CN106047372A - Liquid crystal aligning agent, liquid crystal alignment film, manufacturing method for liquid crystal alignment film, liquid crystal component, manufacturing method for liquid crystal component, and compound - Google Patents

Liquid crystal aligning agent, liquid crystal alignment film, manufacturing method for liquid crystal alignment film, liquid crystal component, manufacturing method for liquid crystal component, and compound Download PDF

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Publication number
CN106047372A
CN106047372A CN201610140356.4A CN201610140356A CN106047372A CN 106047372 A CN106047372 A CN 106047372A CN 201610140356 A CN201610140356 A CN 201610140356A CN 106047372 A CN106047372 A CN 106047372A
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liquid crystal
group
compound
aligning agent
film
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CN106047372B (en
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伊藤贤
伊藤贤一
秋池利之
植阪裕介
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JSR Corp
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JSR Corp
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/14—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to a carbon atom of a six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J41/00—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring
    • C07J41/0033—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005
    • C07J41/0055—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005 the 17-beta position being substituted by an uninterrupted chain of at least three carbon atoms which may or may not be branched, e.g. cholane or cholestane derivatives, optionally cyclised, e.g. 17-beta-phenyl or 17-beta-furyl derivatives
    • 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
    • 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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a manufacturing method for the liquid crystal alignment film, a liquid crystal component, a manufacturing method for the liquid crystal component, and a compound. The liquid crystal aligning agent includes a polymer ingredient and a compound [A] having groups of (1) and (2). (1) is selected from at least one group of group classes consisting of groups formed by directly connecting 2 or more rings or connecting the rings via connection groups and groups having condensed rings. (2) is selected from at least one group of group classes consisting of -NR1R2 (wherein, R1 and R2 are each independently either univalent alkyl or protecting groups having the number of hydrogen atoms and carbon atoms being 1-10), protection isocyanate groups, protection isothiocyanate groups, groups containing oxazoline rings, groups containing Meldrum acid, and groups represented by a formula (g-1). According to the liquid crystal aligning agent containing the compound (A), a liquid crystal component having excellent image residual characteristics and voltage retaining characteristics can be acquired.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and manufacture method thereof, liquid crystal cell and manufacture method thereof, And compound
Technical field
The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film, the manufacture method of liquid crystal orientation film, liquid crystal cell, liquid crystal The manufacture method of element and compound.
Background technology
In the past, as liquid crystal display cells, electrode structure or physical property of liquid crystal molecule of being used etc. are developed different Multiple type of drive person, the most known twisted nematic (Twisted Nematic, TN) type or STN Super TN (Super Twisted Nematic, STN) type, vertical orientated (Vertical Alignment, VA) type, coplanar switching (In-Plane Switching, IPS) type, fringing field switching (fringe field switching, FFS) type, optical compensation curved (Optically Compensation Bend, OCB) the various liquid crystal display cells such as type.These liquid crystal display cells include the liquid crystal making liquid crystal molecular orientation Alignment films.For the aspect that the various characteristics such as the affinity with regard to thermostability, mechanical strength and liquid crystal are good, liquid crystal orientation film Material be use polyimides or its predecessor etc. (referring for example to patent documentation 1).Patent Document 1 discloses a kind of multiple Closing film and be used as liquid crystal orientation film, described composite membrane contains makes the polyamic acid with specific part-structure and to amylene epoxide Polymer and liquid crystal that benzoic acid (to cyano-phenyl) oxide reacts and obtains form.
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 11-64856 publication
Summary of the invention
[inventing problem to be solved]
In recent years, liquid crystal display cells was not only used for the display device of PC etc. as in the past, and for such as liquid crystal The multiple uses such as TV or auto-navigation system, mobile phone, smart mobile phone, information display.Along with described liquid crystal display cells Multipurpose, than before for the requirement of display quality is become strict, it is desirable to image residue is less and voltage retention Higher liquid crystal display cells.
The present invention is to be formed in view of described problem, and one of purpose is to provide one can obtain image residue characteristic and voltage is protected Hold the aligning agent for liquid crystal of the liquid crystal cell of excellent.
[solving the technological means of problem]
The present inventors study with keen determination in order to reach the problem of prior art as above, it was found that pass through Aligning agent for liquid crystal is allocated specific compound, it is possible to resolve described problem, thus complete the present invention.Specifically, by this Bright provide following aligning agent for liquid crystal, liquid crystal orientation film, the manufacture method of liquid crystal orientation film, liquid crystal cell, liquid crystal cell Manufacture method and compound.
The present invention provides a kind of aligning agent for liquid crystal on the one hand, and it contains component of polymer and has following (1) and (2) The compound [A] of group.
(1) choosing freely has that the ring of more than 2 is direct or the group of structure that links via concatenating group and having At least one group in the group that the group of condensed ring is formed.
(2) choosing freely-NR1R2(wherein, R1And R2Be separately hydrogen atom, the monovalent hydrocarbon of carbon number 1～10 or Protection group), protect NCO, protect isothiocyanate group, the group comprising oxazoline ring structure, comprise Michaelis acid In the group that group represented by the group of (Meldrum ' s acid) structure and following formula (g-1) is formed at least one Plant group.
[changing 1]
(in formula (g-1), R3And R6It is separately hydrogen atom or the alkyl of carbon number 1～3, R4And R5Independently Ground is hydrogen atom, the alkyl of carbon number 1～3 or " *2-CH2-O-R11”(R11For hydrogen atom or the alkyl of carbon number 1～3； “*2" represent and R4And R5The associative key of the carbon atom of institute's bond)；“*1" represent associative key)
The present invention provides a kind of aligning agent for liquid crystal on the one hand, and it is by component of polymer and to have described (1) and (2) Group compound [A] allotment and obtain.
It addition, the one side at other provides a kind of liquid crystal orientation film, it is to use described aligning agent for liquid crystal to be formed.And then The manufacture method of a kind of liquid crystal orientation film is provided, forms film on substrate comprising: coated by described aligning agent for liquid crystal Step；And described film is carried out light irradiation and gives the step of liquid crystal aligning ability.It addition, and then provide a kind of liquid crystal Element, it includes described liquid crystal orientation film or utilizes described manufacture method and the liquid crystal orientation film that obtains.
The present invention provides the manufacture method of a kind of liquid crystal cell on the one hand, comprising: have a pair substrate of conducting film On this conducting film, it is coated with described aligning agent for liquid crystal and forms the step of film；Will be formed with a pair substrate of this film, via Liquid crystal layer and oppositely disposed and construct the step of liquid crystal cells in the way of described film is relative；And to conducting electricity intermembranous applying Under the state of voltage, described liquid crystal cells is carried out the step of light irradiation.It addition, the present invention provides one in other one side There is the compound [A] of the group of described (1) and (2).
[effect of invention]
According to the aligning agent for liquid crystal containing described compound [A], image residue characteristic and the liquid of voltage retention performance excellence can be obtained Crystal cell.
Accompanying drawing explanation
Fig. 1 is the figure representing the electrode structure used in embodiment.
[explanation of symbol]
A, B: electrode
Detailed description of the invention
" aligning agent for liquid crystal "
The aligning agent for liquid crystal of the present invention is the polymer composition using component of polymer and specific additive component to obtain Thing.Hereinafter, each composition of the aligning agent for liquid crystal for preparing the present invention and other compositions of optionally arbitrarily allotment are entered Row explanation.
<component of polymer>
The aligning agent for liquid crystal of the present invention contains component of polymer.The main framing of polymer is not particularly limited, and include, for example: Polyamic acid, poly amic acid ester, polyimides, polysiloxanes, polyester, polyamide, polybenzoxazole predecessor, polyphenyl And azoles, cellulose derivative, polyacetals, polystyrene derivative, poly-(styrene-phenylmaleimide) derive The main framings such as thing, poly-(methyl) acrylate.Additionally, (methyl) acrylate refers to comprise acrylate and methacrylate. When preparing aligning agent for liquid crystal, polymer can be used alone one, it is possible to is used in combination of two or more.
If the most fully showing image residue (image sticking) minimizing brought by following compound [A] (particularly to hand over The minimizing of stream electricity (Alternating Current, AC) image retention) effect viewpoint for, the polymer of aligning agent for liquid crystal becomes At least one being preferably selected from the group being made up of polyamic acid, poly amic acid ester and polyimides is divided (to be also referred to as below For " polymer [P] ").Polymer [P] such as can be by making the free tetracarboxylic dianhydride of choosing, tetrabasic carboxylic acid diester and tetrabasic carboxylic acid diester The tetracarboxylic acid derivatives of at least one in the group that dihalide is formed reacts with diamidogen and obtains.
[polyamic acid]
Polyamic acid in the present invention such as can obtain by making tetracarboxylic dianhydride react with diamidogen.
(tetracarboxylic dianhydride)
The tetracarboxylic dianhydride used in the synthesis of polyamic acid include, for example: aliphatic tetracarboxylic dianhydride, ester ring type tetrabasic carboxylic acid Dianhydride, aromatic tetracarboxylic acid's dianhydride etc..As the concrete example of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydride such as can arrange Lift butane tetracarboxylic acid dianhydride etc.；
Ester ring type tetracarboxylic dianhydride include, for example: 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid two Acid anhydride, 5-(2,5-dioxotetrahydro furan-3-base)-3a, 4,5,9b-tetrahydrochysene naphtho-[1,2-c] furan-1,3-diketone, 5-(2,5-dioxo four Hydrogen furan-3-base)-8-methyl-3a, 4,5,9b-tetrahydrochysene naphtho-[1,2-c] furan-1,3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-bis- Ketone-6-volution-3 '-(oxolane-2 ', 5 '-diketone), 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxyl Anhydride, 3,5,6-tri-carboxyl-2-carboxymethyl group norbornane-2:3,5:6-dianhydride, dicyclo [3.3.0] octane-2,4,6,8-tetrabasic carboxylic acid 2:4,6:8- Dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid 2:3,5:6-dianhydride, 4,9-dioxa three ring [5.3.1.02,6] hendecane-3,5,8,10- Tetrone, 1,2,4,5-cyclopentanetetracarboxylic's dianhydrides, dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydrides, ethylenediaminetetraacetic acid two Acid anhydride, Pentamethylene. tetracarboxylic dianhydride, ethylene glycol bis (trimellitic anhydride), 1,3-PD double (trimellitic anhydride) etc.；
Aromatic tetracarboxylic acid's dianhydride include, for example: pyromellitic acid anhydride, 4,4 '-(hexafluoroisopropyli,ene) two phthalic acid Acid anhydride, following formula (H-1-1)～formula (H-1-4) respectively represented by compound etc.；In addition, Japan Patent can be used special Open the tetracarboxylic dianhydride described in 2010-97188 publication.
[changing 2]
The one or be used in combination of two or more additionally, described tetracarboxylic dianhydride can be used alone.
The tetracarboxylic dianhydride used in synthesis preferably comprises ester ring type tetracarboxylic dianhydride, more preferably comprises to have and selects free ring The tetrabasic carboxylic acid of at least one part-structure in the group that butane ring structure, cyclopentane ring structure and cyclohexane ring structure are formed Dianhydride (hereinafter also referred to " specific tetracarboxylic dianhydride ").Specifically, choosing freely 1,2,3,4-ring fourths are particularly preferably comprised Alkane tetracarboxylic dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides, 5-(2,5-dioxotetrahydro furan-3-base)-3a, 4,5,9b-naphthanes And [1,2-c] furan-1,3-diketone, 5-(2,5-dioxotetrahydro furan-3-base)-8-methyl-3a, 4,5,9b-tetrahydrochysene naphtho-[1,2-c] furan -1,3-diketone, Pentamethylene. tetracarboxylic dianhydride, dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydrides and cyclopentanetetracarboxylic's dianhydride At least one compound in the group formed.
Relative to the total amount of the tetracarboxylic dianhydride used in the synthesis of polyamic acid, the usage amount of specific tetracarboxylic dianhydride (makes With in the case of two or more for its total amount) be preferably set to 10 moles of more than %, be more preferably set to 20 moles of more than %, Especially preferably it is set to 30 moles of more than %.
(diamidogen)
In the synthesis of polyamic acid use diamidogen 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, 1,3- Propane diamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine, 1, double (amino methyl) hexamethylene of 3-etc.；Alicyclic ring Formula diamidogen include, for example: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine) etc.；
Aromatic diamine include, for example: dodecyloxy diaminobenzene, tetradecyloxyaniline diaminobenzene, pentadecane epoxide two Aminobenzene, hexadecane epoxide diaminobenzene, octadecane epoxide diaminobenzene, cholesteric alkyl oxy diaminobenzene, cholesteryl Epoxide diaminobenzene, diaminobenzoic acid cholesteric Arrcostab, diaminobenzoic acid cholesteryl ester, diaminobenzoic acid Pilus Caprae seu Ovis Steroid Arrcostab, 3, double (4-amino benzoyl epoxide) cholestane of 6-, 3, double (4-amino-benzene oxygen) cholestane of 6-, 1, double (the 4-((ammonia of 1- Base phenyl) methyl) phenyl)-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) the phenyl)-4-(4-heptyl cyclohexyl) of 1- Hexamethylene, N-(2,4-diamino-phenyl)-4-(4-heptyl cyclohexyl) Benzoylamide, following formula (E-1)
[changing 3]
(in formula (E-1), XIAnd XIIIt is separately singly-bound ,-O-, *-COO-or *-OCO-(wherein, " * " Represent and XIAssociative key), RIFor the alkane diyl of carbon number 1～3, RIIFor singly-bound or the alkane diyl of carbon number 1～3, a is 0 Or 1, b is the integer of 0～2, and c is the integer of 1～20, and d is 0 or 1；Wherein, a and b will not be 0 simultaneously)
The diamidogen of the side chain types such as represented compound:
P-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 4-aminophenyl-4 '-aminobenzoic Acid esters, 4,4 '-chrysoidine, 1, double (4-amino-benzene oxygen) pentane of 5-, 1,7-double (4-amino-benzene oxygen) heptane, double [2-(4- Aminophenyl) ethyl] adipic acid, double (4-aminophenyl) methyl amine of N, N-, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acids, 4,4 '-benzidine-3-carboxylic acid, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2, double [4-(the 4-aminobenzene of 2- Epoxide) phenyl] propane, 9, double (4-aminophenyl) fluorenes of 9-, 2, double [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, the double (4-of 2- Aminophenyl) HFC-236fa, 4,4 '-(to phenylenediisopropylidene) dianils, 4,4 '-(metaphenylene two isopropylidene) dianils, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl etc.；
Diaminourea organosiloxane include, for example: 1,3-double (3-aminopropyl)-tetramethyl disiloxanes etc.；In addition, may be used Use the diamidogen described in Japanese Patent Laid-Open 2010-97188 publication.
As the concrete example of the compound represented by described formula (E-1), include, for example following formula (E-1-1)～formula (E-1-4) Compound etc. represented by Fen Bie.
[changing 4]
The diamidogen used in the synthesis of polyamic acid can be enumerated: has the free nitrogen heterocyclic ring of choosing, secondary amine base and tertiary amine base institute The diamidogen of at least one structure (hereinafter also referred to " containing N structure ") in the group of composition；There is the diamidogen etc. of carboxyl. According to by have the diamidogen containing N structure be used for raw material at least some of in polymer, it becomes possible to improve by liquid crystal display unit For the aspect improving effect that image residue caused by the DC voltage of part reduces preferably.It addition, according to by carboxylic Diamidogen for raw material at least some of in polymer, just with the interaction of following compound [A] raising, it is possible to increase by For the aspect improving effect that image residue caused by the alternating voltage of liquid crystal display cells reduces preferably.
Having in the diamidogen containing N structure, the nitrogen heterocyclic ring that this diamidogen can have include, for example: pyrroles, imidazoles, pyrazoles, Triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinolin, naphthyridines, quinoxaline, Phthalazines, triazine, carbazole, acridine, piperidines, piperazine, pyrrolidine, hexamethylene imine etc..Wherein, it is however preferred to have choosing At least one in the group that free pyridine, pyrimidine, pyrazine, piperidines, piperazine, quinoline, carbazole and acridine are formed.
There is secondary amine base that the diamidogen containing N structure can have and tertiary amine base is e.g. represented by following formula (N-1).
[changing 5]
(in formula (N-1), R23For hydrogen atom or the monovalent hydrocarbon of carbon number 1～10；" * " is the knot being binding on alkyl Close key)
In described formula (N-1), R23Monovalent hydrocarbon include, for example: the alkyl such as methyl, ethyl, propyl group；Cyclohexyl etc. Cycloalkyl；The aryl such as phenyl, aminomethyl phenyl etc..R23It is preferably hydrogen atom or methyl.
As the concrete example of the diamidogen having containing N structure, include, for example: DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidines, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 3,6- Proflavin, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-biphenyl Amine, N, N '-bis-(4-aminophenyl)-N, N '-dimethylbenzidine, following formula (N-1-1)～formula (N-1-8) are the most represented Compound etc..
[changing 6]
During synthesizing polyamides acid, for fully obtaining the viewpoint improving effect that the image residue of liquid crystal display cells reduces, Relative to total scale of construction of the diamidogen used in synthesis, the use ratio with the diamidogen containing N structure is preferably set to 0.1 mole of % Above, more preferably it is set to 1 mole of more than %, is especially preferably set to 2 moles of more than %.It addition, this use ratio is upper Limit be preferably set to 60 moles of below %, be more preferably set to 50 moles of below %, be especially preferably set to 40 moles of % with Under.There is the diamidogen containing N structure can be used alone one or be used in combination of two or more.
During synthesizing polyamides acid, by by have the diamidogen containing N structure be used for raw material at least some of in, and obtain conduct There is the polyamic acid of polymer containing N structure.Wherein, it is thus achieved that the method with the polyamic acid containing N structure does not limit In described, the most also can obtain by making to have method that tetracarboxylic dianhydride containing N structure and diamidogen carry out reacting.
As long as carboxylic diamidogen has at least one carboxyl and 2 one-level amino in intramolecular, remaining structure there is no It is particularly limited to.
As the concrete example of carboxylic diamidogen, include, for example: 3,5-diaminobenzoic acids, 2,4-diaminobenzoic acid, 2,5- Diaminobenzoic acid, 4,4 '-benzidine-3-carboxylic acid, 4,4 '-diaminodiphenyl-methane-3-carboxylic acid, 4,4 '-diamino-diphenyl The monocarboxylic acids such as ethane-3-carboxylic acid；
4,4 '-benzidine-3,3 '-dicarboxylic acids, 4,4 '-benzidine-2,2 '-dicarboxylic acids, 3,3 '-benzidine-4,4 '-dicarboxyl Acid, 3,3 '-benzidine-2,4 '-dicarboxylic acids, 4,4 '-diaminodiphenyl-methane-3,3 '-dicarboxylic acids, 4,4 '-diamino-diphenyl second Alkane-3,3 '-dicarboxylic acids, 4,4 '-diamino-diphenyl ether-3, the dicarboxylic acids etc. such as 3 '-dicarboxylic acids.
During synthesizing polyamides acid, for the viewpoint of image residue characteristic, relative to total scale of construction of the diamidogen used in synthesis, The use ratio of carboxylic diamidogen is preferably set to 1 mole of more than %, is more preferably set to 5 moles of more than %, particularly preferably For being set to 10 moles of more than %.It addition, the higher limit of this use ratio there is no particular restriction, with regard to voltage retention viewpoint and Speech, relative to total scale of construction of the diamidogen used in synthesis, is preferably set to 80 moles of below %, is more preferably set to 70 moles Below %.One in described diamidogen can be used alone or suitably select two or more use by the most carboxylic diamidogen.
Irradiated by light, in the case of the film formed utilizing aligning agent for liquid crystal gives liquid crystal aligning ability, it is possible to At least some of middle of component of polymer uses the polymer with light orientation structure.The concrete example of light orientation structure can be adopted With the group being demonstrated light orientation by photoisomerization or photodimerization, photolysis etc..Specifically, include, for example: Containing azo-compound or derivatives thereof as the group containing azo of basic framework, containing cinnamic acid or derivatives thereof as base The group containing cinnamic acid of this skeleton, containing chalcone derivative or derivatives thereof as basic framework the group containing chalcone derivative, contain Benzophenone or derivatives thereof as the group containing benzophenone of basic framework, containing coumarin or derivatives thereof as substantially The group containing coumarin of skeleton, containing Tetramethylene. or derivatives thereof as the structure containing Tetramethylene. of basic framework, containing double Ring [2.2.2] octene or derivatives thereof is as the structure containing dicyclo [2.2.2] octene of basic framework, containing following formula (4)
[changing 7]
(in formula (4), X3For sulphur atom or oxygen atom；" * " represents associative key respectively；Wherein, in 2 " * " extremely Few one is binding on aromatic rings)
Represented part-structure is as the structure etc. of basic framework.
The polyamic acid with light orientation structure such as can have the four of light orientation structure by comprising in forming at monomer Carboxylic acid dianhydride and there is at least any one the polymerization of diamidogen of light orientation structure and obtain.In the case of Gai, anti-with regard to light For the viewpoint of answering property, relative to the total amount of the monomer used in the synthesis of polymer, there is the monomer of light orientation structure Use ratio be preferably set to 20 moles of more than %, be more preferably set to 30 moles of %～80 moles of %.
(synthesis of polyamic acid)
Polyamic acid optionally can carry out anti-by making tetracarboxylic dianhydride as above and diamidogen together with molecular weight regulator Answer and obtain.The tetracarboxylic dianhydride of synthetic reaction being supplied to polyamic acid is preferably relative to diamidogen with the use ratio of diamidogen Amino 1 equivalent, the anhydride group of tetracarboxylic dianhydride becomes 0.2 equivalent～the ratio of 2 equivalents, more preferably becomes 0.3 equivalent ～1.2 ratios of equivalent.
Molecular weight regulator include, for example: the single acid anhydride of the acid such as maleic anhydride, phthalic anhydride, itaconic anhydride, aniline, The monoamine compound such as cyclo-hexylamine, n-butylamine, the monoisocyanate compound such as phenyl isocyanate, naphthyl isocyanate etc.. Relative to total 100 weight portion of the tetracarboxylic dianhydride used and diamidogen, the use ratio of molecular weight regulator preferably sets It is below 20 weight portions.
The synthetic reaction of polyamic acid is preferably and carries out in organic solvent.Reaction temperature now be preferably-20 DEG C～ 150 DEG C, the response time is preferably 0.1 hour～24 hours.
In reaction use organic solvent include, for example: aprotic polar solvent, phenol system solvent, alcohol, ketone, ester, ether, Halogenated hydrocarbon, hydrocarbon etc..In these organic solvents, it is preferable to use select free aprotic polar solvent and phenol system solvent to be formed Group (organic solvent of the first group) in more than one, or selected from the first group organic solvent in one with One in the group (organic solvent of the second group) that upper and the free alcohol of choosing, ketone, ester, ether, halogenated hydrocarbon and hydrocarbon are formed Above mixture.In the latter case, relative to the organic solvent of the first group and the conjunction of the organic solvent of the second group Metering, the use ratio of the organic solvent of the second group is preferably below 50 weight %, below more preferably 40 weight %.
Particularly preferred organic solvent is preferably with choosing free METHYLPYRROLIDONE, N,N-dimethylacetamide, N, N- Dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, tetramethylurea, HMPA, metacresol, xylenol and halogen More than one in the group that change phenol is formed are as solvent, or use the one of these solvents with the scope of described ratio Plant the above and mixture of other organic solvents.It is total that the usage amount (a) of organic solvent is preferably set to relative to reaction solution Amount (a+b), the total amount (b) of tetracarboxylic dianhydride and diamidogen becomes 0.1 weight %～the amount of 50 weight %.
As previously discussed, it is thus achieved that the reaction solution that polyamic acid is dissolved.This reaction solution can be supplied directly to liquid crystal and take To the preparation of agent, it is possible to be available to the preparation of aligning agent for liquid crystal after being separated by polyamic acid contained in reaction solution.Polyamides The separation of amino acid and purification can be carried out according to known method.
[poly amic acid ester]
Poly amic acid ester in the present invention such as may utilize following methods and obtains: [I] makes to be obtained by described synthetic reaction Polyamic acid and esterifying agent (such as methanol, ethanol, DMF diethyl acetal, N, N-diethylformamide Diethyl acetal etc.) method that carries out reacting；[II] makes the method that tetrabasic carboxylic acid diester and diamidogen carry out reacting；[III] makes tetrabasic carboxylic acid Diester dihalide and diamidogen carry out the method etc. reacted.
Poly amic acid ester contained in aligning agent for liquid crystal can only have amic acid esters structure, it is possible to for amic acid structure and amide Acrylate structure the partial esterification thing deposited.Additionally, the reaction solution that poly amic acid ester dissolves can be supplied directly to liquid crystal The preparation of alignment agent, it is possible to be available to the preparation of aligning agent for liquid crystal after being separated by poly amic acid ester contained in reaction solution.
[polyimides]
Polyimides in the present invention such as can be by carrying out dehydration closed-loop by the polyamic acid synthesized in this way, in addition acyl Imidization and obtain.
Polyimides can by the amic acid structure being had as the polyamic acid of its predecessor is all carried out dehydration closed-loop and Become complete acid imide compound, it is possible to for only a part for amic acid structure being carried out dehydration closed-loop, and make amic acid structure with Imide ring structure the part acid imide compound deposited.It is 10% that the polyimides used in reaction is preferably its acid imide rate Above, more preferably 20%～99%, especially preferably 20%～85%.This acid imide rate is the acyl relative to polyimides The quantity of amino acid structure and the total of the quantity of imide ring structure, represent with percentage rate shared by the quantity of imide ring structure Ratio.Herein, a part for imide ring is alternatively different imide ring.
The dehydration closed-loop of polyamic acid preferably utilizes following methods to carry out: the method heating polyamic acid；Or Polyamic acid is dissolved in organic solvent, this solution adds dehydrant and dehydration closed-loop catalyst, optionally carries out The method of heating.Wherein, the method preferably utilizing the latter.
Adding in the solution of polyamic acid in the method for dehydrant and dehydration closed-loop catalyst, dehydrant such as can use: The anhydride such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.Relative to 1 mole of the amic acid structure of polyamic acid, dehydrant Usage amount is preferably set to 0.01 mole～20 moles.Dehydration closed-loop catalyst such as can use pyridine, trimethylpyridine, two The tertiary amine such as picoline, triethylamine.Relative to the dehydrant used 1 mole, the usage amount of dehydration closed-loop catalyst Preferably it is set to 0.01 mole～10 moles.The organic solvent used in dehydration closed-loop reaction can enumerate the conjunction as polyamic acid User in one-tenth and illustrate organic solvent dehydration closed-loop reaction reaction temperature be preferably 0 DEG C～180 DEG C, more preferably 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 this way.This reaction solution can be supplied directly to the system of aligning agent for liquid crystal Standby, it is possible to be available to the preparation of aligning agent for liquid crystal after autoreaction solution removes dehydrant and dehydration closed-loop catalyst, also Can polyimides separate after be available to the preparation of aligning agent for liquid crystal, or also can by the polyimides that separated the most again It is supplied to the preparation of aligning agent for liquid crystal.These purification process can be carried out according to known method.In addition, polyimides Also can be obtained by the imidizate of poly amic acid ester.
It is 10 weights that polyamic acid, poly amic acid ester and the polyimides obtained in this way is preferably when being made into concentration When measuring the solution of %, there is the solution viscosity person of 10mPa s～800mPa s, more preferably there is 15mPa s～500mPa s Solution viscosity person.Additionally, the solution viscosity (mPa s) of described polymer is to using the good solvent of this polymer (such as Gamma-butyrolacton, METHYLPYRROLIDONE etc.) and the polymer solution that concentration is 10 weight % prepared, use E type to rotate Viscometer, the value measured at 25 DEG C.
Polyamic acid, poly amic acid ester and polyimides utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) weight average molecular weight (Mw) of polystyrene conversion that measures be preferably 1,000～ 500,000, more preferably 2,000～300,000.It addition, the quantity of Mw and the polystyrene conversion measured by GPC The molecular weight distribution (Mw/Mn) represented by ratio of mean molecule quantity (Mn) is preferably less than 10, more preferably less than 7. By being in molecular weight ranges as above, it can be ensured that the good orientation of liquid crystal cell and stability.
<compound [A]>
When preparing the aligning agent for liquid crystal of the present invention, in addition to component of polymer, also use and there is following (1) and (2) The compound [A] of group.
(1) structure selecting the ring freely with more than 2 directly or to link via concatenating group is (hereinafter also referred to " many Ring structure ") group and there is at least one group in the group that the group of condensed ring is formed.
(2) choosing freely-NR1R2(wherein, R1And R2Be separately hydrogen atom, the monovalent hydrocarbon of carbon number 1～10 or Protection group), protect NCO, protect isothiocyanate group, the group comprising oxazoline ring structure, comprise Michaelis acid At least one group in the group that group represented by the group of structure and described formula (g-1) is formed.
About the group of described (1), the ring constituting multiring structure is preferably phenyl ring or cyclohexane ring.This group is had If the quantity more than 2 of ring, then be not particularly limited, preferably 2～4.Additionally, constitute the multiple of multiring structure Ring can be the most identical, it is possible to different.In the case of ring is phenyl ring or cyclohexane ring, the binding site of ring is preferably relatively It is para-position in other groups.
Concatenating group include, for example :-O-,-CO-,-COO-,-NRb-、-CONRb-(RbFor hydrogen atom, carbon number 1～6 Alkyl or protection group), the alkane diyl of carbon number 1～10, by least one methylene of the alkane diyl of carbon number 1～10 by-O-, -CO-、-COO-、-NRb-or-CONRbThe substituted bilvalent radical of-institute etc..
RbProtection group can enumerate at least any one and any monovalent organic radical etc. that departs from by heat, light, acid and alkali.RbPreferably For any monovalent organic radical departed from least through heat, as its concrete example, include, for example: carbamate system protection group, Amide system protection group, imide series protection group, sulfonamide system protection group, following formula (1-1)～formula (1-4) are the most represented Group etc..
[changing 8]
(in formula (1-1)～formula (1-4), Ar1For the monovalence fragrance ring group of carbon number 6～10, R11For carbon number 1～12 Alkyl；" * " represents the associative key being binding on nitrogen-atoms)
The Ar of described formula (1-2)1For removing the group of 1 hydrogen atom, concrete example on the aromatic rings of carbon number 6～10 Can enumerate such as: phenyl, naphthyl etc..The R of formula (1-4)11The alkyl of carbon number 1～12 include, for example: methyl, second Base, propyl group, butyl, amyl group, hexyl etc., these alkyl can be straight-chain, it is possible to for branch-like.
For the aspect that the detachment by heat is high, RbIt is preferably carbamate system therein protection group.Concrete as it Example, include, for example: tert-butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethyl epoxide carbonyl, 1,1-diformazan Base-2-cyano ethyl epoxide carbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2-(TMS) ethyoxyl Carbonyl etc..Wherein, just by the high aspect of hot detachment and can be by by the R departed from by heating during maskingbAnd For the aspect that the compound come is expelled to outside film as gas, preferably tert-butoxycarbonyl (BOC yl).
As the concrete example of multiring structure, include, for example: 4,4 '-biphenylene, 4,4 '-bis-cyclohexylidenes and following formula (6-1) group etc.～represented by formula (6-9) difference.
[changing 9]
(in formula, " BOC " represents tert-butoxycarbonyl；" * " represents associative key)
In the group of described (1), if condensed ring has a ring of more than 2 and each ring has the ring of more than 2 atoms Formula structure, then be not particularly limited, and include, for example: naphthalene nucleus, anthracene nucleus, phenanthrene ring, steroid core etc..In these, have The group of condensed ring preferably has the group of steroid skeleton.The group with steroid skeleton is preferably carbon number 17～51, Include, for example: cholesteryl, cholesteric alkyl, lanostane base, cholesteric alkyloxycarbonyl, cholesteryl epoxide carbonyl, Cholesteric alkyl oxy, cholesteryl epoxide etc..
About the group of described (2), group "-NR1R2R in "1And R2The alkyl of carbon number 1～10 include, for example: Straight-chain or the alkyl of branch-like such as methyl, ethyl, propyl group, butyl, amyl group, hexyl；Cyclohexyl, methylcyclohexyl etc. Ester ring type alkyl；The aromatic hydrocarbyls etc. such as phenyl, aminomethyl phenyl, benzyl.At R1、R2Concrete in the case of protection group Example can apply described RbIn the explanation of illustration enumerated.In described, R1And R2It is preferably hydrogen atom, the alkyl of carbon number 1～3 Or tert-butoxycarbonyl.Additionally, R1And R2Can be the most identical, it is possible to different.
Protection different (sulfur) cyanic acid ester group in the group of described (2) is preferably by utilizing the arbitrary of heat, light, acid and alkali The deprotection of person and regenerate the group of different (sulfur) cyanic acid ester group.Concrete example can be enumerated and make different (sulfur) cyanic acid ester group and active hydrogen Compound (block agent) carry out reacting and the group etc. that obtains.Additionally, so-called " reactive hydrogen " refers to the hydrogen that detachment is high Atom, preferably refers to that the acid ionization constant pKa in water is less than 20 persons.Additionally, different (sulfur) cyanic acid ester group is to comprise isocyanide Perester radical and the implication of isothiocyanate group.
Block agent can use known person, include, for example: alcohol based compound, phenol system compound, active methylene group based compound, Mercaptan based compound, acid amide based compound, acid imide based compound, imidazole compound, pyrazoles based compound, urea Based compound, oxime compound, amine compound, imines based compound, pyridine based compound etc..As these compounds Concrete example, alcohol based compound include, for example: methanol, ethanol, propanol, butanol, 2-Ethylhexyl Alcohol, methyl cellosolve, Butyl cellosolve, methyl carbitol, benzyl alcohol, Hexalin etc.；
Phenol system compound include, for example: phenol, cresol, ethyl-phenol, butylphenol, nonyl phenol, dinonyl phenol, Styrenated phenol, hydroxybenzoate etc.；
Active methylene group based compound include, for example: dimethyl malenate, diethyl malonate, methyl acetoacetate, second Ethyl acetoacetic acid ethyl ester, pentanedione etc.；Mercaptan based compound include, for example: butanethiol, lauryl mercaptan etc.；Acid Amide based compound include, for example: acetanilide, amide, epsilon-caprolactams, δ-valerolactam, butyrolactam etc.； Acid imide based compound include, for example: succinic acid acid imide, maleic acid acid imide etc.；
Imidazole compound include, for example: imidazoles, 2-methylimidazole etc.；Pyrazoles based compound include, for example: 3-methyl Pyrazoles, 3，5-dimethylpyrazole, 3,5-ethylpyrazol etc.；Urea based compound include, for example: urea, thiourea, ethylidene-urea etc.； Oxime compound include, for example: formaldoxime, aldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone-oxime etc.；Amine system Compound include, for example: diphenylamine, aniline, carbazole etc.；Imines based compound include, for example: ethylenimine, poly- Ethylenimine etc.；Pyridine based compound include, for example: 2 hydroxy pyrimidine, 2-hydroxyquinoline etc..
Protection different (sulfur) cyanic acid ester group in the group of described (2) is de-protected base preferably by heating during rear baking Group.For reducing the viewpoint of the compound remaining quantity in film come by protection group, the carbon number of protection group be preferably 1～ 10, more preferably 1～6, especially preferably carbon number 1～4.
The group comprising oxazoline ring structure can enumerate the group removing any 1 hydrogen atom on oxazoline ring.It addition, bag Group containing Michaelis acid structure can enumerate the group removing any 1 hydrogen atom in Michaelis acid.
In described formula (g-1), R3、R6And R11The alkyl of carbon number 1～3 include, for example: methyl, ethyl, positive third Base, isopropyl.For the viewpoint that the image residue characteristic making liquid crystal display cells is good, R6And R11Be preferably hydrogen atom or Person's methyl, more preferably hydrogen atom.
R4And R5The alkyl of carbon number 1～3 can enumerate described R3Group illustrated in.Just make image residue characteristic good For viewpoint, preferably hydrogen atom, *3-CH2-OH or *3-CH2-OCH3.Additionally, R4And R5Can be the most identical, it is possible to Different.
The molecular weight of compound [A] is preferably less than 2,000.Just make the dissolubility to solvent and aligning agent for liquid crystal to substrate For the viewpoint that coating is good, molecular weight is more preferably 1, and less than 500, especially preferably 1, less than 200, particularly preferably Less than 1,000.
As the preference of compound [A], include, for example " R8-CmH2m-R9" (wherein, R8For the group of described (1), R9Group for described (2)；M is the integer of 1～20).Herein, R9It is preferably following formula (r-1)～formula (r-7) Any one represented group.R8It is preferably " *-X1-R10-R11" (wherein, X1For singly-bound, oxygen atom ,-CO-or-COO-, R10For multiring structure, R11For hydrogen atom, alkyl or fluoroalkyl；" * " represents associative key) or " *-X2-R12" (its In, X1For singly-bound, oxygen atom ,-CO-or-COO-, R12For cholesteryl, cholesteric alkyl or lanostane base；“*” Represent associative key).
As the concrete example of compound [A], include, for example the change represented by following formula (A1-1)～formula (A1-22) difference Compound etc..
[changing 10]
[changing 11]
[changing 12]
(in formula (A1-1)～formula (A1-22), R7For following formula (r-1)～any one represented base of formula (r-7) Group, m is the integer of 1～20, and n is the integer of 0～20, and 1 and k is separately the integer of 0～10)
[changing 13]
(in formula, " * " represents associative key)
Relative to total 100 weight portion of the component of polymer in aligning agent for liquid crystal, the allotment ratio of compound [A] preferably sets It is 0.1 weight portion～50 weight portions.If the allotment ratio of compound [A] is less than 0.1 weight portion, then it is difficult to obtain liquid fully The improvement effect that the image residue of crystal display element reduces, if more than 50 weight portions, is then excess quantity along with compound [A], and The misgivings that the electric retention performance of the film-strength or liquid crystal aligning, liquid crystal display cells that there is liquid crystal orientation film declines.About The lower limit of the allotment ratio of compound [A], more preferably relative to total 100 weight of the component of polymer in aligning agent for liquid crystal Part and be more than 1 weight portion, more than especially preferably 3 weight portions, more than particularly preferably 5 weight portions.It addition, about The upper limit of the allotment ratio of compound [A], below more preferably 40 weight portions, below especially preferably 30 weight portions.Additionally, Compound [A] can be used alone one or be used in combination of two or more.These compounds [A] can by by vitochemical often Method is appropriately combined to be synthesized.
In aligning agent for liquid crystal, compound [A] can be that it is at least some of with component of polymer interaction, it is possible to not be polymerized It is present in aligning agent for liquid crystal under the state of thing interaction between component.Through speculating, contain compound [A] by aligning agent for liquid crystal, Such as can have, by heating during rear baking, functional group's (such as carboxyl etc.) that the group with described (2) carries out reacting Polymer (hereinafter also referred to " particular polymers ") and compound [A] between produce and interact, and improve shadow further As residual reduces and the improvement effect of voltage retention.Additionally, so-called " interaction " refers to intermolecular in this specification Form covalent bond, or form the molecular separating force more weak compared with covalent bond (such as: ion-dipole interaction, dipole-dipole phase Interaction, hydrogen bond, van der waals force etc. are in the intermolecular electromagnetism educational level played a role).
<other compositions>
The aligning agent for liquid crystal of the present invention also can not hinder in the range of the purpose of the present invention and effect, formulating polymer composition with And other compositions beyond compound [A].Other compositions described include, for example intramolecular and have at least one optical polymerism base Compound (hereinafter also referred to " photopolymerizable compound ") etc..
(photopolymerizable compound)
In the case of photopolymerizable compound can be for carrying out light irradiation at the film forming use aligning agent for liquid crystal, improve The purpose of the orientation restraint etc. of liquid crystal orientation film uses.Optical polymerism base include, for example has polymerism unsaturated bond Groups etc., specifically, can enumerate: (methyl) acryloyl group epoxide, styryl, (methyl) acrylamido, vinyl, Ethenylidene, vinyl epoxide (CH2=CH-O-), maleimide base etc..Photopolymerizable compound is had As long as the quantity of optical polymerism base is more than 1, preferably more than 2, more preferably 2～4.Optical polymerism The molecular weight of compound is preferably 2, and less than 000, more preferably 1, less than 500.
For the aspect that photoreactivity is high, described photopolymerizable compound preferably uses (methyl) acrylate compounds. Specifically, include, for example: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) Lauryl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2-methoxy acrylate, first Single official such as epoxide triethylene glycol (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate Can (methyl) acrylate；Ethylene glycol bisthioglycolate (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, tetramethylolmethane three (first Base) acrylate, polyethers (methyl) acrylate, Ethoxylated bisphenol A bis-(methyl) acrylate, following formula (B1-1)～ Formula (B1-3)
[changing 14]
(in formula (B1-1)～formula (B1-3), RxFor hydrogen atom or methyl)
Compound represented by Fen Bie etc. multifunctional (methyl) acrylate etc..
In the case of being allocated in aligning agent for liquid crystal by photopolymerizable compound, its allotment ratio is relative in aligning agent for liquid crystal Total 100 weight portion of contained polymer, is preferably set to below 40 weight portions, be more preferably set to 0.5 weight portion～ 30 weight portions, are especially preferably set to 1 weight portion～20 weight portions.
Additionally, as other compositions, in addition to described, include, for example: intramolecular has the change of at least one epoxy radicals Compound, functional silanes compound, surfactant, filler, defoamer, sensitizer, dispersant, antioxidant, Closely sealed auxiliary agent, antistatic additive, leveling agent, antibacterial etc..The allotment ratio of these compounds can according to the compound allocated, Suitably set in the range of the effect not hindering the present invention.
[solvent]
The aligning agent for liquid crystal of the present invention is prepared as component of polymer, compound [A] and other compositions of optionally using are preferably The aqueous constituent being dispersed or dissolved in suitable organic solvent.
The organic solvent used include, for example: METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, 1,3-dimethyl -1-imidazolidinone, gamma-butyrolacton, butyrolactam, DMF, N,N-dimethylacetamide, 3-methoxyl group-N, N- Dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N, N, 2-trimethylpropanamide, 1-butoxy-2-propanol, two Pyruvic alcohol, propylene-glycol diacetate, dipropylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, glycol monoethyl ether, lactic acid Butyl ester, butyl acetate, methyl methoxypropionate, ethyl ethoxy-c acid esters, ethylene glycol monomethyl ether, ethylene glycol, second Glycol-positive propyl ether, ethylene glycol-diisopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), glycol dimethyl ether, ethylene glycol ethyl ethers Ether acetic acid ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol monomethylether acetate, diethylene glycol monoethyl ether acetas, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, Diisoamyl ether, ethylene carbonate, propylene carbonate etc..These solvents can be used alone one or by two or more mixing Use.
(the total weight of the composition beyond the solvent of aligning agent for liquid crystal exists solid component concentration in the aligning agent for liquid crystal of the present invention Ratio shared in the gross weight of aligning agent for liquid crystal) allow for viscosity, volatility etc. and suitably select, preferably 1 weight % ～10 scopes of weight %.That is, the aligning agent for liquid crystal of the present invention is by coating substrate surface in aftermentioned mode, be preferably into Row heating, and form the film as liquid crystal orientation film or become the film of liquid crystal orientation film.Now, dense at solid constituent Degree is less than in the case of 1 weight %, and the thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.On the other hand, In the case of solid component concentration is more than 10 weight %, the thickness of film becomes excessive and is difficult to obtain good liquid crystal aligning Film, the viscosity that additionally, there are aligning agent for liquid crystal increases and the tendency of coating decline.Temperature when preparing aligning agent for liquid crystal is excellent Elect 10 DEG C～50 DEG C as, more preferably 20 DEG C～30 DEG C.
" liquid crystal orientation film and liquid crystal cell "
The liquid crystal orientation film of the present invention is to utilize the aligning agent for liquid crystal prepared in this way to be formed.It addition, the liquid of the present invention Crystal cell includes using described aligning agent for liquid crystal and the liquid crystal orientation film that formed.The drive pattern of liquid crystal cell there is no limit especially Fixed, can be applicable to: TN type, STN type, IPS type, FFS type, VA type, multidomain vertical orientation (Multi-domain Vertical Alignment, MVA) type, polymer stabilizing orientation (Polymer sustained alignment, PSA) type etc. is multiple drives Dynamic model formula.
The liquid crystal cell of the present invention may utilize the method comprising such as below step 1～step 3 and manufactures.Step 1 basis Required drive pattern and use different substrates.Step 2 and step 3 are common in each drive pattern.
[step 1: the formation of film]
First, by coating of liquid crystalline alignment agent on substrate, then coated face is heated and on substrate, form film.
(1-1) in the case of the liquid crystal cell manufacturing TN type, STN type, VA type, MVA type or PSA type, will It is provided with two pieces of substrates of patterned nesa coating as a pair, the formation of the transparent conductive film in each substrate On face, preferably utilize flexographic printing process, spin-coating method, roll-coater method or ink jet printing method to be respectively coated liquid crystal aligning Agent.Herein, substrate such as can use: the glass such as float glass, soda-lime glass；Comprise polyethylene terephthalate, poly-right The transparency carrier of the plastics such as terephtha-late, polyether sulfone, Merlon, poly-(ester ring type alkene).It is arranged at the one of substrate Nesa coating on face can use: comprises stannum oxide (SnO2) nesa (NESA) film (PPG register of company of the U.S. Trade mark), comprise indium oxide-tin oxide (In2O3-SnO2) tin indium oxide (Indium Tin Oxide, ITO) film etc..It is coated with During cloth aligning agent for liquid crystal, in order to make substrate surface and nesa coating better with the cementability of film, it is possible to substrate table The pre-treatment of functional silanes compound, functionality titanium compound etc. is implemented to be pre-coated with in the face forming film in face.
After coating of liquid crystalline alignment agent, preheat (pre-for the purpose of the sagging etc. preventing be coated with alignment agent, preferably enforcement Baking).Prebake conditions temperature is preferably 30 DEG C～200 DEG C, and the prebake conditions time is preferably 0.25 minute～10 minutes.Then, For the purpose removed completely by solvent, additionally carry out hot acyl for the amic acid structure that optionally will be present in polymer sub- The purpose of amination, and implement calcining (baking afterwards) step.Calcining heat (rear baking temperature) now be preferably 80 DEG C～ 300 DEG C, post-bake times is preferably 5 minutes～200 minutes.The thickness of the film formed in this way is preferably 0.001 μm ～1 μm, more preferably 0.005 μm～0.5 μm.
(1-2) in the case of manufacturing IPS type or FFS type liquid crystal cell, by comprising patterned saturating for interdigitated electrode structure Bright conducting film or metal film and be provided with electrode substrate electrode forming surface and be not provided with electrode opposite substrate one Face, is respectively coated aligning agent for liquid crystal, then heats each coated face, forms film whereby.The substrate that now uses and The patterning method of heating condition, nesa coating or metal film after the material of nesa coating, coating process, coating, The pre-treatment of substrate and the preferred thickness of film formed are identical with described (1-1).Metal film can use and such as comprise The film of the metals such as chromium.
In the case of any one of described (1-1) and (1-2), all by coating of liquid crystalline alignment agent on substrate after, remove Organic solvent and form liquid crystal orientation film or become the film of liquid crystal orientation film.
[step 2: alignment capability imparting processes]
In the case of the liquid crystal cell manufacturing TN type, STN type, IPS type or FFS type, implement described step 1 The film of middle formation gives the process of liquid crystal aligning ability.Whereby, the alignment capability of liquid crystal molecule gives becomes to film Liquid crystal orientation film.Alignment capability imparting processes can enumerate friction treatment and light orientation process etc., and described friction treatment is to utilize volume It is wound with the roller of the cloth comprising the fibers such as such as nylon, artificial silk, cotton, by film to certain orientation wiping；Described smooth orientation position Reason is that film is irradiated polarisation or the lonizing radiation of non-polarized.On the other hand, in the situation manufacturing VA type liquid crystal display cells Under, the film formed in described step 1 can be directly used as liquid crystal orientation film, but also this film can be implemented alignment capability and compose Give process.
In the case of being come by light orientation process to give liquid crystal aligning ability to film, the lonizing radiation irradiating film such as may be used Use ultraviolet and the luminous ray of the light comprising 150nm～800nm wavelength.In the case of lonizing radiation are polarisation, can For linear polarization, it is possible to for part polarisation.It addition, be linear polarization or the situation of part polarisation at the lonizing radiation used Under, from vertical direction, real estate can be irradiated, it is possible to be irradiated from incline direction, or these can also be shone Penetrate combination to carry out.In the case of the lonizing radiation irradiating non-polarized, the direction of irradiation is set to incline direction.
The light source used such as can use: low pressure mercury lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon resonate Lamp, xenon lamp, excimer laser etc..The irradiation dose of lonizing radiation is preferably 100J/m2～50,000J/m2, more preferably 300J/m2 ～20,000J/m2.It addition, in order to improve reactivity, it is also possible to film is heated, while film is carried out light irradiation. Temperature when heating is usually 30 DEG C～250 DEG C, preferably 40 DEG C～200 DEG C.It is suitable for the liquid of VA type liquid crystal display cells Brilliant alignment films also can be suitable for the liquid crystal display cells of PSA type.
[step 3: constructing of liquid crystal cells]
(3-1) by preparing to be formed with in this way two pieces of substrates of liquid crystal orientation film, between two pieces of oppositely disposed substrates Configuration liquid crystal manufactures liquid crystal cells.In order to manufacture liquid crystal cells, include, for example following methods: with liquid crystal orientation film to Mode across gap by oppositely disposed for two pieces of substrates, use sealant the periphery of two pieces of substrates to be fitted, by substrate After injecting filling liquid crystal in the cell gap that surface and sealant are divided, the method that hand-hole is sealed；It is being formed with liquid crystal Specified location coating sealant on one of substrate of alignment films, and then the set several portions on liquid crystal aligning face After position dropping liquid crystal, by liquid crystal orientation film to in the way of fit another block substrate, and make liquid crystal on whole of substrate The method (liquid crystal drip-injection (One Drop Filling, ODF) mode) etc. spread out.More satisfactory it is, for manufactured liquid crystal Unit and then till being heated to the temperature that used liquid crystal obtains isotropic phase, is then slowly cooled down to room temperature, goes whereby Except flow orientation when liquid crystal is filled.
As sealant, such as, can use containing sclerosing agent and the epoxy resin etc. of the alumina balls as sept.Liquid crystal Nematic liquid crystal and disc-like liquid crystal, the most preferably nematic liquid crystal can be enumerated, such as, can use: schiff bases (Schiff base) Be liquid crystal, azoxy (azoxy) be liquid crystal, biphenyl system liquid crystal, Phenylcyclohexane system liquid crystal, ester system liquid crystal, terphenyl It is liquid crystal, cyclohexyl biphenyl hexane system liquid crystal, pyrimidine system liquid crystal, two methane series liquid crystal, double-octane system liquid crystal, cubane (cubane) It it is liquid crystal etc..Use alternatively, it is also possible to add following material in these liquid crystal: such as cholesteryl chloride, cholesterol nonyl The cholesteric crystal such as acid esters, cholesteryl carbonate；With trade name " C-15 ", " CB-15 ", (Merck (Merck) is public Department manufactures) chiral agent sold；To decyloxy benzylidene-to ferroelectric liquid crystals etc. such as amino-2-methyl butyl cinnamate.
(3-2) in the case of manufacturing PSA type liquid crystal display cells, except injecting together with liquid crystal or dripping optical polymerism Beyond the aspect of compound, in the way of identical with described (3-1), construct liquid crystal cells.Then, a pair substrate is being had Under the state of the intermembranous applying voltage of some conductions, liquid crystal cells is carried out light irradiation.The voltage herein applied is set to such as 5V～50 The direct current of V or exchange.The light irradiated preferably comprises the ultraviolet of the light of 300nm～400nm wavelength.The irradiation dose of light It is preferably 1,000J/m2～200,000J/m2, more preferably 1,000J/m2～100,000J/m2。
(3-3) using the aligning agent for liquid crystal comprising photopolymerizable compound to be formed in the case of film on substrate, with The mode that described (3-1) is identical constructs liquid crystal cells, then, it is possible to adopt with the following method: through being had a pair substrate Under the state of the intermembranous applying voltage of some conductions, liquid crystal cells is carried out the step of light irradiation, thus manufactures liquid crystal display cells. According to the method, the advantage that available few light irradiation dose realizes PSA pattern.The voltage applied can be set to such as 0.1V ～the direct current of 30V or exchange.About the condition of the light irradiated, the explanation of described (3-2) can be applied.
Then, can be by obtaining liquid crystal cell at the outer surface of liquid crystal cells laminating Polarizer.Fit in liquid crystal cells The Polarizer of outer surface can be enumerated: be referred to as the Polarizer of the light polarizing film of " H-film " with the clamping of cellulose acetate protecting film Or comprising itself Polarizer of H-film, described " H-film " is to make polyvinyl alcohol extend orientation to absorb iodine and form.
The liquid crystal cell of the present invention can be effectively applied to various device, such as, can be used for: clock and watch, pocket game machine, literary composition WP, subnotebook PC, auto-navigation system, video camera, personal digital assistant (Personal Digital Assistant, PDA), digital camera, mobile phone, smart mobile phone, various monitor, LCD TV, information display etc. Various display devices, or light modulation film etc..It addition, the liquid crystal cell using the aligning agent for liquid crystal of the present invention to be formed also can be applied In phase retardation film.
[embodiment]
Hereinafter, by embodiment, the present invention is specifically described further, but the present invention is not limited to these embodiments.
In below example and comparative example, utilize following methods to measure the imidizate of the polyimides in polymer solution Rate, the solution viscosity of polymer solution and the weight average molecular weight of polymer.Hereinafter, sometimes by represented by Formula X Compound is only shown as " compounds X ".
[the acid imide rate of polyimides]
The solution of polyimides is put into pure water, after the precipitation drying under reduced pressure the most fully that will be obtained, dissolves In deuterodimethylsulfoxide, using tetramethylsilane as primary standard substance, at room temperature measure1H-nuclear magnetic resonance, NMR (nuclear Magnetic resonance, NMR).According to obtained1H-NMR spectrum, uses following mathematical expression (1) to obtain acyl Imines rate [%].
Acid imide rate [%]=(1-A1/A2×α)×100…(1)
(in mathematical expression (1), A1The peak area of the proton being derived from NH base for occurring near chemical shift 10ppm, A2For being derived from the peak area of other protons, α is to be that other protons are relative in the predecessor (polyamic acid) of polymer The number ratio of 1 proton of NH base)
[solution viscosity of polymer solution]
The solution viscosity [mPa s] of polymer solution is to using set solvent to be prepared as polymer concentration 10 weight % Solution, uses E type rotating cylinder viscometer to measure at 25 DEG C.
[weight average molecular weight of polymer]
Weight average molecular weight is the polystyrene conversion value that the gel permeation chromatography under the conditions of below utilization measures.
Tubing string: east Cao (Tosoh) (stock) manufactures, TSKgelGRCXLII
Solvent: oxolane
Temperature: 40 DEG C
Pressure: 68kgf/cm2
<synthesis of compound (A)>
[synthesis example 1-1]
Compound (a-1) is synthesized according to following flow process 1.
[changing 15]
Take 4-(2-(4 '-amyl group-[1,1 '-bis cyclohexane]-4-base) ethyl) phenol of 17.8g, the 2-((tert-butoxycarbonyl) of 8.76g Amino) acetic acid is in the 2000mL there-necked flask that there was added stirring rod, and the dichloromethane adding 500g is stirred.Then, It is cooled to 0 DEG C, is added to 1-ethyl-3-(3-dimethylaminopropyl) the carbon imidodicarbonic diamide hydrochlorate and 1.22 of 11.5g The N of g, N-dimethyl aminopyridine, is stirred at room temperature 20 hours.Then, reactant liquor is carried out 3 with the water of 800mL After the washing of secondary separatory, magnesium sulfate is utilized to make organic layer be dried.Then, by utilizing the concentration of rotary evaporator, slowly concentrate Becoming 100g to inner capacities, reclaim by filtering the white solid separated out midway.This white solid is carried out vacuum It is dried, obtains the compound (a-1) of 18.0g whereby.
[synthesis example 1-2]
Compound (a-2) is synthesized according to following flow process 2.
[changing 16]
The synthesis of compound (a-2-1)
Use beta-cholestanol as initial substance, utilize the synthetic method identical with compound (a-1) to obtain compound (a-2-1)。
The synthesis of compound (a-2-2)
The compound (a-2-1) of 16.4g, the dichloromethane of 300g is added in the 200mL eggplant type flask there was added stirring rod Alkane and the trifluoroacetic acid of 17.1g, be stirred at room temperature 1 hour.It is then cooled to 0 DEG C, slowly add 50mL Saturated sodium bicarbonate aqueous solution carry out separatory, organic layer is carried out the washing of 3 separatory with the water of 100mL.Then, pass through Utilize the concentration of rotary evaporator, be slowly concentrated into till inner capacities becomes 30g, will the white that separate out of midway by filtering Solid reclaims.This white solid is vacuum dried, obtains the compound (a-2-2) of 13.1g whereby.
The synthesis of compound (a-2)
The compound (a-2-2) of 8.91g, the tetrahydrochysene of 20mL is added in the 200mL there-necked flask there was added stirring rod Furan and the wet chemical of 2mol/L, be cooled to 0 DEG C.It is slowly added dropwise methylchloroformate wherein, at room temperature Stir 2 hours.Then, reactant liquor is extracted 3 times with the ethyl acetate of 50mL, by the organic layer that obtained with 100mL Distilled water carry out the washing of 3 separatory.Then, by utilizing the concentration of rotary evaporator, being slowly concentrated into inner capacities becomes Till 30g, reclaim by filtering the white solid separated out midway.This white solid is vacuum dried, obtains whereby Obtain the compound (a-2) of 5.53g.
[synthesis example 1-3]
Compound (a-3) is synthesized according to following flow process 3.
[changing 17]
The synthesis of compound (a-3-1)
The 4-(4 '-amyl group-[1,1 '-bis cyclohexane]-4-base) of 16.4g is added in the 100mL there-necked flask there was added stirring rod Phenol, the 9mol/L potassium hydroxide aqueous solution of 20mL, be stirred at room temperature 5 minutes.Then, mixture heating is made Its boiling, drips the 50% monoxone aqueous solution of 14.1g wherein, refluxes 5 hours.Then, reactant liquor is cooled to room Temperature, the 1mol/L aqueous hydrochloric acid solution of dropping 200mL, carry out 3 extractions with the ethyl acetate of 150mL.To be obtained Organic layer carry out the washing of 3 separatory with the distilled water of 100mL.Then, by utilizing the concentration of rotary evaporator, slowly It is concentrated into till inner capacities becomes 40g, by filtering, the white solid that separate out of midway is reclaimed.This white solid is carried out Vacuum drying, obtains the compound (a-3-1) of 13.7g whereby.
The synthesis of compound (a-3)
The compound (a-3-1) of 11.6g, the 2-bromine of 7.38g is added in the 500mL there-necked flask there was added stirring rod Ethylamine hydrobromate, the methanol of 300mL and the N-methylmorpholine of 3.64g, be stirred, be added to 9.96 The DMT-MM of g.After being stirred at room temperature 1 hour, add the 1mol/L potassium hydroxide-methanol solution of 120g, backflow 2 Hour.Then, reactant liquor is injected in the water of 500mL, utilizes the diethyl ether of 300mL to carry out 3 extractions.Then, With the 1mol/L hydrochloric acid water of 300mL, organic layer is carried out 1 separatory washing, and the saturated sodium bicarbonate water with 200mL is molten Liquid carries out 1 separatory washing, carries out 3 separatory washings with the water of 200mL.Then, by utilizing the dense of rotary evaporator Contracting, is slowly concentrated into till organic layer becomes 50g, is reclaimed by the white solid that separate out of midway by filtering.To this white Solid is vacuum dried, and obtains the compound (a-3) of 9.01g whereby.
[synthesis example 1-4]
Compound (a-4) is synthesized according to following flow process 4.
[changing 18]
The synthesis of compound (a-4)
The compound (a-1) of 5.14g, the dichloromethane of 30mL is added in the 100mL eggplant type flask there was added stirring rod Alkane and the trifluoroacetic acid of 5.7g, be stirred at room temperature 2 hours.Then, utilize wet chemical to be neutralized by reactant liquor, 3 extractions are carried out with the ethyl acetate of 100mL.The organic layer obtained is carried out 3 separatory with the distilled water of 100mL Washing.Then, by utilizing the concentration of rotary evaporator, slowly it is concentrated into till inner capacities becomes 30g, will by filtering The white solid that midway separates out reclaims.This white solid is vacuum dried, obtains the compound (a-4) of 3.93g whereby.
[synthesis example 1-5]
Compound (a-5) is synthesized according to following flow process 5.
[changing 19]
The synthesis of compound (a-5)
Use 4-(4-heptyl cyclohexyl) benzoic acid and 3-amino-1-propanol as initial substance, utilize and compound (a-1) phase Same synthetic method obtains compound (a-5).
[synthesis example 1-6]
Compound (a-6) is synthesized according to following flow process 6.
[changing 20]
The synthesis of compound (a-6-1)
Use 4-(2-(4 '-amyl group-[1,1 '-bis cyclohexane]-4-base) ethyl) phenol as initial substance, utilize and compound (a-3-1) Identical synthetic method obtains compound (a-6-1).
The synthesis of compound (a-6)
The compound (a-6-1) of 7.73g, the Michaelis of 2.88g is added in the 100mL there-necked flask there was added stirring rod Acid, the N of 2.44g, N-dimethyl aminopyridine, the dichloromethane of 50mL, it is cooled to 0 DEG C.It is added to 4.12g's N, N '-dicyclohexylcarbodiimide, stirs 2 hours at 0 DEG C.Then, reactant liquor is carried out kieselguhr filtration, will filter Liquid carries out 1 separatory washing with the 1mol/L aqueous hydrochloric acid solution of 50mL, carries out 3 separatory washings with the water of 50mL. Then, by utilizing the concentration of rotary evaporator, slowly it is concentrated into till inner capacities becomes 20g, will midway analysis by filtering White yellow solid out reclaims.This solid is vacuum dried, obtains the compound (a-6) of 9.30g whereby.
[synthesis example 1-7]
Compound (a-7) is synthesized according to following flow process 7.
[changing 21]
The synthesis of compound (a-7)
Use (E)-3-(4 ((4-(4,4,4-trifluoro butoxy) benzoyl) epoxide) phenyl) acrylic acid and 3-(dimethylamino) Ethanol, as initial substance, utilizes the synthetic method identical with compound (a-1) to obtain compound (a-7).
[synthesis example 1-8]
Compound (c-1) is synthesized according to following flow process 8.
[changing 22]
The synthesis of compound (c-1)
4-(2-(4 '-amyl group-[1,1 '-bis cyclohexane]-4-of 7.13g is added in the 300mL there-necked flask there was added stirring rod Base) ethyl) phenol, the ethanol of 120mL and the sodium hydroxide of 0.96g, be stirred at room temperature 20 minutes.Drip wherein Add the chloropropylene oxide of 5.55g, be stirred at room temperature 9 hours.Then, by utilizing the concentration of rotary evaporator to distill removal Solvent, carries out 3 extractions by residue with the ethyl acetate of 100mL.The organic layer obtained is carried out with the water of 100mL 3 separatory washings, utilize rotary evaporator to distill removal solvent.Utilize silica gel to carry out column purified to residue, obtain whereby The compound as white yellow solid (c-1) of 6.60g.
[synthesis example 1-9]
Compound (c-2) is synthesized according to following flow process 9.
[changing 23]
The synthesis of compound (c-2)
Using 4-(4-heptyl cyclohexyl) benzoic acid and glycerol 1,2-carbonic ester, as initial substance, utilizes and compound (a-1) Identical synthetic method obtains compound (c-2).
<synthesis of polymer>
[synthesis example 2-1]
1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides of 100 molar part as tetracarboxylic dianhydride and 100 as diamidogen are rubbed You are dissolved in METHYLPYRROLIDONE (N-methyl-2-pyrrolidone, NMP), at room temperature by the p-phenylenediamine of part Carry out reaction in 6 hours, it is thus achieved that the solution of the polyamic acid containing 20 weight %.The polyamic acid obtained in this place is as poly- Compound (PA-1).
[synthesis example 2-2～synthesis example 2-7]
In addition to the tetracarboxylic dianhydride that will be used and the kind of diamidogen and quantitative change are more as described in table 1 below, with synthesis Mode synthesizing polyamides acid (polymer (PA-2)～polymer (PA-7)) that example 2-1 is identical.
[table 1]
In table 1, the numeric representation in the parantheses of tetracarboxylic dianhydride and diamidogen is relative to the tetracarboxylic dianhydride for synthetic polymer Total 100 molar part for the use ratio [molar part] of each compound.Below the abbreviation of the compound in table 1 is respectively Implication.
<tetracarboxylic dianhydride>
T-1:1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides
T-2:2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides
T-3: dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydrides
T-4: pyromellitic acid anhydride
<diamidogen>
D-1: p-phenylenediamine
D-2:4,4 '-diamino-diphenyl ether
D-3:4,4 '-diaminodiphenyl-methane
D-4:3,5-diaminobenzoic acid
D-5:4,4 '-[4,4 '-propane-1,3-diyl is double (piperidines-Isosorbide-5-Nitrae-diyl)] diphenylamines (change represented by described formula (N-1-1) Compound)
D-6:3,5-diaminobenzoic acid cholesteric Arrcostab
[synthesis example 2-8]
In addition to the tetracarboxylic dianhydride that will be used and the kind of diamidogen and quantitative change are more as described in described table 1, with described The mode synthesizing polyamides acid that synthesis example 2-1 is identical.Then, this reactant liquor drips the N of 80 molar part, N-dimethyl methyl Amide diethyl acetal, then carries out reaction in 2 hours, it is thus achieved that containing poly amic acid ester (as " polymerization at 50 DEG C Thing (PAE-1) ") solution.The weight average molecular weight of polymer (PAE-1) is 30,000.
[synthesis example 2-9]
In addition to the tetracarboxylic dianhydride that will be used and the kind of diamidogen and quantitative change are more as described in described table 1, with described The mode synthesizing polyamides acid that synthesis example 2-1 is identical.Then, the polyamic acid solution obtained adds pyridine and acetic acid Acid anhydride, carries out chemical imidization.Reaction solution after chemical imidization is concentrated, becomes 10 weight % with concentration Mode utilizes NMP to prepare.The acid imide rate of the polyimides (polymer (PI-1)) obtained is about 50%.
<embodiment 1>
(1) preparation of aligning agent for liquid crystal
Containing polymer (PA-1) as in the solution of component of polymer, with the allotment ratio of compound [A] relative to poly- Polymer component 100 weight portion and become the mode of 10 weight portions to add the NMP of compound (a-1) as compound [A] molten Liquid, and then add NMP and butyl cellosolve (butyl cellosolve, BC) and, as solvent, be sufficiently stirred for, make solvent Consist of NMP: BC=50: 50 (weight ratios), solid component concentration are the solution of 5.0 weight %.Using aperture is 1 μm Filter this solution is filtered, prepare aligning agent for liquid crystal (J-1) whereby.
(2) manufacture of liquid crystal display cells
Prepare, at one side, there are 2 system transparent electrodes (electrode A and electrode B) comprising ito film and can be to electrode A And electrode B is applied independently two pieces of glass substrates of voltage.On the respective electrode forming surface of this pair glass substrate, profit It is coated with the aligning agent for liquid crystal (J-1) of described preparation with rotator, the heating plate of 80 DEG C carries out the prebake conditions of 1 minute. Then, toast after the heating plate of 230 DEG C being carried out 10 minutes, form the film of thickness about 0.08 μm.Then, in office The outer rim in the face with film of one piece of substrate, coating there was added the epoxy resin adhesive of the alumina balls of a diameter of 5.5 μm After, across gap by oppositely disposed for two pieces of substrates, make outer edge against each other, crimp and make bonding agent harden.Then, certainly After liquid crystal injecting port is filled between a pair substrate nematic liquid crystal (Merck (Merck) company manufactures, MLC-6608), profit With acrylic acid series photo-hardening bonding agent, liquid crystal injecting port is sealed.
(3) evaluation of image residue characteristic (AC image retention characteristic)
The liquid crystal display cells of described manufacture is positioned over 25 DEG C, in the environment of 1 air pressure, electrode B is not applied voltage, right The resultant voltage of electrode A applying alternating voltage 3.5V and DC voltage 5V 2 hours.The most at once to electrode A and electrode B The voltage of exchange 4V is applied both.Measure from the moment that two electrodes start to apply the voltage of exchange 4V until visually Time till the difference of the photopermeability that cannot confirm electrode A and electrode B.This time situation less than 20 seconds is evaluated as Image residue characteristic " good 1 (◎) ", was evaluated as image residue characteristic by 20 seconds less than the situation of 60 seconds " good 2 (zero) ", it was evaluated as image residue characteristic " can 1 (△) " by 60 seconds less than the situation of 100 seconds, by 100 Second it is " can 2 (△ △) " less than image residue evaluating characteristics when 150 seconds, and by the situation of more than 150 seconds It is evaluated as image residue characteristic " bad (×) " as a result, the image residue characteristic of this liquid crystal display cells is " good 2 (zero) ".
(4) evaluation of voltage retention
For the liquid crystal display cells of described manufacture, at 60 DEG C, application time, the span of 167 milliseconds with 60 microseconds are executed After adding the voltage of 1V, measure from apply releasing the voltage retention after 1,000 millisecond (Voltage Holding Ratio, VHR).Determinator is the VHR-1 using Dongyang Te Kenika (Toyo Techniea) (stock) to manufacture.To be measured The situation that voltage retention is more than 96% be evaluated as " good (zero) ", by 92% less than 96% situation evaluation For " can (△) ", the situation less than 92% is evaluated as " bad (×) " as a result, the voltage of this liquid crystal display cells Conservation rate is 96.5%, for " good (zero) ".
<embodiment 5, embodiment 6, embodiment 8, embodiment 9 and comparative example 1～comparative example 3>
In addition to the polymer that will be used and the kind of additive and quantitative change are more as described in table 2 below, with embodiment 1 identical mode prepares aligning agent for liquid crystal (J-5), aligning agent for liquid crystal (J-6), aligning agent for liquid crystal (J-8), liquid crystal respectively Alignment agent (J-9) and aligning agent for liquid crystal (R-1)～aligning agent for liquid crystal (R-3).It addition, use prepared liquid crystal respectively Alignment agent, manufactures liquid crystal display cells in the way of identical with described embodiment 1, carries out image residue characteristic and voltage keeps The evaluation of rate.The results are shown in table 2 below.
<embodiment 2>
(1) preparation of aligning agent for liquid crystal
In addition to the polymer that will be used and the kind of additive and quantitative change are more as described in table 2 below, with embodiment 1 identical mode prepares aligning agent for liquid crystal (J-2).
(2) preparation of liquid-crystal composition LC1
For the nematic liquid crystal (Merck (Merck) company manufactures, MLC-6608) of 10g, add under 0.3 weight % State the photopolymerizable compound represented by formula (b-3-1), mix, obtain liquid-crystal composition LC1 whereby.
[changing 24]
(3) manufacture of liquid crystal display cells
It is being respectively provided with as shown in Figure 1 patterned for slit-shaped and the ITO electrode (electrode A that is divided into multiple region And electrode B) two pieces of glass substrates each electrode surface on, use liquid crystal orientation film printer (Japan description printing (stock) system Make) it is coated with the aligning agent for liquid crystal (J-2) of described preparation.Then, heating (prebake conditions) 1 point in the heating plate of 80 DEG C Clock and remove solvent, in the heating plate of 150 DEG C, then heat (afterwards baking) 10 minutes, forming average film thickness is 0.06 μm Film.For this film, after ultra-pure water carries out 1 minute ultrasonic washing, 100 DEG C of cleaning ovens are dried 10 Minute, it is thus achieved that there is the substrate of liquid crystal orientation film.Repeat this operation, it is thus achieved that a pair (two pieces) have the base of liquid crystal orientation film Plate.Additionally, the pattern of the electrode used is pattern of the same race with the electrode pattern in PSA pattern.
Then, in each outer rim with liquid crystal orientation film of the pair of substrate, coating there was added the oxygen of a diameter of 5.5 μm Change aluminum ball epoxy resin adhesive after, by have the face of liquid crystal orientation film relative in the way of overlap crimping, make bonding agent harden. Then, after filling the liquid-crystal composition LC1 of described preparation in liquid crystal injecting port between a pair substrate, acrylic acid series light is utilized Liquid crystal injecting port is sealed by cured adhesive.For the liquid crystal cells obtained, to the exchange applying frequency 60Hz between electrode 10V, when liquid crystal drive, utilizes the ultraviolet lamp using metal halide lamp in light source, with 100,000 J/m2Irradiation dose carry out irradiation ultraviolet radiation.Additionally, this irradiation dose is to use the quantometer measured with wavelength 365nm benchmark The value measured.
(4) evaluation of liquid crystal display cells
For the liquid crystal display cells of described acquisition, carry out image residue characteristic in the same manner as example 1 and voltage is protected The evaluation of holdup.Its result is, is that image residue characteristic " good 2 (zero) ", voltage retention are " good in this embodiment (zero) evaluation ".
<embodiment 3, embodiment 4>
In addition to the polymer that will be used and the kind of additive and quantitative change are more as described in table 2 below, with embodiment 1 identical mode prepares aligning agent for liquid crystal (J-3), aligning agent for liquid crystal (J-4) respectively.It addition, except the liquid that will be used Aspect that brilliant alignment agent is changed and replace liquid-crystal composition LC1 and the nematic liquid that Merck (Merck) company manufactured Brilliant " MLC-6608 " is filled in beyond the aspect between a pair substrate, manufactures liquid crystal display unit in the same way as in example 2 Part, carries out the evaluation of image residue characteristic and voltage retention.These results are shown in table 2 below.
<embodiment 7>
(1) preparation of aligning agent for liquid crystal
In addition to the polymer that will be used and the kind of additive and quantitative change are more as described in table 2 below, with embodiment 1 identical mode prepares aligning agent for liquid crystal (J-7).
(2) manufacture of liquid crystal display cells
Use rotator, the aligning agent for liquid crystal (J-7) of described preparation is coated with the 2 system transparent electricity comprising ito film On each transparent electrical pole-face of two pieces of (a pair) glass substrates of pole (electrode A and electrode B).Then, carry out at 80 DEG C Heating (prebake conditions) in 1 minute, then, has carried out in the baking oven of nitrogen displacement in storehouse, has heated (after bake at 200 DEG C Roasting) 1 hour, form the film that thickness is 0.1 μm.Then, for these film coated surface, use Hg-Xe lamp to pass Orchid-Taylor prism, irradiates 50mJ/cm from the vertical direction of real estate2The polarisation ultraviolet comprising 313nm open-wire line, it is thus achieved that There is a pair substrate of liquid crystal orientation film.Additionally, this irradiation dose is to use the quantometer measured with wavelength 365nm benchmark The value measured.
Then, one of for carried out in a pair substrate of described photo-irradiation treatment, it is being formed with liquid crystal orientation film The edge, periphery in face, remains liquid crystal injecting port and screen painting coating there was added the epoxy of alumina balls of a diameter of 5.5 μm After resin adhesive, with the projecting direction one on real estate of plane of polarisation when liquid crystal orientation film formation face is relative and light irradiates The mode caused, by a pair substrate overlap crimping, heats 1 hour at 150 DEG C and makes bonding agent carry out thermmohardening.
Then, in liquid crystal injecting port between a pair substrate fill nematic liquid crystal (Merck (Merck) company manufacture, MLC-6608), after, epoxy bonding agent is utilized to be sealed by liquid crystal injecting port.And then, in order to remove flowing when liquid crystal injects Orientation, and it is heated to 150 DEG C, then it is slowly cooled down to room temperature.
(3) evaluation of liquid crystal display cells
For the liquid crystal display cells of described acquisition, carry out image residue characteristic in the same manner as example 1 and voltage is protected The evaluation of holdup.Its result is, is that image residue characteristic " good 2 (zero) ", voltage retention are " good in this embodiment (zero) evaluation ".
[table 2]
In table 2, the numeric representation in the parantheses of component of polymer and additive is relative to for preparing the poly-of aligning agent for liquid crystal The allotment ratio (weight portion) of each compound for total 100 weight portion of polymer component."-" refers to not use this hurdle Compound.In additive in table 2, " b-1 " and " b-2 " refers respectively to following compound, in addition, refers to Described formula (a-1)～formula (a-7), formula (c-1) and formula (c-2) respectively represented by compound.
<additive>
Compound represented by b-1: following formula (b-1)
Compound represented by b-2: following formula (b-2)
[changing 25]
As shown in table 2, in embodiment 1～embodiment 9, the image residue characteristic of the liquid crystal display cells obtained is " good Evaluation well ".It addition, the evaluation that voltage retention performance is " well " or "available".On the other hand, utilization comprises use The polymer of side chain type diamidogen and without in the comparative example 3 of the aligning agent for liquid crystal of compound [A], image residue characteristic and voltage Retention performance is the evaluation of "available", and embodiment is excellent.It addition, in comparative example 1 and comparative example 2, voltage retention performance is The evaluation of " bad ".According to these results, according to will there is reactive base (group of described (1)) and demonstrate The aligning agent for liquid crystal that the additive of the group (groups of described (2)) of vertical orientated property is allocated together with component of polymer, can Do not undermine the electrical characteristic of liquid crystal display cells and reduce AC image retention fully.

Claims (12)

1. an aligning agent for liquid crystal, it contains component of polymer and has the compound of group of following (1) and (2) [A],
(1) choosing freely has that the ring of more than 2 is direct or the group of structure that links via concatenating group and having At least one group in the group that the group of condensed ring is formed；
(2) choosing freely-NR1R2, protect NCO, protect isothiocyanate group, the base comprising oxazoline ring structure At least one in the group that group represented by the group roll into a ball, comprised Michaelis acid structure and following formula (g-1) is formed Group, wherein, R1And R2It is separately hydrogen atom, the monovalent hydrocarbon of carbon number 1～10 or protection group；
In formula (g-1), R3And R6It is separately hydrogen atom or the alkyl of carbon number 1～3；R4And R5Separately For hydrogen atom, the alkyl of carbon number 1～3 or *2-CH2-O-R11, wherein, R11For hydrogen atom or the alkyl of carbon number 1～3； *2Represent and R4And R5The associative key of the carbon atom of institute's bond；*1Represent associative key.
Aligning agent for liquid crystal the most according to claim 1, it is sub-that it comprises the free polyamic acid of choosing, poly amic acid ester and polyamides At least one polymer [P] in the group that amine is formed is as described component of polymer.
Aligning agent for liquid crystal the most according to claim 2, it contains and has the free nitrogen heterocyclic ring of choosing, secondary amine base and three grades At least one in the group that amino the is formed polymer containing N structure is as described polymer [P], wherein, described nitrogen-containing hetero Ring does not comprise the imide ring that polyimides is had.
4., according to the aligning agent for liquid crystal described in Claims 2 or 3, it contains makes the free tetracarboxylic dianhydride of choosing, tetrabasic carboxylic acid diester And the tetracarboxylic acid derivatives of at least one in the group that formed of tetrabasic carboxylic acid diester dihalide, with comprising, there is carboxyl and 2 The polymer that the diamidogen of the compound of individual one-level amino carries out reacting and obtains is as described polymer [P].
Aligning agent for liquid crystal the most according to any one of claim 1 to 3, wherein relative to the tune of described component of polymer Total 100 weight portion of dosage, the allotment ratio of described compound [A] is 0.1 weight portion～50 weight portions.
Aligning agent for liquid crystal the most according to any one of claim 1 to 3, the most more contains the change with optical polymerism base Compound.
7. an aligning agent for liquid crystal, it is by component of polymer and the compound [A] of the group with following (1) and (2) Allocate and obtain:
(1) choosing freely has that the ring of more than 2 is direct or the group of structure that links via concatenating group and having At least one group in the group that the group of condensed ring is formed；
(2) choosing freely-NR1R2, protect NCO, protect isothiocyanate group, the base comprising oxazoline ring structure At least one in the group that group represented by the group roll into a ball, comprised Michaelis acid structure and following formula (g-1) is formed Group, wherein, R1And R2It is separately hydrogen atom, the monovalent hydrocarbon of carbon number 1～10 or protection group；
In formula (g-1), R3And R6It is separately hydrogen atom or the alkyl of carbon number 1～3；R4And R5Separately For hydrogen atom, the alkyl of carbon number 1～3 or *2-CH2-O-R11, wherein, R11For hydrogen atom or the alkyl of carbon number 1～3； *2Represent and R4And R5The associative key of the carbon atom of institute's bond；*1Represent associative key.
8. a liquid crystal orientation film, it uses aligning agent for liquid crystal according to any one of claim 1 to 7 to be formed.
9. a manufacture method for liquid crystal orientation film, comprising: by liquid crystal according to any one of claim 1 to 7 Alignment agent coats the step forming film on substrate；And described film is carried out light irradiation and gives liquid crystal aligning ability Step.
10. a liquid crystal cell, it includes liquid crystal orientation film according to claim 8.
The manufacture method of 11. 1 kinds of liquid crystal cells, comprising:
On this kind of conducting film of a pair substrate with conducting film, it is coated with according to any one of claim 1 to 7 Aligning agent for liquid crystal and form the step of film；
Will be formed with a pair substrate of described film, via liquid crystal layer and in the way of described film is relative oppositely disposed and construct The step of liquid crystal cells；And
When applying voltage intermembranous to described conduction, described liquid crystal cells is carried out the step of light irradiation.
The compound of 12. 1 kinds of groups with following (1) and (2), wherein:
(1) choosing freely has that the ring of more than 2 is direct or the group of structure that links via concatenating group and having At least one group in the group that the group of condensed ring is formed；
(2) choosing freely-NR1R2, protect NCO, protect isothiocyanate group, the base comprising oxazoline ring structure At least one in the group that group represented by the group roll into a ball, comprised Michaelis acid structure and following formula (g-1) is formed Group, wherein, R1And R2It is separately hydrogen atom, the monovalent hydrocarbon of carbon number 1～10 or protection group；
In formula (g-1), R3And R6It is separately hydrogen atom or the alkyl of carbon number 1～3；R4And R5Separately For hydrogen atom, the alkyl of carbon number 1～3 or *2-CH2-O-R11, wherein, R11For hydrogen atom or the alkyl of carbon number 1～3； *2Represent and R4And R5The associative key of the carbon atom of institute's bond；*1Represent associative key.
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