CN103627406B - Crystal aligning agent, liquid crystal orienting film and liquid crystal display cells - Google Patents

Crystal aligning agent, liquid crystal orienting film and liquid crystal display cells Download PDF

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Publication number
CN103627406B
CN103627406B CN201310339587.4A CN201310339587A CN103627406B CN 103627406 B CN103627406 B CN 103627406B CN 201310339587 A CN201310339587 A CN 201310339587A CN 103627406 B CN103627406 B CN 103627406B
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liquid crystal
aligning agent
crystal aligning
compound
acid
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CN103627406A (en
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植阪裕介
加藤孝人
野口峻
野口峻一
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JSR Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention relates to a kind of crystal aligning agent, liquid crystal orienting film and liquid crystal display cells.The present invention provides a kind of not only coating on substrate good, and is difficult to make galley swelling, and the crystal aligning agent that continuous printing is good.The crystal aligning agent of the present invention comprises: select at least one polymer (A) in the formed group of free polyamic acid, polyimides, poly amic acid ester and polysiloxane；And comprise the solvent of compound (p1) represented by following formula (1).(in formula (1), R1And R3It is separately 1 valency alkyl of the carbon number 1～3 of straight-chain or branch-like, R2Alkane diyl for the carbon number 2～5 of straight-chain or branch-like.).

Description

Crystal aligning agent, liquid crystal orienting film and liquid crystal display cells
Technical field
The present invention relates to a kind of crystal aligning agent, liquid crystal orienting film and liquid crystal display cells, especially relate to And the good crystal aligning agent of a kind of printing and the liquid crystal that uses this crystal aligning agent to make join To film and liquid crystal display cells.
Background technology
In the past, liquid crystal display cells had developed electrode structure or the physical property etc. of liquid crystal molecule used The liquid crystal display cells of different multiple type of drive, the most known have 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 switching (Fringe Field Switching, FFS) type, optical compensation curved (Optically Compensated Bend, OCB) the various liquid crystal display cells such as type.These liquid crystal display cells have There is the liquid crystal orienting film for making liquid crystal alignment.Parent with regard to thermostability, mechanical strength and liquid crystal For the aspect good with the various characteristics such as property, the material of liquid crystal orienting film is to use polyamic acid or poly- Acid imide, polysiloxane etc..
In crystal aligning agent, component of polymer is dissolved in solvent, is coated with by by this crystal aligning agent On substrate, carry out heating and forming liquid crystal orienting film.Herein, in order to make polymer uniform dissolve, The solvent of crystal aligning agent generally uses such as METHYLPYRROLIDONE or gamma-butyrolacton etc. non-proton Property polar solvent.It addition, in order to make crystal aligning agent when being coated on substrate by crystal aligning agent Coating (printing) is good, and by surfaces such as such as butyl cellosolves (butyl cellosolve) The relatively low organic solvent of warp tension ratio and above-mentioned organic solvent with (referring for example to patent documentation 1 or patent Document 2).
The method on substrate that crystal aligning agent is coated be application method of spin coating or lithography, The multiple method such as ink-jet method.In these methods, lithography is typically to utilize following hectographic printing Device is carried out, and this hectographic printing device is in the galley comprising the resins such as APR (registered trade mark) Coating of liquid crystalline orientation agent, utilizes this galley, crystal aligning agent is needed on substrate (referring for example to Patent documentation 3).
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2010-97188 publication
[patent documentation 2] Japanese Patent Laid-Open 2010-156934 publication
[patent documentation 3] Japanese Patent Laid-Open 2001-343649 publication
But, in order to improve the coating of crystal aligning agent and normally used butyl cellosolve easily makes APR resin swelling.Therefore, by lithographic printing, the crystal aligning agent comprising butyl cellosolve is being coated with In the case of being distributed on substrate, carry out by repeatedly crystal aligning agent being coated in galley, print The meeting swelling of brush version, thus worry printing can decline.It addition, the solvent composition requirement of crystal aligning agent Even if in the case of being carried out continuously printing, it is also difficult to separate out polymer on the printer, printing is (even Continuous printing) good.In view of above-mentioned background, in order to the printing making crystal aligning agent is good, it is desirable to Find a kind of not only coating on substrate good, and be difficult to make the organic molten of galley swelling Agent, and be precipitation organic molten being also difficult to produce on the printer polymer when continuous printing Agent.
Summary of the invention
The present invention is to be formed in view of above-mentioned problem, and main purpose is for providing a kind of not only on substrate Coating is good, and is difficult to make galley swelling, and the crystal aligning agent that continuous printing is good.
Present inventor et al. actively studies to reach the problem of prior art as above, It was found that by using at least some of as solvent of specific compound, it is possible to resolve above-mentioned class Topic, thus complete the present invention.Specifically, by the present invention provide following crystal aligning agent, Liquid crystal orienting film and liquid crystal display cells.
In one technical scheme of the present invention, it is provided that a kind of crystal aligning agent, it contains: select free polyamides At least one in the formed group of amino acid, polyimides, poly amic acid ester and polysiloxane is gathered Compound (A)；And comprise the solvent of compound (p1) represented by following formula (1).
[changing 1]
In formula (1), R1And R3Be separately straight-chain or branch-like carbon number 1～3 1 Valency alkyl, R2Alkane diyl for the carbon number 2～5 of straight-chain or branch-like.
By use compound (p1) as solvent at least some of of crystal aligning agent, can not only Enough coatings good to crystal aligning agent imparting when being printed on substrate, and APR can be made Version is difficult to swelling.Even if it addition, above-mentioned crystal aligning agent is in the case of being carried out continuously printing, also difficult To produce the precipitation of polymer on the printer, printing is good.
In another technical scheme of the present invention, it is provided that one does not contain only above-claimed cpd (p1), and And possibly together with choosing freely 1, compound represented by 3-dimethyl-2-imidazolidinone, following formula (2), And at least one compound (p2) in the formed group of compound represented by following formula (3) It is used as the crystal aligning agent of solvent composition.
[changing 2]
In formula (2), R4And R5Be separately hydrogen atom, 1 valency alkyl of carbon number 1～6, Or between the carbon-carbon bond of this alkyl, comprise the 1 valency base of "-O-", R4With R5Can mutually bond and shape Become ring structure；R6Alkyl for carbon number 1～6.
[changing 3]
In formula (3), R7For between 1 valency alkyl of carbon number 2～5 or the carbon-carbon bond in this alkyl Comprise the 1 valency base of "-O-".
It addition, in a technical scheme of the present invention, it is provided that a kind of liquid formed by above-mentioned crystal aligning agent Brilliant alignment film and include the liquid crystal display cells of this liquid crystal orienting film.The liquid crystal orienting film of the present invention by Then using above-mentioned crystal aligning agent to be formed, so uniform film can be formed, and film quality is good. It addition, in the case of using this liquid crystal orienting film to manufacture liquid crystal display cells, manufacturing can in processing procedure Reducing printing bad, result can improve the yield of goods.
Detailed description of the invention
The crystal aligning agent of the present invention is not only to comprise choosing free polyamic acid, polyimides, polyamide At least one polymer (A) in acid esters and the formed group of polysiloxane becomes as polymer Point, and this polymer (A) forms for being dissolved in solvent.Hereinafter, this crystal aligning agent is entered Row explanation.
<polyamic acid>
The polyamic acid of the present invention can obtain with diamine reactant by making tetracarboxylic dianhydride.
[tetracarboxylic dianhydride]
Aliphatic tetrabasic carboxylic acid is include, for example for synthesizing the tetracarboxylic dianhydride of the polyamic acid of the present invention Dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc..As these tetracarboxylic dianhydrides' Concrete example:
Aliphatic tetracarboxylic dianhydride include, for example: 1,2,3,4-butane tetracarboxylic acid dianhydride etc.；
Ester ring type tetracarboxylic dianhydride include, for example: 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride, 2,3,5-tri- Carboxyl 2-Cyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-bis-side oxygen-3-furyl)-naphthalene And [1,2-c] furan-1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydrochysene-2,5-bis-side oxygen-3- Furyl)-naphtho-[1,2-c] furan-1,3-diketone (1,3,3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphth O [1,2-c] furan-1,3-dione), 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-volution-3 '-(tetrahydrochysene Furan-2 ', 5 '-diketone), 5-(2,5-bis-side oxygen tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acids Acid anhydride, 3,5,6-tri-carboxyl-2-carboxymethyl group norbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxylic dicyclos [3.3.0] octane-2:4,6:8-dianhydride, 4,9-dioxa three ring [5.3.1.02,6] hendecane-3,5,8,10-tetrones, Cyclopentanetetracarboxylic's dianhydride etc.；
Aromatic tetracarboxylic acid's dianhydride include, for example pyromellitic acid anhydride etc.；In addition, can use Tetracarboxylic dianhydride described in Japanese Patent Laid-Open 2010-97188 publication.Additionally, above-mentioned tetrabasic carboxylic acid Dianhydride can be used alone a kind or two or more be applied in combination.
The just transparency and for the viewpoints such as the dissolubility of solvent, excellent for the tetracarboxylic dianhydride of synthesis Elect as and comprise ester ring type tetracarboxylic dianhydride.It addition, in ester ring type tetracarboxylic dianhydride, preferably comprise choosing Free 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-bis-side oxygen -3-furyl)-naphtho-[1,2-c] furan-1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydrochysenes -2,5-bis-side oxygen-3-furyl)-naphtho-[1,2-c] furan-1,3-diketone, 2,4,6,8-tetracarboxylic dicyclos [33.0] Octane-2:4,6:8-dianhydride and 1, at least in 2,3,4-the formed groups of Tetramethylene. tetracarboxylic dianhydride Kind, particularly preferably comprise choosing freely 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides, 2,4,6,8-tetracarboxylic Dicyclo [3.3.0] octane-2:4,6:8-dianhydride and 1,2,3,4-the formed groups of Tetramethylene. tetracarboxylic dianhydride In at least one.
Comprising choosing freely 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides, 2,4,6,8-tetracarboxylic dicyclos [3.3.0] Octane-2:4,6:8-dianhydride and 1, at least in 2,3,4-the formed groups of Tetramethylene. tetracarboxylic dianhydride In the case of planting as above-mentioned tetracarboxylic dianhydride, relative to the tetracarboxylic dianhydride for synthesizing polyamides acid Total amount, the total content of these compounds is preferably 10 moles of more than %, more preferably 20 moles %～100 moles of %.
[diamidogen]
The diamidogen used to synthesize the polyamic acid of the present invention include, for example: aliphatic diamine, Ester ring type diamidogen, aromatic diamine, diaminourea organosiloxane etc..As the concrete example of these diamidogen, Aliphatic diamine include, for example: m-xylene diamine (metaxylylene diamine), 1,3-propane diamine, Tetra-methylenedimine, five methylene diamine, hexamethylene diamine etc.；
Ester ring type diamidogen include, for example: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexylamine), 1,3-double (amino methyl) hexamethylene etc.；
Aromatic diamine include, for example: p-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-two ADP base thioether, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(three Methyl fluoride)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2, the double [4-(4-of 2- Amino-benzene oxygen) phenyl] propane, 9, double (4-aminophenyl) fluorenes of 9-, 2, the double [4-(4-amino-benzene oxygen) of 2- Phenyl] HFC-236fa, 2,2-double (4-aminophenyl) HFC-236fa, 4,4 '-(to phenylenediisopropylidene) Dianil, 4,4 '-(metaphenylene two isopropylidene) dianils, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '- Double (4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavins, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6- Diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-benzidine, N, N '- Double (4-aminophenyl)-N, N '-dimethylbenzidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 1-(4-amino Phenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indenes-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3- Trimethyl-1H-indenes-6-amine, 3,5-diaminobenzoic acid, cholesteric alkyl oxy-3,5-diaminobenzene (cholestanyloxy-3,5-diaminobenzene), cholesteryl epoxide-3,5-diaminobenzene (cholestenyloxy-3,5-diaminobenzene), cholesteric alkyl oxy-2,4-diaminobenzene, cholesteric Thiazolinyl epoxide-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteric Arrcostab (cholestanyl 3,5-diaminobenzoate), 3,5-diaminobenzoic acid cholesteryl ester (cholestenyl 3,5-diaminobenzoate), 3,5-diaminobenzoic acid lanostane base ester (lanostanyl 3,5-diaminobenzoate), 3, double (the 4-aminobenzoic acyloxy) cholestane of 6- (3,6-bis (4-aminobenzoyloxy) cholestane), 3, double (4-amino-benzene oxygen) cholestane of 6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethyl Benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 1, double (4-((aminophenyl) methyl) benzene of 1- Base)-4-butyl cyclohexane, 1, double (4-((aminophenyl) methyl) phenyl)-4-heptylcyclohexane of 1-, 1,1-is double (4-((amino-benzene oxygen) methyl) phenyl)-4-heptylcyclohexane, 1, double (4-((aminophenyl) methyl) benzene of 1- Base)-4-(4-heptyl cyclohexyl) hexamethylene, 2,4-diamino-N, N-diallyl aniline, 4-amino-benzylamine, 3-amino-benzylamine and following formula (A-1-1)～formula (A-1-3)
[changing 4]
Compound etc. represented by Fen Bie；
Diaminourea organosiloxane include, for example: 1,3-double (3-aminopropyl)-tetramethyl disiloxanes Deng；In addition, the diamidogen described in Japanese Patent Laid-Open 2010-97188 publication can be used.This Outward, these diamidogen can be used alone a kind or two or more be applied in combination.
The diamidogen used when synthesizing the polyamic acid of the present invention is preferably and comprises relative to total diamidogen The aromatic diamine of 30 moles of more than %, more preferably comprises 50 moles of more than %, particularly preferably Comprise 80 moles of more than %.
It addition, in the case of the crystal aligning agent used for liquid crystal display element of vertical orientation type, in order to compose Give good vertical orientation, preferably use and there is pre-dumping (pretilt) composition person as diamidogen.Specifically For, this diamidogen with pre-dumping composition include, for example: dodecyloxy-2,4-diaminobenzene, Tetradecyloxyaniline-2,4-diaminobenzene, pentadecane epoxide-2,4-diaminobenzene, hexadecane epoxide-2,4-bis- Aminobenzene, octadecane epoxide-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecane oxygen Base-2,5-diaminobenzene, pentadecane epoxide-2,5-diaminobenzene, hexadecane epoxide-2,5-diaminobenzene, Octadecane epoxide-2,5-diaminobenzene, cholesteric alkyl oxy-3,5-diaminobenzene, cholesteryl epoxide-3,5- Diaminobenzene, cholesteryl epoxide-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteric Arrcostab, 3,5-diaminobenzoic acid cholesteryl esters, 3,5-diaminobenzoic acid lanostane base ester, 3, the double (4-of 6- Aminobenzoic acyloxy) cholestane, 3,6-double (4-amino-benzene oxygen) cholestane, 4-(4 '-trifluoromethoxy Benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl epoxide) hexamethylene Base-3,5-diaminobenzoic acid ester, 1, double (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane of 1-, 1,1-double (4-((aminophenyl) methyl) phenyl)-4-heptylcyclohexane, 1, double (4-((amino-benzene oxygen) first of 1- Base) phenyl)-4-heptylcyclohexane, 1, double (4-((aminophenyl) methyl) the phenyl)-4-(4-heptyl cyclohexyl) of 1- Diamidogen etc. represented by hexamethylene, above-mentioned formula (A-1).Additionally, the diamidogen with pre-dumping composition can It is used alone a kind or two or more is applied in combination.
Relative to total diamidogen, the total amount of the diamidogen with pre-dumping composition preferably comprise 5 moles of % with On, more preferably comprise 10 moles of more than %.
[molecular weight regulator]
During synthesizing polyamides acid, suitable molecular weight regulator can be used, with tetrabasic carboxylic acid as above Dianhydride and diamidogen synthesize the polymer of end modified type together.By forming the polymerization of this end modified type Thing, it is possible to do not undermine the effect of the present invention, and improve the coating (printing of crystal aligning agent further Property).
Molecular weight regulator include, for example monoester anhydride, monoamine compound, monoisocyanate compound etc.. As the concrete example of these molecular weight regulators, monoester anhydride include, for example: maleic anhydride, neighbour Phthalate anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydrides, positive 14 Alkyl succinic anhydride, n-hexadecyl succinic anhydrides etc.；Monoamine compound include, for example: aniline, Cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, 1-Aminooctane etc.；Monoisocyanates chemical combination Thing include, for example: carbanil, naphthyl isocyanate etc..
Relative to total 100 weight portion of the tetracarboxylic dianhydride used and diamidogen, molecular-weight adjusting The use ratio of agent is preferably set to below 20 weight portions, is more preferably set to below 10 weight portions.
<synthesis of polyamic acid>
The use ratio of tetracarboxylic dianhydride and diamidogen of synthetic reaction for the polyamic acid of the present invention Being preferably, relative to amino 1 equivalent of diamidogen, the anhydride group of tetracarboxylic dianhydride becomes 0.2 equivalent～2 The ratio of equivalent, more preferably becomes 0.3 equivalent～the ratio of 1.2 equivalents.
The synthetic reaction of polyamic acid is preferably and carries out in organic solvent.Reaction temperature now is preferred For-20 DEG C～150 DEG C, more preferably 0 DEG C～100 DEG C.It addition, the response time is preferably 0.1 hour～ 24 hours, more preferably 0.5 hour～12 hours.
Herein, organic solvent include, for example: aprotic polar solvent, phenol series solvent, alcohol, ketone, Ester, ether, halogenated hydrocarbons (halogenated hydrocarbon), hydrocarbon etc..
As the concrete example of these organic solvents, above-mentioned aprotic polar solvent include, for example: N- N-methyl-2-2-pyrrolidone N, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, N, N-diformazan Yl acetamide, DMF, dimethyl sulfoxide, gamma-butyrolacton, tetramethylurea, pregnancy Base phosphoric triamide (hexamethylphosphoric triamide) etc.；Above-mentioned phenol series solvent such as can arrange Lift: phenol, metacresol, xylenol, halogenated phenol etc.；Above-mentioned alcohol include, for example: methanol, second Alcohol, isopropanol, Hexalin, ethylene glycol, propylene glycol, BDO, triethylene glycol, ethylene glycol Monomethyl ether etc.；
Above-mentioned ketone include, for example: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene etc.； Above-mentioned ester include, for example: ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, acetic acid fourth Ester, methoxy methyl propionate, ethoxyl ethyl propionate, diethyl oxalate, diethyl malonate, Isoamyl propionate, isoamyl isobutyrate etc.；Above-mentioned ether include, for example: diethyl ether, isoamyl ether, Ethylene glycol monomethyl ether, ethylene glycol, ethylene glycol-positive propyl ether, ethylene glycol-diisopropyl ether, ethylene glycol-positive fourth 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 acetas, diethyl two Alcohol monoethyl ether acetate, oxolane etc.；
Above-mentioned halogenated hydrocarbons include, for example: dichloromethane, 1,2-dichloroethanes, Isosorbide-5-Nitrae-dichloroetane, three Ethyl chloride, chlorobenzene, o-dichlorohenzene etc.；Above-mentioned hydrocarbon include, for example: hexane, heptane, octane, benzene, Toluene, dimethylbenzene etc..
In these organic solvents, it is preferable to use select free aprotic polar solvent and phenol series solvent In formed group (organic solvent of the first group) more than one or selected from the first group In organic solvent more than a kind and the free alcohol of choosing, ketone, ester, ether, halogenated hydrocarbons and the formed group of hydrocarbon More than one mixture in (organic solvent of the second group).In the case of the latter, relatively In the organic solvent of the first group and the total amount of the organic solvent of the second group, having of the second group The use ratio of machine solvent is preferably below 50 weight %, below more preferably 40 weight %, especially It is preferably below 30 weight %.
The usage amount (a) of organic solvent is preferably set to: relative to the total amount (a+b) of reaction solution, The total amount (b) of tetracarboxylic dianhydride and diamidogen becomes 0.1 weight %～the amount of 50 weight %.
Obtain the reaction solution dissolved by polyamic acid in the above described manner.This reaction solution can be direct It is supplied to the preparation of crystal aligning agent, it is also possible to after being isolated by polyamic acid contained in reaction solution again It is supplied to the preparation of crystal aligning agent, or the polyamic acid of isolation can also be available to after purification The preparation of crystal aligning agent.Polyamic acid is being carried out dehydration closed-loop to make the situation of polyimides Under, above-mentioned reaction solution can be supplied directly to dehydration closed-loop reaction, it is also possible to by institute in reaction solution Dehydration closed-loop reaction it is available to after the polyamic acid isolation contained, or can also be by the polyamide of isolation Acid is available to dehydration closed-loop reaction after purification.The isolation of polyamic acid and purification can be according to many institute's weeks The method known is carried out.
<polyimides and the synthesis of polyimides>
Polyimides contained in the crystal aligning agent of the present invention can be by synthesizing in the above described manner Polyamic acid carries out dehydration closed-loop, in addition imidizate and obtain.
Above-mentioned polyimides can be the amic acid knot being had as the polyamic acid of its predecessor Structure all carries out complete acid imide compound obtained by dehydration closed-loop, it is also possible to be only by amic acid structure A part carries out dehydration closed-loop and makes amic acid structure and imide ring structure the part acid imide deposited Compound.The acid imide rate of the polyimides of the present invention is preferably more than 30%, more preferably 40%～ 99%, especially preferably 50%～99%.This acid imide rate is to represent relative to polyamides with percentage rate Imide ring structure for the amic acid number of structures of imines and the total of imide ring number of structures Ratio shared by quantity.Herein, a part for imide ring can be different acid imide (isoimide) Ring.
The dehydration closed-loop of polyamic acid preferably utilizes the method heating polyamic acid, or profit It is dissolved in organic solvent with by polyamic acid, in this solution, adds dehydrant and dehydration closed-loop is urged Agent, the method optionally carrying out heating is carried out.Wherein, later approach is preferably utilized.
Add in the method for dehydrant and dehydration closed-loop catalyst in the solution of above-mentioned polyamic acid, de- Water preparation such as can use the anhydride such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.Relative to polyamic acid 1 mole of amic acid structure, the usage amount of dehydrant is preferably set to 0.01 mole～20 moles.De- Water ring-closing catalyst such as can use: pyridine (pyridine), collidine (collidine), diformazan The tertiary amines such as pyridine (lutidine), triethylamine (triethylamine).Relative to the dehydration used Agent 1 mole, the usage amount of dehydration closed-loop catalyst is preferably set to 0.01 mole～10 moles.De- The organic solvent used in water ring-closure reaction can be enumerated as the organic solvent for synthesizing polyamides acid And the organic solvent illustrated.The reaction temperature of dehydration closed-loop reaction is preferably 0 DEG C～180 DEG C, more preferably It it is 10 DEG C～150 DEG C.Response time is preferably 1.0 hours～120 hours, more preferably 2.0 hours～ 30 hours.
Obtain the reaction solution containing polyimides in the above described manner.This reaction solution can be supplied directly to The preparation of crystal aligning agent, it is also possible to remove dehydrant and dehydration closed-loop catalyst from reaction solution After be available to the preparation of crystal aligning agent, it is also possible to be available to liquid crystal after being isolated by polyimides and join To the preparation of agent, or the polyimides of isolation can also be available to crystal aligning agent after purification Preparation.These purification process can be carried out according to well-known method.
<poly amic acid ester>
Poly amic acid ester contained in the crystal aligning agent of the present invention such as may utilize following methods and obtains : [I] by make the compound of polyamic acid and the hydroxyl obtained by above-mentioned synthetic reaction, halogenide, Compound etc. containing epoxy radicals carries out reacting the method synthesized；[II] makes tetrabasic carboxylic acid diester anti-with diamidogen The method answered；[III] makes the method for tetrabasic carboxylic acid diester dihalide and diamine reactant.
Herein, the compound of the hydroxyl used in method [I] include, for example: methanol, ethanol, third The alcohols such as alcohol；The phenols such as phenol, cresol etc..It addition, halogenide include, for example: bromomethane, Bromic ether, bromo-octadecane, chloromethane, chlorooctadecane, 1,1,1-tri-fluoro-2-iodoethane etc.； Compound containing epoxy radicals include, for example expoxy propane etc..The tetrabasic carboxylic acid diester used in method [II] Such as by using above-mentioned alcohols, the tetracarboxylic dianhydride illustrated in the synthesis of above-mentioned polyamic acid can be entered Row open loop and obtain.It addition, method [III] in use tetrabasic carboxylic acid diester dihalide can by make with The chlorination that the tetrabasic carboxylic acid diester of aforesaid way acquisition and thionyl chloride (thionyl chloride) etc. are suitable Agent is reacted and is obtained.The diamidogen used in method [II] and method [III] can use above-mentioned polyamic acid Synthesis in illustrate diamidogen etc..Additionally, poly amic acid ester can only have amic acid esters structure, it is possible to Being amic acid structure and amic acid esters structure the partial esterification thing deposited.
<solution viscosity of polymer and weight average molecular weight>
Polyamic acid, polyimides and the poly amic acid ester obtained in the above described manner is preferably when by it When making the solution that concentration is 10 weight %, there is the solution viscosity of 10mPa s～800mPa s Compound, more preferably has the compound of the solution viscosity of 15mPa s～500mPa s.Additionally, The solution viscosity (mPa s) of above-mentioned polymer is to use E type rotating cylinder viscometer, to using this polymerization The good solvent of thing (such as gamma-butyrolacton, METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone etc.) polymer solution that concentration is 10 weight % prepared, at 25 DEG C It is worth obtained by lower mensuration.It addition, to polyamic acid contained in the crystal aligning agent of the present invention, polyamides Imines and poly amic acid ester, utilize gel permeation chromatography (Gel-Permeation Chromatography, GPC) weight average molecular weight of polystyrene conversion that measures is preferably 500～100,000, more preferably 1,000～50,000.
<polysiloxane>
The polysiloxane of the present invention such as can by be preferably suitable organic solvent, water and In the presence of catalyst, water-disintegrable silane compound is hydrolyzed or hydrolytic condensation and obtain.
Include, for example for synthesizing the hydrolysable silanes compound of polysiloxane: methyl trichlorine silicon Alkane, MTMS, MTES, phenyl trichlorosilane, phenyl trimethoxy Base silane, phenyl triethoxysilane, dimethyl dichlorosilane (DMCS), methyl dimethoxysilane, methyl two Ethoxysilane, dimethyldichlorosilane, dimethyldimethoxysil,ne, dimethyl diethoxy silicon Alkane, diphenyl dichlorosilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, chlorine two Methyl-monosilane, methoxyl group dimethylsilane, ethyoxyl dimethylsilane, chlorine trimethyl silane, bromine three Methyl-monosilane, iodine trimethyl silane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethyl TMOS, tetraethoxysilane, octadecyl trichlorosilane alkane, octadecyl trimethoxysilane, Vinyl trichlorosilane, vinyltrimethoxy silane, VTES, pi-allyl three Chlorosilane, allyltrimethoxysilanis, allyltriethoxysilane,
3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxysilicane Alkane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl two Ethoxysilane, 3-glycidoxypropyl dimethyl methoxy silane, 3-glycidoxypropyl third Base dimethylethoxysilane, 2-glycidoxypropyl ethyl trimethoxy silane, 2-(+)-2,3-Epoxy-1-propanol oxygen Base ethyl triethoxysilane, 2-glycidoxypropyl ethyl-methyl dimethoxysilane, 2-shrink sweet Oil epoxide ethyl-methyl diethoxy silane, 2-glycidoxypropyl ethyl dimethyl methoxy silane, 2-glycidoxypropyl ethyl dimethylethoxysilane, 4-glycidoxypropyl butyl trimethoxy silicon Alkane, 4-glycidoxypropyl butyl triethoxysilane, 4-glycidoxypropyl butyl methyl dimethoxy Base silane, 4-glycidoxypropyl butyl methyl diethoxy silane, 4-glycidoxypropyl butyl two Methylmethoxysilane, 4-glycidoxypropyl Butyldimethyl Ethoxysilane, 2-(3,4-epoxide rings Hexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, 3-(3,4- Epoxycyclohexyl) propyl trimethoxy silicane, 3-(3,4-epoxycyclohexyl) propyl-triethoxysilicane, (first Base) acrylic acid (3-Ethyloxetane-3-base) methyl ester, (methyl) acrylic acid (3-methy oxetane -3-base) methyl ester,
3-(methyl) acryloxypropyl trichlorosilane, 3-(methyl) acryloxypropyl trimethoxy Silane, 3-(methyl) acryloxypropyl triethoxysilane, 2-(methyl) acryloyl-oxyethyl three Chlorosilane, 2-(methyl) acryloyl-oxyethyl trimethoxy silane, 2-(methyl) acryloyl-oxyethyl Triethoxysilane, 4-(methyl) acryloxy butyl trichlorosilane, 4-(methyl) acryloxy fourth Base trimethoxy silane, 4-(methyl) acryloxy butyl triethoxysilane etc..Additionally, " (first Base) acryloxy " it is to comprise " acryloxy " and the implication of " methacryloxy ".
Synthesis polysiloxane time spendable organic solvent include, for example hydrocarbon, ketone, ester, ether, Alcohol etc..Herein, above-mentioned hydrocarbon include, for example: toluene, dimethylbenzene etc.；Above-mentioned ketone include, for example: Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, metacetone, Ketohexamethylene etc.；Above-mentioned Ester include, for example: ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetic acid Ester, 3-methoxybutyl acetas, ethyl lactate etc.；Above-mentioned ether include, for example: glycol dinitrate Ether, ethylene glycol diethyl ether, oxolane, dioxanes etc.；Above-mentioned alcohol include, for example: 1-hexanol, 4-methyl-2-amylalcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol list-positive propyl ether, second two Alcohol list-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list-positive propyl ether etc..These Preferably with non-water-soluble organic solvent in organic solvent.Additionally, these organic solvents can be independent Use a kind or two or more is used in mixed way.
Relative to total silane compound 100 weight portion, in the case of synthesizing above-mentioned polysiloxane The usage amount of organic solvent is preferably 10 weight portions～10,000 weight portion, more preferably 50 weight Part～1,000 weight portions.It addition, relative to the total silane compound used, manufacture and have above-mentioned gathering The usage amount of water during organic siloxane is preferably 0.5 times mole～100 times moles, more preferably 1 times Mole～30 times moles.
During the synthesis of above-mentioned polysiloxane, spendable catalyst include, for example: acid, alkali metal Compound, organic base, titanium compound, zirconium compounds etc..Herein, above-mentioned acid include, for example: salt Acid, sulphuric acid, nitric acid, formic acid, ethanedioic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid etc.； Above-mentioned alkali metal compound include, for example: sodium hydroxide, potassium hydroxide, Feldalat NM, Feldalat KM, Sodium ethylate, potassium ethoxide etc.；Above-mentioned organic base include, for example: ethamine, diethylamine, piperazine, piperidines, The one-level of pyrrolidine, pyrroles etc～two grades of organic amines, triethylamine, three-n-propylamine, three-n-butylamine, Pyridine, 4-dimethylaminopyridine, diazabicycloundecene (diazabicycloundecene) it Three grades of organic amines of class, the level Four organic amine etc. of Tetramethylammonium hydroxide etc.
Above-mentioned catalyst is particularly preferably organic base.The usage amount of organic base according to the kind of organic base, The reaction conditions such as temperature etc. and different, it should suitably set, such as relative to total silane compound, It is preferably 0.01 times mole～3 times moles, more preferably 0.05 times mole～1 times mole.
Hydrolysis when manufacturing above-mentioned polysiloxane or hydrolysis-condensation reaction are preferably by by water Solution property a kind of silane compound or two or more be dissolved in organic solvent, by the solution of gained with Organic base and water mixing, such as, utilize oil bath etc. to carry out heating to implement.
During hydrolysis-condensation reaction preferably, preferably heating-up temperature is set to less than 130 DEG C, more preferably It is 40 DEG C～100 DEG C, is preferably heating 0.5 hour～12 hours, more preferably heating 1 hour～8 Hour.Add and hanker, mixed liquor can be stirred, it is also possible to be placed under counterflow condition.
After reaction terminates, it is preferably and the organic solvent layer of fractional distillation from reactant liquor is cleaned with water.Carry out During this cleaning, for cleaning operation becomes easy aspect, it is preferable to use comprise the water of a small amount of salt, Such as aqueous ammonium nitrate solution etc. about 0.2 weight % is carried out.Clean after may proceed to clean Till water layer becomes neutrality, then by organic solvent layer optionally with dead plaster, molecular sieve After desiccant such as (molecular sieves) is dried, removes solvent, thus can obtain as target Polysiloxane.Additionally, the polysiloxane of the present invention can also use commercially available product.
Polysiloxane contained in the crystal aligning agent of the present invention can use by making by above-mentioned contracting The reactive polysiloxane closing reaction acquisition reacts with reactive compounds, and in reactivity The polysiloxane of the structure being derived from reactive compounds it is imported with on the side chain of polysiloxane. Herein, reactive polysiloxane include, for example have epoxy radicals, unsaturated double-bond, sulfydryl, The polysiloxane of amino etc..It addition, reactive compounds include, for example: have chain alkyl Compound, there is the structure that the ring (such as phenyl ring or cyclohexane ring etc.) of more than 2 links Compound, there is the compound of steroid skeleton, there is the compound etc. of unsaturated double-bond.
Additionally, reactive polysiloxane can be according to vitochemical with the reaction of reactive compounds Common method is carried out.Such as, in the case of reactive polysiloxane has epoxy radicals, can By use carboxylic acid as reactive compounds, and import on the side chain of reactive polysiloxane It is derived from the structure of reactive compounds.It addition, there is unsaturated double-bond at reactive polysiloxane In the case of, can have the compound of sulfydryl or amino as reactive compounds by use, and The structure being derived from reactive compounds is imported on the side chain of reactive polysiloxane.
In the polysiloxane of the present invention, the weight of the polystyrene conversion that GPC measures is utilized to put down Average molecular weight is preferably 500～100,000, more preferably 1,000～30,000, especially preferably 1,000～20,000.
<solvent>
Solvent contained in the crystal aligning agent of the present invention is used for dissolving above-mentioned component of polymer, or uses In improving coating when being coated on substrate by crystal aligning agent.The especially LCD alignment of the present invention Agent includes at least the compound (p1) represented by following formula (1) as solvent composition.This compound (p1) have the property that not only good to the coating of substrate, and be difficult to make to be generally used for liquid APR resin swelling in the galley of the printer of brilliant orientation agent.By using this compound (p1) As solvent, solvent can be made to be difficult to penetrate in galley when printing.Even if it addition, being carried out continuously In the case of printing, printer being also difficult to separate out component of polymer, continuous printing also becomes good.
[changing 5]
(in formula (1), R1And R3It it is separately the carbon number 1～3 of straight-chain or branch-like 1 valency alkyl, R2Alkane diyl for the carbon number 2～5 of straight-chain or branch-like.)
The R of formula (1)1And R3In, the alkyl of carbon number 1～3 can be saturated, it is also possible to unsaturated, Can be straight-chain, it is also possible to be branch-like.R1And R3Concrete example include, for example: methyl, The alkyl of the carbon numbers 1～3 such as ethyl, n-pro-pyl, isopropyl；The carbon number such as vinyl, pi-allyl 2 or 3 1 valency unsaturated alkyl etc..It is preferably R1And R3For methyl.Additionally, in formula (1), R1And R3Can be the most identical, it is also possible to different.
R2The alkane diyl of carbon number 2～5 can be straight-chain, it is also possible to be branch-like, its concrete example Include, for example: ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,3-diyl, fourth Alkane-Isosorbide-5-Nitrae-diyl, pentane-1,5-diyl etc..
The preferred concrete example of compound (p1) include, for example ethylene acetate, propylene glycol diethyl The aklylene glycol diacetate esters such as acid esters.The most preferably use propylene-glycol diacetate.
For the viewpoint that the coating making crystal aligning agent when coating on substrate is good, relative to The total amount of solvent contained in crystal aligning agent, the content of compound (p1) be preferably 5 weight % with On, more than more preferably 10 weight %.It addition, for may refrain from the viewpoint that polymer separates out, relatively The total amount of solvent contained in crystal aligning agent, the upper limit of the content of compound (p1) is preferably 90 Below weight %, below more preferably 70 weight %, below especially preferably 50 weight %.
[compound (p2)]
Solvent contained in the crystal aligning agent of the present invention is preferably and not only comprises above-claimed cpd (p1), But also comprise choosing freely 1, compound represented by 3-dimethyl-2-imidazolidinone, following formula (2), And at least one compound (p2) in the formed group of compound represented by following formula (3). These compounds (p2) all above-mentioned polymer of solubilized (A), it addition, boiling point is the highest.Therefore, By using these organic solvents as the solvent composition of crystal aligning agent, crystal aligning agent can printed When brushing on substrate, suppression solvent volatilizees from printer, can suppress the component of polymer on printer Precipitation.Further, since the boiling point of solvent will not be too high, so carrying out after printing preheating (in advance Baking) in the case of, it is possible to reduce the quantity of solvent remaining in film after preheating.Thus, can be in Dust is suppressed to be attached to film coated surface after preheating, it is possible to the yield of suppression goods declines.
[changing 6]
(in formula (2), R4And R5Be separately hydrogen atom, 1 valency alkyl of carbon number 1～6, Or between the carbon-carbon bond of this alkyl, comprise the 1 valency base of "-O-", R4With R5Can mutually bond and shape Become ring structure；R6Alkyl for carbon number 1～6.)
[changing 7]
(in formula (3), R7For between 1 valency alkyl of carbon number 2～5 or the carbon-carbon bond in this alkyl Comprise the 1 valency base of "-O-".)
[compound represented by above-mentioned formula (2)]
R in above-mentioned formula (2)4And R51 valency alkyl of carbon number 1～6 can be saturated, it is also possible to Unsaturated.It addition, R4And R5Can be between the carbon-to-carbon singly-bound in 1 valency alkyl of carbon number 1～6 Comprise the group of "-O-".R4And R5Concrete example except can enumerate such as carbon number 1～6 alkyl, The ester ring type alkyl of carbon number 3～6, carbon number 5 or 6 aromatic hydrocarbyl beyond, also can be set forth in this The group etc. of "-O-" is comprised between the carbon-carbon bond of a little groups.Additionally, in formula (1), R4And R5Can The most identical, it is also possible to different.
Herein, the alkyl of carbon number 1～6 include, for example: methyl, ethyl, n-pro-pyl, isopropyl, Normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, amyl group, hexyl etc..The ester ring type of carbon number 3～6 Alkyl include, for example cyclopenta, cyclohexyl etc..The aromatic hydrocarbyl of carbon number 5 or 6 include, for example Phenyl etc..
R4And R5Can be by mutual bond, and and R4And R5The nitrogen-atoms of institute's bond forms ring together. R4、R5Mutually bond and the ring that formed include, for example pyrrolidine ring, piperidine ring etc..It addition, these Ring bond can there be the 1 valency chain alkyl such as methyl.
R4And R5It is preferably hydrogen atom or the alkyl of carbon number 1～3, more preferably hydrogen atom or first Base.
R6The alkyl of carbon number 1～6 can be straight-chain, it is also possible to be branch-like, specifically, Above-mentioned R can be enumerated4And R5Carbon number 1～6 alkyl explanation in illustrated group.
The concrete example of the compound represented by above-mentioned formula (2) include, for example: 3-butoxy-N, N-bis- Methyl propanamide, 3-methoxyl group-N, N-dimethylpropionamide, 3-hexyloxy-N, N-dimethylpropionamide, Isopropoxy-N-isopropyl-propionic acid amide., n-butoxy-N-isopropyl-propionic acid amide. etc..
[compound represented by above-mentioned formula (3)]
R in above-mentioned formula (3)71 valency alkyl of carbon number 2～5 can be saturated, it is also possible to insatiable hunger With, can be straight-chain, it is also possible to be branch-like.It addition, R7Can be at the 1 of carbon number 2～5 The 1 valency base of "-O-" is comprised between the carbon-to-carbon singly-bound of valency alkyl.R7Concrete example except enumerating such as Beyond the alkyl of carbon number 2～5, thiazolinyl, alkynyl, also can be set forth in the carbon-to-carbon singly-bound in these groups Between comprise the group (hereinafter also referred to " oxygen-containing group ") etc. of "-O-".
Herein, R7The alkyl of carbon number 2～5 include, for example ethyl, n-pro-pyl, isopropyl, just Butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl etc.；The thiazolinyl of carbon number 2～5 Include, for example vinyl, 1-acrylic, 2-acrylic, 1-methyl ethylene, 2-methyl-1-propylene Base etc.；The alkynyl of carbon number 2～5 include, for example: acetenyl, 2-propynyl, 2-butyne base etc..
It addition, above-mentioned oxygen-containing group include, for example the alkoxyalkyl etc. of carbon number 2～5, its concrete example Include, for example: methoxy, methoxy ethyl, methoxy-propyl, methoxybutyl, ethoxy Ylmethyl, ethoxyethyl group etc..
R7It is preferably alkyl or the alkoxyalkyl of above-mentioned middle carbon number 2～5.
The concrete example of the compound represented by above-mentioned formula (3) include, for example: N-ethyl-2-pyrrolidine Ketone, N-propyl group-2-Pyrrolidone, N-butyl-2-Pyrrolidone, N-(tert-butyl group)-2-Pyrrolidone, N-amyl group-2-Pyrrolidone, N-methoxy-propyl-2-Pyrrolidone, N-ethoxyethyl group-2-pyrrolidine Ketone, N-methoxybutyl-2-Pyrrolidone etc..In these compounds, can particularly preferably use N-second Base-2-Pyrrolidone, N-amyl group-2-Pyrrolidone, N-(tert-butyl group)-2-Pyrrolidone, N-methoxyl group Propyl group-2-Pyrrolidone.Additionally, the change that these can be illustrated by the compound represented by above-mentioned formula (3) Compound is used alone a kind or two or more is applied in combination.
Just for the deliquescent viewpoint of component of polymer, contained molten relative in crystal aligning agent The total amount of agent, the content of above-claimed cpd (p2) is preferably set to more than 5 weight %, more preferably It is set to more than 10 weight %.It addition, the upper limit of content there is no particular restriction, but relative to LCD alignment The total amount of solvent contained in agent, is preferably set to below 90 weight %.Additionally, compound (p2) Above-claimed cpd can be used alone a kind or two or more is applied in combination.
[other solvents]
For prepare the solvent of the crystal aligning agent of the present invention it be also possible to use above-claimed cpd (p1) and Other solvents beyond compound (p2).These other solvents include, for example: N-methyl-2-pyrrolidine Ketone, gamma-butyrolacton, butyrolactam, DMF, N,N-dimethylacetamide, 4- Hydroxy-4-methyl-2-pentanone (diacetone alcohol), glycol monoethyl ether, butyl lactate, butyl acetate, Methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol, ethylene glycol- Positive propyl ether, ethylene glycol-diisopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), 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 acetas, diethylene glycol monoethyl ether acetas, dipropyl Glycol monomethyl ether (dipropylene glycol monomethylether, DPM), diisobutyl ketone, Isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, propylene carbonate, tertiary fourth Alcohol, tert-pentyl alcohol etc..Additionally, above-claimed cpd can be used alone a kind or by 2 kinds by other solvents Use mixed above.
It addition, the solvent composition in the crystal aligning agent of the present invention is by by such as diacetone alcohol, tertiary fourth The tertiary alcohol such as alcohol, tert-pentyl alcohol and above-claimed cpd (p1) are also used as other solvents above-mentioned, can enter The swelling of one step suppression galley (APR version), the most preferably.
For making the good viewpoint of printing, total relative to solvent contained in crystal aligning agent Amount, the content of other solvents above-mentioned is preferably below 80 weight %, below more preferably 50 weight %, Below especially preferably 30 weight %.It addition, in the case of using tertiary alcohol as other solvents, Relative to the total amount of solvent contained in crystal aligning agent, the content of other solvents above-mentioned is preferably 1 weight Amount %～50 weight %, more preferably 5 weight %～40 weight %.
<other additives>
The crystal aligning agent of the present invention contains polymer as above and solvent, it is also possible to optionally Containing other compositions.These other compositions include, for example: other polymer beyond above-mentioned polymer, Intramolecular have at least one epoxy radicals compound (hereinafter referred to as " compound containing epoxy radicals "), Functional silanes compound etc..
[other polymer]
Other polymer above-mentioned can be used for improving solution properties or electrical characteristic.These other polymer are such as Can enumerate: polyester, polyamide, cellulose derivative, polyacetals, polystyrene derivative, poly-(benzene Ethylene-phenylmaleimide) derivant, poly-(methyl) acrylate etc..Gathering these other In the case of compound makes an addition in crystal aligning agent, relative to the polymer total amount in said composition, on The allotment ratio stating other polymer is preferably below 50 weight %, more preferably 0.1 weight %～40 Weight %, especially preferably 0.1 weight %～30 weight %.
[compound containing epoxy radicals]
Compound containing epoxy radicals can be used for improving the cohesiveness with substrate surface of liquid crystal orienting film.This Place, the compound containing epoxy radicals include, for example: Ethylene glycol diglycidyl ether, Polyethylene Glycol two contract Water glycerin ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol two contract Water glycerin ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol two contract Water glycerin ether, trihydroxymethylpropanyltri diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-double (N, N-diglycidyl amino methyl) Hexamethylene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-bis-shrinks sweet Oil base-benzylamine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-hexamethylene Amine etc..
In the case of these epoxides are made an addition in crystal aligning agent, relative to LCD alignment Total 100 weight portion of polymer contained in agent, the allotment ratio of this epoxide is preferably 40 Below weight portion, more preferably 0.1 weight portion～30 weight portions.
[functional silanes compound]
Above-mentioned functional silanes compound can make for the purpose of the printing improving crystal aligning agent With.This functional silanes compound include, for example: 3-TSL 8330,3-ammonia Base propyl-triethoxysilicane, 2-TSL 8330,2-aminopropyl triethoxysilicane Alkane, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropan Ylmethyl dimethoxysilane, 3-ureido-propyl trimethoxy silane, 3-ureido-propyl triethoxysilicane Alkane, N-ethoxy carbonyl-3-TSL 8330, N-tri-ethoxy silylpropyl Sanya Ethyl triamine, 10-trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxy silane base-3,6- Diaza nonyl acetas, 9-trimethoxy silane base-3,6-diaza methyl pelargonate, N-benzyl-3-ammonia Base propyl trimethoxy silicane, N-phenyl-3-TSL 8330, glycidoxypropyl first Base trimethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 3-glycidoxypropyl third Base trimethoxy silane etc..
In the case of these functional silanes compounds are made an addition in crystal aligning agent, relative to poly- Total 100 weight portion of compound, the allotment ratio of this functional silanes compound is preferably 2 weight portions Hereinafter, more preferably 0.02 weight portion～0.2 weight portion.
Other additives contained in crystal aligning agent in addition to the foregoing, it be also possible to use intramolecular and have The compound of at least one oxetanylmethoxy or antioxidant etc..
Solid component concentration (the one-tenth beyond the solvent of crystal aligning agent in the crystal aligning agent of the present invention The ratio that the total weight divided is shared in the gross weight of crystal aligning agent) allow for viscosity, volatilization Property etc. suitably selects, preferably 1 weight %～the scope of 10 weight %.That is, the liquid crystal of the present invention Orientation agent, by coating substrate surface in aftermentioned mode, is preferably heated, and is formed as liquid The film of brilliant alignment film or become the film of liquid crystal orienting film, but now, little at solid component concentration In the case of 1 weight %, the thickness of film becomes too small and cannot obtain good liquid crystal orienting film. On the other hand, in the case of solid component concentration is more than 10 weight %, the thickness of film becomes excessive And good liquid crystal orienting film cannot be obtained, and it addition, the viscosity of crystal aligning agent increases, coating characteristics It is deteriorated.
The scope of particularly preferred solid component concentration makes during coating of liquid crystalline orientation agent according on substrate Method and different.Such as in the case of utilizing method of spin coating, solid component concentration is the most excellent Elect 1.5 weight %～the scope of 4.5 weight % as.In the case of utilizing lithography, the most excellent Elect as and solid component concentration is set to 3 weight %～the scope of 9 weight %, thus solution viscosity is set For 12mPa s～the scope of 50mPa s.In the case of utilizing ink-jet method, particularly preferably will be solid Body constituent concentration is set to 1 weight %～the scope of 5 weight %, thus solution viscosity is set to 3mPa s～ The scope of 15mPa s.
Temperature when preparing the crystal aligning agent of the present invention is preferably 10 DEG C～50 DEG C, and more preferably 20 DEG C～30 DEG C.
<liquid crystal orienting film and liquid crystal display cells>
The liquid crystal orienting film of the present invention is to utilize the crystal aligning agent prepared in the above described manner to be formed.Separately Outward, the liquid crystal display cells of the present invention includes that the liquid crystal using the crystal aligning agent of the present invention to be formed is joined To film.The drive pattern of the liquid crystal display cells of the application present invention is not particularly limited, and can be applicable to The multiple drive modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type.Hereinafter, The manufacture method of the liquid crystal display cells of the present invention is illustrated, and to the present invention in this explanation The manufacture method of liquid crystal orienting film illustrate.
The liquid crystal display cells of the present invention such as can be manufactured by the step of following (1)～(3). Step (1) uses different substrates according to required drive pattern.Step (2) and step (3) In each drive pattern common.
[step (1): the formation of film]
First on substrate, it is coated with the crystal aligning agent of the present invention, then coated face is heated, by This forms film on substrate.
(1-1) in the case of manufacturing TN type, STN type or VA type liquid crystal display cells, will It is provided with two pieces of substrates of patterned nesa coating as a pair, at this each transparent conductive film On formation face, preferably utilize lithography, method of spin coating, roll-coater method or ink-jet print Brush method is respectively coated the crystal aligning agent of the present invention.The coating process of crystal aligning agent is preferably applied Lithography in these coating processes.Therefore, substrate such as can use: floating glass (float processed Glass), the glass such as soda-lime glass (soda glass)；Comprise polyethylene terephthalate, gather benzene The transparency carrier of the plastic cement such as dioctyl phthalate fourth diester, polyether sulfone, Merlon, poly-(ester ring type alkene). The nesa coating of the one side being arranged at substrate can use and comprise stannum oxide (SnO2) NESA film (beautiful PPG register of company of state trade mark), comprise indium oxide-tin oxide (In2O3-SnO2) ito film etc.. In order to obtain patterned nesa coating, such as, can utilize following methods: formed patternless After nesa coating, the method forming pattern by photoetch (photo etching)；Formed thoroughly The method etc. of the shade with desirable pattern is used during bright conducting film.During coating of liquid crystalline orientation agent, in order to Make substrate surface and nesa coating better with the cohesiveness of film, it is also possible to answer in substrate surface The front place of functional silanes compound, functionality titanium compound etc. is implemented to be pre-coated with in the face forming film Reason.
After coating of liquid crystalline orientation agent, for preventing the purpose such as sagging of be coated with orientation agent, it is preferably Implement to preheat (prebake conditions).Prebake conditions temperature is preferably 30 DEG C～200 DEG C, more preferably 40 DEG C～ 150 DEG C, particularly preferably 40 DEG C～100 DEG C.The prebake conditions time is preferably 0.25 minute～10 minutes, More preferably 0.5 minute～5 minutes.Then, solvent is removed completely, optionally for being polymerized Present in thing, amic acid structure carries out the purpose of hot-imide and implements calcining and (toast afterwards (postbake)) step.This calcining (baking afterwards) temperature is preferably 80 DEG C～300 DEG C, more preferably 120 DEG C～250 DEG C.Post-bake times is preferably 5 minutes～200 minutes, more preferably 10 minutes～ 100 minutes.So, the thickness of the film formed is preferably 0.001 μm～1 μm, more excellent Elect 0.005 μm～0.5 μm as.
(1-2) in the case of manufacturing IPS type or FFS type liquid crystal display cells, in being provided with bag Electrode containing the patterned nesa coating for interdigitated electrode structure or the substrate of the electrode of metal film is formed Face and be not provided with the one side of opposite substrate of electrode, is respectively coated the crystal aligning agent of the present invention, Then each coated face is heated, be consequently formed film.The substrate now used and electrically conducting transparent The pattern of heating condition, nesa coating or metal film after the material of film, coating process, coating Change method, the pre-treatment of substrate and the preferred thickness of film formed are identical with above-mentioned (1-1). Metal films is as used the film comprising the metals such as chromium.
Under the either case of above-mentioned (1-1) and (1-2), all by coating of liquid crystalline on substrate After orientation agent, remove organic solvent and be formed into the film of alignment film.Now, at the liquid of the present invention In brilliant orientation agent, contained polymer is polyamic acid, or has imide ring structure and amic acid The imide amination polymer of structure, or there is amic acid esters structure and the polymer of amic acid structure In the case of, it is also possible to carry out dehydration closed-loop reaction by heating further after film is formed, system Become further through the film of imidizate.
[step (2): orientation ability imparting processes]
Then, by the film being formed on substrate, optionally carry out friction treatment or light irradiates Process, to give LCD alignment ability to this film.
First, about friction treatment, TN type, STN type, IPS type or FFS type liquid are being manufactured In the case of crystal display element, the film formed in above-mentioned steps (1) is implemented at following friction Reason, i.e. utilizes the roller being wound with the cloth such as comprising the fibers such as nylon, artificial silk, cotton, to certain side To wiping.Thus, the orientation ability of liquid crystal molecule is imparted on film become liquid crystal orienting film. On the other hand, in the case of manufacturing VA type liquid crystal display cells, can be by shape in above-mentioned steps (1) The film become is directly used as liquid crystal orienting film but it also may this film is implemented friction treatment.
In addition it is also possible to the liquid crystal orienting film after friction treatment to be carried out further following process: pass through A part of irradiation ultraviolet radiation of liquid crystal orienting film is made the pre-dumping in a part of region of liquid crystal orienting film The process of angle change；Or after the part on liquid crystal orienting film surface forms resist film, to just now The different direction of friction treatment carry out friction treatment, then remove the process of resist film；So that Liquid crystal orienting film has different LCD alignment abilities in each region.In the case of Gai, gained can be improved The visual field characteristic of liquid crystal display cells.
On the other hand, in the case of utilizing photo-irradiation treatment (light orientation method), film is formed After substrate, by coated surface is irradiated polarisation or the lonizing radiation of non-polarized, and this film is given LCD alignment ability.Herein, lonizing radiation such as can use the light comprising 150nm～800nm wavelength Ultraviolet or luminous ray.Wherein, the light of 300nm～400nm wavelength is preferably comprised Ultraviolet.In the case of the lonizing radiation generation polarisation (linear polarization or part polarisation) used, Light direction of illumination can be set to the direction vertical with coated surface, it is also possible to is set to incline to give tilt angle Tilted direction.On the other hand, in the case of the lonizing radiation irradiating non-polarized, it is necessary to from incline direction pair Coated surface carries out light irradiation.
Light source such as can use: low pressure mercury lamp (low pressure mercury lamp), water under high pressure Silver lamp (high pressure mercury lamp), deuterium lamp (deuterium lamp), metal halide Lamp (metal halide lamp), argon resonance lamp (argon resonance lamp), xenon lamp (xenon Lamp), excimer laser (excimer laser) etc..The ultraviolet energy of above-mentioned preferred wavelength region Enough utilizations are by light source with such as light filter (filter), diffraction grating (diffraction grating) etc. also Means etc. obtain.The irradiation dose of lonizing radiation is preferably 1J/m2Less than 10,000J/m2, More preferably 10J/m2～5,000J/m2。
[step (3): constructing of liquid crystal cells]
By preparing two pieces of substrates being formed with liquid crystal orienting film in the above described manner, oppositely disposed two Configure liquid crystal between block substrate and manufacture liquid crystal cells.When manufacturing liquid crystal cells, include, for example following 2 The method of kind.
First method is in itself previously known method.First, by each liquid crystal orienting film to in the way of, every Gap (cell gap) by oppositely disposed for two pieces of substrates, use sealant by the periphery of two pieces of substrates Portion fits, after injecting filling liquid crystal in the cell gap divided by substrate surface and sealant, and will Hand-hole seals, and thus can manufacture liquid crystal cells.It addition, second method is referred to as (the One Drop that instils Fill, ODF) method of mode.Can be by its in the two pieces of substrates being formed with liquid crystal orienting film In predetermined portion on one piece of substrate, be coated with the encapsulant of such as ultraviolet light photopolymerization, and then at liquid After several positions dropping liquid crystal of the regulation on brilliant orientation face, by liquid crystal orienting film to in the way of paste Close another block substrate, and liquid crystal is pressed off on whole of substrate, then whole to substrate Irradiating ultraviolet light, cures the sealant, thus manufactures liquid crystal cells.Utilizing the feelings of any one method Under condition, it is generally desirable to by the liquid crystal cells manufactured in the above described manner, and then be heated to being used After liquid crystal becomes the temperature of isotropic phase (isotropic phase), it is slowly cooled down to room temperature, thus Remove flowing orientation when liquid crystal is filled.
Sealant such as can use containing sclerosing agent and as the alumina balls of sept (spacer) Epoxy resin etc..
Liquid crystal can enumerate nematic crystal (nematic liquid crystal) and smectic crystal (smectic liquid crystal), the most preferably nematic crystal, such as can use: schiff bases (Schiff base) be liquid crystal, azoxy (azoxy) be liquid crystal, biphenyl system liquid crystal, benzyl ring Hexane system liquid crystal, ester system liquid crystal, terphenyl (terphenyl) are liquid crystal, xenyl hexamethylene methane series liquid Crystalline substance, pyrimidine system liquid crystal, dioxanes system liquid crystal, double-octane system liquid crystal, cubane (cubane) are Liquid crystal etc..Use alternatively, it is also possible to add following material in these liquid crystal: such as chlorination cholesteric Alcohol (cholesteryl chloride), cholesteryl nonanoate (cholesteryl nonanoate), cholesterol The cholesterol liquid crystals (cholesteric liquid crystal) such as carbonic ester (cholesteryl carbonate)； The chirality sold as trade name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) Agent (chiral agent)；To decyloxy benzylidene-to amino-2-methyl butyl cinnamate (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) ferroelectric liquid crystals such as (ferroelectric liquid crystal) etc..
Then, by the outer surface laminating Polarizer at liquid crystal cells, the liquid crystal of the present invention can be obtained Display element.The Polarizer of the outer surface fitting in liquid crystal cells can be enumerated: protects with cellulose acetate Film clamping is referred to as the Polarizer of the light polarizing film of " H-film ", should " H-film " be to make poly-second Enol extends orientation while making it absorb the film of iodine；Or comprise itself Polarizer of H-film.
Additionally, in the case of film is carried out friction treatment, two pieces of substrates are with rubbing in each film Wiping direction mutually forms the angle of regulation, such as, become orthogonal or antiparallel (antiparallel) Mode is oppositely disposed.It addition, in the case of film is carried out light irradiation, if liquid crystal orienting film is water Flat regiospecific, then the straight line irradiated being formed in two pieces of substrates of liquid crystal orienting film by adjustment is inclined The polarization direction angulation of light lonizing radiation and each substrate and the angle of Polarizer, can obtain tool There are TN type or the liquid crystal display cells of STN type liquid crystal cells.On the other hand, at liquid crystal orienting film In the case of vertical orientation, held by the orientation to be formed in two pieces of substrates of liquid crystal orienting film Easily the direction of axle becomes parallel mode Component units, on the unit, by Polarizer with its polarisation side The mode forming 45° angle degree to axle easy with orientation is fitted, and may be made with vertical orientation type liquid crystal list The liquid crystal display cells of unit.
The liquid crystal display cells of the present invention can be effectively applied to multiple device, such as, can be used in: Clock and watch, portable game (portable video game), word processor (word processor), Notes type PC (note type personal computer), auto-navigation system (car Navigation system), camera with recording device (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart mobile phone (smartphone), the display device of various monitors (monitor), LCD TV etc..
[embodiment]
Hereinafter, utilize embodiment that the present invention is specifically described further, but the present invention is not by this The restriction of a little embodiments.
The solution viscosity of each polymer solution in synthesis example, the acid imide rate of polyimides, weight Mean molecule quantity and epoxide equivalent are to utilize following methods to measure.
[solution viscosity of polymer solution]
The solution viscosity (mPa s) of polymer solution is to use E type rotating cylinder viscometer, to using rule Fixed solvent and be adjusted to the solution that polymer concentration is 10 weight %, at 25 DEG C measure.
[the acid imide rate of polyimides]
The solution of polyimides is put into pure water, the precipitation of gained is reduced pressure the most fully After drying, it is dissolved in deuterodimethylsulfoxide, using tetramethylsilane as primary standard substance, in room temperature Lower mensuration1H-nuclear magnetic resonance, NMR (1H-Nuclear Magnetic Resonance,1H-NMR).According to institute ?1H-NMR spectrum, utilizes following mathematical expression (1) to obtain acid imide rate [%].
Acid imide rate [%]=(1-A1/A2×α)×100...(1)
(in mathematical expression (1), A1For the matter being derived from NH base occurred near chemical shift 10ppm The peak area of son, A2For being derived from the peak area of other protons, α is that other protons are relative to polymerization The number ratio of 1 proton of the NH base in the predecessor (polyamic acid) of thing.)
[weight average molecular weight of polymer]
Weight average molecular weight is the polyphenyl that the gel permeation chromatography under the conditions of below utilization measures Ethylene scaled value.
Tubing string: east Cao (Tosoh) (stock) manufactures, TSKgelGRCXLII
Solvent: oxolane
Temperature: 40 DEG C
Pressure: 68kgf/cm2
[epoxide equivalent]
Epoxide equivalent is to utilize the hydrochloric acid-methyl ethyl ketone method described in JIS C2105 to measure.
<synthesis of polymer (A)>
[synthesis example 1: the synthesis of polyimides (PI-1)]
Using as tetracarboxylic dianhydride 2,3,5-tricarboxylics cyclopentyl acetic acid dianhydride 22.4g (0.1 mole), As the p-phenylenediamine 8.6g (0.08 mole) and 3 of diamidogen, 5-diaminobenzoic acid cholesteric Arrcostab 10.5g (0.02 mole) is dissolved in METHYLPYRROLIDONE (NMP) 166g, at 60 DEG C Under carry out 6 hours reaction, it is thus achieved that containing the solution of polyamic acid 20 weight %.The gained that fractional distillation is a small amount of Polyamic acid solution, adds NMP and makes the solution that polyamic acid concentration is 10 weight %, to this Solution viscosity obtained by solution mensuration is 90mPa s.
Then, adding NMP in the polyamic acid solution of gained and making polyamic acid concentration is 7 The solution of weight %, adds pyridine 11.9g and acetic anhydride 15.3g, carries out 4 hours at 110 DEG C Dehydration closed-loop reacts.After dehydration closed-loop reaction, with new NMP, intrasystem solvent is carried out solvent Displacement (is removed to system by this operation, the pyridine used in being reacted by dehydration closed-loop and acetic anhydride Outward；The most identical), it is derived from being about the polyimides (PI-1) 26 of 68% containing acid imide rate The solution of weight %.The gained polyimide solution that fractional distillation is a small amount of, adds NMP and makes polyamides Asia Amine concentration is the solution of 10 weight %, is 45mPa s to solution viscosity obtained by this solution mensuration.Connect , reaction solution is injected in excessive methanol, make reaction product precipitate.By this precipitation Thing cleans with methanol, under reduced pressure, is dried 15 hours at 40 DEG C, is derived from polyimides (PI-1).
[synthesis example 2: the synthesis of polyimides (PI-2)]
Using as tetracarboxylic dianhydride 2,3,5-tricarboxylics cyclopentyl acetic acid dianhydride 22.5g (0.1 mole), As diamidogen p-phenylenediamine 7.6g (0.07 mole), 3,5-diaminobenzoic acid cholesteric Arrcostab 5.2 G (0.01 mole) and 4,4 '-diaminodiphenyl-methane 4.0g (0.02 mole) are dissolved in 157g NMP in, at 60 DEG C, carry out reaction in 6 hours, it is thus achieved that molten containing polyamic acid 20 weight % Liquid.The gained polyamic acid solution that fractional distillation is a small amount of, adding NMP and making polyamic acid concentration is 10 The solution of weight %, is 110mPa s to solution viscosity obtained by this solution mensuration.
Then, adding NMP in the polyamic acid solution of gained and making polyamic acid concentration is 7 The solution of weight %, adds pyridine 16.6g and acetic anhydride 21.4g, carries out 4 hours at 110 DEG C Dehydration closed-loop reacts.After dehydration closed-loop reaction, with new NMP, intrasystem solvent is carried out solvent Displacement, is derived from being about polyimides (PI-2) 26 weight % of 82% containing acid imide rate Solution.The gained polyimide solution that fractional distillation is a small amount of, adds NMP and makes polyimides concentration and be The solution of 10 weight %, is 62mPa s to solution viscosity obtained by this solution mensuration.Then, will be anti- Answer solution to be injected in excessive methanol, make reaction product precipitate.By this precipitate with methanol Clean, under reduced pressure, be dried 15 hours at 40 DEG C, be derived from polyimides (PI-2).
[synthesis example 3: the synthesis of polyimides (PI-3)]
Using 2,4,6,8-tetracarboxylic dicyclo [33.0] octane-2:4 as tetracarboxylic dianhydride, 6:8-dianhydride 24.9 G (0.10 mole), p-phenylenediamine 8.6g (0.08 mole) and 3 as diamidogen, 5-diaminobenzene Formic acid cholesteric Arrcostab 10.4g (0.02 mole) is dissolved in the NMP of 176g, at 60 DEG C Carry out reaction in 6 hours, it is thus achieved that containing the solution of polyamic acid 20 weight %.The a small amount of gained of fractional distillation gathers Amic acid solution, adds NMP and makes the solution that polyamic acid concentration is 10 weight %, molten to this Solution viscosity obtained by liquid mensuration is 103mPa s.
Then, adding NMP in the polyamic acid solution of gained and making polyamic acid concentration is 7 The solution of weight %, adds pyridine 11.9g and acetic anhydride 15.3g, carries out 4 hours at 110 DEG C Dehydration closed-loop reacts.After dehydration closed-loop reaction, with new NMP, intrasystem solvent is carried out solvent Displacement, is derived from being about polyimides (PI-3) 26 weight % of 71% containing acid imide rate Solution.The gained polyimide solution that fractional distillation is a small amount of, adds NMP and makes polyimides concentration and be The solution of 10 weight %, is 57mPa s to solution viscosity obtained by this solution mensuration.Then, will be anti- Answer solution to be injected in excessive methanol, make reaction product precipitate.By this precipitate with methanol Clean, under reduced pressure, be dried 15 hours at 40 DEG C, be derived from polyimides (PI-3).
[synthesis example 4: the synthesis of polyimides (PI-4)]
Using 2,3,5-tricarboxylics cyclopentyl acetic acid dianhydride 110g (0.50 mole) as tetracarboxylic dianhydride And 1,3,3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydrochysene-2,5-bis-side oxygen-3-furyl) naphtho-[1,2-c] furan Mutter-1,3-diketone 160g (0.50 mole), as diamidogen p-phenylenediamine 91g (0.85 mole), 1,3-double (the 4-aminobenzene of double (3-aminopropyl) tetramethyl disiloxane 25g (0.10 mole) and 3,6- Formyloxy) cholestane 25g (0.040 mole) and (0.015 rubs as the aniline 1.4g of monoamine You) be dissolved in the NMP of 960g, carry out at 60 DEG C 6 hours reaction, be derived from containing The solution of polyamic acid.The gained polyamic acid solution that fractional distillation is a small amount of, adds NMP and makes polyamides Amino acid concentration is the solution of 10 weight %, is 60mPa s to solution viscosity obtained by this solution mensuration.
Then, in the polyamic acid solution of gained, add 2, the NMP of 700g, add pyridine 390g And acetic anhydride 410g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, With new gamma-butyrolacton, intrasystem solvent is carried out solvent displacement, be derived from containing acid imide rate It is about the solution about 2,500g of polyimides (PI-4) 15 weight % of 95%.A small amount of this of fractional distillation is molten Liquid, adds NMP, makes the solution that polyimides concentration is 10 weight %, to this solution mensuration The solution viscosity obtained is 70mPa s.Then, reaction solution is injected in excessive methanol, Reaction product is made to precipitate.This precipitate is cleaned with methanol, under reduced pressure, is dried 15 at 40 DEG C Hour, it is derived from polyimides (PI-4).
[synthesis example 5: the synthesis of polyimides (PI-5)]
Using as tetracarboxylic dianhydride 2,3,5-tricarboxylics cyclopentyl acetic acid dianhydride 22.4g (0.1 mole), As diamidogen p-phenylenediamine 8.6g (0.08 mole), 4,4 '-diaminodiphenyl-methane 2.0g (0.01 Mole) and 4,4 '-diaminourea-2,2 '-bis-(trifluoromethyl) biphenyl 3.2g (0.01 mole) are dissolved in In the NMP of 324g, at 60 DEG C, carry out reaction in 4 hours, it is thus achieved that containing polyamic acid 10 weight The solution of %.
Then, in the polyamic acid solution of gained, add the NMP of 360g, add pyridine 39.5g And acetic anhydride 30.6g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.Dehydration closed-loop reacts After, with new NMP, intrasystem solvent is carried out solvent displacement, it is thus achieved that containing acid imide rate be The solution of polyimides (PI-5) 10 weight % of about 93%.The a small amount of gained polyimides of fractional distillation is molten Liquid, is 30mPa s to solution viscosity obtained by this solution mensuration.Then, reaction solution is injected into In excessive methanol, reaction product is made to precipitate.This precipitate is cleaned with methanol, in decompression Under, be dried 15 hours at 40 DEG C, be derived from polyimides (PI-5).
[synthesis example 6: the synthesis of polyimides (PI-6)]
Except the diamidogen used being changed to 3,5-diaminobenzoic acid 0.08 mole and cholesteric alkyl Epoxide-2, beyond 4-diaminobenzene 0.02 mole, utilize the method identical with above-mentioned synthesis example 1 to obtain poly- Amic acid solution.The gained polyamic acid solution that fractional distillation is a small amount of, adds NMP and makes polyamic acid Concentration is the solution of 10 weight %, is 80mPa s to solution viscosity obtained by this solution mensuration.
Then, the method identical with above-mentioned synthesis example 1 is utilized to carry out imidizate, it is thus achieved that containing acyl Imines rate is about the solution of polyimides (PI-6) 26 weight % of 65%.The gained that fractional distillation is a small amount of Polyimide solution, adds NMP and makes the solution that polyimides concentration is 10 weight %, to this Solution viscosity obtained by solution mensuration is 40mPa s.Then, reaction solution is injected into excessive Methanol in, make reaction product precipitate.This precipitate is cleaned with methanol, under reduced pressure, 40 DEG C Under be dried 15 hours, be derived from polyimides (PI-6).
[synthesis example 7: the synthesis of polyamic acid (PA-1)]
Using as tetracarboxylic dianhydride 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride 200g (1.0 moles), make For the 2 of diamidogen, 2 '-dimethyl-4,4 '-benzidine 210g (1.0 moles) is dissolved in 370g's NMP and gamma-butyrolacton 3, in the mixed solvent of 300g, carry out reaction in 3 hours at 40 DEG C, obtain Solid component concentration be 10 weight %, solution viscosity be the polyamic acid solution of 160mPa s.Connect , this polyamic acid solution is injected in excessive methanol, make reaction product precipitate.Will This precipitate cleans with methanol, under reduced pressure, is dried 15 hours at 40 DEG C, is derived from polyamide Acid (PA-1).
[synthesis example 8: the synthesis of polyamic acid (PA-2)]
Except the tetracarboxylic dianhydride used is set as pyromellitic acid anhydride 0.9 mole and 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride 0.1 mole, and diamidogen is set as p-phenylenediamine 0.2 mole with And 4, beyond 4 '-diamino-diphenyl ether, utilize the method identical with above-mentioned synthesis example 7, it is thus achieved that solid Constituent concentration be 10 weight %, solution viscosity be the polyamic acid solution of 170mPa s.Then, will This polyamic acid solution is injected in excessive methanol, makes reaction product precipitate.By this precipitation Thing cleans with methanol, under reduced pressure, is dried 15 hours at 40 DEG C, is derived from polyamic acid (PA-2).
[synthesis example 9: the synthesis of polyamic acid (PA-3)]
Using as tetracarboxylic dianhydride 2,3,5-tricarboxylics cyclopentyl acetic acid dianhydride 7.0g (0.031 mole), As represented by the following formula (R-1) of diamidogen compound (r1) 13g (relative to 2,3,5-tricarboxylics Cyclopentyl acetic acid dianhydride 1 mole, is equivalent to 1 mole) it is dissolved in the NMP of 80g, 60 Carry out reaction in 4 hours at DEG C, be derived from the solution containing polyamic acid (PA-3) 20 weight %. The solution viscosity of this polyamic acid solution is 2,000mPa s.Additionally, compound (r1) is based on day The record of this patent JP 2011-100099 publication synthesizes.Then, by this polyamic acid solution It is injected in excessive methanol, makes reaction product precipitate.This precipitate is cleaned with methanol, Under reduced pressure, it is dried 15 hours at 40 DEG C, is derived from polyamic acid (PA-3).
[changing 8]
[synthesis example 10: the synthesis of polysiloxane (APS-1)]
In the reaction vessel possessing blender, thermometer, Dropping funnel and reflux cooling pipe, throw Enter 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (2-(3,4-epoxycyclohexyl) ethyl Trimethoxysilane, ECETS) 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, At room temperature mix.Then, Dropping funnel is utilized, after spending 30 minutes dropping deionized water 100g, Stir under reflux on one side, at 80 DEG C, carry out reaction in 6 hours.After reaction terminates, taking-up has Machine layer, utilizes 0.2 weight % aqueous ammonium nitrate solution, cleans becoming neutrality to the water after cleaning, Solvent and water are removed in the most under reduced pressure distillation, are derived from reactive polysiloxane (EPS-1) as the transparency liquid of thickness.This reactivity polysiloxane is carried out1H-NMR divides Analysis, result, near chemical shift (δ)=3.2ppm, obtains based on ring as described in theoretical strength The peak value of epoxide, confirms not produce in reaction the side reaction of epoxy radicals.The reactive poly-organosilicon of gained Weight average molecular weight Mw of oxygen alkane is 3,500, and epoxide equivalent is 180g/ mole.
Then, in the there-necked flask of 200mL, reactive polysiloxane (EPS-1) 10.0 is put into G, the methyl iso-butyl ketone (MIBK) 30.28g as solvent, the 4-dodecyloxy as reactive compounds Benzoic acid 3.98g and UCAT18X (trade name, the general sieve in Sanya (San-Apro) as catalyst (stock) manufactures) 0.10g, stirs at 100 DEG C and reacts for 48 hours.After reaction terminates, instead Answer interpolation ethyl acetate in mixture, the solution of gained is washed 3 times, use magnesium sulfate by organic layer After drying, solvent is removed in distillation, is derived from LCD alignment polysiloxane (APS-1) 9.0 g.Weight average molecular weight Mw of resulting polymers is 9,900.
<preparation of crystal aligning agent>
[embodiment 1]
Containing in the polyimides (PI-1) solution as polymer (A), add NMP and Propylene-glycol diacetate is as solvent, and making group of solvents becomes NMP: PGDAc=50: 50 (weight Than), solid component concentration be the solution of 6.5 weight %.The filter using aperture to be 1 μm came Filter this solution, thus prepare crystal aligning agent (S-1).Additionally, crystal aligning agent (S-1) is mainly used In manufacturing vertical orientation type liquid crystal display cells.
<the bloating tendency evaluation of galley>
Use is used for preparing the solvent of above-mentioned crystal aligning agent (S-1), and the swelling to APR version is easy Degree (bloating tendency) is evaluated.APR version is to be irradiated subsclerotic aqueous photonasty tree by ultraviolet The resin plate that fat is formed, is generally used for the galley of liquid crystal orienting film printer.What is called makes liquid crystal join In the case of agent contacts with APR version, APR version is difficult to swelling, refers to that during printing, crystal aligning agent is difficult To penetrate in APR version, printing is good.Bloating tendency evaluation is by APR version being joined at liquid crystal Impregnating 1 day in agent, the weight change measuring the APR version before and after dipping is carried out.Now, exist In the case of the increments of the weight of APR version is less than 4%, APR version is difficult to swelling, is evaluated as good (zero), in the case of increments is more than 4%, the easy swelling of APR version, be evaluated as bad (×). This evaluation result is shown in table 1 below.
<evaluation of printing>
For above-mentioned prepared crystal aligning agent, to the printing when being carried out continuously the printing to substrate Property (continuous printing) is evaluated.Evaluation is to carry out as follows.First, for prepared Crystal aligning agent (S-1), use liquid crystal orienting film printer (Japan description printer (stock) system Make, Angstromer form " S40L-532 "), by crystal aligning agent to anilox roll (anilox roll) Dripping quantity be set to come and go under conditions of 20 (about 0.2g), coat with comprising ito film On the transparent electrical pole-face of the glass substrate of transparency electrode.Coating to substrate is to use with 1 minute interval New substrate implements 20 times.
Then, (one way, one way) is distributed in anilox roll with 1 minute interval by crystal aligning agent On, carry out the operation (hereinafter referred to as dry run (idling)) making anilox roll contact with galley every time, Add up to and carry out 10 times (therebetween, not carrying out the printing to glass substrate).Additionally, this dry run be for The operation specially implementing the printing of crystal aligning agent under harsh situation and carry out.
After 10 dry runs, glass substrate is then used formally to print.In formal printing, After dry run, put into 5 pieces of substrates, by each substrate after applied crystal aligning agent with 30 seconds intervals At 80 DEG C, heat (prebake conditions) 1 minute and after removing solvent, at 200 DEG C, heat (baking afterwards) 10 minutes, form thickness and be about the film of 80nm.Seen by the microscope utilizing multiplying power to be 20 times Examine this film to evaluate printing.Evaluation is to carry out as follows: by the 1st time after dry run The formal situation having printed the precipitation not observing polymer is evaluated as excellent (zero), after dry run Observe the precipitation of polymer during the 1st formal printing, but implementing between 5 formal printings no longer Observe that the situation of the precipitation of polymer is evaluated as well (△), after 5 formal printings will be repeated Still observe the situation of the precipitation of polymer be evaluated as bad (×).This evaluation result is shown in following In table 1.Additionally, in the case of the crystal aligning agent that printing is good, be informed in even by experiment Between continuous input substrate, the precipitation of polymer improves (disappearance).It addition, and then by dry run time Number is changed to 15 times, 20 times, 25 times, evaluates crystal aligning agent the most in the same manner as described above Printing.Its evaluation result is shown in table 1 below the most in the lump.
[table 1]
Additionally, the mark of the solvent composition in table 1 is respectively following meanings.
A:N-N-methyl-2-2-pyrrolidone N
B: propylene-glycol diacetate
C: gamma-butyrolacton
D:N-ethyl-2-pyrrolidone
E:N-amyl group-2-Pyrrolidone
F:1,3-dimethyl-2-imidazolidinone
I: butyl cellosolve
J: propylene-glycol ethyl ether
K: propylene glycol-positive propyl ether
L: propylene glycol-1-methyl ether acetate
M: diacetone alcohol
[embodiment 2～embodiment 17 and comparative example 1～comparative example 4]
Except the polymer used (A) and the kind of solvent and composition are changed to respectively as Beyond above-mentioned table 1 is described, utilizes the method identical with above-described embodiment 1 to prepare liquid crystal respectively and join To agent (S-2)～crystal aligning agent (S-17) and crystal aligning agent (SR-1)～crystal aligning agent (SR-4).It addition, carry out the bloating tendency of galley and print in the way of identical with above-described embodiment 1 The evaluation of brush.The results are shown in above-mentioned table 1.Additionally, in table 1, polymer (A) Allotment ratio represents each polymer phase total amount 100 weight % for polymer contained in crystal aligning agent Containing ratio (weight %).It addition, crystal aligning agent (S-2)～crystal aligning agent (S-14), liquid Brilliant orientation agent (SR-1)～crystal aligning agent (SR-4) are mainly for the manufacture of vertical orientation type liquid crystal Showing element, crystal aligning agent (S-15) is mainly for the manufacture of TN type liquid crystal display cells, and liquid crystal is joined To agent (S-16) mainly for the manufacture of IPS type liquid crystal display cells, crystal aligning agent (S-17) is main It is used for utilizing light orientation method to manufacture vertical orientation type liquid crystal display cells.
As shown in table 1, with the solvent phase ratio of use in comparative example, the solvent used in embodiment is the most difficult So that APR version swelling.Therefore, in the case of the crystal aligning agent of embodiment, it may be said that can The expansion of galley during suppression printing, can be spread evenly across crystal aligning agent on substrate.
It addition, about continuous printing, the crystal aligning agent of embodiment is all good, wherein, uses State compound (p2) be used as the embodiment 3 of solvent for making polymer dissolve～embodiment 6, In embodiment 9～embodiment 17 the best.

Claims (5)

1. a crystal aligning agent, it is characterised in that contain:
Select the formed group of free polyamic acid, polyimides, poly amic acid ester and polysiloxane In at least one polymer (A)；And
Comprise the solvent of compound (p1) represented by following formula (1), described compound (p1) The total amount that content is described solvent 5 weight % more than:
[changing 1]
In formula (1), R1And R3Be separately straight-chain or branch-like carbon number 1～3 1 Valency alkyl, R2Alkane diyl for the carbon number 2～5 of straight-chain or branch-like.
Crystal aligning agent the most according to claim 1, it is characterised in that: possibly together with choosing freely Compound represented by 1,3-dimethyl-2-imidazolidinone, following formula (2) and following formula (3) Represented at least one compound (p2) in the formed group of compound is used as described solvent:
[changing 2]
In formula (2), R4And R5Be separately hydrogen atom, 1 valency alkyl of carbon number 1～6, Or between the carbon-carbon bond of described alkyl, comprise the 1 valency base of "-O-", R4With R5Can mutually bond and Form ring structure；R6Alkyl for carbon number 1～6
[changing 3]
In formula (3), R7For 1 valency alkyl of carbon number 2～5 or the carbon-carbon bond in described alkyl Between comprise the 1 valency base of "-O-".
Crystal aligning agent the most according to claim 2, it is characterised in that: comprise choosing and freely gather At least one in the formed group of amic acid, polyimides and poly amic acid ester is as described polymerization Thing (A), described polyamic acid be make to comprise choosing freely 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides, 2,4,6,8-tetracarboxylic dicyclo [3.3.0] octane-2:4,6:8-dianhydride and 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride The tetracarboxylic dianhydride of at least one in formed group obtains with diamine reactant.
4. a liquid crystal orienting film, it is characterised in that use as any one of claims 1 to 3 Described crystal aligning agent is formed.
5. a liquid crystal display cells, it is characterised in that include liquid crystal as claimed in claim 4 Alignment film.
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