CN106047374A

CN106047374A - Liquid crystal aligning agent, liquid crystal aligning film, manufacturing method for liquid crystal aligning film, and liquid crystal element

Info

Publication number: CN106047374A
Application number: CN201610164665.5A
Authority: CN
Inventors: 菅野尚基; 秋池利之; 冈田敬; 加藤孝人
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2015-04-16
Filing date: 2016-03-22
Publication date: 2016-10-26
Anticipated expiration: 2036-03-22
Also published as: CN106047374B; TW201638216A; KR102454060B1; JP2016206645A; TWI698490B; JP6672821B2; KR20160123991A

Abstract

The invention provides a liquid crystal aligning agent which is not liable to swell a printing plate and is good in printing performance, a liquid crystal aligning film, a manufacturing method for the liquid crystal aligning film, and a liquid crystal element. The liquid crystal aligning agent contains polymer (A) selected from at least one of the group formed by polyamide acid, polyamide acid ester, polyimide and polysiloxane; a first solvent which is selected from at least one of a group formed by compounds represented by formulas (1)-(4); and a second solvent, the surface tension of which is less than 30dyn/cm. R1 and R2 are respectively a methyl or ethyl.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and manufacture method thereof and liquid crystal cell

Technical field

The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film and manufacture method thereof and liquid crystal cell.

Background technology

In the past, the different multiple type of drive such as electrode structure or the physical property of liquid crystal molecule that used developed by liquid crystal cell, such as Known twisted nematic (Twisted Nematic, TN) type or STN Super TN (Super Twisted Nematic, STN) type, Vertical orientated (Vertical Alignment, VA) type, coplanar switch type (IPS (In-Plane Switching) type), edge Field switching (Fringe Field Switching, FFS) type, optical-compensation bent (OCB (Optical Compensated Bend) Type) etc. various liquid crystal cells.These liquid crystal cells have to make the liquid crystal orientation film of liquid crystal molecular orientation.With regard to thermostability, machine For the aspect that the various characteristics such as the affinity of tool intensity and liquid crystal are good, the materials'use polyamic acid of liquid crystal orientation film or polyamides Imines etc..

About aligning agent for liquid crystal, make component of polymer be dissolved in solvent, aligning agent for liquid crystal coated substrate and heats, It is consequently formed liquid crystal orientation film.Herein, the solvent of aligning agent for liquid crystal generally uses the organic solvent that the dissolubility of polymer is high, The such as aprotic polar such as METHYLPYRROLIDONE or gamma-butyrolacton solvent.It addition, in order to make to be coated with aligning agent for liquid crystal The coating (printing) of aligning agent for liquid crystal when being distributed in substrate is good, and molten with such as butyl with aprotic polar solvent The surface tension such as fine agent are than relatively low organic solvent (referring for example to patent documentation 1 or patent documentation 2).

As the method that aligning agent for liquid crystal is coated substrate, application spin-coating method or the multiple method such as flexographic printing process, ink-jet method. Such as flexographic printing process generally uses following hectographic printing device to carry out, and aligning agent for liquid crystal is coated with by described hectographic printing device In comprising the galley of the resins such as APR (registered trade mark), and utilize galley that aligning agent for liquid crystal is transferred to (example on substrate As with reference to patent documentation 3).

[prior art literature]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 2010-97188 publication

[patent documentation 2] Japanese Patent Laid-Open 2010-156934 publication

[patent documentation 3] Japanese Patent Laid-Open 2001-343649 publication

Summary of the invention

[problem that invention to be solved]

Using the coating improving aligning agent for liquid crystal, as purpose, the existence of normally used butyl cellosolve easily makes APR resin swelling Tendency.Therefore, in the case of utilizing hectographic printing that the aligning agent for liquid crystal comprising butyl cellosolve is coated substrate, have because of weight Multiple carry out the coating to galley and galley swelling, the worry that thus printing reduces.It addition, as the solvent of aligning agent for liquid crystal Composition, it is desirable to even if being not easy to separate out to printer thus printing (continuous printing being carried out continuously polymer in the case of printing Property) good.

The present invention is in view of described problem forms, and one of purpose is difficult to make galley swelling and the good liquid crystal of printing for providing a kind of Alignment agent.

[solving the means of problem]

The present inventor et al. has carried out positive research to realize the problem of prior art as above, it was found that pass through group Close and use specific organic solvent to can solve the problem that described problem as solvent, thus complete the present invention.Specifically, by the present invention Following aligning agent for liquid crystal, liquid crystal orientation film and manufacture method thereof and liquid crystal cell are provided.

On the one hand the present invention's is wherein to provide a kind of aligning agent for liquid crystal, and it contains: polymer (A), select free polyamic acid, At least one in the group that poly amic acid ester, polyimides and polysiloxane are formed；1st solvent, selects free following formula (1) compound represented by the compound represented by, the compound represented by following formula (2), following formula (3) and following formula (4) at least one in the group that the compound represented by is formed；And the 2nd solvent, surface tension is less than 30dyn/cm.

[changing 1]

(in formula (4), R¹And R²It is separately methyl or ethyl)

By the mixed solvent comprising described 1st solvent and described 2nd solvent being used as the solvent composition of aligning agent for liquid crystal, can obtain Galley is difficult to the aligning agent for liquid crystal of swelling.Even if it addition, polymer is not easy to separate out to printing in the case of being carried out continuously printing On machine, and printing can be made good.

Described 2nd solvent preferably select the compound represented by the compound represented by free following formula (5), following formula (6), At least one in the group that compound represented by following formula (7) and the compound represented by following formula (8) are formed.Pass through By these compounds at least one be used as the 2nd solvent, can the suppression of the swelling of galley and continuous printing aspect obtain more High improvement effect.

[changing 2]

(in formula (5), R⁵And R⁷It is separately the alkyl of the monovalence of carbon number 1～3, R⁶Alkane diyl for carbon number 2～5)

[changing 3]

R⁸-O-R⁸ (6)

(in formula (6), R⁸There is between the carbon-carbon bond for the straight-chain of carbon number 3～5 or the alkyl of branch-like the monovalence of "-O-" The base of monovalence that replaces through hydroxyl of at least one hydrogen atom of alkyl of base, the straight-chain of carbon number 3～5 or branch-like or The alkyl of the branch-like of carbon number 3～5)

[changing 4]

(in formula (7), X¹For-C (OH) R^a-(wherein, R^aAlkyl for carbon number 1 or 2) ,-CO-or-COO-* (wherein, * represent and R⁹Associative key), R⁹Alkyl for carbon number 1～4)

[changing 5]

R³-O-R⁴-OH (8)

(in formula (8), R³For the alkyl of carbon number 1～6, R⁴Alkane diyl for carbon number 2～4)

A kind of liquid crystal orientation film formed by described aligning agent for liquid crystal of offer is provided.It addition, another aspect is for carrying For the manufacture method of a kind of liquid crystal orientation film, comprising: described aligning agent for liquid crystal is coated formed on substrate film step, And described film is carried out light irradiation and makes the step of liquid crystal orientation film.It addition, in turn on the one hand for provide one possess by The liquid crystal cell of the liquid crystal orientation film that described aligning agent for liquid crystal is formed.

The liquid crystal orientation film of the present invention is to use described aligning agent for liquid crystal to be formed, and therefore can form uniform film and film quality is good. It addition, in the case of using described aligning agent for liquid crystal to manufacture liquid crystal cell, can reduce printing in a manufacturing process bad, result can The yield realizing product improves.

Detailed description of the invention

Hereinafter, each composition contained in the aligning agent for liquid crystal of the present invention and other compositions of optionally and arbitrarily allocating are illustrated.

Additionally, in this manual, so-called " alkyl " refers to comprise chain alkyl, ester ring type alkyl and the implication of aromatic hydrocarbyl. So-called " chain alkyl " refers to without circulus on main chain, but the straight-chain alkyl being only made up of chain structure and branch-like hydrocarbon Base.Wherein it is possible to be saturated, it is also possible to be unsaturated.So-called " ester ring type alkyl ", refers to that the structure only comprising ester ring type hydrocarbon is made The alkyl of aromatic ring structure is not contained for ring structure.Wherein, it is not necessary to be only made up of the structure of ester ring type hydrocarbon, it is also comprised A part has the alkyl of chain structure.So-called " aromatic hydrocarbyl ", refers to the alkyl comprising aromatic ring structure as ring structure. Wherein, it is not necessary to be only made up of aromatic ring structure, it is also possible in one part, comprise chain structure or the structure of ester ring type hydrocarbon. So-called " organic group ", refers to comprise the base of carbon atom, it is also possible to comprise hetero atom in the structure.

The aligning agent for liquid crystal of the present invention contains the free polyamic acid of choosing, poly amic acid ester, polyimides and polysiloxane and is formed Group in the polymer of at least one (A).

[polyamic acid]

Polyamic acid in the present invention such as can obtain by making tetracarboxylic dianhydride react with diamidogen.

(tetracarboxylic dianhydride)

Tetracarboxylic dianhydride for the synthesis of polyamic acid include, for example: aliphatic tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, Aromatic tetracarboxylic acid's dianhydride etc..As the concrete example of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydride include, for example 1,2,3,4- Butane tetracarboxylic acid dianhydride etc.；

Ester ring type tetracarboxylic dianhydride include, for example: 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-Tetramethylene. tetracarboxylic acids Acid dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho- [1,2-c] furan-1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furan -1,3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-volution-3 '-(oxolane-2 ', 5 '-diketone), 5-(2,5-dioxotetrahydro -3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tri-carboxyl-2-carboxymethyl group norbornane-2:3,5:6-dianhydride, double Ring [3.3.0] octane-2,4,6,8-tetrabasic carboxylic acid 2:4,6:8-dianhydride, 4,9-dioxa three ring [5.3.1.0^2,6] hendecane-3,5,8,10-tetrones, ring Hexane tetracarboxylic dianhydride etc.；

Aromatic tetracarboxylic acid's dianhydride include, for example pyromellitic acid anhydride etc.；In addition, it be also possible to use Japanese Patent Laid-Open Tetracarboxylic dianhydride described in 2010-97188 publication.Additionally, tetracarboxylic dianhydride can be used alone one or be applied in combination two kinds with On.

Just can make the good aspect of electrical characteristics and can further improve polymer phase for comprising following 1st solvent and the 2nd solvent Solvent deliquescent aspect for, the tetracarboxylic dianhydride used in synthesis preferably comprises ester ring type tetracarboxylic dianhydride.Separately Outward, in ester ring type tetracarboxylic dianhydride, preferably comprise choosing freely 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides, 1,3,3a, 4,5,9b- Hexahydro-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furan-1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydrochysenes -2,5-dioxo-3-furyl)-naphtho-[1,2-c] furan-1,3-diketone, dicyclo [3.3.0] octane-2,4,6,8-tetrabasic carboxylic acid 2:4,6:8-dianhydride, 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride and 1,3-dimethyl-1, at least in the group that 2,3,4-Tetramethylene. tetracarboxylic dianhydrides are formed Kind, particularly preferably comprise choosing freely 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides, dicyclo [3.3.0] octane-2,4,6,8-tetrabasic carboxylic acids 2:4,6:8-dianhydride, 1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides and 1,3-dimethyl-1, the group that 2,3,4-Tetramethylene. tetracarboxylic dianhydrides are formed In at least one.

Comprising choosing freely 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides, dicyclo [3.3.0] octane-2,4,6,8-tetrabasic carboxylic acid 2:4,6:8-dianhydride, 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride and 1,3-dimethyl-1, at least one in the group that 2,3,4-Tetramethylene. tetracarboxylic dianhydrides are formed In the case of tetracarboxylic dianhydride, the total amount of the tetracarboxylic dianhydride used in the synthesis relative to polyamic acid, these compounds Preferably 10 moles more than % of total content, more preferably 20 moles %～100 moles of %.

(diamidogen)

Diamidogen used in the synthesis of polyamic acid include, for example: aliphatic diamine, ester ring type diamidogen, aromatic diamine, two Amido organosilicon oxygen alkane etc..As the concrete example of these diamidogen, aliphatic diamine include, for example: m-xylene diamine, 1,3-the third two Amine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine, 1, double (amino methyl) hexamethylene of 3-etc.；

Ester ring type diamidogen include, for example Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine) etc.；

Aromatic diamine include, for example: p-phenylenediamine, N-[4-(2-amino-ethyl) phenyl] benzene-Isosorbide-5-Nitrae-diamidogen, N-[4-(amino methyl) Phenyl] benzene-Isosorbide-5-Nitrae-diamidogen, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl -4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 4，4′-diaminodipohenyl ether, 1,3-double (4-amino-benzene oxygen) Propane, 9, double (4-aminophenyl) fluorenes of 9-, 2, double [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, double (4-aminophenyl) hexafluoro of 2- Propane, 4,4 '-(to phenylenediisopropylidene) dianils, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, DAP, 3,6-diamino Base carbazole, N, N '-bis-(4-aminophenyl)-benzidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3- Trimethyl-1H-indenes-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indenes-6-amine, 3,5-diaminobenzoic acid, gallbladder Steroid alkyl oxy-3,5-diaminobenzene, cholesteryl epoxide-3,5-diaminobenzene, cholesteric alkyl oxy-2,4-diaminobenzene, 3,5-bis- Amino benzoic Acid cholesteric Arrcostab, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, 3,6- Double (4-amino benzoyl epoxide) cholestane, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 1,1- Double (4-((aminophenyl) methyl) phenyl)-4-heptylcyclohexane, 1, double (4-((aminophenyl) methyl) the phenyl)-4-(4-heptyl cyclohexyl) of 1- Hexamethylene, 2,4-diamino-N, N-diallyl aniline, 4-aminobenzyl amine and following formula (D-1)

[changing 6]

(in formula (D-1), X^IAnd X^IIBe separately singly-bound ,-O-, *-COO-, *-OCO-or *-NH-CO-(wherein, Associative key and diamino-phenyl bond with " * "), R^IAnd R^IIBeing separately the alkane diyl of carbon number 1～3, a is 0 or 1, B is the integer of 0～2, and c is the integer of 1～20, and n is 0 or 1, and m is 0 or 1；Wherein, it is 0 during a and b difference, X^IIn the case of *-NH-CO-, n is 0)

Represented compound etc.；

Diaminourea organosiloxane include, for example 1, double (3-aminopropyl)-tetramethyl disiloxanes of 3-etc.；In addition, also can make With the diamidogen described in Japanese Patent Laid-Open 2010-97188 publication.Additionally, these diamidogen can be used alone, one or combination make With two or more.

The concrete example of the compound represented by described formula (D-1) include, for example following formula (D-1-1)～formula (D-1-4) difference Represented compound etc..

[changing 7]

Diamidogen for the synthesis of polyamic acid preferably comprises the aromatic diamine of 30 moles of more than % relative to whole diamidogen, More preferably comprise 50 moles of more than %, particularly preferably comprise 80 moles of more than %.

In the case of by give liquid crystal aligning ability to film to the film irradiation light formed by aligning agent for liquid crystal, can will be polymerized Part or all of thing (A) is set to the polymer with light orientation structure.Herein, so-called light orientation structure, refer to bag Concept containing both light orientation base and breakdown type light orientation section.Light orientation structure specifically can use by by photoisomerization or Photodimerization, photolysis etc. and the structure that shows the multiple compounds of light orientation and come, include, for example: containing diphenyl diimide or Its derivant as basic framework the base containing diphenyl diimide, containing cinnamic acid or derivatives thereof as basic framework containing cinnamic acid structure Base, containing chalcone (chalcone) or derivatives thereof as basic framework the base containing chalcone, containing benzophenone or its Derivant as basic framework the base containing benzophenone, containing coumarin or derivatives thereof as basic framework containing coumarin Base, containing Tetramethylene. or derivatives thereof as the structure containing Tetramethylene. of basic framework, containing dicyclo [2.2.2] octene or derivatives thereof As the structure containing dicyclo [2.2.2] octene of basic framework, containing following formula (b)

[changing 8]

(in formula (b), X²For sulphur atom or oxygen atom；" * " represents associative key respectively；Wherein, at least one in two " * " It is binding on aromatic rings)

Represented part-structure is as the structure etc. of basic framework.

The polyamic acid as polymer (A) have light orientation base as light orientation structure in the case of, just there is height and take For the aspect of ability, preferably there is the polymer of cinnamic acid structure.This polyamic acid can be by such as by following formula (R1) diamidogen with cinnamic acid structure～represented by formula (R7) is used as raw material to carry out being polymerized obtaining.

[changing 9]

(in formula (R1)～formula (R5), R¹For alkyl or the fluoroalkyl of carbon number 3～12 of carbon number 3～12, a is 1～6 Integer)

The polyamic acid as polymer (A) have breakdown type light orientation section as light orientation structure in the case of, described poly- The preferred concrete example of compound (A) include, for example: has the polymer of dicyclo [2.2.2] octene skeleton, have Tetramethylene. skeleton Polymer, there is the polymer of part-structure come by the compound represented by following formula (c) and there is on main chain institute State the polymer etc. of structure represented by formula (b).

[changing 10]

(in formula (c), A¹For singly-bound or the organic group of bivalence, B¹Organic group for bivalence；R¹⁰For substituent group, n1 is 0～4 Integer)

The polyamic acid with breakdown type light orientation section such as can utilize following methods etc. when tetracarboxylic dianhydride is with the reaction of diamidogen Obtain: [1] by Tetramethylene. tetracarboxylic dianhydride, dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydrides or there is described formula (b) institute The tetracarboxylic dianhydride of the structure represented is used as at least one of method of the tetracarboxylic dianhydride used in reaction；[2] by described formula Diamidogen represented by (c) or there is the diamidogen of the structure represented by described formula (b) be used as at least one of the diamidogen used in reaction The method of part.

When synthesis has the polyamic acid of light orientation structure, for photoreactive viewpoint, relative to the synthesis of polyamic acid Used in tetracarboxylic dianhydride and the total amount of diamidogen, the use ratio of the monomer with light orientation structure is preferably set to 20 moles of more than %, preferred are set to 30 moles of %～80 moles of %.

(synthesis of polyamic acid)

Polyamic acid can by making tetracarboxylic dianhydride as above and diamidogen optionally carry out reacting together with molecular weight regulator and Obtain.It is supplied to the tetracarboxylic dianhydride of the synthetic reaction of polyamic acid and the use ratio of diamidogen preferably relative to the amino of diamidogen 1 equivalent, the anhydride group of tetracarboxylic dianhydride becomes 0.2 equivalent～the ratio of 2 equivalents.Molecular weight regulator include, for example: along fourth The single acid anhydride of the acid such as enedioic acid acid anhydride, phthalic anhydride, itaconic anhydride；The monoamine compounds such as aniline, cyclo-hexylamine, n-butylamine；Different The monoisocyanate compound such as phenyl-cyanate, naphthyl isocyanate etc..Relative to the tetracarboxylic dianhydride used and the total of diamidogen 100 weight portions, the use ratio of molecular weight regulator is preferably set to below 20 weight portions.

The synthetic reaction of polyamic acid is preferably carried out in organic solvent.Reaction temperature now preferably-20 DEG C～ 150 DEG C, preferably 0.1 hour～24 hours response time.

Organic solvent used in reaction include, for example: aprotic polar solvent, phenol system solvent, alcohol, ketone, ester, ether, Halogenated hydrocarbon, hydrocarbon etc..Particularly preferred organic solvent is preferably with represented by choosing freely described formula (1)～formula (4) difference Compound, METHYLPYRROLIDONE, N,N-dimethylacetamide, DMF, dimethyl sulfoxide, gamma-butyrolacton, More than one in the group that tetramethylurea, HMPA, metacresol, xylenol and halogenation phenol are formed as solvent, Or use more than one of these solvents with other organic solvents (such as butyl cellosolve, diethylene glycol in the range of described ratio Diethyl ether etc.) mixture.The usage amount (a) of organic solvent is preferably set to the total amount (b) of tetracarboxylic dianhydride and diamidogen 0.1 weight %～the amount of 50 weight % is become relative to the total amount (a+b) of reaction solution.

Obtain the reaction solution dissolved by polyamic acid in the manner.Described reaction solution can be supplied directly to liquid crystal The preparation of alignment agent, it is also possible to be available to the preparation of aligning agent for liquid crystal after being separated by polyamic acid contained in reaction solution.

[polyimides]

Polyimides in the present invention such as can be by carrying out dehydration closed-loop and imidizate to the polyamic acid synthesized in this way Obtain.Polyimides can be that the amic acid structure with the polyamic acid as its precursor all carries out dehydration closed-loop and forms Complete acid imide compound, it is also possible to be only a part for amic acid structure to be carried out dehydration closed-loop and make amic acid structure and acid imide Ring structure the part acid imide compound deposited.The acid imide rate preferably more than 30% of the polyimides in the present invention, more preferably Be 40%～99%, and then preferably 50%～99%.Described acid imide rate is the amic acid structure relative to polyimides The total of quantity of quantity and imide ring structure, represent the ratio shared by the quantity of imide ring structure with percentage rate.Herein, A part for imide ring can also be different imide ring.

The dehydration closed-loop of polyamic acid is carried out preferably with following methods: the method heating polyamic acid；Maybe will be poly- Amic acid is dissolved in organic solvent, adds dehydrant and dehydration closed-loop catalyst and optionally carry out the side heated in described solution Method.Wherein it is preferred that the method utilizing the latter.

The solution of polyamic acid adds in the method for dehydrant and dehydration closed-loop catalyst, dehydrant such as can use acetic anhydride, The anhydride such as propionic andydride, trifluoroacetic anhydride.Relative to 1 mole of the amic acid structure of polyamic acid, the usage amount of dehydrant is preferred It is set to 0.01 mole～20 moles.Dehydration closed-loop catalyst such as can use pyridine, collidine, two picolins, triethyl group The tertiary amines such as amine.Relative to the dehydrant used 1 mole, the usage amount of dehydration closed-loop catalyst is preferably set to 0.01 and rubs You～10 moles.Organic solvent for dehydration closed-loop reaction can enumerate the organic solvent as the synthesis for polyamic acid and example The organic solvent shown.Dehydration closed-loop reaction reaction temperature preferably 0 DEG C～180 DEG C, preferably 1.0 hours response time～ 120 hours.

Obtain the reaction solution containing polyimides in this way.Described reaction solution can be supplied directly to the system of aligning agent for liquid crystal It is standby, it is also possible to after autoreaction solution removes dehydrant and dehydration closed-loop catalyst, to be available to the preparation of aligning agent for liquid crystal, it is also possible to The preparation of aligning agent for liquid crystal it is available to after being separated by polyimides.These purification process can be carried out according to known method.Except this In addition, polyimides can also be obtained by the imidizate of poly amic acid ester.

[poly amic acid ester]

Poly amic acid ester in the present invention such as may utilize following methods and obtains: [I] makes the polyamides obtained by described synthetic reaction The method that amino acid and esterifying agent (such as methanol or ethanol, DMF diethyl acetal etc.) carry out reacting；[II] makes Tetrabasic carboxylic acid diester and diamidogen are in organic solvent, at suitable dehydration catalyst (such as 4-(4,6-dimethoxys-1,3,5-triazines-2- Base)-4-methyl morpholine halogenide, phosphorus system condensing agent etc.) in the presence of carry out the method reacted；[III] makes tetrabasic carboxylic acid diester dihalide Thing and diamidogen are in organic solvent, react in the presence of suitable alkali (such as pyridine, triethylamine, sodium hydroxide etc.) Method etc..

Poly amic acid ester contained in aligning agent for liquid crystal can only have amic acid esters structure, it is also possible to is amic acid structure and amic acid Ester structure the partial esterification thing deposited.Additionally, the reaction solution that poly amic acid ester dissolves can be supplied directly to aligning agent for liquid crystal Preparation, it is also possible to be available to the preparation of aligning agent for liquid crystal after being separated by poly amic acid ester contained in reaction solution.

Polyamic acid, poly amic acid ester and the polyimides obtained in this way is preferably when being made into concentration 10 weight % Solution time there is 10mPa s～the solution viscosity of 800mPa s, more preferably there is 15mPa s～the solution of 500mPa s Viscosity.Additionally, the solution viscosity (mPa s) of described polymer is to use E type rotating cylinder viscometer described poly-to using at 25 DEG C The polymer solution of concentration 10 weight % prepared by the good solvent (such as gamma-butyrolacton, METHYLPYRROLIDONE etc.) of compound Value obtained by being measured.

About polyamic acid, poly amic acid ester and polyimides contained in the aligning agent for liquid crystal of the present invention, utilize gel infiltration color The weight average molecular weight of the polystyrene conversion that spectrometry (Gel Permeation Chromatography, GPC) measures is preferred Be 500～100,000, more preferably 1,000～50,000.

[polysiloxane]

Polysiloxane in the present invention such as can by water-disintegrable silane compound preferably suitable organic solvent, water and Be hydrolyzed in the presence of catalyst or hydrolytic condensation and obtain.

Water-disintegrable silane compound used in the synthesis of polysiloxane include, for example: tetramethoxy-silicane, four ethoxies Base silane, MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, three The alkoxysilane compound containing trialkylsilyl group in molecular structure such as methoxy silane base propylsuccinic anhydride, dimethyldimethoxysil,ne, dimethyldiethoxysilane； 3-mercaptopropyi trimethoxy silane, 3-Mercaptopropyltriethoxysilane, mercapto methyl triethoxysilane, 3-ureido-propyl three Methoxy silane, 3-TSL 8330, APTES, N-(3-Cyclohexylamino) propyl group three The alkoxysilane compound containing trialkylsilyl group in molecular structure of the nitrogenous sulfur such as methoxy silane；3-glycidoxypropyltrimewasxysilane, 3-(+)-2,3-Epoxy-1-propanol oxygen Base propyl-triethoxysilicane, 3-glycidoxypropyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy The silane compound containing epoxy radicals such as base silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane；3-(methyl) acryloxy Propyl trimethoxy silicane, 3-(methyl) acryloxypropyl dimethoxysilane, 3-(methyl) acryloxypropyl Diethoxy silane, vinyltrimethoxy silane, VTES, to styryl trimethoxy silane etc. containing not The alkoxysilane compound containing trialkylsilyl group in molecular structure etc. of saturated bond.Hydrolysable silanes compound can be used alone the one in these silane compounds or combination Use two or more.Additionally, " (methyl) acryloxy " refers to comprise " acryloxy " and " methacryloxy ".

Described hydrolysis-condensation reaction can be by making one or more of silane compound as described with water preferably suitable In the presence of catalyst and organic solvent, reaction is carried out.When hydrolysis-condensation reaction, relative to silane compound (total amount) 1 Mole, the use ratio of water preferably 0.5 mole～100 moles, more preferably 1 mole～30 moles.

The catalyst used during hydrolysis-condensation reaction include, for example: acid, alkali metal compound, organic base (triethylamine or Tetramethyl ammonium hydroxide etc.), titanium compound, zirconium compounds etc..The usage amount of catalyst is anti-according to the kind of catalyst, temperature etc. Answer condition etc. and different, should set aptly, such as relative to the total amount of silane compound, preferably 0.01 times mole～3 Times mole, more preferably 0.05 times mole～1 times mole.

The organic solvent used during described hydrolysis-condensation reaction include, for example: hydrocarbon, ketone, ester, ether, alcohol etc..These are organic In solvent, it is preferred to use the water-insoluble or organic solvent of slightly water-soluble.Relative to the silane compound used in reaction Add up to 100 weight portions, use ratio preferably 10 weight portion of organic solvent～10,000 weight portion, more preferably 50 weights Amount part～1,000 weight portions.

Described hydrolysis-condensation reaction the most such as utilizes oil bath etc. to carry out heating to implement.When hydrolysis-condensation reaction, preferably Be that heating-up temperature is set to less than 130 DEG C, be preferably set to 0.5 hour～12 hours heat time heating time.After the completion of reaction, Polysiloxane can be obtained by autoreaction liquid divides the organic solvent layer taken remove solvent.

It is applied to the situation of aligning agent for liquid crystal of TN type, STN type or vertical alignment-type liquid crystal display device or utilizes light In the case of alignment method gives liquid crystal aligning ability to film, liquid crystal aligning base or light can be imported on the side chain of polysiloxane The specific bases such as orientation base.The method of the polysiloxane that synthesis has these specific bases on side chain is not particularly limited, such as Following methods can be enumerated: mixed to the silane compound containing epoxy radicals or the silane compound containing epoxy radicals and other silane compounds Compound is hydrolyzed condensation and synthesizes and have the polysiloxane of epoxy radicals, then makes the polysiloxane containing epoxy radicals of gained The method etc. reacted is carried out with the carboxylic acid with described specific base.The reaction of the polysiloxane containing epoxy radicals and carboxylic acid can be according to public affairs The method known is carried out.

The weight average molecular weight (Mw) utilizing polystyrene conversion that GPC measures of polysiloxane is preferably in 500～100, the scope of 000, preferred it is in 1,000～30, the scope of 000, and then preferably 1,000～20,000. If the weight average molecular weight of polysiloxane is in described scope, then easily operate when manufacturing liquid crystal orientation film, and gained Liquid crystal orientation film there is the sufficient strength of materials and characteristic.

The component of polymer of aligning agent for liquid crystal preferred embodiment can enumerate implementation below etc.:

[1] in the group that the component of polymer of aligning agent for liquid crystal is formed by the free polyamic acid of choosing, poly amic acid ester and polyimides At least one；

[2] in the group that the component of polymer of aligning agent for liquid crystal is formed by the free polyamic acid of choosing, poly amic acid ester and polyimides At least one and polysiloxane.

In the embodiment of described [2], as long as the content ratio of polysiloxane sets aptly, relative to aligning agent for liquid crystal In the total amount of component of polymer, be preferably set to below 50 weight %, preferred be set to more than 30 weight %.

In the case of the film utilizing optical alignment method to form use aligning agent for liquid crystal gives liquid crystal aligning ability, relative to liquid crystal Total scale of construction of polymer (A) contained in alignment agent, the use ratio of the polymer with light orientation structure preferably sets It is more than 10 weight %, preferred is set to 30 weight %～100 weight %, and then be preferably set to 50 weight %～100 Weight %.The one or be applied in combination two or more additionally, polymer (A) can be used alone.

The aligning agent for liquid crystal of the present invention is the aqueous compositions that component of polymer is dispersed or dissolved in solvent.Described liquid crystal takes Following 1st solvent and the 2nd solvent is contained as solvent to agent.

[the 1st solvent]

1st solvent is choosing compound freely represented by described formula (1), the compound represented by described formula (2), described formula (3) At least one in the group that compound represented by represented compound and described formula (4) is formed.Described formula (4) R¹And R²Preferably methyl.Compound represented by described formula (4) can enumerate N,N-dimethylacetamide, N, N-diethyl Acetamides etc., wherein it is preferred that N,N-dimethylacetamide.Compound represented by described formula (4) can be used alone one or It is applied in combination two or more.For more preferably obtaining the aspect of the effect of the present invention, wherein, the 1st solvent is preferably described Compound represented by formula (1) and the compound represented by described formula (3).The one additionally, the 1st solvent can be used alone, or Also use be can be combined two or more.

[the 2nd solvent]

2nd solvent is the solvent that surface tension is less than 30dyn/cm.Additionally, in this specification, surface tension (dyn/cm) is Value at 25 DEG C.Wherein, the 2nd solvent preferably selects the compound represented by free described formula (5), described formula (6) institute table In the group that compound represented by the compound shown, described formula (7) and the compound represented by described formula (8) are formed extremely Few one.

(compound represented by formula (5))

The R of described formula (5)⁵And R⁷In the alkyl of carbon number 1～3 include, for example: methyl, ethyl, n-pro-pyl, isopropyl Alkyl Deng carbon number 1～3；The unsaturated chain alkyl etc. of the monovalence of the carbon number such as vinyl, pi-allyl 2 or 3.In these bases, R⁵And R⁷Preferably methyl or ethyl.Additionally, R⁵And R⁷May be the same or different each other.R⁶The alkane diyl of carbon number 2～5 Include, for example: ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,3-diyl, butane-Isosorbide-5-Nitrae-diyl, pentane-1,5- Diyl etc..

The preferred concrete example of the compound represented by described formula (5) include, for example: ethylene acetate, propylene glycol diethyl The alkane glycol diacetates such as acid esters.Wherein, it is preferable to use propylene-glycol diacetate.Compound represented by described formula (5) Can be used alone a kind of described compound or be applied in combination two or more.

(compound represented by formula (6))

Compound represented by described formula (6) has two R⁸It is binding on the structure of an oxygen atom respectively.As this compound, R⁸Include, for example for having the concrete example of the compound of the base of the monovalence of "-O-" between the carbon-carbon bond of the alkyl of carbon number 3～5 Diethylene glycol dimethyl ether, diethylene glycol diethyl ether etc.；R⁸The monovalence replaced through hydroxyl for the hydrogen atom of the alkyl of carbon number 3～5 The concrete example of compound of base include, for example dipropylene glycol etc.；R⁸Concrete example for the compound of the alkyl of branch-like such as can arrange Lift: diisopropyl ether, isoamyl ether, two-secondary butyl ether, two-secondary amyl ether etc..Change in these compounds, represented by described formula (6) In compound preferably diethylene glycol diethyl ether and isoamyl ether at least any one.Additionally, the change represented by described formula (6) Compound can be used alone a kind of described compound or be applied in combination two or more.

(compound represented by formula (7))

X in described formula (7)¹Preferably base "-C (OH) R^a-", more preferably base "-C (OH) (CH₃)-”.It addition, R⁹ The alkyl of carbon number 1～4 can be that straight-chain is alternatively branch-like, preferably methyl or ethyl.

The preferred concrete example of the compound represented by described formula (7) include, for example diacetone alcohol, pentanedione, acetyl second Acetoacetic esters etc., the most preferably use diacetone alcohol.Additionally, the compound represented by described formula (7) can be used alone one Plant described compound or be applied in combination two or more.

(compound represented by formula (8))

In described formula (8), R³The alkyl preferably methyl of carbon number 1～6, ethyl, n-pro-pyl, isopropyl, normal-butyl or Isobutyl group, particularly preferably normal-butyl.R⁴The alkane diyl preferably ethylidene of carbon number 2～4, sub-n-pro-pyl or sub-isopropyl Base, particularly preferably ethylidene.

The preferred concrete example of the compound represented by described formula (8) include, for example ethylene glycol-n-butyl ether (butyl cellosolve), Ethylene glycol monomethyl ether, ethylene glycol, ethylene glycol-positive propyl ether, ethylene glycol-diisopropyl ether etc., the most preferably make spent glycol- N-butyl ether.A kind of described compound or the be applied in combination two or more additionally, compound represented by described formula (8) can be used alone.

With regard to because of with the 1st solvent and with and printing and galley be difficult to bloating tendency improve the aspect that effect is high for, wherein, 2 solvents are more desirably selected from being made up of the compound represented by described formula (5) and the compound represented by described formula (7) At least one in group, and then the compound represented by the most described formula (7).

For the viewpoint of the suppression and coating that take into account the precipitation of the polymer on printer, relative to aligning agent for liquid crystal, institute is solvent-laden Total scale of construction, content ratio preferably 5 weight % of the 1st solvent in aligning agent for liquid crystal～95 weight %, more preferably 10 Weight %～90 weight %.

It addition, may refrain from the precipitation of polymer, and for making the viewpoint that the coating to substrate (printing) is good, relative to Total scale of construction of solvent contained in aligning agent for liquid crystal, content ratio preferably 1 weight % of the 2nd solvent～70 weight %, more Preferably 3 weight %～60 weight %.2nd solvent can be used alone a kind of described compound or be applied in combination two or more.

The particularly preferred range of the 1st solvent and the 2nd solvent is according to combined solvent or the kind of solvent that used and not With.Such as, about the particularly preferred scope of the use ratio of the 1st solvent, it is represented by described formula (5) at the 2nd solvent In the case of compound represented by compound, described formula (6) or the compound represented by described formula (7), particularly preferably It is set to 20 weight %～80 weight % relative to the aligning agent for liquid crystal solvent-laden total scale of construction of institute.It addition, be described at the 2nd solvent In the case of compound represented by formula (8), the 1st solvent is particularly preferably solvent-laden totally relative to aligning agent for liquid crystal institute Measure and be set to 40 weight %～90 weight %.

As the particularly preferred scope of the use ratio of the 2nd solvent, about the compound represented by described formula (5), described formula (6) compound represented by and the compound represented by described formula (7), particularly preferably molten relative to contained by aligning agent for liquid crystal Total scale of construction of agent and be set to 10 weight %～50 weight %.It addition, about the compound represented by described formula (8), particularly preferably Be relative to aligning agent for liquid crystal institute solvent-laden total scale of construction and be set to 5 weight %～30 weight %.

For just making the viewpoint that the coating to substrate is good, the ratio of the 1st solvent and the 2nd solvent preferably will be relative to the 1st The usage amount of the 2nd solvent of the usage amount of solvent is set to more than 0.03 times with mass ratio range, preferred is set to more than 0.05 times. It addition, for may refrain from the viewpoint of the precipitation of polymer, be preferably set to less than 2.5 times, preferred be set to 2.0 times with Under.

[the 3rd solvent]

Solvent contained in the aligning agent for liquid crystal of the present invention is used as other solvents beyond described 1st solvent and the 2nd solvent (the 3rd solvent).Described 3rd solvent include, for example: METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, γ-Ding Nei Ester, butyrolactam, DMF, N,N-dimethylacetamide, glycol monoethyl ether, butyl lactate, acetic acid fourth Ester, methoxy methyl propionate, ethoxyl ethyl propionate, glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetas, diethylene glycol monoethyl ether acetas, dipropylene glycol monomethyl ether (dipropylene glycol monomethyl ether, DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, Ethylene carbonate, propylene carbonate etc..A kind of described compound or be used in mixed way two or more additionally, the 3rd solvent can be used alone.

For fully obtaining the aspect of effect of the present invention, the 1st solvent in the aligning agent for liquid crystal of the present invention and the conjunction of the 2nd solvent More than 10 weight % that solvent contained by the content ratio preferably aligning agent for liquid crystal of meter is overall.More than more preferably 30 weight %, And then preferably 50 is more than weight %.

Relative to the solvent-laden total scale of construction of aligning agent for liquid crystal, the content ratio of the 3rd solvent is preferably less than 90 weight %, more Preferably less than 70 weight %, and then preferably less than 50 weight %.

The aligning agent for liquid crystal of the present invention contains component of polymer as described and solvent, the most also can contain other compositions.Described Other compositions include, for example: other polymer beyond polymer (A) (such as polyester, polyamide, polystyrene derivative, Poly-(methyl) acrylate etc.), in intramolecular, there is the compound of at least one epoxy radicals, functional silanes compound, photopolymerization Property compound, surfactant, filler, defoamer, sensitizer, dispersant, antioxidant, contiguity auxiliary agent, antistatic additive, Leveling agent, antibacterial etc..The allotment ratio of these compositions can be according to the compound allocated, at the model of the effect not hindering the present invention Set aptly in enclosing.

(the total weight of the composition beyond the solvent of aligning agent for liquid crystal is at liquid crystal for solid component concentration in the aligning agent for liquid crystal of the present invention Ratio shared in the gross weight of alignment agent) consider that viscosity, volatility etc. select, preferably 1 weight %～10 aptly The scope of weight %.That is, the aligning agent for liquid crystal of the present invention is by coating substrate surface in aftermentioned mode, and preferably carries out Heating, and form the film as liquid crystal orientation film or become the film of liquid crystal orientation film.Now, at solid component concentration less than 1 In the case of weight %, the thickness of film becomes too small and becomes to be difficult to obtain good liquid crystal orientation film.On the other hand, at solid In the case of constituent concentration is more than 10 weight %, the thickness of film becomes excessive and is difficult to obtain good liquid crystal orientation film, and The viscosity that there is aligning agent for liquid crystal increases and the tendency that makes coating characteristics reduce.

The scope of particularly preferred solid component concentration is different according to the method used when being coated on substrate by aligning agent for liquid crystal. Such as in the case of utilizing spin-coating method, particularly preferably solid component concentration is 1.5 weight %～the scope of 4.5 weight %.? In the case of utilizing flexographic printing process, particularly preferably solid component concentration is set to 3 weight %～the scope of 9 weight %, and Thus solution viscosity is set to 12mPa s～the scope of 50mPa s.In the case of utilizing ink-jet method, particularly preferably will be solid Body constituent concentration is set to 1 weight %～the scope of 5 weight %, and solution viscosity is thus set to 3mPa s～the scope of 15mPa s. Prepare the temperature preferably 10 DEG C～50 DEG C during aligning agent for liquid crystal, more preferably 20 DEG C～30 DEG C.

The liquid crystal orientation film of the present invention is to be formed by the aligning agent for liquid crystal prepared in this way.It addition, the liquid crystal cell of the present invention The liquid crystal orientation film possessing the described aligning agent for liquid crystal of use and formed.The drive pattern of application liquid crystal cell is not particularly limited, and can answer For TN type, STN type, IPS type, FFS type, VA type, multidomain vertical orientation (Multi-domain Vertical Alignment, MVA) multiple drive modes such as type, polymer stabilizing orientation (Polymer sustained alignment, PSA) type.The present invention Liquid crystal cell such as available comprise the following steps 1～the method for step 3 manufacture.About step 1, according to desired Drive pattern and the substrate that used is different.Step 2 and step 3 are general in each drive pattern.

[step 1: the formation of film]

First, substrate is coated with the aligning agent for liquid crystal of the present invention, then coated face is heated, thus formed on substrate and be coated with Film.

(1-1) in the case of the liquid crystal cell manufacturing TN type, STN type, VA type, MVA type or PSA type, by two pieces The substrate being provided with the nesa coating patterned is set to a pair, on the formation face of the transparent conductive film in each substrate, and profit It is respectively coated aligning agent for liquid crystal with preferably flexographic printing process, spin-coating method, rolling method or ink jet printing method.Herein, substrate is such as Can use: the glass such as float glass (float glass), soda-lime glass；Comprise polyethylene terephthalate, poly terephthalic acid fourth The transparency carrier of the plastics such as diester, polyether sulfone, Merlon, poly-(ester ring type alkene).Set by one of them face of substrate Nesa coating can use and comprise stannum oxide (SnO₂) nesa (NESA) film (PPG register of company of U.S. trade mark), bag Containing indium oxide-tin oxide (IN₂O₃-SnO₂) tin indium oxide (Indium Tin Oxide, ITO) film etc..

After coating of liquid crystalline alignment agent, for the purpose of the dropping liquid that prevents be coated with alignment agent etc., preferably implement preparation heating (pre- Baking).Prebake conditions temperature preferably 30 DEG C～200 DEG C, preferably 0.25 minute～10 minutes prebake conditions time.Thereafter, For the purpose of being removed completely by solvent, the most optionally the amic acid structure being present in polymer will be carried out hot-imide as mesh , and implement calcining (baking afterwards) step.Calcining heat (rear baking temperature) preferably 80 DEG C～300 DEG C now, after Baking time preferably 5 minutes～200 minutes.The thickness of the film formed in this way preferably 0.001 μm～1 μm, More preferably 0.005 μm～0.5 μm.

(1-2) in the case of manufacturing IPS type or FFS type liquid crystal display cells, pattern has been carried out being provided with to comprise with interdigitated electrode structure The nesa coating changed or the electrode forming surface of the substrate of the electrode of metal film and be not provided with one of them face of opposite substrate of electrode On be respectively coated aligning agent for liquid crystal, then each coated face is heated, is consequently formed film.About the substrate now used and The patterning method of heating condition, nesa coating or metal film after the material of nesa coating, coating process, coating, substrate Pre-treatment and the preferred thickness etc. of film that formed, identical with described (1-1).Metal films comprises as used The film of the metals such as chromium.

Under the either case of described (1-1) and (1-2), it is all organic molten by removing after coating of liquid crystalline alignment agent on substrate Matchmaker and be formed into the film of liquid crystal orientation film.

[step 2: alignment capability imparting processes]

In the case of the liquid crystal display cells manufacturing TN type, STN type, IPS type or FFS type, implement in described step 1 The film formed gives the process of liquid crystal aligning ability.Thus, the alignment capability of liquid crystal molecule is imparted to film and becomes liquid crystal and take To film.Alignment capability imparting processes and include, for example: utilizes and is wound with the roller of the cloth comprising the fibers such as nylon, artificial silk, cotton to painting Film carries out the friction treatment of wiping in a certain direction, and film irradiates the light orientation process etc. of the lonizing radiation of polarisation or non-polarized.Separately On the one hand, in the case of manufacturing VA type liquid crystal display cells, the film formed can be taken directly as liquid crystal in described step 1 Use to film, it is possible to described film is implemented alignment capability imparting and processes.

In the case of utilizing light orientation process to give liquid crystal aligning ability to film, the lonizing radiation being irradiated film such as can make With ultraviolet and the luminous ray of the light of the wavelength comprising 150nm～800nm.In the case of lonizing radiation are polarisation, can be straight Line polarisation is alternatively part polarisation.It addition, in the case of the lonizing radiation used are linear polarization or part polarisation, irradiation can be certainly The direction being perpendicular to real estate is carried out, it is possible to carry out from incline direction, maybe these can be combined and carry out.Irradiating non-polarized Lonizing radiation in the case of, the direction of irradiation is set to incline direction.

The light source used such as can use: low pressure mercury lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon resonance lamp, Xenon lamp, excimer laser etc..The preferably ultraviolet of wave-length coverage can be by by light source and such as wave filter, diffraction grating etc. and use Means etc. obtain.The irradiation dose of lonizing radiation preferably 100J/m²～50,000J/m², more preferably 300J/m²~ 20,000J/m².It addition, in order to improve reactivity, film can be heated while carrying out the light to film and irradiating.Heat Time temperature be usually 30 DEG C～250 DEG C, preferably 40 DEG C～200 DEG C.For the liquid crystal display cells of VA type preferably Liquid crystal orientation film can be preferably also used for the liquid crystal display cells of PSA (Polymer sustained alignment) type.

[step 3: liquid crystal cells (cell) constructs]

Prepare two pieces of substrates being formed with liquid crystal orientation film in this way, between two pieces of oppositely disposed substrates, configure liquid crystal, thus Manufacture liquid crystal cells.In order to manufacture liquid crystal cells, include, for example: (1) by liquid crystal orientation film to in the way of across gap will Two pieces of substrates are oppositely disposed, and use sealant to be fitted by the periphery of two pieces of substrates, divided by substrate surface and sealant After injecting filling liquid crystal in cell gap, the method that hand-hole is sealed；(2) it is being formed with one of base of liquid crystal orientation film After commitment positions coating sealant on plate, and then the set several positions dropping liquid crystal on liquid crystal aligning face, take with liquid crystal To film to mode fit another block substrate, and the method (liquid crystal drip-injection (One that liquid crystal is spread out on whole of substrate Drop Fill, ODF) mode) etc..To manufactured liquid crystal cells, it is generally desirable to and then it is each to be heated to used liquid crystal acquirement Till the temperature of same sex phase, then it is slowly cooled down to room temperature, thus removes flow orientation when liquid crystal is filled.

Sealant such as can use containing sclerosing agent and the epoxy resin etc. of the alumina balls as sept (spacer).Liquid crystal can Enumerate nematic crystal and disc-like liquid crystal, wherein it is preferred that nematic crystal, such as, can use: schiff bases (Schiff base) Be liquid crystal, azoxy (azoxy) be liquid crystal, biphenyl system liquid crystal, Phenylcyclohexane system liquid crystal, ester system liquid crystal, terphenyl system Liquid crystal, xenyl hexamethylene methane series liquid crystal, pyrimidine system liquid crystal, two methane series liquid crystal, double-octane system liquid crystal, cubane (cubane) It it is liquid crystal etc..Additionally, it is possible to add in these liquid crystal such as cholesteryl liquid crystal (cholesteric liquid crystal), chiral agent, Ferroelectric liquid crystals etc. and use.

In the case of manufacturing PSA type liquid crystal display cells, except injecting or drip the side of photopolymerizable compound together with liquid crystal Beyond face, by with described identical in the way of construct liquid crystal cells.Thereafter, at the conduction intermembranous applying voltage that a pair substrate is had State under liquid crystal cells is carried out light irradiation.It addition, using the aligning agent for liquid crystal shape on substrate comprising photopolymerizable compound In the case of becoming film, it is also possible to the mode identical with described (3-1) constructs liquid crystal cells, thereafter, through to a pair substrate institute Under the state of the intermembranous applying voltage of conduction having, liquid crystal cells is carried out the step of light irradiation to manufacture liquid crystal cell.

And, can be by obtaining the liquid crystal display cells of the present invention at the outer surface of liquid crystal cells laminating Polarizer.Fit in liquid The Polarizer of the outer surface of brilliant unit can be enumerated: be referred to as the polarisation of the light polarizing film of " H-film " with the clamping of cellulose acetate protecting film Plate or comprise itself Polarizer of H-film, described " H-film " is to make polyvinyl alcohol extend orientation to absorb iodine and form.

Additionally, in the case of film is carried out friction treatment, two pieces of substrates are formed set with the frictional direction in each film each other Angle, the most orthogonal or antiparallel mode are oppositely disposed.It addition, in the case of film is carried out light irradiation, if liquid crystal aligning Film is horizontal alignment, then be formed with linear polarization lonizing radiation in two pieces of substrates of liquid crystal orientation film, that irradiated by adjustment The angle of angle that polarization direction is formed and each substrate and Polarizer, can obtain and have TN type or STN type liquid crystal cells Liquid crystal cell.On the other hand, in the case of liquid crystal orientation film is vertical orientated property, can make in the following manner to have and vertically take Liquid crystal cell to type liquid crystal cells: to be formed with the side that the direction of the easy axis of orientation in two pieces of substrates of liquid crystal orientation film becomes parallel Formula Component units, and Polarizer of fitting in the way of the angle that the polarization direction of Polarizer is at 45 ° with easy axis of orientation shape thereon.

The liquid crystal cell of the present invention can be effectively applied to multiple device, such as, can be used for: at clock and watch, pocket game machine, word Reason device, notes type personal computer, auto-navigation system, video camera, personal digital assistant (Personal Digital Assistant, PDA), the display device of digital camera, mobile phone, smart mobile phone, various monitor, LCD TV etc. or light modulation film etc..It addition, The liquid crystal cell using the aligning agent for liquid crystal of the present invention and formed also apply be applicable to phase retardation film.

[embodiment]

Hereinafter, according to embodiment, the present invention is specifically described further, but the present invention is not limited by these embodiments.

The solution viscosity of each polymer solution in synthesis example, acid imide rate, weight average molecular weight and the epoxy of polyimides Equivalent is to utilize following method to measure.

[solution viscosity of polymer solution]

About the solution viscosity (mPa s) of polymer solution, use E type rotating cylinder viscometer to using set solvent at 25 DEG C And the solution being adjusted to polymer concentration 10 weight % is measured.

[the acid imide rate of polyimides]

The solution of polyimides is put into pure water, after at room temperature the precipitation to gained is sufficiently carried out drying under reduced pressure, is dissolved in In deuterodimethylsulfoxide, material on the basis of tetramethylsilane, at room temperature measure¹H-nuclear magnetic resonance, NMR (¹H-Nuclear Magnetic Resonance,¹H-NMR).According to gained¹H-NMR spectrum, utilizes following numerical expression (1) to obtain acid imide rate [%].

Acid imide rate [%]=(1-A¹/A²×α)×100...(1)

(in numerical expression (1), A¹For near chemical shift 10ppm occur the PeakArea come by the proton of NH base, A²For the PeakArea come by other protons, α is that other protons are relative to the NH base in the precursor (polyamic acid) of polymer The number ratio of a proton)

[weight average molecular weight of polymer]

Weight average molecular weight Mw is the polystyrene conversion value that the gel permeation chromatography under conditions of below utilization measures.

Tubing string: east Cao (Tosoh) (stock) manufactures, TSKgelGRCXLII

Solvent: oxolane

Temperature: 40 DEG C

Pressure: 68kgf/cm²

[epoxide equivalent]

Epoxide equivalent is to utilize salt described in Japanese Industrial Standards (Japanese Industrial Standards, JIS) C 2105 Acid-methyl ethyl ketone method measures.

[synthesis example 1: the synthesis of polyimides (PI-1)]

Using 2,3,5-tricarboxylics cyclopentyl acetic acid dianhydride (TCA) 22.4g (0.1 mole) as tetracarboxylic dianhydride, as diamidogen P-phenylenediamine (PDA) 8.6g (0.08 mole) and 3,5-diaminobenzoic acid cholesteric Arrcostab (HCDA) 10.5g (0.02 Mole) be dissolved in METHYLPYRROLIDONE (NMP) 166g, at 60 DEG C, carry out reaction in 6 hours, it is thus achieved that containing 20 The solution of the polyamic acid of weight %.Divide the polyamic acid solution taking a small amount of gained, add NMP and make polyamic acid concentration 10 The solution of weight %, solution viscosity obtained by mensuration is 90mPa s.

Then, in the polyamic acid solution of gained, add NMP and make the solution of polyamic acid concentration 7 weight %, add pyrrole Pyridine 11.9g and acetic anhydride 15.3g and at 110 DEG C, carry out the reaction of 4 hours dehydration closed-loops.After dehydration closed-loop reaction, utilize new NMP carries out solvent displacement and (utilizes this operation the pyridine used in dehydration closed-loop reaction and acetic anhydride to be gone intrasystem solvent Except in addition to system.The most identical), it is derived from the polyimides (PI-1) of acid imide rate about 68% containing 26 weight % Solution.Divide the polyimide solution taking a small amount of gained, add NMP and make the solution of polyimides concentration 10 weight %, measure Obtained by solution viscosity be 45mPa s.Then, reaction solution is injected in the methanol of surplus, makes product precipitate.Utilize Described precipitate is carried out by methanol, is under reduced pressure dried 15 hours with 40 DEG C, is derived from polyimides (PI-1).

[synthesis example 2: the synthesis of polyimides (PI-2)]

Using the TCA 22.5g (0.1 mole) as tetracarboxylic dianhydride, as PDA 7.6g (0.07 mole), the HCDA of diamidogen 5.2g (0.01 mole) and 4,4 '-diaminodiphenyl-methane (DDM) 4.0g (0.02 mole) are dissolved in NMP 157g, Reaction in 6 hours is carried out, it is thus achieved that the solution of the polyamic acid containing 20 weight % at 60 DEG C.Divide the polyamic acid taking a small amount of gained Solution, adds NMP and makes the solution of polyamic acid concentration 10 weight %, and solution viscosity obtained by mensuration is 110mPa s.

Then, in the polyamic acid solution of gained, add NMP and make the solution of polyamic acid concentration 7 weight %, add pyrrole Pyridine 16.6g and acetic anhydride 21.4g and at 110 DEG C, carry out the reaction of 4 hours dehydration closed-loops.After dehydration closed-loop reaction, utilize new NMP carries out solvent displacement to intrasystem solvent, is derived from the polyimides of acid imide rate about 82% containing 26 weight % (PI-2) solution.Divide the polyimide solution taking a small amount of gained, add NMP and make polyimides concentration 10 weight % Solution, solution viscosity obtained by mensuration is 62mPa s.Then, reaction solution is injected in the methanol of surplus, makes product Precipitation.Utilize methanol that described precipitate is carried out, be under reduced pressure dried 15 hours with 40 DEG C, be derived from polyimides (PI-2)。

[synthesis example 3: the synthesis of polyimides (PI-3)]

Using dicyclo [3.3.0] octane-2 as tetracarboxylic dianhydride, 4,6,8-tetrabasic carboxylic acid 2:4, (0.10 rubs 6:8-dianhydride (BODA) 24.9g You), be dissolved in NMP 176g as the PDA 8.6g (0.08 mole) and HCDA 10.4g (0.02 mole) of diamidogen, Reaction in 6 hours is carried out, it is thus achieved that the solution of the polyamic acid containing 20 weight % at 60 DEG C.Divide the polyamic acid taking a small amount of gained Solution, adds NMP and makes the solution of polyamic acid concentration 10 weight %, and solution viscosity obtained by mensuration is 103mPa s.

Then, in the polyamic acid solution of gained, add NMP and make the solution of polyamic acid concentration 7 weight %, add pyrrole Pyridine 11.9g and acetic anhydride 15.3g and at 110 DEG C, carry out the reaction of 4 hours dehydration closed-loops.After dehydration closed-loop reaction, utilize new NMP carries out solvent displacement to intrasystem solvent, is derived from the polyimides of acid imide rate about 71% containing 26 weight % (PI-3) solution.Divide the polyimide solution taking a small amount of gained, add NMP and make polyimides concentration 10 weight % Solution, solution viscosity obtained by mensuration is 57mPa s.Then, reaction solution is injected in the methanol of surplus, makes product Precipitation.Utilize methanol that described precipitate is carried out, be under reduced pressure dried 15 hours with 40 DEG C, be derived from polyimides (PI-3)。

[synthesis example 4: the synthesis of polyimides (PI-4)]

Using the TCA 110g (0.50 mole) and 1,3,3a as tetracarboxylic dianhydride, 4,5,9b-hexahydro-8-methyl-5-(tetrahydrochysene-2,5-dioxies Generation-3-furyl) naphtho-[1,2-c] furan-1,3-diketone 160g (0.50 mole), as diamidogen PDA 91g (0.85 mole), 1,3-double (4-amino benzoyl epoxide) cholestane 25 of double (3-aminopropyl) tetramethyl disiloxane 25g (0.10 mole) and 3,6- G (0.040 mole), and the aniline 1.4g (0.015 mole) as monoamine is dissolved in NMP 960g, enters at 60 DEG C Row reaction in 6 hours, is derived from the solution containing polyamic acid.Point take the polyamic acid solution of a small amount of gained, add NMP and Making the solution of polyamic acid concentration 10 weight %, solution viscosity obtained by mensuration is 60mPa s.

Then, the polyamic acid solution of gained adds NMP 2,700g, and add pyridine 390g and acetic anhydride 410g and Dehydration closed-loop reaction in 4 hours is carried out at 110 DEG C.After dehydration closed-loop reaction, utilize new gamma-butyrolacton that intrasystem solvent is carried out Solvent is replaced, and is derived from about 2, the polyimides (PI-4) of the acid imide rate about 95% containing 15 weight % of 500g molten Liquid.Divide and take a small amount of described solution, add NMP and make the solution of polyimides concentration 10 weight %, solution obtained by mensuration Viscosity is 70mPa s.Then, reaction solution is injected in the methanol of surplus, makes product precipitate.Utilize methanol to described Precipitate is carried out, and is under reduced pressure dried 15 hours with 40 DEG C, is derived from polyimides (PI-4).

[synthesis example 5: the synthesis of polyimides (PI-5)]

Using the TCA 22.4g (0.1 mole) as tetracarboxylic dianhydride, as PDA 8.6g (0.08 mole), the DDM of diamidogen 2.0g (0.01 mole) and 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine 3.2g (0.01 mole) is dissolved in NMP 324g In, at 60 DEG C, carry out reaction in 4 hours, it is thus achieved that the solution of the polyamic acid containing 10 weight %.

Then, the polyamic acid solution of gained adds NMP 360g, and add pyridine 39.5g and acetic anhydride 30.6g and Dehydration closed-loop reaction in 4 hours is carried out at 110 DEG C.After dehydration closed-loop reaction, utilize new NMP that intrasystem solvent is carried out solvent Displacement, it is thus achieved that the solution of the polyimides (PI-5) of the acid imide rate about 93% containing 10 weight %.Divide and take the poly-of a small amount of gained Amic acid solution, solution viscosity obtained by mensuration is 30mPa s.Then, reaction solution is injected in the methanol of surplus, makes anti- Product is answered to precipitate.Utilize methanol that described precipitate is carried out, be under reduced pressure dried 15 hours with 40 DEG C, be derived from polyamides Imines (PI-5).

[synthesis example 6: the synthesis of polyimides (PI-6)]

The diamidogen used is changed to 3,5-diaminobenzoic acid (3,5DAB) 0.08 mole and cholesteric alkyl oxy-2,4-diaminourea Benzene (HCODA) 0.02 mole, in addition, utilizes the method identical with described synthesis example 1 to obtain polyamic acid solution.Point Take the polyamic acid solution of a small amount of gained, add NMP and make the solution of polyamic acid concentration 10 weight %, molten obtained by mensuration Fluid viscosity is 80mPa s.

Then, the method identical with described synthesis example 1 is utilized to carry out imidizate, it is thus achieved that the acid imide rate containing 26 weight % The solution of the polyimides (PI-6) of about 65%.Divide the polyimide solution taking a small amount of gained, add NMP and make polyamides Asia The solution of amine concentration 10 weight %, solution viscosity obtained by mensuration is 40mPa s.Then, reaction solution is injected into surplus In methanol, product is made to precipitate.Utilize methanol that described precipitate is carried out, be under reduced pressure dried 15 hours with 40 DEG C, It is derived from polyimides (PI-6).

[synthesis example 7: the synthesis of polyamic acid (PA-1)]

Using 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (CB) 200g (1.0 moles) as tetracarboxylic dianhydride, as diamidogen 2,2 '- Dimethyl-4,4 '-benzidine 210g (1.0 moles) is dissolved in NMP 370g and gamma-butyrolacton 3, in the mixed solvent of 300g, Carry out at 40 DEG C 3 hours reaction, it is thus achieved that solid component concentration 10 weight %, solution viscosity 160mPa s polyamic acid molten Liquid.Then, described polyamic acid solution is injected in the methanol of surplus, and makes product precipitate.Utilize methanol to described heavy Shallow lake thing is carried out, and is under reduced pressure dried 15 hours with 40 DEG C, is derived from polyamic acid (PA-1).

[synthesis example 8: the synthesis of polyamic acid (PA-2)]

The tetracarboxylic dianhydride used is set to pyromellitic acid anhydride (PMDA) 0.9 mole and CB 0.1 mole, and diamidogen is set to PDA 0.2 mole and 4，4′-diaminodipohenyl ether (DDE) 0.8 mole, in addition, utilize identical with described synthesis example 7 Method obtains solid component concentration 10 weight %, the polyamic acid solution of solution viscosity 170mPa s.Then, by described polyamide Acid solution is injected in the methanol of surplus, and makes product precipitate.Methanol is utilized described precipitate to be carried out, under reduced pressure It is dried 15 hours with 40 DEG C, is derived from polyamic acid (PA-2).

[synthesis example 9: the synthesis of polyamic acid (PA-3)]

Using the TCA 7.0g (0.031 mole) as tetracarboxylic dianhydride, as the chemical combination represented by the following formula (R-1) of diamidogen Thing 13g (being equivalent to 1 mole relative to 1 mole of TCA) is dissolved in NMP 80g, carries out 4 hours instead at 60 DEG C Should, it is thus achieved that the solution of the polyamic acid (PA-3) containing 20 weight %.The solution viscosity of described polyamic acid solution is 2,000 mPa·s.Additionally, the compound represented by following formula (R-1) is based on the record of Japanese Patent Laid-Open 2011-100099 publication And synthesize.Then, described polyamic acid solution is injected in the methanol of surplus, and makes product precipitate.Utilize methanol to institute State precipitate to be carried out, be under reduced pressure dried 15 hours with 40 DEG C, be derived from polyamic acid (PA-3).

[changing 11]

[synthesis example 10: the synthesis of polysiloxane (ASP-1)]

In the reaction vessel possessing blender, thermometer, addition funnel and reflux cooling pipe, put into 2-(3,4-epoxycyclohexyl) Ethyl trimethoxy silane (ECETS) 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, at room temperature carried out Mixing.Then, after utilizing addition funnel to spend 30 minutes dropping deionized water 100g, stirring under reflux, while at 80 DEG C Under carry out 6 hours reaction.After reaction terminates, organic layer is taken out, utilize 0.2 weight % aqueous ammonium nitrate solution to clean to cleaning Water become neutrality till, the most under reduced pressure solvent and water are distilled and remove, thus obtain anti-with the form of the transparency liquid of thickness Answering property polysiloxane (EPS-1).Described reactive polysiloxane (EPS-1) is carried out¹H-NMR analyzes, knot Fruit obtains the peak value based on epoxy radicals of theoretical strength near chemical shift (δ)=3.2ppm, thus confirms not produce in reaction The side reaction of epoxy radicals.Weight average molecular weight Mw of the reactive polysiloxane of gained is 3,500, and epoxide equivalent is 180 G/ mole.

Then, in the there-necked flask of 200mL, the reactive polysiloxane (EPS-1) of 10.0g is put into, as solvent Methyl iso-butyl ketone (MIBK) 30.28g, as the 4-dodecyl p-methoxybenzoic acid 3.98g of reactive compounds and as catalyst UCAT 18X (trade name, the general sieve in Sanya (San-Apro) (stock) manufactures) 0.10g, little at present with 100 DEG C of stirrings 48 React.After reaction terminates, the solution obtained adding ethyl acetate in the reactive mixture carries out three washings, uses sulfur After organic layer is dried by acid magnesium, solvent distillation is removed, is derived from the liquid crystal aligning polysiloxane of 9.0g (ASP-1).Weight average molecular weight Mw of the polymer of gained is 9,900.

[synthesis example 11: the synthesis of polyamic acid (PI-7)]

Using the TCA 220g (1.0 moles) as tetracarboxylic dianhydride, and 3-(2, the 4-diamino phenoxy) cholesteric as diamidogen Alkane 49g (0.1 mole), 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyls-1H-indenes-5-amine 53g (0.2 mole), following Compound 54g (0.2 mole) and DDM 99g (0.5 mole) represented by formula (d-2) are dissolved in NMP 1, in 900g, Reaction in 6 hours is carried out, it is thus achieved that containing the solution of polyamic acid at 60 DEG C.Divide the polyamic acid solution taking a small amount of gained, measure Obtained by solution viscosity be about 1,400mPa s.

Then, the polyamic acid solution of gained adds NMP 2,400g, and adds pyridine 120g (relative to described polyamide The amic acid unit 1 mole that had of acid and be equivalent to 1.5 moles) and acetic anhydride 153g (had relative to described polyamic acid The molal quantity of some amic acid unit and be equivalent to 1.5 times moles), at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.Dehydration After ring-closure reaction, utilize new NMP that intrasystem solvent is carried out solvent displacement, it is thus achieved that containing the imidizate of about 15 weight % The solution of the polyimides (PI-7) of rate about 61%.

[changing 12]

[embodiment 1]

Polyimides (PI-1) is used as polymer (A), is added to the N as solvent, N-dimethylpropionamide (DMP) And diacetone alcohol (DAA), making group of solvents becomes DMP: DAA=60: 40 (weight ratios), solid component concentration 6.5 weight The solution of %.Described solution is filtered by the filter using aperture 1 μm, thus prepares aligning agent for liquid crystal (S-1).Additionally, Aligning agent for liquid crystal (S-1) is mainly used in the manufacture of the liquid crystal display cells of vertical orientating type.

Described aligning agent for liquid crystal (S-1) is used to evaluate the swelling easness (swelling characteristic) of APR version.APR version is to utilize ultraviolet The resin plate that line irradiates subsclerotic aqueous photoresist and formed, generally makes in the galley of liquid crystal orientation film printer With.In the case of making aligning agent for liquid crystal contact with APR version, APR version is difficult to swelling and refers to: when printing, aligning agent for liquid crystal is difficult to Immerse to printing is good in APR version.The evaluation of swelling characteristic is by APR version being impregnated in aligning agent for liquid crystal 1 day, And the weight change measuring the APR version before and after dipping is carried out.Now, the increment rate (swelling rate) in the weight of APR version is little In the case of 4.0%, APR version is difficult to swelling and is evaluated as good (zero), in the case of increment rate is more than 4.0%, and APR Version easily swelling and be evaluated as bad (×).Its result, in described embodiment, swelling rate is 3.5%, swelling characteristic " good (zero) ". Swelling rate is to use following numerical expression (2) to calculate.

Swelling rate [%]=(W²-W¹)/W¹)×100...(2)

(in numerical expression (2), W¹For the weight of the APR version before dipping, W²Weight for the APR version after dipping)

About the aligning agent for liquid crystal (S-1) of described middle preparation, to carrying out continuously to the printing in the case of the printing of substrate (even Continuous printing) it is evaluated.Evaluate and carry out as follows.First, liquid crystal orientation film printer (Japan's description printer is used (stock) manufacture, En Gusiteluo (Angstrom) form " S40L-532 "), with by aligning agent for liquid crystal (S-1) to anilox roll Dripping quantity be set to come and go the condition of 20 (about 0.2g), be printed in glass substrate saturating of the transparency electrode that band comprises ito film On prescribed electrode face.About the printing to substrate, use new substrate with 1 minute interval, while implementing 20 times.

Then, with 1 minute interval by aligning agent for liquid crystal (S-1) distribution (one way) to anilox roll, when the time comes, carry out adding up to 10 The secondary operation (hereinafter referred to as dry run) (the most not carrying out the printing to glass substrate) making anilox roll contact with galley. Additionally, described dry run is the operation carried out to implement the printing of aligning agent for liquid crystal wittingly under harsh situation.

After the dry run of 10 times, glass substrate is then used formally to print.In formal printing, with 30 seconds after dry run Clock interval puts into 5 pieces of substrates, at 80 DEG C, each substrate after printing is carried out heating (prebake conditions) in 1 minute and is removed by solvent, Then at 200 DEG C, carry out heating in 10 minutes (baking afterwards), form the film of thickness about 80nm.By utilizing multiplying power 20 times Microscope described film is observed and evaluates printing (continuous printing).About evaluation, by the 1st after dry run Secondary formal printing not observed, the situation of the precipitation of polymer is set to continuous printing " good (zero) ", by the after dry run 1 formal printing is observed the precipitation of polymer, but becomes not observe the precipitation of polymer during implementing 5 formal printings Situation be set to continuous printing " can (△) ", will still observe the precipitation of polymer after being repeated 5 formal printings Situation is set to continuous printing " bad (×) ".Its result, continuous printing " good (zero) " in described embodiment.Additionally, by Experiment understands, and in the aligning agent for liquid crystal that printing is good, during putting into substrate continuously, the precipitation of polymer becomes good (disappearance). It addition, and then the number of times of dry run is changed to 15 times, 20 times, 25 times, and respectively by with described identical in the way of evaluate liquid crystal The printing of alignment agent as a result, in the described embodiment, is " good (zero) " when dry run is set to 15 times and 20 times, It is " can (△) " when 25 times.

[embodiment 2～embodiment 32 and comparative example 1, comparative example 2]

By the polymer used and the kind of solvent and composition respectively as described in table 1 below as change, except this with Outward, the method identical with described embodiment 1 is utilized to prepare aligning agent for liquid crystal (S-2)～aligning agent for liquid crystal (S-32), liquid respectively Brilliant alignment agent (SR-1) and aligning agent for liquid crystal (SR-2).It addition, about each aligning agent for liquid crystal, with identical with described embodiment 1 Mode evaluate swelling characteristic and the printing of galley.The result these evaluated is shown in table 1 below.

[table 1]

In table 1, about using two kinds of polymer as component of polymer (embodiment 21～embodiment 32), illustrate each poly-in the lump Compound is relative to the use ratio (weight ratio) of total scale of construction 100 weight portion of the polymer used.In each aligning agent for liquid crystal, (S-2)～(S-20), (SR-1) and (SR-2) is mainly used in the manufacture of liquid crystal display cells of vertical orientating type, (S-21)～ (S-24) manufacture of the liquid crystal display cells of TN type it is mainly used in, (S-25)～(S-28) and (S-30)～(S-32) It is mainly used in the manufacture of the liquid crystal display cells of IPS type, and (S-29) is mainly used in the manufacture of liquid crystal display cells of FFS type.

In table 1, the total amount of the solvent used in the preparation relative to aligning agent for liquid crystal of each compound of numeric representation of solvent composition Allotment ratio (weight ratio).The symbol of solvent composition is respectively following meanings.

A:N, N-dimethylpropionamide (compound represented by described formula (1))

B:N, N-diethylformamide (compound represented by described formula (2))

C: tetramethylurea (compound represented by described formula (3))

D:N, N-dimethyl acetylamide

E:N-N-methyl-2-2-pyrrolidone N

F:N-ethyl-2-pyrrolidone

G: gamma-butyrolacton

H: butyl cellosolve

J: propylene-glycol diacetate

K: diacetone alcohol

L: diethylene glycol diethyl ether

M: isoamyl ether

From described result, the aligning agent for liquid crystal of embodiment is all difficult to make galley swelling, and continuous printing is the best.Relative to This, about the aligning agent for liquid crystal of comparative example, result is that swelling characteristic is poorer than embodiment.

[embodiment 29A]

To there is on one side the glass substrate of the metal electrode comprising chromium patterned with comb teeth-shaped and be not provided with electrode It is set to a pair to glass substrate, uses rotator in the face with electrode of glass substrate and to one of them face of glass substrate On be respectively coated the aligning agent for liquid crystal (S-29) of described middle preparation.Then, utilize the heating plate of 80 DEG C to carry out 1 minute prebake conditions, Thereafter, carried out in the baking oven of nitrogen displacement in case, carried out heating in 1 hour (baking afterwards) with 200 DEG C, form thickness 0.1 The film of μm.Then, Hg-Xe lamp and Glan-Taylor prism (Glan-Taylor prism) are used respectively, with polarisation ultraviolet 10,000J/m²From the vertical direction of real estate, these film coated surface are irradiated, it is thus achieved that there is a pair substrate of liquid crystal orientation film.

Then, utilizing screen painting, the periphery in the one of face with liquid crystal orientation film in a pair substrate is coated with mixed with directly The epobond epoxyn of the alumina balls of footpath 3.5 μm, then make the liquid crystal orientation film of a pair substrate in the face of to, to irradiate polarisation During ultraviolet, the mode in opposite direction of each substrate is overlapping and crimps, and spends 1 hour by binding agent thermmohardening at 150 DEG C.Continue And, after the liquid crystal " MLC-7028 " Merck (Merck) company manufactured is by the gap between liquid crystal injecting port filling to substrate, utilize Liquid crystal injecting port is sealed by epoxy adhesive.And then, in order to remove flow orientation when liquid crystal injects, and to it at 150 DEG C Heat, be then slowly cooled down to room temperature.Then, on the two sides, outside of substrate polarization direction with Polarizer orthogonal and With the optical axis of the polarisation ultraviolet of liquid crystal orientation film the mode that the projecting direction of real estate is orthogonal fitted Polarizer, thus manufacture liquid crystal Display element.

Light and shade for the liquid crystal display cells of described middle manufacture, when utilizing optical microscope to observe the voltage of applying/releasing 5V The presence or absence of abnormal area in change.Evaluate and carry out as follows: the situation not observing abnormal area is set to liquid crystal aligning " good Good ", it will be observed that the situation of abnormal area is set to liquid crystal aligning " bad ".Its result, does not observes in described liquid crystal display cells To abnormal area, liquid crystal aligning is " well ".

Claims

1. an aligning agent for liquid crystal, it contains:

Polymer (A), selects in the group that free polyamic acid, poly amic acid ester, polyimides and polysiloxane are formed At least one；

1st solvent, selects the compound represented by the compound represented by free following formula (1), following formula (2), following formula (3) at least one in the group that the compound represented by and the compound represented by following formula (4) are formed；And

2nd solvent, surface tension is less than 30dyn/cm,

In formula (4), R¹And R²It is separately methyl or ethyl.

Aligning agent for liquid crystal the most according to claim 1, wherein said 2nd solvent is for selecting free following formula (5) represented Compound, the compound represented by following formula (6), the compound represented by following formula (7) and following formula (8) represented The group that formed of compound at least one,

In formula (5), R⁵And R⁷It is separately the alkyl of the monovalence of carbon number 1～3, R⁶For the alkane diyl of carbon number 2～5,

R⁸-O-R⁸ (6)

In formula (6), R⁸For having the monovalence an of-O-between the carbon-carbon bond of the alkyl of the straight-chain of carbon number 3～5 or branch-like The base of the monovalence that at least one hydrogen atom of the alkyl of base, the straight-chain of carbon number 3～5 or branch-like replaces through hydroxyl or carbon The alkyl of the branch-like of several 3～5,

In formula (7), X¹For-C (OH) R^a-,-CO-or-COO-*, R⁹For the alkyl of carbon number 1～4, wherein, R^aFor methyl Or ethyl, * represents and R⁹Associative key,

R³-O-R⁴-OH (8)

In formula (8), R³For the alkyl of carbon number 1～6, R⁴Alkane diyl for carbon number 2～4.

Aligning agent for liquid crystal the most according to claim 1 and 2, the content of the total of wherein said 1st solvent and the 2nd solvent More than 10 weight % that solvent contained by aligning agent for liquid crystal is overall.

Aligning agent for liquid crystal the most according to claim 1 and 2, the content of wherein said 2nd solvent is contained by aligning agent for liquid crystal 1 weight % of solvent entirety～70 weight %.

Aligning agent for liquid crystal the most according to claim 1 and 2, the content of wherein said 1st solvent is contained by aligning agent for liquid crystal 5 weight % of solvent entirety～95 weight %.

Aligning agent for liquid crystal the most according to claim 1 and 2, wherein said polymer (A) comprises choosing freely makes tetrabasic carboxylic acid Dianhydride and diamine reactant and at least one in group that the polyamic acid, poly amic acid ester and the polyimides that obtain are formed, institute State tetracarboxylic dianhydride and comprise choosing freely 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides, dicyclo [3.3.0] octane-2,4,6,8-tetrabasic carboxylic acid 2:4,6:8- Dianhydride, 1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides and 1,3-dimethyl-1, in the group that 2,3,4-Tetramethylene. tetracarboxylic dianhydrides are formed extremely Few one.

Aligning agent for liquid crystal the most according to claim 1 and 2, wherein said polymer (A) comprise have light orientation knot The polymer of structure.

8. a manufacture method for liquid crystal orientation film, comprising:

Aligning agent for liquid crystal according to claim 7 is coated the step forming film on substrate；And

Described film is carried out light irradiation and makes the step of liquid crystal orientation film.

9. a liquid crystal orientation film, it is to use aligning agent for liquid crystal according to any one of claim 1 to 7 to be formed.

10. a liquid crystal cell, it possesses liquid crystal orientation film according to claim 9.