crystal cells, implements remaining caused by long-term exchange driving for gained unit As evaluating.The angle delta value of the liquid crystal cells after long-term exchange driving is 0.08 degree.In addition, the bright spot carried out in unit is seen Examine, as a result bright spot number is less than 10, is good.

(comparative example 9)

It is 100nm using method formation thickness same as Example 8 in addition to using above-mentioned aligning agent for liquid crystal (4) Film.It is 26 to coated surface irradiation extinction ratio across polarizer:1 wavelength through linear polarization is 254nm ultraviolet 0.2J/cm².Thereafter, heated 14 minutes on 230 DEG C of hot plate, so as to obtain the substrate of subsidiary liquid crystal orientation film.Except using Outside the substrate of the subsidiary liquid crystal orientation film, FFS driving liquid crystal cells are made using method same as Example 8, for institute Unit is obtained to implement by the long-term caused after image evaluation of exchange driving.The angle delta value of the liquid crystal cells after long-term exchange driving is 0.15 degree.In addition, carrying out the bright spot observation in unit, as a result bright spot number is more than 10, is bad.

(comparative example 10)

It is 100nm using method formation thickness same as Example 8 in addition to using above-mentioned aligning agent for liquid crystal (5) Film.It is 26 to coated surface irradiation extinction ratio across polarizer:1 wavelength through linear polarization is 254nm ultraviolet 0.3J/cm².Thereafter, heated 14 minutes on 230 DEG C of hot plate, so as to obtain the substrate of subsidiary liquid crystal orientation film.Except using Outside the substrate of the subsidiary liquid crystal orientation film, FFS driving liquid crystal cells are made using method same as Example 8, for institute Unit is obtained to implement by the long-term caused after image evaluation of exchange driving.The angle delta value of the liquid crystal cells after long-term exchange driving is 0.20 degree.In addition, carrying out the bright spot observation in unit, as a result bright spot number is more than 10, is bad.

(comparative example 11)

It is 100nm using method formation thickness same as Example 8 in addition to using above-mentioned aligning agent for liquid crystal (6) Film.It is 26 to coated surface irradiation extinction ratio across polarizer:1 wavelength through linear polarization is 254nm ultraviolet 0.4J/cm².Thereafter, heated 14 minutes on 230 DEG C of hot plate, so as to obtain the substrate of subsidiary liquid crystal orientation film.Except using Outside the substrate of the subsidiary liquid crystal orientation film, FFS driving liquid crystal cells are made using method same as Example 8, for institute Unit is obtained to implement by the long-term caused after image evaluation of exchange driving.The angle delta value of the liquid crystal cells after long-term exchange driving is 0.20 degree.In addition, carrying out the bright spot observation in unit, as a result bright spot number is more than 10, is bad.

(comparative example 12)

It is 100nm using method formation thickness same as Example 8 in addition to using above-mentioned aligning agent for liquid crystal (7) Film.It is 26 to coated surface irradiation extinction ratio across polarizer:1 wavelength through linear polarization is 254nm ultraviolet 0.6J/cm².Thereafter, heated 14 minutes on 230 DEG C of hot plate, so as to obtain the substrate of subsidiary liquid crystal orientation film.Except using Outside the substrate of the subsidiary liquid crystal orientation film, FFS driving liquid crystal cells are made using method same as Example 8, for institute Unit is obtained to implement by the long-term caused after image evaluation of exchange driving.The angle delta value of the liquid crystal cells after long-term exchange driving is 0.24 degree.In addition, carrying out the bright spot observation in unit, as a result bright spot number is more than 10, is bad.

[table 2]

	Bright spot is evaluated	After image evaluates (orientation)
			Embodiment 8	Well	0.04°
Embodiment 9	Well	0.10°
			Embodiment 10	Well	0.08°
Embodiment 11	Well	0.12°
			Comparative example 9	It is bad	0.15°
Comparative example 10	Well	0.20°
			Comparative example 11	Well	0.20°
Comparative example 12	It is bad	0.24°

Industrial applicability

The liquid crystal orientation film obtained by aligning agent for liquid crystal of the present invention makes the bright spot for spending the principal element of reduction as a comparison few, And the liquid crystal that can be reduced in IPS type of drive, FFS type of drive represent to produce in element it is remaining caused by exchange driving Picture, can obtain the excellent IPS type of drive of after image characteristic, the liquid crystal of FFS type of drive and represent element.

Liquid crystal with liquid crystal orientation film of the present invention represents the of excellent in reliability of element, can be widely used for big picture, high definition Liquid crystal TV set, middle-size and small-size auto-navigation system, smart mobile phone clear and that pursue high expression quality etc..

It should illustrate, by the specification of Japanese patent application filed in 28 days October in 2014 2014-219597, right The full content of claim and summary is quoted so far, is used as the disclosure of description of the invention.

Claims

1. a kind of aligning agent for liquid crystal, it is characterised in that it contains selected from by polyimide precursor and the acyl of the polyimide precursor At least one kind of polymer (A) in the group of imines fluidized polymer composition, the polyimide precursor has shown in following formula (1) Construction unit shown in construction unit and following formula (2),

In formula (1), formula (2), X₁And X₂It is each independently the group selected from the structure composition as shown in following formula (X1-1) and (X1-2) In it is at least one kind of；R₁、R₂、R₃、R₄And R₆It is each independently the alkyl of hydrogen atom or carbon number 1~4；R₅For carbon number 1 ~4 alkyl；N is 1~6 integer,

2. aligning agent for liquid crystal according to claim 1, wherein, the content ratio phase of the construction unit shown in above-mentioned formula (1) 1 mole of the entire infrastructure unit for above-mentioned polymer (A) is 10~50 moles of %, also, the structure list shown in above-mentioned formula (2) The content ratio of member is 20~90 moles of % relative to 1 mole of the entire infrastructure unit of above-mentioned polymer (A).

3. aligning agent for liquid crystal according to claim 1 or 2, wherein, construction unit and following formula (2) institute shown in formula (1) The construction unit shown is optionally present in same polyimide precursor, or the construction unit shown in formula (1) and following formula (2) institute The construction unit shown is optionally present in different polyimide precursors.

4. according to aligning agent for liquid crystal according to any one of claims 1 to 3, wherein, in above-mentioned formula (1) and (2), X₁And X₂ For the formula (X1-2).

5. according to aligning agent for liquid crystal according to any one of claims 1 to 4, wherein, in formula (1) and formula (2), R₁And R₂For The alkyl of carbon number 1~3, R₃、R₄、R₅And R₆For hydrogen atom, n is 1~3 integer.

6. according to aligning agent for liquid crystal according to any one of claims 1 to 5, it contains 2~10 mass % polymer (A).

7. according to aligning agent for liquid crystal according to any one of claims 1 to 6, it is used for light orientation.

8. a kind of manufacture method of liquid crystal orientation film, wherein, to being coated with liquid crystal aligning according to any one of claims 1 to 7 Agent and film irradiation polarized UV rays obtained from burning till.

9. liquid crystal orientation film according to claim 7, wherein, polarized UV rays have 100~800nm wavelength.

10. a kind of liquid crystal represents element, it has the liquid crystal orientation film described in claim 8 or 9.

11. liquid crystal according to claim 10 represents element, wherein, liquid crystal is negative type liquid crystal material.