CN103666486A

CN103666486A - Liquid crystal orientation agent, liquid crystal orientation film, manufacturing method of liquid crystal orientation film, and liquid crystal display element

Info

Publication number: CN103666486A
Application number: CN201310367443.XA
Authority: CN
Inventors: 植阪裕介; 野口峻一; 加藤孝人; 片桐宽; 清水成夫; 杉山文隆; 伊藤贤一
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2012-08-30
Filing date: 2013-08-21
Publication date: 2014-03-26
Also published as: KR20140029167A; JP6146135B2; TWI567133B; TW201408729A; KR101978655B1; JP2014063133A

Abstract

The invention relates to a liquid crystal orientation agent, a liquid crystal orientation film, a manufacturing method of the liquid crystal orientation film, and a liquid crystal display element. The liquid crystal orientation agent has good printing performance with respect to a substrate and good continuous printing performance and prevents swelling of printing plates. The liquid crystal orientation agent contains at last one polymer (A) selected from the group formed by polyamide acid, polyimide, polyamide acid ester and polysiloxane, a first solvent containing more than one of N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolone, 3-methoxy-N, N-dimethylpropionamide and so on, and a second solvent containing more than one of propylene glycol diacetate, diethylene glycol diethyl ether, diisoamyl ether diacetone alcohol and so on.

Description

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

Technical field

The present invention relates to manufacture method and the liquid crystal display device of a kind of crystal aligning agent, liquid crystal orienting film, liquid crystal orienting film, specifically, relate to the good crystal aligning agent of a kind of printing and the liquid crystal orienting film of making of this crystal aligning agent and liquid crystal display device.

Background technology

In the past, liquid crystal display device has been developed electrode structure or the different multiple type of drive such as physical property of the liquid crystal molecule that uses, for example known have a twisted nematic (Twisted Nematic, TN) type or STN Super TN (Super Twisted Nematic, STN) type, vertical orientation (Vertical Alignment, VA) type, coplanar switching (In-Plane Switching, IPS) type, fringing field switch (Fringe Field Switching, FFS) the various liquid crystal display device such as type, optical compensation curved (Optically Compensated Bend, OCB) type.These liquid crystal display device have for making the liquid crystal orienting film of liquid crystal alignment.With regard to thermotolerance, physical strength, with the good aspect of the various characteristicses such as affinity of liquid crystal with regard to, the material of liquid crystal orienting film can be used polyamic acid (polyamic acid) or polyimide (polyimide), organopolysiloxane (polyorganosiloxane) etc.

In crystal aligning agent, described component of polymer is dissolved in solvent, by this crystal aligning agent is coated on substrate, heats and forms liquid crystal orienting film.In order to make polymkeric substance uniform dissolution, as the solvent of crystal aligning agent, conventionally use non-proton property polar solvents such as METHYLPYRROLIDONE or gamma-butyrolactone herein.In addition, the coating (printing) of the crystal aligning agent when making crystal aligning agent coat on substrate is good, and this solvent is will be such as the lower organic solvent of the surface tension such as ethylene glycol butyl ether and non-proton property polar solvent use (for example, with reference to patent documentation 1 or patent documentation 2).

The method that crystal aligning agent is coated on substrate can be applied the several different methods such as method of spin coating or offset printing (offset printing) method, ink jet method.In these methods, offset printing method normally utilizes following hectographic printing device to carry out, the coating of liquid crystalline orientation agent in the press plate that comprises resins such as APR (registered trademark) etc. of this hectographic printing device, utilize press plate, crystal aligning agent is needed on to (for example, with reference to patent documentation 3) on substrate.

[prior art document]

[patent documentation]

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

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

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

Yet normally used ethylene glycol butyl ether easily makes the swelling of APR resin in order to improve crystal aligning agent to the coating of substrate.Therefore, by offset printing, the crystal aligning agent that comprises ethylene glycol butyl ether is coated in the situation on substrate, by repeatedly crystal aligning agent being coated in press plate, press plate meeting swelling, therefore worrying printing can decline.In addition, even if the solvent composition of crystal aligning agent requires, in the situation that printing continuously, to be also difficult to separate out polymkeric substance on printing press, printing (continuous printing) is good.

Summary of the invention

The present invention forms in view of above-mentioned problem, and main purpose is for providing a kind of not only good to the coating of substrate, and is difficult to make press plate swelling, and the good crystal aligning agent of continuous printing.

The people such as the inventor carry out active research in order to reach the problem of prior art as above, found that, by using specific organic solvent as solvent, can solve above-mentioned problem, thereby complete the present invention.Particularly, by the present invention, provide following crystal aligning agent, liquid crystal orienting film and liquid crystal display device.

In a technical scheme of the present invention, provide a kind of crystal aligning agent, it contains: at least one polymkeric substance (A), and it selects in the cohort that free polyamic acid, polyimide, poly amic acid ester and organopolysiloxane form; The 1st solvent, it is represented compound, the represented compound and 1 of following formula (2) of the free following formula (1) of choosing, 3-dimethyl-2-imidazolinone (1,3-dimethyl-2-imidazolidinone) form at least one in cohort; The 2nd solvent, it is represented represented compound and represented at least one in cohort that compound forms of following formula (5) of compound, following formula (4) of the free following formula (3) of choosing.

[changing 1]

(in formula (1), R ¹for thering is the 1 valency base of " O-" between 1 valency alkyl of carbon number 2～5 or the C-C in this alkyl.)

[changing 2]

(in formula (2), R ²and R ³be respectively 1 valency alkyl of hydrogen atom, carbon number 1～6 or the 1 valency base between the C-C of this alkyl with " O-" independently, R ²with R ³bond and form ring structure mutually; R ⁴alkyl for carbon number 1～6.)

[changing 3]

(in formula (3), R ⁵and R ⁷be 1 valency alkyl of carbon number 1～3 independently respectively, R ⁶alkane two bases (alkanediyl) for carbon number 2～5.)

[changing 4]

(in formula (4), R ⁸1 valency base, the straight chain shape of carbon number 3～5 or at least 1 hydrogen atom of branch-like alkyl between the C-C for the straight chain shape at carbon number 3～5 or branch-like alkyl with 1 " O-" replaces the 1 valency base that forms or the branch-like alkyl of carbon number 3～5 through hydroxyl.)

[changing 5]

(in formula (5), X ¹for-C (OH) R ^a-(wherein, R ^aalkyl for carbon number 1 or 2) ,-CO-or-(wherein, * represents and R COO-* ⁹associative key), R ⁹alkyl for carbon number 1～4.)

The mixed solvent that comprises described the 1st solvent and described the 2nd solvent by use is as the solvent composition of crystal aligning agent, can obtain the coating of substrate well, and press plate is difficult to the crystal aligning agent of swelling.In addition, even if in the situation that printing continuously, polymkeric substance is also difficult to separate out on printing press, can make printing good.

In addition, in a technical scheme of the present invention, the liquid crystal display device that a kind of liquid crystal orienting film being formed by described crystal aligning agent is provided and comprises this liquid crystal orienting film.Liquid crystal orienting film of the present invention is owing to forming with described crystal aligning agent, so not only can form uniformly and film, and membranous good.In addition, in the situation that manufacturing liquid crystal display device with this liquid crystal orienting film, can in manufacturing processing procedure, reduce printing bad, the yield that result can realize goods improves.

Embodiment

Crystal aligning agent of the present invention comprises and selects free polyamic acid, polyimide, poly amic acid ester and organopolysiloxane to form at least one polymkeric substance (A) in cohort as component of polymer, and this polymkeric substance (A) is dissolved in solvent and forms.Below, this crystal aligning agent is described.

< polymkeric substance (A) >

[polyamic acid]

Polyamic acid of the present invention can be by making tetracarboxylic dianhydride react to obtain with diamines.

(tetracarboxylic dianhydride)

For the synthesis of the tetracarboxylic dianhydride of polyamic acid of the present invention such as enumerating: aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.Concrete example as these tetracarboxylic dianhydrides:

Aliphatics tetracarboxylic dianhydride for example can enumerate: 1,2,3,4-butane tetracarboxylic acid dianhydride etc.;

Ester ring type tetracarboxylic dianhydride for example can enumerate: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic base NSC 60134 dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-volution-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyls-2-carboxyl methyl norbornane-2:3, 5:6-dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [33.0] octane-2:4, 6:8-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, hexanaphthene tetracarboxylic dianhydride etc.,

Aromatic tetracarboxylic acid's dianhydride is such as enumerating: pyromellitic acid anhydride etc.; In addition, can use the tetracarboxylic dianhydride who records in Japanese Patent Laid-Open 2010-97188 communique.In addition, described tetracarboxylic dianhydride can be used alone a kind or two or more is used in combination.

With regard to the transparency and to regard to the viewpoints such as solvability of solvent, for the synthesis of tetracarboxylic dianhydride be preferably and comprise ester ring type tetracarboxylic dianhydride.In addition, in ester ring type tetracarboxylic dianhydride, be preferably and comprise choosing free 2, 3, 5-tricarboxylic base NSC 60134 dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride, and 1, 2, 3, 4-tetramethylene at least one in cohort that tetracarboxylic dianhydride forms, be particularly preferably and comprise choosing free 2, 3, 5-tricarboxylic base NSC 60134 dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride, and 1, 2, 3, 4-tetramethylene at least one in cohort that tetracarboxylic dianhydride forms.

Comprising freely 2,3,5-tricarboxylic base NSC 60134 dianhydride, 2 of choosing, 4,6,8-tetracarboxylic dicyclo [3.3.0] octane-2:4,6:8-dianhydride and 1,2,3,4-tetramethylene tetracarboxylic dianhydride forms at least one in cohort situation as described tetracarboxylic dianhydride, with respect to the total amount of the tetracarboxylic dianhydride for the synthesis of polyamic acid, the total content of these compounds is preferably more than 10 % by mole, more preferably 20 % by mole～100 % by mole.

(diamines)

For the synthesis of the diamines of polyamic acid of the present invention such as enumerating: aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.As the concrete example of these diamines, aliphatie diamine for example can be enumerated: m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine etc.;

Ester ring type diamines for example can be enumerated: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (hexahydroaniline), 1, two (amino methyl) hexanaphthenes of 3-etc.;

Aromatic diamine for example can be enumerated: Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, two (4-amino-benzene oxygen) propane of 1,3-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenylene two isopropylidenes) dianiline, 4,4 '-(metaphenylene two isopropylidenes) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethylammonium-1H-indenes-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethylammonium-1H-indenes-6-amine, 3,5-diaminobenzoic acid, cholestane base oxygen base-3,5-diaminobenzene (cholestanyloxy-3,5-diaminobenzene), cholesteryl oxygen base-3,5-diaminobenzene (cholestenyloxy-3,5-diaminobenzene), cholestane base oxygen base-2,4-diaminobenzene, cholesteryl oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester (cholestanyl3,5-diaminobenzoate), 3,5-diaminobenzoic acid cholesteryl ester (cholestenyl3,5-diaminobenzoate), 3,5-diaminobenzoic acid lanostane base ester (lanostanyl3,5-diaminobenzoate), two (the 4-amino benzoyl oxygen base) cholestane (3,6-bis (4-aminobenzoyloxy) cholestane) of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethyl benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexanes of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptyl hexanaphthenes of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptyl hexanaphthenes of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthenes of 1,1-, 2,4-diamino-N, N-diallyl aniline, 4-amino-benzylamine, 3-amino-benzylamine, and following formula (D-1)

[changing 6]

(in formula (D-1), X ⁱand X ^iIbe singly-bound ,-O-, *-COO-, *-OCO-or *-NH-CO-(wherein, having marked associative key and the diamino-phenyl bond of " * ") independently respectively, R ⁱand R ^iIbe respectively alkane two bases of carbon number 1～3 independently, a is 0 or 1, the b integer that is 0～2, the integer that c is 1～20, n be 0 or 1, m be 0 or 1; Wherein, a and b can be not 0 simultaneously, at X ⁱin situation for *-NH-CO-, n is 0)

Represented compound etc.;

Diamino organo-siloxane for example can be enumerated two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc.; In addition, can use the diamines of recording in Japanese Patent Laid-Open 2010-97188 communique.In addition, these diamines can be used alone a kind or two or more is used in combination.

" X in described formula (D-1) ⁱ-(R ⁱ-X ^iI) _n-" represented divalent base is preferably alkane two bases, *-O-, *-COO-, the *-O-C of carbon number 1～3 ₂h ₄-O-or *-NH-CO-(wherein, having marked associative key and the diamino-phenyl bond of " * ").

Base " C _ch _2c+1" concrete example such as enumerating: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.2 amino in diamino-phenyl are preferably with respect to other groups and are positioned at 2,4-position or 3,5-position.

The concrete example of the compound that described formula (D-1) is represented is such as enumerating the represented compound of following formula (D-1-1)～formula (D-1-4) difference etc.

[changing 7]

In addition, diamines can be used alone a kind of these compounds or two or more is used in combination.

The diamines using during synthetic polyamic acid of the present invention is preferably and with respect to whole diamines, comprises 30 % by mole of above aromatic diamines, more preferably comprises more than 50 % by mole, is particularly preferably and comprises more than 80 % by mole.

In the situation that make the used for liquid crystal display element crystal aligning agent of vertical orientation type, for give good vertical orientation, should use have pre-dumping (pretilt) composition as diamines.Particularly, this diamines with pre-dumping composition for example can be enumerated: dodecyloxy-2,4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxyaniline-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane base oxygen base-3,5-diaminobenzene, cholesteryl oxygen base-3,5-diaminobenzene, cholesteryl oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, two (the 4-amino benzoyl oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethyl benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexanes of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptyl hexanaphthenes of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptyl hexanaphthenes of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthenes of 1,1-, the diamines that described formula (A-1) is represented etc.In addition the diamines that, has a pre-dumping composition can be used alone a kind or two or more is used in combination.

The total amount with the diamines of pre-dumping composition is preferably with respect to whole diamines and comprises more than 5 % by mole, more preferably comprises more than 10 % by mole.

In the situation that utilize light orientation method to using made the filming of crystal aligning agent of the present invention to give LCD alignment, be preferably part or all of the polymkeric substance for the preparation of crystal aligning agent of the present invention (A) is made as to the polymkeric substance with light regiospecific structure.Herein, so-called light regiospecific structure, refers to and comprises the two concept of light regiospecific base and decomposition type light orientation portion.Particularly, light regiospecific structure can adopt by passing through photoisomerization or photodimerization, the various compounds of photolysis etc. and performance bright dipping regiospecific and the structure come, for example can enumerate: contain nitrogen benzide or derivatives thereof as the group containing nitrogen benzide of basic framework, contain styracin or derivatives thereof as the group with styracin structure of basic framework, contain phenyl styryl ketone (chalcone) or derivatives thereof as the group containing phenyl styryl ketone of basic framework, contain benzophenone or derivatives thereof as the group containing benzophenone of basic framework, contain tonka bean camphor (coumarin) or derivatives thereof as the group containing tonka bean camphor of basic framework, contain polyimide or derivatives thereof as basic framework containing the structure of polyimide etc.

In the situation that have light regiospecific base as light regiospecific structure as the polyamic acid of described polymkeric substance (A), with regard to having the aspect of high orientation ability, this light regiospecific base is preferably the group with styracin structure.With regard to being easily directed into the aspect in polymkeric substance, this polymkeric substance (A) is preferably the method that above-mentioned illustrated tetracarboxylic dianhydride is reacted with the diamines that comprises the diamines with styracin structure.As the concrete example with the diamines of styracin structure, for example, can enumerate following formula (R1)～formula (R7):

[changing 8]

(in formula (R1)～formula (R5), R ⁱfor the alkyl of carbon number 3～12 or the fluoroalkyl of carbon number 3～12, the integer that a is 1～6)

The compound that difference is represented etc.

Herein, about described formula (R1)～formula (R5), R ⁱthe alkyl of carbon number 3～12 such as enumerating: propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl etc., these alkyl can be any of straight chain shape or branch-like, are preferably straight chain shape.In addition, the fluoroalkyl of carbon number 3～12 replaces the group that forms etc. such as enumerating in the hydrogen atom that above-mentioned illustrative alkyl is had at least 1 with fluorine atom.A is preferably 1～3 integer, and more preferably 1 or 2.2 amino in diamino-phenyl are preferably with respect to other groups and are positioned at 2,4-position or 3,5-position.

In the situation that have decomposition type light orientation portion as light regiospecific structure as the polyamic acid of described polymkeric substance (A), the preferred concrete example of this polymkeric substance (A) is such as enumerating: have to have on the polymkeric substance of dicyclo [2.2.2] octene skeleton, the polymkeric substance with tetramethylene skeleton, main chain and on the polymkeric substance of styracin structure and main chain, have polymkeric substance of the represented structure of following formula (b) etc.:

[changing 9]

(in formula (b), X ²for sulphur atom or Sauerstoffatom; " * " represents respectively associative key; Wherein, in 2 " * ", at least one is binding on aromatic nucleus).

The described polymkeric substance with decomposition type light orientation portion is such as utilizing following methods etc. to obtain: when tetracarboxylic dianhydride and diamine reactant, for example use tetramethylene tetracarboxylic dianhydride, dicyclo [2.2.2] pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride or there is the tetracarboxylic dianhydride of the represented structure of described formula (b) as the method for at least a portion of the tetracarboxylic dianhydride for reacting; Use has for example following formula (c)

[changing 10]

(in formula (c), A ¹for singly-bound or divalent organic radical, B ¹for divalent organic radical; R ¹⁰for substituting group, the integer that n1 is 0～4)

The compound of represented styracin structure or there is the diamines of the represented structure of described formula (b) as the method for at least a portion of the diamines for reacting.

The tetracarboxylic dianhydride who has the represented structure of described formula (b) herein, for example can enumerate following formula (b-1-1)～formula (b-1-6):

[changing 11]

The compound that difference is represented etc.

In addition, the represented compound of described formula (c) for example can be enumerated following (b-2-1)～(b-2-6)

[changing 12]

The compound that difference is represented etc.In addition, the diamines with the represented structure of described formula (b) for example can be enumerated: compound, 4-aminophenyl-4 '-Aminobenzoate, 3 that described formula (b-2-1)～formula (b-2-5) difference is represented, 3 '-dimethyl-4-aminophenyl-4 '-Aminobenzoate, 3,3 ', 5,5 '-tetramethyl--4-aminophenyl-4 '-Aminobenzoate, 3-methyl-4-aminophenyl-4 '-Aminobenzoate, following formula (b-2-8)～formula (b-2-14)

[changing 13]

The compound that difference is represented etc.

In utilizing light orientation method, to filming, give in the situation of LCD alignment ability, entire amount with respect to the polymkeric substance for the synthesis of polyamic acid of the present invention (A), more than the usage ratio with the polymkeric substance (A) of light regiospecific structure is preferably and is made as 10 % by weight, more preferably be made as 30 % by weight～100 % by weight, be especially preferably and be made as 50 % by weight～100 % by weight.

[molecular weight regulator]

During synthesizing polyamides acid, can use suitable molecular weight regulator, the polymkeric substance of synthetic end modified type together with tetracarboxylic dianhydride as above and diamines.By forming the polymkeric substance of this end modified type, can not undermine effect of the present invention, and further improve the coating (printing) of crystal aligning agent.

Molecular weight regulator is such as enumerating monoester anhydride, monoamine compound, monoisocyanates compound etc.As the concrete example of these molecular weight regulators, monoester anhydride is such as enumerating: MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.; Monoamine compound is such as enumerating: aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine etc.; Monoisocyanates compound is such as enumerating: phenylcarbimide, naphthyl isocyanate etc.

With respect to total 100 weight parts of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight regulator is preferably and is made as below 20 weight parts, is more preferably made as below 10 weight parts.

The synthetic > of < polyamic acid

The tetracarboxylic dianhydride that the building-up reactions of polyamic acid of the present invention is provided and the usage ratio of diamines are preferably, amino 1 equivalent with respect to diamines, tetracarboxylic dianhydride's anhydride group becomes the ratio of 0.2 equivalent～2 equivalent, more preferably becomes the ratio of 0.3 equivalent～1.2 equivalent.

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

Herein, organic solvent is such as enumerating: non-proton property polar solvent, phenol series solvent, alcohol, ketone, ester, ether, halohydrocarbon, hydrocarbon etc.

Concrete example as these organic solvents, described non-proton property polar solvent for example can be enumerated: METHYLPYRROLIDONE, 1, 3-dimethyl-2-imidazolinone, N-ethyl-2-pyrrolidone, N-amyl group-2-Pyrrolidone, N-butyl-2-Pyrrolidone, N-methoxy-propyl-2-Pyrrolidone, N-ethoxyethyl group-2-Pyrrolidone, N-methoxyl group butyl-2-Pyrrolidone, N, N-methylacetamide, N, N-METHYLFORMAMIDE, 3-butoxy-N, N-dimethyl propylene acid amides, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-hexyl oxygen base-N, N-dimethyl propylene acid amides, isopropoxy-N-sec.-propyl-propionic acid amide, n-butoxy-N-sec.-propyl-propionic acid amide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc., described phenol series solvent is such as enumerating: phenol, meta-cresol, xylenol, halogenated phenol etc.,

Described alcohol is such as enumerating: methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triethylene glycol, ethylene glycol monomethyl ether, Pyranton etc.; Described ketone is such as enumerating: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, Acetyl Acetone etc.; Described ester is such as enumerating: ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methyl aceto acetate, methoxy methyl propionate, ethoxyl ethyl propionate, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate, glycol diacetate, propylene-glycol diacetate etc.;

Described ether is such as enumerating: diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF), diisopropyl ether, two-secondary butyl ether, two-secondary amyl ether, isoamyl ether etc.;

Described halohydrocarbon for example can be enumerated: methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.; Described hydrocarbon is such as enumerating: hexane, heptane, octane, benzene,toluene,xylene etc.

In these organic solvents, be preferably and use freely more than one in non-proton property polar solvent and phenol cohort that series solvent forms (A solvent) or be selected from more than one in A solvent of choosing, with more than one the mixture selecting in free alcohol, ketone, ester, ether, halohydrocarbon and cohort that hydrocarbon forms (B solvent).Under latter event, with respect to the total amount of A solvent and B solvent, the usage ratio of B solvent is preferably below 50 % by weight, more preferably, below 40 % by weight, is especially preferably below 30 % by weight.

The usage quantity of organic solvent (a) is preferably and is made as: with respect to the total amount (a+b) of reaction soln, the total amount of tetracarboxylic dianhydride and diamines (b) becomes the amount of 0.1 % by weight～50 % by weight.

Obtain in this way polyamic acid is dissolved to the reaction soln forming.This reaction soln can directly be provided in the preparation of crystal aligning agent, also can will after polyamic acid segregation contained in reaction soln, be provided in again the preparation of crystal aligning agent, or also can will after the polyamic acid purifying through segregation, be provided in again the preparation of crystal aligning agent.Polyamic acid is being carried out to dehydration closed-loop make polyimide in the situation that, described reaction soln directly can be provided in to dehydration closed-loop reaction, also can will after polyamic acid segregation contained in reaction soln, be provided in again dehydration closed-loop reaction, or also can will after the polyamic acid purifying through segregation, be provided in again dehydration closed-loop reaction.The segregation of polyamic acid and purifying can carry out according to well-known method.

The synthetic > of < polyimide and polyimide

In crystal aligning agent of the present invention, contained polyimide can be by synthetic in this way polyamic acid is carried out to dehydration closed-loop, in addition imidization and obtaining.

Described polyimide can be amido acid structure that the polyamic acid as its precursor is had all carry out dehydration closed-loop and complete imide compound, can be also only a part for amido acid structure to be carried out to dehydration closed-loop and the part imide compound that makes amido acid structure and imide ring structure and deposit.The imide rate of polyimide of the present invention is preferably more than 30%, and more preferably 40%～99%, be especially preferably 50%～99%.This imide rate is to represent the shared ratio of imide ring number of structures for the amido acid number of structures of polyimide and the total of imide ring number of structures with percentage.Herein, a part for imide ring can be different imide (isoimide) ring.

The dehydration closed-loop of polyamic acid is preferably the method that polyamic acid is heated of utilizing, or utilizes polyamic acid is dissolved in organic solvent, adds dewatering agent and dehydration closed-loop catalyzer in this solution, and the method optionally heating is carried out.Wherein, be preferably a kind of rear method of utilizing.

In the solution of described polyamic acid, add in the method for dewatering agent and dehydration closed-loop catalyzer, dewatering agent is such as using the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.With respect to 1 mole, the amido acid structure of polyamic acid, the usage quantity of dewatering agent is preferably and is made as 0.01 mole～20 moles.Dehydration closed-loop catalyzer is such as using: the tertiary amines such as pyridine (pyridine), collidine (collidine), two picolins (lutidine), triethylamine (triethylamine).With respect to 1 mole of used dewatering agent, the usage quantity of dehydration closed-loop catalyzer is preferably and is made as 0.01 mole～10 moles.The organic solvent using in dehydration closed-loop reaction can be enumerated as the illustrative organic solvent for the synthesis of the organic solvent of polyamic acid.The temperature of reaction of dehydration closed-loop reaction is preferably 0 ℃～180 ℃, more preferably 10 ℃～150 ℃.Reaction times is preferably 1.0 hours～and 120 hours, more preferably 2.0 hours～30 hours.

Obtain in this way the reaction soln that contains polyimide.This reaction soln can directly be provided in the preparation of crystal aligning agent, also can from reaction soln, remove the preparation that is provided in again crystal aligning agent after dewatering agent and dehydration closed-loop catalyzer, also can will after polyimide segregation, be provided in again the preparation of crystal aligning agent, or can also will after the polyimide purifying through segregation, be provided in again the preparation of crystal aligning agent.These purification process can be carried out according to well-known method.

< poly amic acid ester >

Poly amic acid ester contained in crystal aligning agent of the present invention is such as utilizing following methods to obtain: [I] compound by the polyamic acid that makes to be obtained by described building-up reactions and hydroxyl, halogenide, containing the compound of epoxy group(ing) etc., react synthetic method; [II] makes the method for tetracarboxylic acid diester and diamine reactant; [III] makes the method for tetracarboxylic acid diester dihalide and diamine reactant.

The compound of the hydroxyl herein, using in method [I] is such as enumerating: the alcohols such as methyl alcohol, ethanol, propyl alcohol; The phenols such as phenol, cresols etc.In addition, halogenide for example can be enumerated: methyl bromide, bromic ether, bromo-octadecane, methyl chloride, chlorooctadecane, 1,1, the fluoro-2-iodoethane of 1-tri-etc.; Contain the compound of epoxy group(ing) such as enumerating propylene oxide etc.The tetracarboxylic acid diester using in method [II] for example can be by using described alcohols, and illustrative tetracarboxylic dianhydride in described polyamic acid synthetic is carried out to open loop and obtains.In addition, the tetracarboxylic acid diester dihalide using in method [III] can be reacted and be obtained by the suitable chlorizating agent such as the tetracarboxylic acid diester that makes to obtain in this way and thionyl chloride.The diamines using in method [II] and method [III] can be used in described polyamic acid synthetic illustrative diamines etc.In addition, poly amic acid ester can only have amic acid esters structure, can be also amido acid structure and amic acid esters structure the partial esterification thing deposited.

< soltion viscosity and weight average molecular weight >

The polyamic acid obtaining in this way and polyimide are preferably when being made into concentration and being the solution of 10 % by weight, the compound with the soltion viscosity of 10mPas～800mPas, more preferably has the compound of the soltion viscosity of 15mPas～500mPas.In addition, the soltion viscosity of described polymkeric substance (mPas) is to use E type rotational viscosimeter, to the concentration of using the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of this polymkeric substance to prepare, be the polymers soln of 10 % by weight, at 25 ℃, measure and value.

To polyamic acid contained in crystal aligning agent of the present invention and polyimide, utilize gel permeation chromatography (Gel-Permeation Chromatography, the weight average molecular weight of the polystyrene conversion of GPC) measuring is preferably 500～100,000, more preferably 1,000～50,000.

< organopolysiloxane >

Organopolysiloxane of the present invention for example can be by being preferably under the existence of suitable organic solvent, water and catalyzer, water-disintegrable silane compound is hydrolyzed or hydrolytic condensation and obtaining.

Water-disintegrable silane compound for the synthesis of organopolysiloxane for example can be enumerated: METHYL TRICHLORO SILANE, methyltrimethoxy silane, Union carbide A-162, phenyl-trichloro-silicane, phenyltrimethoxysila,e, dimethyl dichlorosilane (DMCS), methyl dimethoxysilane, dimethyldichlorosilane(DMCS), dimethyldimethoxysil,ne, dimethyldiethoxysilane, diphenyl dichlorosilane, dimethoxydiphenylsilane, methoxyl group dimethylsilane, oxyethyl group dimethylsilane, chlorine trimethyl silane, trimethylammonium bromide silane, iodine trimethyl silane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethoxy-silicane, tetraethoxysilane, octadecyl trichlorosilane alkane, octadecyl Trimethoxy silane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane,

3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyl dimethyl methyl TMOS, 3-glycidoxypropyl dimethylethoxysilane, 2-glycidoxypropyl ethyl trimethoxy silane, 2-glycidoxypropyl ethyl-methyl dimethoxy silane, 2-glycidoxypropyl ethyl dimethyl methyl TMOS, 4-glycidoxypropyl butyl trimethoxy silane, 4-glycidoxypropyl butyl dimethyl methyl TMOS, 4-glycidoxypropyl butyl dimethylethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, 3-(3,4-epoxycyclohexyl) propyl trimethoxy silicane, 3-(3,4-epoxycyclohexyl) propyl-triethoxysilicane, (methyl) vinylformic acid (3-Ethyloxetane-3-yl) methyl esters, (methyl) vinylformic acid (3-methyl trimethylene oxide-3-yl) methyl esters,

3-(methyl) acryloxy propyltrichlorosilan, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 2-(methyl) acryloxy ethyl trichlorosilane, 2-(methyl) acryloxy ethyl trimethoxy silane, 2-(methyl) acryloxy ethyl triethoxysilane, 4-(methyl) acryloxy butyl trichlorosilane, 4-(methyl) acryloxy butyl trimethoxy silane, 4-(methyl) acryloxy butyl triethoxyl silane etc.In addition, " (methyl) acryloxy " is the implication that comprises " acryloxy " and " methacryloxy ".

During synthetic organopolysiloxane, spendable organic solvent is such as enumerating hydrocarbon, ketone, ester, ether, alcohol etc.Herein, described hydrocarbon is such as enumerating: toluene, dimethylbenzene etc.; Described ketone is such as enumerating: methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, metacetone, pimelinketone etc.; Described ester is such as enumerating: ethyl acetate, n-butyl acetate, Isoamyl Acetate FCC, propylene glycol methyl ether acetate, 3-methoxyl group butylacetic acid ester, ethyl lactate etc.; Described ether is such as enumerating: glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), dioxan etc.; Described alcohol is such as enumerating: 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol list-positive propyl ether, ethylene glycol list-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list-positive propyl ether etc.In these organic solvents, be preferably and use non-water-soluble organic solvent.In addition, these organic solvents can be used alone a kind or two or more mix is used.

With respect to whole silane compound 100 weight parts, the usage quantity of the organic solvent in the situation of synthetic described organopolysiloxane is preferably 10 weight part～10,000 weight part, 50 weight part～1 more preferably, 000 weight part.In addition, with respect to used whole silane compounds, the usage quantity of the water while manufacturing described organopolysiloxane is preferably 0.5 times mole～100 times moles, more preferably 1 times mole～30 times moles.

During described organopolysiloxane synthetic, spendable catalyzer is such as enumerating: acid, alkali metal compound, organic bases, titanium compound, zirconium compounds etc.Herein, described acid is such as enumerating: hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid etc.; Described alkali metal compound is such as enumerating: sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc.; Described organic bases for example can be enumerated: one-level～secondary organic amine of ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles and so on, three grades of organic amines of triethylamine, three-Tri N-Propyl Amine, three-n-Butyl Amine 99, pyridine, 4-dimethylaminopyridine, diazabicycloundecene and so on, the level Four organic amine of Tetramethylammonium hydroxide and so on etc.

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

Hydrolysis while manufacturing described organopolysiloxane or hydrolysis-condensation reaction are preferably by a kind of water-disintegrable silane compound or two or more are dissolved in organic solvent, the solution of gained is mixed with organic bases and water, such as utilizing oil bath etc. to heat to implement.

During hydrolysis-condensation reaction, be desirably, be preferably Heating temperature is made as below 130 ℃, more preferably 40 ℃～100 ℃, be preferably heating 0.5 hour～12 hours, more preferably heat 1 hour～8 hours.Add and hanker, mixed solution can be stirred, also can be placed under reflux conditions.

After reaction finishes, be preferably the organic solvent layer of fractionation from reaction solution is cleaned with water.While carrying out this cleaning, with regard to cleaning operation, become and be easy to regard to aspect, to be preferably and to use the water that comprises a small amount of salt, such as the aqueous ammonium nitrate solution of 0.2 % by weight left and right etc., clean.Till cleaning can proceed to water layer after cleaning and becomes neutrality, then after organic solvent layer being optionally dried with siccative such as anhydrous calciumsulphate, molecular sieves (molecular sieves), remove solvent, can obtain the organopolysiloxane as target thus.In addition, organopolysiloxane of the present invention also can be used commercially available product.

In crystal aligning agent of the present invention, contained organopolysiloxane can be used the reactive organopolysiloxane being obtained by described condensation reaction by making, and then reacts with the reactive compounds with ad hoc structure and the organopolysiloxane (organopolysiloxane on side chain with the ad hoc structure that is derived from described reactive compounds) that obtains.Herein, reactive organopolysiloxane is such as enumerating the organopolysiloxane with epoxy group(ing), unsaturated double-bond, sulfydryl, amino etc.In addition, reactive compounds is such as enumerating: have chain alkyl compound, have the structure that 2 above rings (such as phenyl ring or cyclohexane ring etc.) link compound, have steroid skeleton compound, have unsaturated double-bond compound, there is the compound of light regiospecific base etc.

In addition, reactive organopolysiloxane can carry out according to vitochemical common method with reacting of reactive compounds.For example, can be by using the organopolysiloxane that there is epoxy group(ing) on side chain as reactive organopolysiloxane, and use the carboxylic acid with ad hoc structure as reactive compounds, obtain the organopolysiloxane on side chain with this ad hoc structure.In addition, the organopolysiloxane that can have unsaturated double-bond by use is as reactive organopolysiloxane, and use the compound with sulfydryl or amino and ad hoc structure as reactive compounds, obtain the organopolysiloxane on side chain with this ad hoc structure.

In organopolysiloxane of the present invention, utilize the weight average molecular weight of the polystyrene conversion that GPC measures to be preferably 500～100,000, more preferably 1,000～30,000, be especially preferably 1,000～20,000.

Crystal aligning agent of the present invention contains the free described polyamic acid of independent a kind of choosing, polyimide, poly amic acid ester and organopolysiloxane and forms the polymkeric substance in cohort, or contains combination of more than two kinds, is used as polymkeric substance (A).Entire amount with respect to the polymkeric substance in this crystal aligning agent (A), proportional can suitably the selection according to used purposes or environment that contain of containing each polymkeric substance, with regard to the viewpoint of acquisition preferably effect of the present invention, be preferably any that at least comprises polyamic acid and polyimide.In this situation, with respect to the entire amount of polymkeric substance contained in crystal aligning agent (A), the total content of polyamic acid and polyimide is preferably 1 % by weight～100 % by weight, more preferably 5 % by weight～100 % by weight.

< solvent >

Other compositions that crystal aligning agent of the present invention is prepared to component of polymer and optionally allotment disperse or dissolve the liquid composition forming in organic solvent.Crystal aligning agent of the present invention contains the 1st solvent and the 2nd solvent is used as solvent composition, described the 1st solvent is represented compound, the represented compound and 1 of described formula (2) of the free described formula (1) of choosing, 3-at least one in cohort that dimethyl-2-imidazolinone forms, described the 2nd solvent is represented represented compound and represented at least one in cohort that compound forms of described formula (5) of compound, described formula (4) of the free described formula (3) of choosing.

[the 1st solvent]

(the represented compound of formula (1))

In the 1st solvent, about the represented compound of described formula (1), R ¹1 valency alkyl of carbon number 2～5 be preferably chain alkyl, such as enumerating alkyl, thiazolinyl, alkynyl of carbon number 2～5 etc.In addition, the 1 valency base that has " O-" between the C-C in this alkyl is such as enumerating alkoxyalkyl of carbon number 2～5 etc.

As the concrete example of these 1 valency alkyl, the alkyl of carbon number 2～5 is such as enumerating: ethyl, propyl group, butyl, amyl group etc.; The thiazolinyl of carbon number 2～5 is such as enumerating: vinyl, 1-propenyl, 2-propenyl, 3-butenyl etc.; The alkynyl of carbon number 2～5 is such as enumerating: ethynyl, 2-propynyl, 2-butyne base etc.; The alkoxyalkyl of carbon number 2～5 is such as enumerating: methoxymethyl, methoxy ethyl, methoxy-propyl, methoxyl group butyl, ethoxyl methyl, ethoxyethyl group etc.; These groups can be straight chain shapes, can be also branch-like.R ¹be preferably alkyl or the alkoxyalkyl of the carbon number 2～5 in described group.

The concrete example of the compound that described formula (1) is represented is such as enumerating: N-ethyl-2-pyrrolidone, N-(n-propyl)-2-Pyrrolidone, N-sec.-propyl-2-Pyrrolidone, N-(normal-butyl)-2-Pyrrolidone, N-(tertiary butyl)-2-Pyrrolidone, N-(n-pentyl)-2-Pyrrolidone, N-methoxy-propyl-2-Pyrrolidone, N-ethoxyethyl group-2-Pyrrolidone, N-methoxyl group butyl-2-Pyrrolidone etc.In these compounds, can particularly preferably use N-ethyl-2-pyrrolidone, N-(n-pentyl)-2-Pyrrolidone, N-(tertiary butyl)-2-Pyrrolidone, N-methoxy-propyl-2-Pyrrolidone.In addition can be used alone a kind of these illustrative compound or two or more is used in combination of the represented compound of described formula (1).

(the represented compound of formula (2))

In the 1st solvent, about the represented compound of described formula (2), R ²and R ³1 valency alkyl of carbon number 1～6 such as enumerating: the chain alkyl of carbon number 1～6, the ester ring type alkyl of carbon number 3～6, carbon number 5 or aromatic hydrocarbyl of 6 etc.In addition, the 1 valency base that has " O-" between the C-C of this alkyl is such as enumerating alkoxyalkyl of carbon number 2～6 etc.

As the concrete example of these 1 valency alkyl, the chain alkyl of carbon number 1～6 is such as enumerating: methyl, ethyl, propyl group, butyl, amyl group, hexyl etc., these groups can be straight chain shapes, can be also branch-like.In addition, the ester ring type alkyl of carbon number 3～6 is such as enumerating cyclopentyl, cyclohexyl etc.; Aromatic hydrocarbyl is such as enumerating phenyl etc.; The alkoxyalkyl of carbon number 2～6 for example can be enumerated R ¹in the compound enumerated etc.In addition the R in formula (2), ²and R ³can be mutually identical, also can be different.In addition, R ²and R ³can be by mutual bond, and and R ²and R ³the nitrogen-atoms of institute's bond forms ring together.R ², R ³mutually bond and the ring that forms, such as enumerating pyrrolidine ring, piperidine ring etc., can bond have the 1 valency chain alkyl such as methyl on these rings.

R ²and R ³be preferably the alkyl of hydrogen atom or carbon number 1～6, more preferably the alkyl of hydrogen atom or carbon number 1～3, is especially preferably hydrogen atom or methyl.

R ⁴the alkyl of carbon number 1～6 can enumerate described R ²and R ³the explanation of alkyl of carbon number 1～6 in illustrated group.Be preferably the alkyl of carbon number 1～4.

The concrete example of the compound that described formula (2) is represented for example can be enumerated: 3-butoxy-N, N-dimethyl propylene acid amides, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-hexyl oxygen base-N, N-dimethyl propylene acid amides, isopropoxy-N-sec.-propyl-propionic acid amide, n-butoxy-N-sec.-propyl-propionic acid amide etc.In addition, the represented compound of described formula (2) can be used alone a kind or two or more is used in combination.

Wherein, the 1st solvent is preferably freely represented compound and at least one in cohort that DMI forms of described formula (1) of choosing, more preferably selects R in the represented compound of free described formula (1) ¹for the alkyl of carbon number 2～5 or the compound of alkoxyalkyl and at least one in cohort that DMI forms.

Suitably suppress when printing on substrate with regard to viewpoint that the component of polymer on printing press separates out, with respect to the entire amount of solvent contained in crystal aligning agent, more than the usage quantity of the 1st solvent is preferably and is made as 5 % by weight, more than being more preferably made as 10 % by weight.In addition, there is no particular restriction for the upper limit of this usage quantity, with respect to the entire amount of solvent contained in crystal aligning agent, is preferably and is made as below 95 % by weight, is more preferably made as below 90 % by weight.Can be used alone a kind of described compound or two or more is used in combination of the 1st solvent.

In addition, polymkeric substance (A) described in described the 1st solvent-soluble solution, and boiling point is moderately high.Therefore infer, by the solvent composition as crystal aligning agent by the 1st solvent, crystal aligning agent suppresses solvent while printing on substrate and volatilizees from printing press, can suppress separating out of component of polymer, and result can make printing (particularly continuous printing) good.Therefore in addition, because the boiling point of solvent can be not too high, the in the situation that of preheating (prebake conditions (prebake)) after printing, can reduce after preheating and remain in the quantity of solvent in filming.Thus, after can suppressing to preheat, at film coated surface adhesive dust, the yield that can suppress goods declines.

[the 2nd solvent]

(the represented compound of formula (3))

In the 2nd solvent, about the represented compound of described formula (3), R ⁵and R ⁷in the alkyl of carbon number 1～3 such as enumerating: the alkyl of the carbon numbers 1～3 such as methyl, ethyl, n-propyl, sec.-propyl; The carbon number such as vinyl, allyl group 2 or 1 valency unsaturated alkyl of 3 etc.In these alkyl, R ⁵and R ⁷be preferably methyl or ethyl.In addition R, ⁵and R ⁷can be mutually identical, also can be different.

R ⁶alkane two bases of carbon number 2～5 for example can enumerate: ethylidene, propane-1,2-bis-bases, propane-1,3-bis-bases, butane-1,3-bis-bases, butane-Isosorbide-5-Nitrae-bis-base, pentane-1,5-bis-bases etc.

The preferred concrete example of the compound that described formula (3) is represented is such as enumerating: the aklylene glycol diacetate esters such as glycol diacetate, propylene-glycol diacetate.Wherein can preferably use propylene-glycol diacetate.Can be used alone a kind of described compound or two or more is used in combination of the represented compound of described formula (3).

(the represented compound of formula (4))

The represented compound of described formula (4) has 2 R ⁸be binding on respectively 1 structure on Sauerstoffatom.As this compound, R ⁸between the C-C for the alkyl at carbon number 3～5, there is the concrete example of compound of 1 valency base of 1 " O-" such as enumerating: diethylene glycol dimethyl ether, diethylene glycol diethyl ether etc.; R ⁸the concrete example of compound that replaces the 1 valency base forming through hydroxyl for the hydrogen atom of the alkyl of carbon number 3～5 is such as enumerating: dipropylene glycol etc.; R ⁸for the concrete example of the compound of branch-like alkyl is such as enumerating: diisopropyl ether, isoamyl ether, two-secondary butyl ether, two-secondary amyl ether etc.In these compounds, the represented compound of described formula (4) be preferably in diethylene glycol diethyl ether and isoamyl ether at least any.In addition can be used alone a kind of described compound or two or more is used in combination of the represented compound of described formula (4).

(the represented compound of formula (5))

X in described formula (5) ¹be preferably base " C (OH) R ^a-", base " C (OH) (CH more preferably ₃)-".In addition, R ⁹the alkyl of carbon number 1～4 can be straight chain shape, can be also branch-like, be preferably methyl or ethyl.

The preferred concrete example of the compound that described formula (5) is represented is such as enumerating: Pyranton, Acetyl Acetone, methyl aceto acetate etc., can particularly preferably be used Pyranton.In addition can be used alone a kind of described compound or two or more is used in combination of the represented compound of described formula (5).

Wherein, the 2nd solvent more preferably selects freely represented compound and represented at least one in cohort that compound forms of described formula (5) of described formula (3), is especially preferably the represented compound of described formula (5).

Just not only suppress separating out of polymkeric substance, and make the good aspect of coating (printing) for substrate, with respect to the entire amount of solvent contained in crystal aligning agent, the usage quantity of the 2nd solvent is preferably 1 % by weight～70 % by weight, more preferably 3 % by weight～60 % by weight.Can be used alone a kind of described compound or two or more is used in combination of the 2nd solvent.

In addition, just make with regard to the good viewpoint of the coating of substrate, the ratio of the 1st solvent and the 2nd solvent is preferably with respect to the usage quantity of the 1st solvent and more than the usage quantity of the 2nd solvent is made as to 0.03 times (weight), more than being more preferably made as 0.05 times (weight).In addition, with regard to the viewpoint of separating out of inhibition polymkeric substance, be preferably and be made as below 2.5 times (weight), be more preferably made as below 2.0 times (weight).

In addition infer, APR (the registered trademark that described the 2nd solvent is difficult to make the press plate of the printing press used when crystal aligning agent is coated on substrate to be used, identical below) resin swelling, during printing, solvent is difficult to infiltrate in press plate, can make thus printing (particularly continuous printing) good.

[the 3rd solvent]

In crystal aligning agent of the present invention, contained solvent can also be used described the 1st solvent and the 2nd solvent other solvents (the 3rd solvent) in addition.The 3rd solvent for example can be enumerated: METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (ethylene glycol butyl ether), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, dipropylene glycol monomethyl ether (dipropylene glycol monomethyl ether, DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, ethylene carbonate, propylene carbonate etc.In addition can be used alone a kind of described compound or two or more mix is used of the 3rd solvent.

With respect to the entire amount of solvent contained in crystal aligning agent, the content of described the 3rd solvent is preferably below 80 % by weight, more preferably, below 70 % by weight, is especially preferably below 50 % by weight, is particularly preferably below 30 % by weight.

Other additives of < >

Crystal aligning agent of the present invention contains polymkeric substance as above and solvent, also can optionally contain other compositions.These other compositions are such as enumerating: in other polymkeric substance beyond described polymkeric substance, molecule, have the compound (hereinafter referred to as " containing the compound of epoxy group(ing) "), functional silanes compound of at least one epoxy group(ing) etc.

[other polymkeric substance]

Described other polymkeric substance can be used for improving solution properties or electrical specification.These other polymkeric substance are such as enumerating: polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.The in the situation that of in these other polymkeric substance are made an addition to crystal aligning agent, with respect to the polymkeric substance total amount in said composition, the allotment ratio of described other polymkeric substance is preferably below 50 % by weight, and more preferably 0.1 % by weight～40 % by weight, is especially preferably 0.1 % by weight～30 % by weight.

[containing the compound of epoxy group(ing)]

Containing the compound of epoxy group(ing), can be used for improving liquid crystal orienting film and tackiness substrate surface or electrical specification.Herein, compound containing epoxy group(ing) for example can be enumerated: ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-glycidyl-benzylamine, N, N-glycidyl-amino methyl hexanaphthene, N, N-diglycidyl-hexahydroaniline etc.

The in the situation that of in these epoxy compoundss are made an addition to crystal aligning agent, total 100 weight parts with respect to polymkeric substance contained in crystal aligning agent, the allotment ratio of these epoxy compoundss is preferably below 40 weight parts, more preferably 0.1 weight part～30 weight part.

[functional silanes compound]

Described functional silanes compound can be used for the object that improves the printing of crystal aligning agent.This functional silanes compound for example can be enumerated: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-tri-ethoxy silylpropyl diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidoxypropyl methyltrimethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 3-glycidoxypropyltrimewasxysilane etc.

The in the situation that of in these functional silanes compounds are made an addition to crystal aligning agent, with respect to total 100 weight parts of polymkeric substance, the allotment ratio of these functional silanes compounds is preferably below 2 weight parts, more preferably 0.02 weight part～0.2 weight part.

In addition,, except above-mentioned, in crystal aligning agent, other contained additives can be used and in molecule, have the compound of at least one oxa-cyclobutyl or antioxidant etc.

Solid component concentration in crystal aligning agent of the present invention (the total weight of the composition beyond the solvent of crystal aligning agent in the gross weight of crystal aligning agent shared ratio) is to consider that viscosity, volatility etc. suitably select, and is preferably the scope of 1 % by weight～10 % by weight.; crystal aligning agent of the present invention is by coating substrate surface in aftermentioned mode; be preferably and heat; and formation filming or becoming filming of liquid crystal orienting film as liquid crystal orienting film; but now; in the situation that solid component concentration is less than 1 % by weight, the thickness of filming becomes too small and cannot obtain good liquid crystal orienting film.On the other hand, in the situation that solid component concentration surpasses 10 % by weight, the thickness of filming becomes excessive and cannot obtain good liquid crystal orienting film, and in addition, the viscosity of crystal aligning agent increases, coating characteristics variation.

The method that the scope of particularly preferred solid component concentration is used during according to coating of liquid crystalline orientation agent on substrate and difference.For example, in the situation that utilizing method of spin coating, solid component concentration is particularly preferably the scope of 1.5 % by weight～4.5 % by weight.In the situation that utilizing offset printing method, be particularly preferably the scope that solid component concentration is made as to 3 % by weight～9 % by weight, thus soltion viscosity is made as to the scope of 12mPas～50mPas.In the situation that utilizing ink jet method, be particularly preferably the scope that solid component concentration is made as to 1 % by weight～5 % by weight, thus soltion viscosity is made as to the scope of 3mPas～15mPas.Temperature while preparing crystal aligning agent of the present invention is preferably 10 ℃～50 ℃, more preferably 20 ℃～30 ℃.

< liquid crystal orienting film and liquid crystal display device >

Liquid crystal orienting film of the present invention is to utilize the crystal aligning agent of preparation in this way to form.In addition, liquid crystal display device of the present invention comprises the liquid crystal orienting film forming with crystal aligning agent of the present invention.The drive pattern of applying liquid crystal display device of the present invention is not particularly limited, can be applicable to the multiple drive modes such as TN type, STN type, IPS type, FFS type, VA type, multi-zone vertical alignment nematic (Multi-domain Vertical Alignment, MVA) type.

Liquid crystal display device of the present invention for example can be manufactured by the step of following (1)～(3).Step (1) is used different substrates according to required drive pattern.Step (2) and step (3) are common in each drive pattern.

[step (1): the formation of filming]

First on substrate, be coated with crystal aligning agent of the present invention, then coated face heated, on substrate, form and film thus.

(1-1) in the situation that manufacturing TN type, STN type, VA type or MVA type liquid crystal display device, using two substrates that are provided with patterned nesa coating as a pair of, on described each transparent conducting film formation face, be preferably and utilize offset printing method, method of spin coating, roll-coater method (roll coater method) or ink jet printing method to be coated with respectively crystal aligning agent of the present invention.As the coating process of crystal aligning agent, because crystal aligning agent of the present invention has the characteristic that is difficult to make the swelling of APR version, so can be preferably applied to the offset printing method in these methods.Herein, substrate is such as enumerating: the glass such as float glass (floatglass), soda glass (soda glass); The transparency carrier that comprises the plastic cement such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).The nesa coating that is arranged at the one side of substrate can be used and comprise stannic oxide (SnO ₂) NESA film (U.S. must big will (PPG) register of company trade mark), comprise Indium sesquioxide-stannic oxide (In ₂o ₃-SnO ₂) ITO film etc.In order to obtain patterned nesa coating, for example, can utilize following methods: form after patternless nesa coating, by photoetch (photo etching), form the method for pattern; While forming nesa coating, use the method for the shade with required pattern etc.During coating of liquid crystalline orientation agent, better for the tackiness that makes substrate surface and nesa coating and film, also can, to forming the face of filming in substrate surface, implement to be coated with in advance the pre-treatment of functional silanes compound, functionality titanium compound etc.

After coating of liquid crystalline orientation agent, for the objects such as sagging that prevent be coated with orientation agent, be preferably and implement to preheat (prebake conditions).Prebake conditions temperature is preferably 30 ℃～200 ℃, more preferably 40 ℃～150 ℃, is particularly preferably 40 ℃～100 ℃.The prebake conditions time is preferably 0.25 minute～and 10 minutes, more preferably 0.5 minute～5 minutes.Then, solvent is removed completely, optionally for the amido acid structure existing in polymkeric substance is carried out to the object of hot-imide, implemented calcining (rear baking (postbake)) step.This calcining (baking afterwards) temperature is preferably 80 ℃～300 ℃, more preferably 120 ℃～250 ℃.Rear baking time is preferably 5 minutes～and 200 minutes, more preferably 10 minutes～100 minutes.So, the thickness of formed film is preferably 0.001 μ m～1 μ m, more preferably 0.005 μ m～0.5 μ m.

(1-2) in the situation that manufacturing IPS type liquid crystal display device or FFS type liquid crystal display device, in being provided with the electrode forming surface of the substrate that comprises the patterned electrode for the nesa coating of interdigitated electrode structure or metallic membrane and not being provided with the one side of the subtend substrate of electrode, be coated with respectively crystal aligning agent of the present invention, then each coated face is heated, form and film thus.The patterning method of heating condition, nesa coating or metallic membrane after the substrate that now used and the material of nesa coating, coating process, coating is, the pre-treatment of substrate and formed preferred thickness of filming are identical with described (1-1).Metallic membrane is such as using the film that comprises the metals such as chromium.

In described (1-1) and arbitrary situation (1-2), all by after coating of liquid crystalline orientation agent on substrate, removal organic solvent forms and becomes filming of alignment film.Now, in crystal aligning agent of the present invention, contained polymkeric substance is polyamic acid, or have in the situation of imide amination polymer of imide ring structure and amido acid structure, also can, by further heating and carry out dehydration closed-loop reaction, make further filming through imidization after the formation of filming.

[step (2): orientation ability is given processing]

Then, by being formed at filming on substrate, optionally carry out friction treatment or photo-irradiation treatment, this is filmed and gives LCD alignment ability.

First, about friction treatment, in the situation that manufacturing TN type, STN type, IPS type or FFS type liquid crystal display device, the friction treatment of filming and being implemented as follows to formation in described step (1): utilize the roller that is wound with the cloth that comprises fibers such as nylon, artificial silk, cotton, to certain orientation friction.Thus, the orientation ability of liquid crystal molecule is imparted to film above becomes liquid crystal orienting film.On the other hand, in the situation that manufacturing VA type or MVA type liquid crystal display device, filming of formation in described step (1) directly can be used as to liquid crystal orienting film, but also can be to this enforcement friction treatment of filming.

In addition, also can further carry out following processing to the liquid crystal orienting film after friction treatment: by the processing that makes the tilt angle in a part of region of liquid crystal orienting film change a part of irradiation ultraviolet radiation of liquid crystal orienting film; Or form after resist film in the part on liquid crystal orienting film surface, to the direction that the friction treatment from is just now different, carry out friction treatment, then remove the processing of resist film; Thereby make liquid crystal orienting film in each region, there is different LCD alignment abilities.In this situation, can improve the visual field characteristic of gained liquid crystal display device.

In the situation that utilizing photo-irradiation treatment (light orientation method), for the substrate of filming after forming, by coated surface being irradiated to the radioactive rays of polarisation or non-polarisation, and this is filmed and gives LCD alignment ability.Herein, radioactive rays for example can be used ultraviolet ray or the visible rays of the light that comprises wavelength 150nm～800nm.Wherein, be preferably the ultraviolet ray of the light that comprises wavelength 300nm～400nm.In the situation that used radioactive rays generation polarisation (linear polarization or part polarisation), rayed direction can be made as the direction vertical with coated surface, also can be made as in order to give tilt angle vergence direction.On the other hand, in the situation that irradiate the radioactive rays of non-polarisation, must to coated surface, carry out rayed from vergence direction.

Light source is such as using: Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.The ultraviolet ray of described preferred wavelength region may can utilize light source and means such as spectral filter, diffraction grating etc. use etc. are obtained.The irradiation dose of radioactive rays is preferably 1J/m ²above and be less than 15,000J/m ², 10J/m more preferably ²above, 10,000J/m ²below.

[step (3): liquid crystal cells construct]

By preparing two substrates that are formed with in this way liquid crystal orienting film, between two substrates of subtend configuration, configure liquid crystal and manufacture liquid crystal cells.While manufacturing liquid crystal cells, for example, can enumerate following 2 kinds of methods.

The first method is front known method for it.First, mode with each liquid crystal orienting film subtend, across gap (cell gap), two substrate subtends are configured, use sealing agent by the periphery laminating of two substrates, in the cell gap of being divided by substrate surface and sealing agent, inject after filling liquid crystal, by filling orifice sealing, can manufacture liquid crystal cells thus.In addition, the second method is the method that is called instillation (One Drop Fill, ODF) mode.Can be by the regulation position on the wherein substrate in being formed with two substrates of liquid crystal orienting film, be coated with for example sealing material of ultraviolet light photopolymerization, and then several positions of the regulation on LCD alignment face drip after liquid crystal, with the mode of liquid crystal orienting film subtend another piece substrate of fitting, and liquid crystal is spread out on whole of substrate, then whole the irradiating ultraviolet light to substrate, makes hardening seal, thereby manufactures liquid crystal cells.In the situation that utilizing any method, it is desirable to by the liquid crystal cells of manufacturing in this way, and then be heated to used liquid crystal and become after the temperature of isotropic phase (isotropic phase), be slowly cooled to room temperature, thus the mobile orientation when removing liquid crystal and filling.

Sealing agent contains stiffening agent and as epoxy resin of the alumina balls of spacer (spacer) etc. such as using.

Liquid crystal can be enumerated nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (smectic liquid crystal), wherein be preferably nematic liquid crystal, such as using: schiff bases (Schiffbase) is that liquid crystal, azoxy (azoxy) are that liquid crystal, biphenyl are that liquid crystal, Santosol 360 are that liquid crystal, ester are that liquid crystal, terphenyl (terphenyl) are that liquid crystal, xenyl hexamethylene methane series liquid crystal, pyrimidine are that liquid crystal, dioxan are that liquid crystal, double-octane are that liquid crystal, cubane (cubane) are liquid crystal etc.In addition, also can in these liquid crystal, add following material uses: cholesterol liquid crystals (cholesteric liquid crystal) such as cholesteryl chloride (cholestil chloride), cholesteryl nonanoate (cholesteryl nonanoate), cholesteryl carbonate (cholesteryl carbonate); The chirality agent of selling as trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company); To oxygen base α-tolylene-to ferroelectric liquid crystals such as amino-2-methyl butyl laurate (p-decyloxybenzylidene-p-amino-2-methylbutylcinmamate) (ferroelectric liquid crystal) etc. in the last of the ten Heavenly stems.

Then, the outer surface laminating Polarizer by liquid crystal cells, can obtain liquid crystal display device of the present invention.The Polarizer that fits in the outside surface of liquid crystal cells can be enumerated: with rhodia protective membrane clamping, being called as the Polarizer that the light polarizing film of " H film " forms, should " H film " be to make polyvinyl alcohol extend the film that orientation makes its absorption iodine on one side; Or comprise itself Polarizer of H film.

In addition, in the situation that carrying out friction treatment to filming, two substrates are angles that frictional direction in respectively filming forms regulation mutually, for example, become the mode subtend configuration of quadrature or antiparallel (antiparallel).In addition, to filming, carrying out in light-struck situation, if liquid crystal orienting film is horizontal direction matching, by adjustment, be formed with the polarization direction angulation of the linear polarization radioactive rays that irradiate and the angle of each substrate and Polarizer in two substrates of liquid crystal orienting film, can obtain the liquid crystal display device with TN type liquid crystal cells or STN type liquid crystal cells.On the other hand, in the situation that liquid crystal orienting film is vertical orientation, by becoming parallel mode Component units to be formed with the direction of the easy axle of orientation (easy orientation axis) in two substrates of liquid crystal orienting film, on this unit, Polarizer is fitted in the mode of its polarization direction and the easy axle shape of orientation angle at 45 °, can be made into the liquid crystal display device with vertical orientation type liquid crystal cells.

Liquid crystal display device of the present invention can be effectively applied to multiple device, for example can be used in: clock and watch, portable game machine (portable video game), word processor (word processor), notes type PC (note type personal computer), auto-navigation system (carnavigation system), video camera (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart mobile phone (smartphone), various watch-dogs (monitor), the display unit of LCD TV etc.

[embodiment]

Below, utilize embodiment to be further specifically described the present invention, but the present invention is not subject to the restriction of these embodiment.

Imide rate, weight average molecular weight and the epoxy equivalent (weight) of the soltion viscosity of each polymers soln in synthesis example, polyimide are to utilize following methods to measure.

[soltion viscosity of polymers soln]

The soltion viscosity of polymers soln (mPas) is to use E type rotational viscosimeter, to using the solvent of regulation, polymer concentration is adjusted into the solution of 10 % by weight, at 25 ℃, measures.

[the imide rate of polyimide]

The solution of polyimide is fed in pure water, the precipitation of gained at room temperature fully after drying under reduced pressure, is dissolved in deuterate dimethyl sulfoxide (DMSO), using tetramethylsilane as primary standard, at room temperature measure ¹h-nucleus magnetic resonance ( ¹h-Nuclear Magnetic Resonance, ¹h-NMR).According to gained ¹h-NMR spectrum, utilizes following mathematical expression (x) to obtain imide rate [%].

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

(in mathematical expression (x), A ¹for near the peak area of the proton that is derived from NH base that occurs chemical shift 10ppm, A ²for being derived from the peak area of other protons, α is that other protons are with respect to the number ratio of 1 proton of the NH base in the precursor (polyamic acid) of polymkeric substance.)

[weight average molecular weight of polymkeric substance, number average molecular weight]

Weight average molecular weight Mw and number average molecular weight Mn are the polystyrene conversion values of utilizing the gel permeation chromatography under following condition to measure.

Tubing string: eastern Cao (Tosoh) (thigh) manufactures, TSKgel GRCXLII

Solvent: tetrahydrofuran (THF)

Temperature: 40 ℃

Pressure: 68kgf/cm ²

[epoxy equivalent (weight)]

Epoxy equivalent (weight) is to utilize hydrochloric acid-methyl ethyl ketone method of recording in JIS C2105 to measure.

Synthetic (1) > of < polymkeric substance (A)

[synthesis example 1: polyimide (PI-1) synthetic]

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic base NSC 60134 dianhydride (TCA) 224g (0.1 mole), as the Ursol D (p-phenylenediamine of diamines, PDA) 86g (0.08 mole) and 3,5-diaminobenzoic acid cholestane base ester (HCDA) 105g (0.02 mole), be dissolved in METHYLPYRROLIDONE (NMP) 166g, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains polyamic acid 20 % by weight.The gained polyamic acid solution that fractionation is a small amount of, adds NMP and makes the solution that polyamic acid concentration is 10 % by weight, to this measured in solution and soltion viscosity be 90mPas.

Then, in the polyamic acid solution of gained, append NMP and make the solution that polyamic acid concentration is 7 % by weight, add pyridine 11.9g and diacetyl oxide 15.3g, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new NMP, intrasystem solvent is carried out to solvent exchange and (by this operation, the pyridine and the diacetyl oxide that in dehydration closed-loop reaction, use are removed to outside system; Identical below), the solution of polyimide (PI-1) 26 % by weight that acquisition contains imide rate approximately 68% thus.The gained polyimide solution that fractionation is a small amount of, adds NMP and makes the solution that polyimide concentration is 10 % by weight, to this measured in solution and soltion viscosity be 45mPas.Then, reaction soln is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyimide (PI-1) thus.

[synthesis example 2: polyimide (PI-2) synthetic]

Using the TCA22.5g as tetracarboxylic dianhydride (0.1 mole), PDA7.6g (0.07 mole), HCDA52g (0.01 mole) and 4 as diamines, 4 '-diaminodiphenyl-methane (DDM) 4.0g (0.02 mole), be dissolved in NMP157g, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains polyamic acid 20 % by weight.The gained polyamic acid solution that fractionation is a small amount of, adds NMP and makes the solution that polyamic acid concentration is 10 % by weight, to this measured in solution and soltion viscosity be 110mPas.

Then, in the polyamic acid solution of gained, append NMP and make the solution that polyamic acid concentration is 7 % by weight, add pyridine 16.6g and diacetyl oxide 21.4g, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new NMP, intrasystem solvent is carried out to solvent exchange, obtain thus the solution of polyimide (PI-2) 26 % by weight that contain imide rate approximately 82%.The gained polyimide solution that fractionation is a small amount of, adds NMP and makes the solution that polyimide concentration is 10 % by weight, to this measured in solution and soltion viscosity be 62mPas.Then, reaction soln is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyimide (PI-2) thus.

[synthesis example 3: polyimide (PI-3) synthetic]

Using as tetracarboxylic dianhydride's 2,4,6,8-tetracarboxylic dicyclo [3.3.0] octane-2:4,6:8-dianhydride (BODA) 24.9g (0.10 mole), as PDA8.6g (0.08 mole) and the HCDA10.4g (0.02 mole) of diamines, be dissolved in NMP176g, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains polyamic acid 20 % by weight.The gained polyamic acid solution that fractionation is a small amount of, adds NMP and makes the solution that polyamic acid concentration is 10 % by weight, to this measured in solution and soltion viscosity be 103mPas.

Then, in the polyamic acid solution of gained, append NMP and make the solution that polyamic acid concentration is 7 % by weight, add pyridine 11.9g and diacetyl oxide 15.3g, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new NMP, intrasystem solvent is carried out to solvent exchange, obtain thus the solution of polyimide (PI-3) 26 % by weight that contain imide rate approximately 71%.The gained polyimide solution that fractionation is a small amount of, adds NMP and makes the solution that polyimide concentration is 10 % by weight, to this measured in solution and soltion viscosity be 57mPas.Then, reaction soln is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyimide (PI-3) thus.

[synthesis example 4: polyimide (PI-4) synthetic]

Using the TCA110g as tetracarboxylic dianhydride (0.50 mole) and 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl) naphtho-[1, 2-c] furans-1, 3-diketone 160g (0.50 mole), PDA91g (0.85 mole) as diamines, 1, two (3-aminopropyl) the tetramethyl disiloxane 25g (0.10 mole) and 3 of 3-, two (4-amino benzoyl oxygen base) the cholestane 25g (0.040 mole) of 6-, and as the aniline 1.4g (0.015 mole) of monoamine, be dissolved in NMP960g, at 60 ℃, carry out reaction in 6 hours, obtain thus the solution that contains polyamic acid.The gained polyamic acid solution that fractionation is a small amount of, adds NMP and makes the solution that polyamic acid concentration is 10 % by weight, to this measured in solution and soltion viscosity be 60mPas.

Then, in the polyamic acid solution of gained, append NMP2,700g, adds pyridine 390g and diacetyl oxide 410g, carries out dehydration closed-loop reaction in 4 hours at 110 ℃.After dehydration closed-loop reaction, with new gamma-butyrolactone, intrasystem solvent is carried out to solvent exchange, obtain thus the solution approximately 2 of polyimide (PI-4) 15 % by weight that contain imide rate approximately 95%, 500g.This solution that fractionation is a small amount of, adds NMP, makes the solution that polyimide concentration is 10 % by weight, to this measured in solution and soltion viscosity be 70mPas.Then, reaction soln is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyimide (PI-4) thus.

[synthesis example 5: polyimide (PI-5) synthetic]

Using the TCA22.4g as tetracarboxylic dianhydride (0.1 mole), as the PDA8.6g (0.08 mole), 4 of diamines, 4 '-diaminodiphenyl-methane 2.0g (0.01 mole) and 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl 3.2g (0.01 mole), be dissolved in NMP324g, at 60 ℃, carry out reaction in 4 hours, obtain the solution that contains polyamic acid 10 % by weight.

Then, in the polyamic acid solution of gained, append NMP360g, add pyridine 39.5g and diacetyl oxide 30.6g, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new NMP, intrasystem solvent is carried out to solvent exchange, obtain the solution of polyimide (PI-5) 10 % by weight that contain imide rate approximately 93%.The gained polyimide solution that fractionation is a small amount of, to this measured in solution and soltion viscosity be 30mPas.Then, reaction soln is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyimide (PI-5) thus.

[synthesis example 6: polyimide (PI-6) synthetic]

Except used diamines is changed to 3,5-diaminobenzoic acid (3,5DAB) 0.08 mole and cholestane base oxygen base-2, beyond 0.02 mole of 4-diaminobenzene (HCODA), utilize the method identical with described synthesis example 1 to obtain polyamic acid solution.The gained polyamic acid solution that fractionation is a small amount of, adds NMP and makes the solution that polyamic acid concentration is 10 % by weight, to this measured in solution and soltion viscosity be 80mPas.

Then, utilize the method identical with described synthesis example 1 to carry out imidization, obtain the solution of polyimide (PI-6) 26 % by weight that contain imide rate approximately 65%.The gained polyimide solution that fractionation is a small amount of, adds NMP and makes the solution that polyimide concentration is 10 % by weight, to this measured in solution and soltion viscosity be 40mPas.Then, reaction soln is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyimide (PI-6) thus.

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

Using as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CB) 200g (1.0 moles), as 2,2 of diamines '-dimethyl-4,4 '-benzidine 210g (1.0 moles), be dissolved in NMP370g and gamma-butyrolactone 3, in the mixed solvent of 300g, carry out reaction in 3 hours at 40 ℃, obtaining solid component concentration is the polyamic acid solution that 10 % by weight, soltion viscosity are 160mPas.Then, this polyamic acid solution is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyamic acid (PA-1) thus.

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

Except used tetracarboxylic dianhydride being made as to 0.9 mole of pyromellitic acid anhydride (PMDA) and CB0.1 mole, and diamines is made as to PDA0.2 mole and 4,4 '-diamino-diphenyl ether (DDE) is in addition, utilize the method identical with described synthesis example 7, obtaining solid component concentration is the polyamic acid solution that 10 % by weight, soltion viscosity are 170mPas.Then, this polyamic acid solution is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyamic acid (PA-2) thus.

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

Using the TCA7.0g as tetracarboxylic dianhydride (0.031 mole), as the represented compound 13g of the following formula (R-1) of diamines (with respect to TCA1 mole, be equivalent to 1 mole), be dissolved in NMP80g, at 60 ℃, carry out reaction in 4 hours, obtain thus the solution that contains polyamic acid (PA-3) 20 % by weight.The soltion viscosity of this polyamic acid solution is 2,000mPas.In addition, the represented compound of following formula (R-1) is to synthesize according to the record of Japanese Patent Laid-Open 2011-100099 communique.Then, this polyamic acid solution is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyamic acid (PA-3) thus.

[changing 14]

[synthesis example 10: organopolysiloxane (APS-1) synthetic]

In possessing the reaction vessel of stirrer, thermometer, dropping funnel and reflux cooling pipe, drop into 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (ECETS) 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, at room temperature mix.Then, utilize dropping funnel, spend 30 minutes and drip after deionized water 100g, under refluxing stir on one side, at 80 ℃, carry out reaction in 6 hours on one side.After reaction finishes, take out organic layer, utilize 0.2 % by weight aqueous ammonium nitrate solution, till the water after cleaning is extremely cleaned becomes neutrality, then under reduced pressure solvent and water are removed in distillation, obtain thus reactive organopolysiloxane (EPS-1) as the transparent liquid of thickness.This reactivity organopolysiloxane is carried out ¹h-NMR analyzes, and result, near chemical shift (δ)=3.2ppm, obtains the peak value based on epoxy group(ing) as described in theoretical strength, confirms the side reaction that does not produce epoxy group(ing) in reaction.The weight average molecular weight Mw of the reactive organopolysiloxane of gained is 3,500, and epoxy equivalent (weight) is 180g/ mole.

Then, to dropping into reactive organopolysiloxane (EPS-1) 10.0g in the there-necked flask of 200mL, as the methyl iso-butyl ketone (MIBK) 30.28g of solvent, as the 4-dodecyloxy phenylformic acid 3.98g of reactive compounds and as the UCAT18X (trade(brand)name of catalyzer, general sieve in Sanya (San-Apro) (thigh) is manufactured) 0.10g reacts 48 hours at 100 ℃ under stirring.After reaction finishes, add ethyl acetate in reaction mixture, by the solution washing of gained 3 times, after using magnesium sulfate that organic layer is dry, solvent is removed in distillation, obtains thus LCD alignment organopolysiloxane (APS-1) 9.0g.The weight average molecular weight Mw of resulting polymers is 9,900.

The preparation of < crystal aligning agent (1) >

[embodiment 1]

Use polyimide (PI-1) as polymkeric substance (A), add wherein N-ethyl-2-pyrrolidone (NEP) and propylene-glycol diacetate (PGDAc) as solvent, making solvent composition is NEP: PGDAc=50: 50 (weight ratios), solid component concentration are the solution of 65 % by weight.With the strainer that aperture is 1 μ m, filter this solution, prepare thus crystal aligning agent (S-1).In addition, crystal aligning agent (S-1) is mainly for the manufacture of the liquid crystal display device of vertical orientation type.

The evaluation > of the swelling of < press plate

Use described crystal aligning agent (S-1), the swelling easness (swelling) of APR version is evaluated.APR version is the resin plate being formed by the subsclerotic aqueous photoresist of uviolizing, is generally used for the press plate of liquid crystal orienting film printing press.In the situation that crystal aligning agent is contacted with APR version, APR version is difficult to swelling, and while referring to printing, crystal aligning agent is difficult to infiltrate in APR version, and printing is good.The evaluation of swelling is by APR version is flooded 1 day in crystal aligning agent, measures the changes in weight of the APR version of dipping front and back and carries out.Now, in the situation that the increasing amount of the weight of APR version is less than 4%, APR version, being difficult to swelling, being evaluated as good (zero), is 4% above in the situation that in increasing amount, and the easy swelling of APR version, is evaluated as bad (*).This evaluation result is shown in to following table 1.

The evaluation > of < printing

For above-mentioned prepared crystal aligning agent, for the printing (continuous printing) when carrying out continuously the printing of substrate, evaluate.Evaluation is to carry out as follows.First, for prepared crystal aligning agent (S-1), (Japan's description printing press (thigh) is manufactured to use liquid crystal orienting film printing press, Angstromer form " S40L-532 "), crystal aligning agent being made as the dripping quantity of anilox roll (anilox roll) under the condition that comes and goes 20 (about 0.2g), be printed on the transparent electrical pole-face of the glass substrate with transparency electrode that comprises ITO film.To the printing of substrate, be to take within 1 minute, as interval, to use new substrate to implement 20 times.

Then, take and as interval, crystal aligning agent is distributed to (oneway in 1 minute, one way) in anilox roll, the operation that at every turn makes anilox roll contact with press plate is (following, be called idling (idling)), add up to and carry out (not carrying out the printing to glass substrate therebetween) 10 times.In addition, this idling is the operation of carrying out in order specially to implement the printing of crystal aligning agent under harsh situation.

After 10 idlings, then with glass substrate, formally print.In formal printing, after idling, take and as interval, 5 substrates are dropped into for 30 seconds, each substrate after printing is heated to (prebake conditions) 1 minute at 80 ℃ and remove after solvent, heating at 200 ℃ (baking afterwards) 10 minutes, forms filming of the about 80nm of thickness.By utilize multiplying power be 20 times microscopic examination this film, evaluate printing (continuous printing).Evaluation is to carry out as follows: by the average evaluation of separating out of not observing polymkeric substance from the 1st time idling formal printing, be continuous printing " good (zero) ", during by the 1st time after idling formal printing, observe separating out of polymkeric substance, but the average evaluation of separating out of no longer observing polymkeric substance in the processes of implementing 5 formal printings is continuous printing " good (△) ", by the average evaluation of separating out that repeatedly carries out still observing after 5 formal printings polymkeric substance, be continuous printing " bad (*) ".This evaluation result is shown in following table 1.In addition, in the situation that the good crystal aligning agent of printing is informed in the process of continuous input substrate by experiment, polymkeric substance separate out goodization (disappearance).In addition, and then the number of times of idling is changed to 15 times, 20 times, 25 times, respectively in the same manner as described above, evaluate the printing of crystal aligning agent.Its evaluation result is also shown in following table 1 in the lump.

[table 1]

[table 2]

The mark of the solvent composition in described table 1 and table 2 is respectively following implication.

A:N-ethyl-2-pyrrolidone

B:N-amyl group-2-Pyrrolidone

C:1,3-dimethyl-2-imidazolinone

D: propylene-glycol diacetate

E: Pyranton

F: diethylene glycol diethyl ether

G: isoamyl ether

H: gamma-butyrolactone

I: propylene carbonate

J:N-N-methyl-2-2-pyrrolidone N-

M: ethylene glycol butyl ether

P: propylene glycol-1-methyl ether acetate

[embodiment 2～embodiment 64 and comparative example 1～comparative example 5]

Except by the kind of used polymkeric substance (A) and solvent and form change to respectively as described in table 1 or table 2 record, utilize the method identical with described embodiment 1, prepare respectively crystal aligning agent (S-2)～crystal aligning agent (S-64) and crystal aligning agent (SR-1)～crystal aligning agent (SR-5).In addition, for each crystal aligning agent, in the mode identical with described embodiment 1, carry out the swelling of press plate and the evaluation of printing.By in the described table 1 of the results are shown in of they and table 2.In addition,, in table 2, about using 2 kinds of polymkeric substance as the embodiment (embodiment 46～embodiment 64) of polymkeric substance (A), represent that in the lump each polymer phase is for the usage ratio (weight ratio) of entire amount 100 weight parts of used polymkeric substance.In addition, in each crystal aligning agent, crystal aligning agent (S-2)～crystal aligning agent (S-45), crystal aligning agent (SR-1)～crystal aligning agent (SR-5) is mainly for the manufacture of vertical orientation type liquid crystal display device, crystal aligning agent (S-46)～crystal aligning agent (S-61) is mainly for the manufacture of TN type liquid crystal display device, crystal aligning agent (S-62) is mainly for the manufacture of the liquid crystal display device of IPS type, crystal aligning agent (S-64) is mainly used in utilizing light orientation method to manufacture vertical orientation type liquid crystal display device, crystal aligning agent (S-63) is mainly for the manufacture of the liquid crystal display device of PSA mode.

[embodiment 65～embodiment 70]

Except the kind of used polymkeric substance (A) and solvent and composition are changed to respectively as recording in following table 3, utilize the method identical with described embodiment 1, prepare respectively crystal aligning agent (S-65)～crystal aligning agent (S-70).In addition, for each crystal aligning agent, in the mode identical with described embodiment 1, carry out the swelling of press plate and the evaluation of printing.By in the following table 3 of the results are shown in of they.In addition,, in table 3, about using 2 kinds of polymkeric substance as embodiment 69, the embodiment 70 of polymkeric substance (A), represent that in the lump each polymer phase is for the usage ratio (weight ratio) of entire amount 100 weight parts of used polymkeric substance.In addition, in each crystal aligning agent, crystal aligning agent (S-65)～crystal aligning agent (S-68) is mainly for the manufacture of vertical orientation type liquid crystal display device, crystal aligning agent (S-69) is mainly for the manufacture of TN type liquid crystal display device, and crystal aligning agent (S-70) is mainly for the manufacture of the liquid crystal display device of PSA mode.

[table 3]

In the mark of the solvent composition in described table 3, the mark beyond the mark of recording in described table 1 and table 2 is respectively following implication.

K:3-methoxyl group-N, N-dimethyl propylene acid amides

1:3-butoxy-N, N-dimethyl propylene acid amides

As shown in table 1, table 2 and table 3, in embodiment, be all difficult to make the swelling of APR version.Therefore,, in the situation that the crystal aligning agent of embodiment, the expansion of the press plate in the time of can suppressing to print, can coat crystal aligning agent on substrate equably.In addition, about continuous printing, in embodiment, be good.On the other hand, compare with embodiment, the continuous printing of the crystal aligning agent of comparative example is poor.In addition, about comparative example 2, comparative example 4, comparative example 5, the degree of the swelling of APR version is large.

Synthetic (2) > of < polymkeric substance (A)

[synthesis example 11: polyamic acid (PA-4) synthetic]

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic base NSC 60134 dianhydride 2.24g (0.01 mole) and being dissolved in METHYLPYRROLIDONE (NMP) 27.1g as the represented compound 2.54g of the described formula (b-2-1) of diamines (0.01 mole), at 40 ℃, carry out reaction in 3 hours, obtain thus the solution 31.8g that contains polyamic acid (PA-4) 15 % by weight.The soltion viscosity of this polyamic acid solution is 65mPas.Then, this polyamic acid solution is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyamic acid (PA-4) thus.

[synthesis example 12: polyamic acid (PA-5) synthetic]

Using the represented compound 4.845g (0.0106 mole) of the described formula (b-1-1) as tetracarboxylic dianhydride, as the Ursol D 1.155g (0.0107 mole) of diamines, be dissolved in NMP54g, at room temperature carry out reaction in 6 hours.Thus, obtain the polyamic acid solution 59g that solid component concentration is 10%, soltion viscosity is 130mPas.Then, this polyamic acid solution is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyamic acid (PA-5) thus.

[synthesis example 13: polyamic acid (PA-6) synthetic]

Using as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride 19.6g (0.10 mole), as the Ursol D 10.8g (0.10 mole) of diamines, be dissolved in NMP369.6g, at room temperature carry out reaction in 6 hours.Then, reaction mixture is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyamic acid (PA-6) thus.

[synthesis example 14: polyimide (PI-7) synthetic]

Using as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic base NSC 60134 dianhydride 5.94g, as 3 of diamines, 5-diaminobenzoic acid 1.65g, cholestane base oxygen base-2,4-diaminobenzene 1.35g, represented compound 2.51g and the represented compound 2.54g of following formula (d-1) of described formula (D-1-4) are dissolved in NMP56g, at 60 ℃, carry out reaction in 6 hours, obtain thus the solution that contains polyamic acid 20 % by weight.This solution that fractionation is a small amount of, adds NMP and makes the solution that polyamic acid concentration is 10% weight, at 25 ℃, measure and soltion viscosity be 60mPas.

[changing 15]

Then, in the polyamic acid solution of gained, append NMP70g, add pyridine 3.15g and diacetyl oxide 4.06g, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new NMP, intrasystem solvent is carried out to solvent exchange, obtain thus and contain the solution that imide rate is 74% polyimide (PI-7) 20 % by weight.This solution that fractionation is a small amount of, adds NMP, makes the solution that polyimide concentration is 10 % by weight, at 25 ℃, measure this solution and soltion viscosity be 55mPas.Then, reaction soln is injected in excessive methyl alcohol, makes resultant of reaction precipitation.This throw out, with washed with methanol, under reduced pressure, at 40 ℃ dry 15 hours, is obtained to polyimide (PI-7) thus.

[synthesis example 15: poly amic acid ester (PAE-1) synthetic]

In adding the four-hole boiling flask of the 100mL that has stirrer, drop into the represented compound 2.68g (950mmol) of following formula (t-1), then add NMP69.9g, stir and make its dissolving.Then, add triethylamine 0.506g (5.00mmol) and the represented compound 2.58g (10.0mmol) of following formula (d-2), stir and make its dissolving.Stir this solution on one side, add 4-(4 on one side, 6-dimethoxy-1,3,5-triazine-2-yl)-4-methyl chlorination morpholine (DMT-MM (15 ± 2 % by weight hydrate)) 9.96g (36.0mmol), and then add NMP12.5g, at room temperature stir 4 hours and obtain the solution that comprises poly amic acid ester (PAE-1).Soltion viscosity at 25 ℃ of this polyamic acid ester solution is 30.9mPas.Then, this polyamic acid ester solution is fed in methyl alcohol (589g), by the throw out filtering separation of gained.By this throw out with washed with methanol after, drying under reduced pressure at 100 ℃, obtains the powder of poly amic acid ester (PAE-1).The number average molecular weight of this poly amic acid ester (PAE-1) is Mn=17,800, and weight average molecular weight is Mw=39,700.

[change] 6]

[embodiment 71～embodiment 75]

Except the kind of used polymkeric substance (A) and solvent and composition are changed to respectively as recording in following table 4, utilize the method identical with described embodiment 1, prepare respectively crystal aligning agent (S-71)～crystal aligning agent (S-75).In addition, for each crystal aligning agent, in the mode identical with described embodiment 1, carry out the swelling of press plate and the evaluation of printing.By in the following table 4 of the results are shown in of they.

[table 4]

The mark of the solvent composition in described table 4 is identical with described table 1, table 2 and table 3.

As shown in table 4, the crystal aligning agent of embodiment 71～embodiment 75 is all difficult to make the swelling of APR version, and continuous printing is also good.In addition, even if in the situation that the number of times of idling is made as 25 times, from the 1st time idling formal printing, also do not observe separating out of polymkeric substance, continuous printing is the evaluation of " good ".

The evaluation > of the manufacture of < liquid crystal display device and LCD alignment

[embodiment 71A]

Using one side there is the glass substrate of the patterned metal electrode that comprises chromium for comb teeth-shaped, with the subtend glass substrate that is not provided with electrode as a pair of, in the face with electrode of glass substrate and the one side of subtend glass substrate, with turner, be coated with respectively above-mentioned prepared crystal aligning agent (S-71).Then, utilize the hot-plate of 80 ℃ to carry out 1 minute prebake conditions, then, in by storehouse, carry out in the baking oven after nitrogen displacement, heating at 200 ℃ (baking afterwards) 1 hour, forming thickness is filming of 0.1 μ m.Then,, to these film coated surface, use respectively Hg-Xe lamp and Glan-Taylor prism (Glan-Taylor prism), with polarisation ultraviolet ray 10,000J/m ², from the vertical direction of real estate, irradiate, obtain a pair of substrate with liquid crystal orienting film.

Then, the periphery of the face with liquid crystal orienting film of the wherein substrate in a pair of substrate, utilize screen painting to be coated with to add that to have diameter be the epoxy resin tackiness agent of the alumina balls of 3.5 μ m, then the liquid crystal orienting film that makes a pair of substrate in the face of to, each substrate when irradiating polarisation ultraviolet ray towards becoming the overlapping crimping of contrary mode, at 150 ℃, spend 1 hour and make tackiness agent heat embrittlement.Then, from liquid crystal injecting port, in the gap between substrate, fill the liquid crystal " MLC-7028 " that Merck & Co., Inc. manufactures, then utilizing epoxy is that tackiness agent seals liquid crystal injecting port.And then, the mobile orientation when eliminating Liquid crystal pour, and be slowly cooled to again room temperature after it is heated at 150 ℃.Then,, on the two sides, outside of substrate, with the polarization direction of Polarizer, mode mutually orthogonal and the projection direction quadrature on real estate with the ultraviolet optical axis of polarisation of liquid crystal orienting film the Polarizer of fitting, manufactures liquid crystal display device thus.

The evaluation > of < LCD alignment

Liquid crystal display device to above-mentioned manufacturing, the having or not of the abnormal area in the variation of the light and shade while utilizing opticmicroscope to observe to apply/remove 5V voltage.Evaluation is to carry out as follows: by the average evaluation of not observing abnormal area, being LCD alignment " well ", is LCD alignment " bad " by the average evaluation of observing abnormal area.Its result is, in this liquid crystal display device, do not observe abnormal area, and LCD alignment is good.

[embodiment 72A]

Except used crystal aligning agent being changed to crystal aligning agent (S-72), in the mode identical with described embodiment 71A, manufacture liquid crystal display device, and the LCD alignment of the liquid crystal display device of manufacturing is evaluated.Its result is, in this liquid crystal display device, do not observe abnormal area, and LCD alignment is good.

[embodiment 73A]

Except used crystal aligning agent being changed to crystal aligning agent (S-73), in the mode identical with described embodiment 71A, manufacture liquid crystal display device, and the LCD alignment of the liquid crystal display device of manufacturing is evaluated.Its result is, in this liquid crystal display device, do not observe abnormal area, and LCD alignment is good.

Claims

1. a crystal aligning agent, is characterized in that containing:

At least one polymkeric substance (A), it selects in the cohort that free polyamic acid, polyimide, poly amic acid ester and organopolysiloxane form;

The 1st solvent, it is freely represented compound, represented compound and at least one in cohort that DMI forms of following formula (2) of following formula (1) of choosing; And

The 2nd solvent, it is freely represented represented compound and represented at least one in cohort that compound forms of following formula (5) of compound, following formula (4) of following formula (3) of choosing:

In formula (1), R ¹for thering is the 1 valency base of " O-" between 1 valency alkyl of carbon number 2～5 or the C-C in described alkyl;

In formula (2), R ²and R ³be respectively 1 valency alkyl of hydrogen atom, carbon number 1～6 or the 1 valency base between the C-C of described alkyl with " O-" independently, R ²with R ³bond and form ring structure mutually; R ⁴alkyl for carbon number 1～6;

In formula (3), R ⁵and R ⁷be 1 valency alkyl of carbon number 1～3 independently respectively, R ⁶alkane two bases for carbon number 2～5;

In formula (4), R ⁸1 valency base, the straight chain shape of carbon number 3～5 or at least 1 hydrogen atom of branch-like alkyl between the C-C for the straight chain shape at carbon number 3～5 or branch-like alkyl with 1 " O-" replaces the 1 valency base that forms or the branch-like alkyl of carbon number 3～5 through hydroxyl;

In formula (5), X ¹for-C (OH) R ^a-,-CO-or-COO-*; Wherein, R ^afor the alkyl of carbon number 1 or 2, * represents and R ⁹associative key; R ⁹alkyl for carbon number 1～4.

2. crystal aligning agent according to claim 1, is characterized in that: the content of described the 2nd solvent is 1 % by weight～70 % by weight of solvent integral body contained in crystal aligning agent.

3. crystal aligning agent according to claim 1 and 2, it is characterized in that: comprise choosing and freely make tetracarboxylic dianhydride react with diamines and the polyamic acid, polyimide and the poly amic acid ester that obtain form in cohort that at least one is used as described polymkeric substance (A), and described tetracarboxylic dianhydride comprises choosing free 2,3,5-tricarboxylic base NSC 60134 dianhydride, 2,4,6,8-tetracarboxylic dicyclo [3.3.0] octane-2:4,6:8-dianhydride and 1,2,3,4-tetramethylene at least one in cohort that tetracarboxylic dianhydride forms.

4. crystal aligning agent according to claim 1 and 2, is characterized in that: described polymkeric substance (A) is for having the polymkeric substance of light regiospecific structure.

5. a manufacture method for liquid crystal orienting film, is characterized in that comprising:

Crystal aligning agent according to claim 4 is coated on substrate and formed the step of filming; And

Described filming carried out rayed and made the step of liquid crystal orienting film.

6. a liquid crystal orienting film, is characterized in that: it is to use to form according to the crystal aligning agent described in any one in claim 1 to 4.

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