CN104854193A - Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Download PDF

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CN104854193A
CN104854193A CN201380065916.9A CN201380065916A CN104854193A CN 104854193 A CN104854193 A CN 104854193A CN 201380065916 A CN201380065916 A CN 201380065916A CN 104854193 A CN104854193 A CN 104854193A
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liquid crystal
composition
formula
carbon number
represent
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CN104854193B (en
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三木德俊
桥本淳
后藤耕平
保坂和义
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1089—Polyisoimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

Abstract

A composition containing component (A), component (B), and component (C), described below. Component (A): at least one type of solvent selected from either formula [1a] or formula [1b]. (In formula [1a], X1 indicates a C1-3 alkyl group. In formula[1b], X2 indicates a C1-3 alkyl group.) Component (B): at least one type of polymer selected from a polyimide precursor or polyimide obtained by reacting : a diamine component including a diamine compound having a carboxyl group; and a tetracarboxylic dianhydride component. Component (C): a polysiloxane obtained by condensation-polymerization of an alkoxysilane including any one type of alkoxysilane indicated by formula [A1], formula[A2], or formula [A3].

Description

Composition, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display device
Technical field
The present invention relates to aligning agent for liquid crystal used in the manufacture of the composition of the formation for resin coating, liquid crystal display device, the liquid crystal orientation film obtained by this aligning agent for liquid crystal and employ the liquid crystal display device of this liquid crystal orientation film.
Background technology
Formed easness and the insulating property etc. of the resin coating be made up of organic materialss such as macromolecular materials receive publicity, in electron device, be widely used as interlayer dielectric or protective membrane etc.As in the well-known liquid crystal display device of display device, the resin coating be made up of organic materials is used as liquid crystal orientation film.
At present, as the resin coating of industrial use, widely use the polyimide organic membrane of excellent in te pins of durability.This polyimide organic membrane is formed as the polyamic acid of polyimide precursor or the composition of polyimide by comprising.That is, polyimide organic membrane is formed by being coated on substrate, through firing process by the composition comprising polyamic acid or polyimide.Now, usually owing to using the high boiling solvent such as METHYLPYRROLIDONE (also referred to as NMP) or gamma-butyrolactone (also referred to as γ-BL) in these compositions, therefore must carry out burning till (such as with reference to patent documentation 1) under the high temperature of 200 DEG C ~ about 300 DEG C.
In recent years, the resin coating formed by the composition comprising polyimide-based polymer (i.e. polyimide precursor or polyimide) and polysiloxane is used to interlayer dielectric or insulating film, and then for liquid crystal orientation film.Particularly, in order to the reliability making the accompanied by long-term of liquid crystal display device drive improves, propose the aligning agent for liquid crystal and liquid crystal orientation film (such as with reference to patent documentation 2) that comprise polyimide-based polymer and polysiloxane.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 09-278724 publication
Patent documentation 2: Japanese Patent Laid-Open 2010-097007 publication
Summary of the invention
Invent technical problem to be solved
Use comprise polyimide-based polymer aligning agent for liquid crystal to form liquid crystal orientation film time, its firing process also must carry out high temperature due to above-mentioned reason and burn till in the technique manufacturing liquid crystal display device.This is because the liquid crystal aligning agent comprising polyimide-based polymer and polysiloxane, owing to NMP or γ-BL being used for solvent to dissolve polyimide-based polymer, therefore also must burn till by high temperature.But, when the substrate of liquid crystal display device uses thin and light but that thermotolerance is low plastic base to replace common plastic base, require to burn till at lower temperatures.Similarly, to burn till with high temperature to suppress the look characteristic of the colored filter of liquid crystal display device and deteriorated, or and then in order to cut down liquid crystal display device manufacture in energy consumption, also must burn till at low temperatures.
In addition, polyimide-based polymer is made to be dissolved in NMP or the γ-BL of the solvent adopted as routine and to form polymers soln, in the aligning agent for liquid crystal obtained by this polymers soln and polysiloxane, the intermiscibility of NMP or the γ-BL that polarity is high and the high polysiloxane of hydrophobicity is poor.Therefore, when being coated on substrate by this aligning agent for liquid crystal, liquid crystal orientation film easily produces the pore with shrinkage cavity (は じ I).That is, the aligning agent for liquid crystal comprising polyimide-based polymer and polysiloxane in the past easily produces the orientation defect being accompanied by pore.
And liquid crystal orientation film is by coating substrate, then burning till film and formed by aligning agent for liquid crystal.Now, in order to reach the object of the film (also referred to as coating) improving liquid crystal orientation film, the generation namely suppressing the pore with shrinkage cavity, require to improve aligning agent for liquid crystal to the infiltration spread of substrate.
The resin coating obtained by the composition comprising polyimide-based polymer and polysiloxane is relative to the resin coating obtained by the composition not containing polysiloxane; chemical stability improves; therefore, except liquid crystal orientation film, also can be used for the interlayer dielectric in other electron device or protective membrane.These films also need the coating forming resin coating by carrying out easy fired and improve resin coating.By carrying out easy fired, the energy consumption in manufacture can be reduced.And by improving coating, the generation with the pore of shrinkage cavity on resin coating can be suppressed.
So, the object of the present invention is to provide a kind of composition having above-mentioned characteristic concurrently.That is, the object of the present invention is to provide a kind of composition comprising polyimide-based polymer and polysiloxane that can be formed resin coating by easy fired.Further object is to provide a kind of composition that can suppress the generation of the pore with shrinkage cavity when forming resin coating.
The present invention also aims to provide a kind of aligning agent for liquid crystal employing above-mentioned composition that can be formed liquid crystal orientation film by easy fired.Further object is to provide a kind of aligning agent for liquid crystal that can suppress the generation of the pore with shrinkage cavity shrinkage cavity when forming liquid crystal orientation film.
Then, the present invention also aims to provide a kind of liquid crystal orientation film corresponding to above-mentioned requirements.That is, object is to provide a kind of liquid crystal orientation film that can be formed by easy fired, and can suppress the liquid crystal orientation film of the orientation defect being accompanied by pore.
Moreover, the present invention also aims to provide a kind of liquid crystal display device possessing liquid crystal orientation film corresponding to above-mentioned requirements.
The technical scheme that technical solution problem adopts
Present inventor has performed further investigation, found that, comprise the solvent with ad hoc structure, the composition being selected from polyimide precursor or at least one polymkeric substance of polyimide and the polysiloxane of ad hoc structure being reacted by the diamine component and tetracarboxylic dianhydride's composition that comprise the diamine compound with carboxyl and obtained is very effective to realizing above-mentioned purpose, thus complete the present invention.
That is, the present invention has following technology contents.
(1) composition, comprises following (A) composition, (B) composition and (C) composition.
(A) composition: at least one solvent being selected from following formula [1a] or formula [1b].
[changing 1]
(in formula [1a], X 1represent the alkyl of carbon number 1 ~ 3, in formula [1b], X 2represent the alkyl of carbon number 1 ~ 3).
(B) composition: at least one polymkeric substance being selected from polyimide precursor or the polyimide being reacted by the diamine component and tetracarboxylic dianhydride's composition that comprise the diamine compound with carboxyl and obtained.
(C) composition: by comprising the organoalkoxysilane polycondensation of any one of the organoalkoxysilane shown in following formula [A1], formula [A2] or formula [A3] and the polysiloxane obtained.
[changing 2]
(A 1) mSi(A 2) n(OA 3) p[A1]
(in formula [A1], A 1represent aliphatic hydrocarbon, phenyl ring, cyclohexane ring, heterocycle or there is the organic radical of carbon number 8 ~ 35 of steroid structure, A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, A 3represent the alkyl of carbon number 1 ~ 5 respectively, m represents the integer of 1 or 2, and n represents the integer of 0 ~ 2, and p represents the integer of 0 ~ 3, and m+n+p is 4).
[changing 3]
(B 1) mSi(B 2) n(OB 3) p[A2]
(in formula [A2], B 1represent the organic radical with the carbon number 2 ~ 12 of vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl, B 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, B 3represent the alkyl of carbon number 1 ~ 5 respectively, m represents the integer of 1 or 2, and n represents the integer of 0 ~ 2, and p represents the integer of 0 ~ 3, and m+n+p is 4).
[changing 4]
(D 1) nSi(OD 2) 4-n[A3]
(in formula [A3], D 1represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, D 2represent the alkyl of carbon number 1 ~ 5, n represents the integer of 0 ~ 3).
(2) composition as described in above-mentioned (1), wherein, described (A) composition is 50 ~ 100 quality % of whole solvents contained in composition.
(3) composition as described in above-mentioned (1) or (2), wherein, the diamine compound with carboxyl of described (B) composition is for having the diamine compound of the structure shown in following formula [2].
[changing 5]
-(CH 2) a-COOH [2]
(in formula [2], a represents the integer of 0 ~ 4).
(4) composition as described in above-mentioned (1) or (2), wherein, the diamine compound with carboxyl of described (B) composition is for having the diamine compound of the structure shown in following formula [2a].
[changing 6]
(in formula [2a], a represents the integer of 0 ~ 4, and n represents the integer of 1 ~ 4).
(5) composition as described in above-mentioned (3) or (4), wherein, described in there is carboxyl diamine compound be in whole diamines used in described (B) composition 20 % by mole ~ 100 % by mole.
(6) composition according to any one of above-mentioned (1) ~ (5), wherein, the diamine component of described (B) composition comprises the diamine compound of at least one being selected from the structure shown in following formula [2b].
[changing 7]
(in formula [2b], Y represents the structure of following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5], and m represents the integer of 1 ~ 4).
[changing 8]
(in formula [2b-1], a represents the integer of 0 ~ 4,
In formula [2b-2], Y 1represent singly-bound ,-(CH 2) a-,-O-,-CH 2o-,-COO-or-OCO-, wherein a is the integer of 1 ~ 15; Y 2represent singly-bound or-(CH 2) b-, wherein b is the integer of 1 ~ 15; Y 3represent singly-bound ,-(CH 2) c-,-O-,-CH 2o-,-COO-or-OCO-, wherein c is the integer of 1 ~ 15; Y 4represent the bivalent cyclic base being selected from phenyl ring, cyclohexane ring or heterocycle, or there is the divalent organic base of carbon number 12 ~ 25 of steroid skeleton, any hydrogen atom in above-mentioned cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; Y 5represent the bivalent cyclic base being selected from phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom in these cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; N represents the integer of 0 ~ 4; Y 6what represent the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18 contains fluoroalkyl, the alkoxyl group of carbon number 1 ~ 18 or the fluoroalkoxy of carbon number 1 ~ 18,
In formula [2b-3], Y 7represent the alkyl of carbon number 8 ~ 22,
In formula [2b-4], Y 8and Y 9separately represent the alkyl of carbon number 1 ~ 6,
In formula [2b-5], Y 10represent the alkyl of carbon number 1 ~ 8).
(7) composition according to any one of above-mentioned (1) ~ (6), wherein, tetracarboxylic dianhydride's composition of described (B) composition is the compound shown in following formula [3].
[changing 9]
(in formula [3], Z 1represent the group being selected from least one structure of following formula [3a] ~ formula [3j]).
[changing 10]
(in formula [3a], Z 2~ Z 5represent hydrogen atom, methyl, chlorine atom or phenyl ring, each other can identical also can be different, in formula [3g], Z 6and Z 7represent hydrogen atom or methyl, each other can identical also can be different).
(8) composition according to any one of above-mentioned (1) ~ (7), wherein, the organoalkoxysilane shown in formula [A2] of described (C) composition is for being selected from allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, methacrylic acid 3-(triethoxysilyl) propyl diester, the at least one of vinylformic acid 3-(trimethoxysilyl) propyl diester or methacrylic acid 3-(trimethoxysilyl) propyl diester.
(9) composition according to any one of above-mentioned (1) ~ (7), wherein, the organoalkoxysilane shown in formula [A2] of described (C) composition is for being selected from least one of 3-glycidoxypropyl (dimethoxy) methyl-monosilane, 3-glycidoxypropyl (diethoxy) methyl-monosilane, 3-glycidoxypropyltrimethoxy base silane or 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane.
(10) composition according to any one of above-mentioned (1) ~ (9), wherein, the polysiloxane of described (C) composition is the polysiloxane obtained by the organoalkoxysilane polycondensation shown in described formula [A1], formula [A2] and formula [A3].
(11) composition according to any one of above-mentioned (1) ~ (10), wherein, containing at least one solvent as the METHYLPYRROLIDONE of (D) composition, N-ethyl-2-pyrrolidone or gamma-butyrolactone.
(12) composition according to any one of above-mentioned (1) ~ (11), wherein, containing 1-hexanol, hexalin, 1 as (E) composition, the at least one solvent of 2-ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, Diethylene Glycol isopropyl ether or diethylene glycol monobutyl ether.
(13) resin coating, the composition according to any one of above-mentioned (1) ~ (12) obtains.
(14) aligning agent for liquid crystal, by above-mentioned (composition according to any one of 1 ~ (12) obtain.
(15) liquid crystal orientation film, uses the aligning agent for liquid crystal described in above-mentioned (14) to obtain.
(16) liquid crystal orientation film, uses the aligning agent for liquid crystal described in above-mentioned (14) to be obtained by ink jet method.
(17) liquid crystal display device, has above-mentioned (15) or the liquid crystal orientation film described in (16).
(18) liquid crystal orientation film as described in above-mentioned (15) or (16), wherein, for possessing the liquid crystal display device that there is between a pair substrate of electrode liquid crystal layer and form, manufacture through following operation, this operation is: between described a pair substrate, configuration packet is containing the liquid-crystal composition of the polymerizable compound utilizing at least one party of active energy beam and heat to be polymerized, and applies voltage while make described polymerizable compound be polymerized between above-mentioned electrode.
(19) liquid crystal display device, has the liquid crystal orientation film described in above-mentioned (18).
(20) liquid crystal orientation film as described in above-mentioned (15) or (16), wherein, for possessing the liquid crystal display device that there is between a pair substrate of electrode liquid crystal layer and form, manufacture through following operation, this operation is: between described a pair substrate, configuration packet is containing the liquid crystal orientation film of the polymerizable group utilizing at least one party of active energy beam and heat to be polymerized, and applies voltage while make described polymerizable group be polymerized between above-mentioned electrode.
(21) liquid crystal display device, has the liquid crystal orientation film described in above-mentioned (20).
Invention effect
Of the present inventionly comprise the solvent with ad hoc structure, the composition being selected from polyimide precursor or at least one polymkeric substance of polyimide and the polysiloxane of ad hoc structure being reacted by the diamine component and tetracarboxylic dianhydride's composition that comprise the diamine compound with carboxyl and obtained can form resin coating by easy fired.In addition, composition of the present invention can suppress the generation with the pore of shrinkage cavity on resin coating when coating substrate.
In addition, the aligning agent for liquid crystal be made up of composition of the present invention can form liquid crystal orientation film by easy fired.This aligning agent for liquid crystal can suppress when coating substrate to form the generation with the pore of shrinkage cavity on liquid crystal orientation film.Therefore, the liquid crystal display device with liquid crystal orientation film obtained thus becomes the liquid crystal display device not having orientation defect, reliability high.
Embodiment
Present inventor has performed further investigation, result obtains following discovery, thus completes the present invention.
The present invention is for comprising the composition of following (A) composition, (B) composition and (C) composition, aligning agent for liquid crystal, use said composition and obtained resin coating, use this aligning agent for liquid crystal and obtained liquid crystal orientation film, and then there is the liquid crystal display device of this liquid crystal orientation film.
(A) composition: at least one solvent (also referred to as specific solvent) being selected from following formula [1a] or formula [1b].
[changing 11]
(in formula [1a], X 1represent the alkyl of carbon number 1 ~ 4, in formula [1b], X 2represent the alkyl of carbon number 1 ~ 4).
(B) composition: at least one polymkeric substance (also referred to as particular polymers) being selected from polyimide precursor or the polyimide being reacted by the diamine component and tetracarboxylic dianhydride's composition that comprise the diamine compound with carboxyl and obtained.
(C) composition: by comprising the organoalkoxysilane polycondensation of any one of the organoalkoxysilane shown in following formula [A1], formula [A2] or formula [A3] and the polysiloxane (also referred to as specific polysiloxane) obtained.
[changing 12]
(A 1) mSi(A 2) n(OA 3) p[A1]
(in formula [A1], A 1represent aliphatic hydrocarbon, phenyl ring, cyclohexane ring, heterocycle or there is the organic radical of carbon number 8 ~ 35 of steroid structure, A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, A 3represent the alkyl of carbon number 1 ~ 5 respectively, m represents the integer of 1 or 2, and n represents the integer of 0 ~ 2, and p represents the integer of 0 ~ 3, and m+n+p is 4).
[changing 13]
(B 1) mSi(B 2) n(OB 3) p[A2]
(in formula [A2], B 1represent the organic radical with the carbon number 2 ~ 12 of vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl, B 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, B 3represent the alkyl of carbon number 1 ~ 5 respectively, m represents the integer of 1 or 2, and n represents the integer of 0 ~ 2, and p represents the integer of 0 ~ 3, and m+n+p is 4).
[changing 14]
(D 1) nSi(OD 2) 4-n[A3]
(in formula [A3], D1 represents the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, and D2 represents the alkyl of carbon number 1 ~ 5, and n represents the integer of 0 ~ 3).
Specific solvent of the present invention is compared with solvent NMP conventional in the composition comprising polyimide-based polymer or γ-BL, and the boiling point of solvent is low, and can dissolve particular polymers of the present invention.Then, specific polysiloxane of the present invention can not only be dissolved in the high solvent of the boiling points such as NMP or γ-BL, and can be dissolved in specific solvent of the present invention, conventional alcoholic solvent or glycolic solvents.Therefore, composition of the present invention can form resin coating by easy fired.
In addition, in composition of the present invention, even if be dissolved in making particular polymers the polymers soln mixing specific polysiloxane or specific polysiloxane in the polymers soln of specific solvent, because specific solvent is not that NMP or γ-BL etc. and so on dissolves the high solvent of polarity, therefore the intermiscibility of the polymers soln of solvent and specific polysiloxane or specific polysiloxane uprises.So, when said composition being coated on substrate, the generation with the pore of shrinkage cavity on resin coating can be suppressed.
Moreover specific solvent of the present invention is compared with NMP conventional in the composition comprising polyimide-based polymer or γ-BL equal solvent, and the surface tension as solvent is low.Therefore, the infiltration spread of composition to substrate of specific solvent is used to uprise.So, the generation with the pore of shrinkage cavity on resin coating can be suppressed.
From above some, composition of the present invention can form resin coating by easy fired, and then can suppress the generation with the pore of shrinkage cavity on resin coating when coating on substrate.And the aligning agent for liquid crystal obtained by composition of the present invention also can obtain above-mentioned effect due to same reason.
Below embodiments of the present invention are illustrated in greater detail.
< specific solvent >
As the specific solvent of the present invention (A) composition for being selected from least one solvent of following formula [1a] or formula [1b].
[changing 15]
(in formula [1a], X 1represent the alkyl of carbon number 1 ~ 3).
(in formula [1b], X 2represent the alkyl of carbon number 1 ~ 3).
Specifically, the structure shown in following formula [1a-1] ~ formula [1a-4] and formula [1b-1] ~ formula [1b-4] can be exemplified.
[changing 16]
[changing 17]
Wherein, from the viewpoint of the boiling point of solvent with obtain difficulty, preferred formula [1a-1], formula [1b-1], formula [1b-2] or formula [1b-3].
In order to be formed resin coating or liquid crystal orientation film by above-mentioned easy fired and make the effect that improves the infiltration spread of substrate higher, specific solvent of the present invention is preferably composition or employs 50 ~ 100 quality % of whole solvents contained in the aligning agent for liquid crystal of said composition.Be more preferably 55 ~ 100 quality %, be more preferably 55 ~ 95 quality % further.
Composition or employ said composition aligning agent for liquid crystal in contained whole solvents, the amount of specific solvent of the present invention is more, then more can present effect of the present invention, namely, resin coating or liquid crystal orientation film can be formed by easy fired, and the infiltration spread of coating solution to substrate can be improved, obtain resin coating or the liquid crystal orientation film of coating excellence.
< particular polymers >
Particular polymers as the present invention (B) composition is be selected from least one polymkeric substance being reacted polyimide precursor or the polyimide obtained by the diamine component and tetracarboxylic dianhydride's composition that comprise the diamine compound with carboxyl.
Polyimide precursor is the structure shown in following formula [A].
[changing 18]
(in formula [A], R 1for quadrivalent organic radical, R 2for there is the divalent organic base of carboxyl, A 1and A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 8, each other can identical also can be different, A 3and A 4represent hydrogen atom, the alkyl of carbon number 1 ~ 5 or ethanoyl, each other can identical also can be different, n represents positive integer).
As above-mentioned diamine component, for having the diamine compound of 2 primary aminos or secondary amino group in molecule; As tetracarboxylic acid composition, tetracarboxylic compound, tetracarboxylic dianhydride, dicarboxylic acid two acetyl halide compound, dicarboxylic acid dialkyl esters compound or dialkyl two acetyl halide compound can be exemplified.
Consider from the reason by adopting the diamine compound with carboxyl shown in following formula [B] and the tetracarboxylic dianhydride shown in following formula [C] to obtain more easily as raw material ratio, the polyamic acid that particular polymers of the present invention is preferably made up of the structural formula of the repeating unit shown in following formula [D] or the polyamide-imide that this polyamic acid obtains through imidization.
[changing 19]
(in formula [B] and formula [C], R 1and R 2with formula [A] in define identical).
[changing 20]
(in formula [D], R 1and R 2with formula [A] in define identical).
In addition, by adopting conventional synthesis gimmick, can in the polymkeric substance of the formula of above-mentioned gained [D] A shown in introducing-type [A] 1and A 2the alkyl of carbon number 1 ~ 8 and the A shown in formula [A] 3and A 4the alkyl of carbon number 1 ~ 5 or ethanoyl.
< has the diamine compound > of carboxyl
The diamine compound with carboxyl of the present invention is the diamine compound in molecule with the structure shown in following formula [2].
[changing 21]
-(CH 2) a-COOH [2]
In formula [2], a represents the integer of 0 ~ 4.Wherein, from the viewpoint of the difficulty obtaining difficulty and synthesis of raw material, be preferably the integer of 0 or 1.
As the diamine compound with the structure shown in formula [2], the structure shown in following formula [2a] specifically can be exemplified.
[changing 22]
In formula [2a], a represents the integer of 0 ~ 4.Wherein, from the viewpoint of the difficulty obtaining difficulty and synthesis of raw material, be preferably 0 or 1.
In formula [2a], n represents the integer of 1 ~ 4.Wherein, from the viewpoint of the difficulty of synthesis, be preferably 1.
The method manufacturing the diamine compound shown in formula of the present invention [2a] is not particularly limited, but can exemplify method shown below as preferred method.
As an example, the diamine compound shown in [2a] is by synthesizing the dinitro matrix compounds shown in following formula [2a-A], being made by nitroreduction it change into amino to obtain again.
[changing 23]
(in formula [2a-A], a represents the integer of 0 ~ 4, and n represents the integer of 1 ~ 4).
The method of the nitroreduction of the dinitro matrix compounds shown in formula [2a-A] is not particularly limited, normally at ethyl acetate, toluene, tetrahydrofuran (THF), two in alkane or alcoholic solvent equal solvent, use palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminum oxide or platinum sulfide carbon etc. as catalyzer, the method making it react under hydrogen, hydrazine or hydrogenchloride.
As the diamine compound with carboxyl of the present invention, the structure shown in following formula [2a-1] ~ formula [2a-4] also can be exemplified.
[changing 24]
In formula [2a-1], A 1represent singly-bound ,-CH 2-,-C 2h 4-,-C (CH 3) 2-,-CF 2-,-C (CF 3) 2-,-O-,-CO-,-NH-,-N (CH 3)-,-CONH-,-NHCO-,-CH 2o-,-OCH 2-,-COO-,-OCO-,-CON (CH 3)-or-N (CH 3) CO-.Wherein, from the viewpoint of the difficulty of synthesis, preferred singly-bound ,-CH 2-,-C (CH 3) 2-,-O-,-CO-,-NH-,-N (CH 3)-,-CONH-,-NHCO-,-COO-or-OCO-.More preferably singly-bound ,-CH 2-,-C (CH 3) 2-,-O-,-CO-,-NH-or-N (CH 3)-.
In formula [2a-1], m 1and m 2represent the integer of 0 ~ 4 respectively, and m 1+ m 2represent the integer of 1 ~ 4.Wherein, m 1+ m 2be preferably 1 or 2.
In formula [2a-2], m 3and m 4represent the integer of 1 ~ 5 respectively.Wherein, from the viewpoint of the difficulty of synthesis, be preferably 1 or 2.
In formula [2a-3], A 2represent side chain or the branched-chain alkyl of carbon number 1 ~ 5.Wherein, the straight chained alkyl of preferred carbon number 1 ~ 3.
In formula [2a-3], m 5represent the integer of 1 ~ 5.Wherein, 1 or 2 are preferably.
In formula [2a-4], A 3represent singly-bound ,-CH 2-,-C 2h 4-,-C (CH 3) 2-,-CF 2-,-C (CF 3) 2-,-O-,-CO-,-NH-,-N (CH 3)-,-CONH-,-NHCO-,-CH 2o-,-OCH 2-,-COO-,-OCO-,-CON (CH 3)-or-N (CH 3) CO-.Wherein, preferred singly-bound ,-CH 2-,-C (CH 3) 2-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH 2o-,-OCH 2-,-COO-or-OCO-.More preferably-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH 2o-,-OCH 2-,-COO-or-OCO-.
In formula [2a-4], m 6represent the integer of 1 ~ 4.Wherein, from the viewpoint of the difficulty of synthesis, be preferably 1.
The diamine compound with carboxyl of the present invention is preferably 20 % by mole ~ 100 % by mole in whole diamine component, is more preferably 30 % by mole ~ 100 % by mole.
The above-mentioned diamine compound with carboxyl can particular polymers according to the present invention to the coating of the solvability of solvent and composition, the characteristic making the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc., use a kind or two or more is used in combination.
< the 2nd diamine compound >
In diamine component for the manufacture of particular polymers of the present invention, also can be used as the diamine compound (also referred to as the 2nd diamine compound) shown in following formula [2b] of the 2nd diamine compound
[changing 25]
(in formula [2b], Y represents the structure of following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5], and m represents the integer of 0 ~ 4).
[changing 26]
In formula [2b-1], a represents the integer of 0 ~ 4.Wherein, from the viewpoint of the difficulty obtaining difficulty and synthesis of raw material, be preferably the integer of 0 or 1.
In formula [2b-2], Y 1represent singly-bound ,-(CH 2) a-(a is the integer of 1 ~ 15) ,-O-,-CH 2o-,-COO-or-OCO-.Wherein, from the viewpoint of the difficulty obtaining difficulty and synthesis of raw material, be preferably singly-bound ,-(CH 2) a-(a is the integer of 1 ~ 15) ,-O-,-CH 2o-or-COO-.Be more preferably singly-bound ,-(CH 2) a-(a is the integer of 1 ~ 10) ,-O-,-CH 2o-or-COO-.
In formula [2b-2], Y 2represent singly-bound or-(CH 2) b-(b is the integer of 1 ~ 15).Wherein, singly-bound or-(CH is preferably 2) b-(b is the integer of 1 ~ 10).
In formula [2b-2], Y 3represent singly-bound ,-(CH 2) c-(c is the integer of 1 ~ 15) ,-O-,-CH 2o-,-COO-or-OCO-.Wherein, from the viewpoint of the difficulty of synthesis, be preferably singly-bound ,-(CH 2) c-(c is the integer of 1 ~ 15) ,-O-,-CH 2o-or-COO-.Be more preferably singly-bound ,-(CH 2) c-(c is the integer of 1 ~ 10) ,-O-,-CH 2o-or-COO-.
In formula [2b-2], Y 4represent the bivalent cyclic base being selected from phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom in these cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom.Y 4it can also be the divalent organic base of the organic radical being selected from the carbon number 12 ~ 25 with steroid skeleton.Wherein, from the viewpoint of the difficulty of synthesis, preferred phenyl ring, cyclohexane ring or there is the organic radical of carbon number 12 ~ 25 of steroid skeleton.
In formula [2b-2], Y 5represent the bivalent cyclic base being selected from phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom in these cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom.Wherein, preferred phenyl ring or cyclohexane ring.
In formula [2b-2], n represents the integer of 0 ~ 4.Wherein, from the viewpoint of the difficulty obtaining difficulty and synthesis of raw material, be preferably 0 ~ 3.Be more preferably 0 ~ 2.
In formula [2b-2], Y 6what represent the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18 contains fluoroalkyl, the alkoxyl group of carbon number 1 ~ 18 or the fluoroalkoxy of carbon number 1 ~ 18.Wherein, the alkyl of preferred carbon number 1 ~ 18, carbon number 1 ~ 10 containing fluoroalkyl, the alkoxyl group of carbon number 1 ~ 18 or the fluoroalkoxy of carbon number 1 ~ 10.More preferably the alkyl of carbon number 1 ~ 12 or the alkoxyl group of carbon number 1 ~ 12.The particularly preferably alkyl of carbon number 1 ~ 9 or the alkoxyl group of carbon number 1 ~ 9.
For the Y in the formula [2b-2] of the substituting group Y in constitutional formula [2b] 1, Y 2, Y 3, Y 4, Y 5, Y 6the combination that (2-1) ~ (2-629) is identical with record in the table 6 ~ table 47 of the 13rd of International Publication publication WO 2011/132751 (2011.10.27 is open) the ~ 34 can be exemplified with the preferably combination of n.In addition, in each table of International Publication publication, the Y in the present invention 1~ Y 6represent as Y1 ~ Y6, Y1 ~ Y6 is replaceable is considered as Y 1~ Y 6.
In formula [2b-3], Y 7represent the alkyl of carbon number 8 ~ 22.
In formula [2b-4], Y 8and Y 9separately represent the alkyl of carbon number 1 ~ 6.
In formula [2b-5], Y 10represent the alkyl of carbon number 1 ~ 8.
The method manufacturing the diamine compound shown in formula of the present invention [2b] is not particularly limited, but can exemplify method shown below as preferred method.
As an example, the diamine compound shown in [2b] is by synthesizing the dinitro matrix compounds shown in following formula [2b-A], being made by nitroreduction it change into amino to obtain again.
[changing 27]
(in formula [2b-A], Y represents the substituting group of at least one structure being selected from above formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5], and m represents the integer of 0 ~ 4).
The method of the nitroreduction of the dinitro matrix compounds shown in formula [2b-A] is not particularly limited, normally at ethyl acetate, toluene, tetrahydrofuran (THF), two in alkane or alcoholic solvent equal solvent, use palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminum oxide or platinum sulfide carbon etc. as catalyzer, the method making it react under hydrogen, hydrazine or hydrogenchloride.
Exemplify the concrete structure of the 2nd diamine compound shown in formula of the present invention [2b] below, but be not limited to these examples.
Namely, as the 2nd diamine compound shown in formula [2b], except mphenylenediamine, 2,4-dimethyl-mphenylenediamine, 2,6-diaminotoluenes, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamino benzylalcohols, 2,4-diamino benzylalcohols, 4, beyond 6-diamino resorcin, also can exemplify the diamine compound of the structure shown in following formula [2b-6] ~ [2b-46].
[changing 28]
(in formula [2b-6] ~ formula [2b-9], A 1represent the alkyl of carbon number 1 ~ 22 or contain fluoroalkyl).
[changing 29]
[changing 30]
[changing 31]
[changing 32]
[changing 33]
[changing 34]
[changing 35]
[changing 36]
[changing 37]
[changing 38]
[changing 39]
[changing 40]
(in formula [2b-34] ~ formula [2b-36], R 1represent-O-,-OCH 2-,-CH 2o-,-COOCH 2-or CH 2oCO-, R 2represent the alkyl of carbon number 1 ~ 22, alkoxyl group, containing fluoroalkyl or fluoroalkoxy).
[changing 41]
(in formula [2b-37] ~ formula [2b-39], R 3represent-COO-,-OCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-or-CH 2-, R 4represent the alkyl of carbon number 1 ~ 22, alkoxyl group, containing fluoroalkyl or fluoroalkoxy).
[changing 42]
(in formula [2b-40] and formula [2b-41], R 5represent-COO-,-OCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-,-CH 2-or-O-, R 6represent fluorine-based, cyano group, trifluoromethyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl.)。
[changing 43]
(in formula [2b-42] and formula [2b-43], R 7represent the alkyl of carbon number 3 ~ 12.The cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is preferably respectively trans-isomer(ide).)。
[changing 44]
(in formula [2b-44] and formula [2b-45], R 8represent the alkyl of carbon number 3 ~ 12.The cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is preferably respectively trans-isomer(ide).)。
[changing 45]
(in formula [2b-46], B 4the alkyl of the carbon number 3 ~ 20 that expression can be replaced by fluorine atoms; B 3represent Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene; B 2represent that Sauerstoffatom or-COO-* (are wherein with key and the B of " * " 3connect); B 1represent that Sauerstoffatom or-COO-* (are wherein with the key of " * " and (CH 2) a 2connect).In addition, a 1represent the integer of 0 or 1; a 2represent the integer of 2 ~ 10; a 3represent the integer of 0 or 1).
The substituting group Y employed in the present invention the 2nd diamine compound Chinese style [2b] adopts the composition of the diamine compound of the structure shown in formula [2b-2] can improve the hydrophobicity of resin coating.And, under the occasion making liquid crystal orientation film, the tilt angle of liquid crystal can be improved.Now, in order to reach the object improving these effects, in above-mentioned diamine compound, formula [2b-28] ~ formula [2b-39] or the diamine compound shown in formula [2b-42] ~ formula [2b-46] is preferably used.Be more preferably formula [2b-24] ~ formula [2b-39] or the diamine compound shown in formula [2b-42] ~ formula [2b-46].In order to improve these effects further, these compounds are preferably more than 5 % by mole less than 80 % by mole of whole diamine component.It is further preferred that from the viewpoint of composition and the coating of aligning agent for liquid crystal and the electrical characteristic as liquid crystal orientation film, these compounds are more than 5 % by mole less than 60 % by mole of whole diamine component.Be particularly preferably more than 10 % by mole less than 60 % by mole of whole diamine component.
2nd diamine compound of the present invention can particular polymers according to the present invention to the solvability of solvent and coating, the characteristic making the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc., use a kind or two or more is used in combination.
Other diamine compound of < >
In particular polymers of the present invention, in the scope not damaging effect of the present invention, except having the 2nd diamine compound shown in the diamine compound of carboxyl and formula [2b] in the molecule shown in formula [2a], formula [2a-1] ~ formula [2a-4], other diamine compound (also referred to as other diamine compound) also can be used as diamine component.
Exemplify the concrete example of this other diamine compound below, but be not limited to these examples.
That is, as other diamine compound, 4 can be exemplified, 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 2,2 '-diaminodiphenyl oxide, 2,3 '-diaminodiphenyl oxide, 4,4 '-alkylsulfonyl dianiline, 3,3 '-alkylsulfonyl dianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diaminodiphenyl sulfide, 4,4 '-diamino-diphenylamine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino-diphenylamine, 2,2 '-diamino-diphenylamine, 2,3 '-diamino-diphenylamine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2 '-diaminobenzophenone, 2,3 '-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, two (3-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, Isosorbide-5-Nitrae-bis-(3-aminophenyl) butane, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminobenzyl) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] pentanoic, 4,4 '-[1,3-phenylene two (methylene radical)] pentanoic, 3,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] pentanoic, 3,4 '-[1,3-phenylene two (methylene radical)] pentanoic, 3,3 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] pentanoic, 3,3 '-[1,3-phenylene two (methylene radical)] pentanoic, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N '-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamide), N, N '-(1,3-phenylene) two (4-aminobenzamide), N, N '-(Isosorbide-5-Nitrae-phenylene) two (3-AB), N, N '-(1,3-phenylene) two (3-AB), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyl) terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, two (4-aminophenyl) anthracene of 9,10-, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 2,2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane, two (4-amino-benzene oxygen) propane of 1,3-, two (3-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (3-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (3-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, 1,7-(3-amino-benzene oxygen) heptane, two (4-amino-benzene oxygen) octane of 1,8-, two (3-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (3-amino-benzene oxygen) nonane of 1,9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) undecane, 1,11-(3-amino-benzene oxygen) undecane, 1,12-(4-amino-benzene oxygen) dodecane, 1,12-(3-amino-benzene oxygen) dodecane, two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-Diaminobutane, 1,5-1,5-DAP, 1，6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1,11-diamino undecane or 1,12-diamino dodecane etc.
In addition, as other diamine compound, can also exemplify and there is alkyl, diamines containing fluoroalkyl, aromatic nucleus, aliphatics ring or heterocycle on two amine side chains, or there is the diamines etc. of the large ring-type substituent be made up of them.Specifically, the diamine compound shown in following formula [DA1] ~ [DA13] can be illustrated.
[changing 46]
[changing 47]
[changing 48]
(in formula [DA1] ~ formula [DA6], A 1represent-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-, A 2represent that the straight-chain of carbon number 1 ~ 22 or the straight-chain of branched-chain alkyl or carbon number 1 ~ 22 or branched are containing fluoroalkyl).
[changing 49]
(in formula [DA7], p represents the integer of 1 ~ 10).
Only otherwise infringement effect of the present invention, the diamine compound shown in following formula [DA8] ~ formula [DA13] also can be used as other diamine compound.
[changing 50]
[changing 51]
(in formula [DA10], m represents the integer of 0 ~ 3, and in formula [DA13], n represents the integer of 1 ~ 5).
Only otherwise infringement effect of the present invention, the diamine compound shown in following formula [DA14] can also be used.
[changing 52]
(in formula [DA14], A 1for being selected from-O-,-NH-,-N (CH 3)-,-CONH-,-NHCO-,-CH 2o-,-OCO-,-CON (CH 3)-or-N (CH 3) divalent organic base of CO-, A 2for the aliphatic alkyl of singly-bound, carbon number 1 ~ 20, non-aromatic ring type alkyl or aromatic hydrocarbyl, A 3be selected from singly-bound ,-O-,-NH-,-N (CH 3)-,-CONH-,-NHCO-,-COO-,-OCO-,-CON (CH 3)-,-N (CH 3) CO-or-O (CH 2) m-(m is the integer of 1 ~ 5), A 4for nitrogenous heteroaromatic, n is the integer of 1 ~ 4).
In addition, the diamine compound shown in following formula [DA15] and formula [DA16] also can be used as other diamine compound.
[changing 53]
Other above-mentioned diamine compound can particular polymers according to the present invention to the coating of the solvability of solvent and composition, the characteristic making the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc., use a kind or two or more is used in combination.
< tetracarboxylic dianhydride composition >
As the tetracarboxylic dianhydride's composition for the manufacture of particular polymers of the present invention, the tetracarboxylic anhydride shown in following formula [3] or its tetracarboxylic acid derivatives (also referred to as specific tetracarboxylic dianhydride's composition) can be exemplified.
[changing 54]
In formula [3], Z 1it is the group of at least one structure being selected from following formula [3a] ~ formula [3j].
[changing 55]
In formula [3a], Z 2~ Z 5the group being selected from hydrogen atom, methyl, chlorine atom or phenyl ring, each other can identical also can be different.
In formula [3g], Z 6and Z 7represent hydrogen atom or methyl, each other can identical also can be different.
As specific tetracarboxylic dianhydride's composition of the present invention formula [3] shown in structure in, the difficulty of the polymerisation reactivity from the viewpoint of the difficulty of synthesizing and when manufacturing polymkeric substance, is preferably formula [3a], formula [3c], formula [3d], formula [3e], formula [3f] or the structure shown in formula [3g].Be more preferably formula [3a], formula [3e], formula [3f] or the structure shown in formula [3g].
Specific tetracarboxylic acid composition of the present invention is preferably more than 1 % by mole in whole tetracarboxylic acid composition.Be more preferably more than 5 % by mole, be particularly preferably more than 10 % by mole.
In addition, use formula [3e], formula [3f] or formula [3g] specific tetracarboxylic dianhydride's composition of structure when, by making its usage quantity be more than 20 % by mole of whole tetracarboxylic dianhydride's composition, required effect can be obtained.Be more preferably more than 30 % by mole.And tetracarboxylic dianhydride's composition also can be all tetracarboxylic dianhydride's composition of the structure of formula [3e], formula [3f] or formula [3g].
In particular polymers of the present invention, only otherwise infringement effect of the present invention, other tetracarboxylic dianhydride's compositions beyond specific tetracarboxylic dianhydride's composition can be used.
As other tetracarboxylic dianhydride's compositions, tetracarboxylic compound shown below, tetracarboxylic dianhydride, dicarboxylic acid two acetyl halide compound, dicarboxylic acid dialkyl esters compound or dialkyl two acetyl halide compound can be exemplified.
Namely, Pyromellitic Acid can be exemplified, 2, 3, 6, 7-naphthalenetetracarbacidic acidic, 1, 2, 5, 6-naphthalenetetracarbacidic acidic, 1, 4, 5, 8-naphthalenetetracarbacidic acidic, 2, 3, 6, 7-anthracene tetracarboxylic acid, 1, 2, 5, 6-anthracene tetracarboxylic acid, 3, 3 ', 4, 4 '-bibenzene tetracarboxylic, 2, 3, 3 ', 4-bibenzene tetracarboxylic, two (3, 4-dicarboxyphenyi) ether, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic, two (3, 4-dicarboxyphenyi) sulfone, two (3, 4-dicarboxyphenyi) methane, 2, 2-two (3, 4-dicarboxyphenyi) propane, 1, 1, 1, 3, 3, 3-hexafluoro-2, 2-two (3, 4-dicarboxyphenyi) propane, two (3, 4-dicarboxyphenyi) dimethylsilane, two (3, 4-dicarboxyphenyi) diphenyl silane, 2, 3, 4, 5-pyridine tetracarboxylic acid, 2, 6-two (3, 4-dicarboxyphenyi) pyridine, 3, 3 ', 4, 4 '-diphenyl sulfone tetraformic acid, 3, 4, 9, 10-perylene tetracarboxylic acid or 1, 3-phenylbenzene-1, 2, 3, 4-cyclobutanetetracarboxylic.
Specific tetracarboxylic dianhydride's composition and other tetracarboxylic acid composition can particular polymers according to the present invention to the coating of the solvability of solvent and composition, make the characteristics such as the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge, use a kind or two or more is used in combination.
The manufacture method > of < particular polymers
In the present invention, the method for synthesis particular polymers is not particularly limited.Usually, reacted by diamine component and tetracarboxylic dianhydride's composition and obtained.Generally speaking, tetracarboxylic dianhydride's composition of at least one being selected from tetracarboxylic acid and derivative thereof is reacted with the diamine component be made up of one or more diamine compounds, thus obtains polyamic acid.Specifically can adopt make tetracarboxylic dianhydride with have primary amino or secondary amino group diamine compound polycondensation and obtain polyamic acid method, tetracarboxylic acid and the diamine compound generation dehydrating polycondensation with primary amino or secondary amino group reacts and obtain the method for polyamic acid or make dicarboxyl acidic group two carboxylic acid halides and there is the diamine compound polycondensation of primary amino or secondary amino group and obtain the method etc. of polyamic acid.
In order to obtain polyamic acid alkyl ester, can adopt make the tetracarboxylic acid of carboxylic acid group's dialkyl group esterification with have primary amino or secondary amino group diamine compound polycondensation method, make dicarboxylic acid two carboxylic acid halides of carboxylic acid group's dialkyl group esterification with have primary amino or secondary amino group diamine compound polycondensation method or be the method for ester group by the converting carboxylate groups of polyamic acid.
In order to obtain polyimide, can adopt and make above-mentioned polyamic acid or polyamic acid alkyl ester closed loop and the method forming polyimide.
The reaction of diamine component and tetracarboxylic acid composition is undertaken by making diamine component and tetracarboxylic acid composition react in organic solvent usually.As organic solvent now used, as long as solubilized is as the solvent of the specific solvent of the present invention (A) composition and the polyimide precursor of generation, be not particularly limited.
As the solvent beyond specific solvent of the present invention, following solvent can be exemplified.
Namely, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, methyl-sulphoxide, gamma-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methylethylketone, pimelinketone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone etc.
These solvents can be used alone, also can be used in combination.And, even the solvent of polyimide precursor can not be dissolved, use after being mixed into above-mentioned solvent in the scope also can not separated out at the polyimide precursor generated.In addition, because the moisture in organic solvent hinders polyreaction, and become the reason that the polyimide precursor of generation is hydrolyzed, therefore preferably use the organic solvent after dehydrating.
Following method can be exemplified: namely, when making diamine component and tetracarboxylic dianhydride reacts in organic solvent, solution diamine component being dispersed or dissolved in organic solvent is stirred, the method for then directly adding tetracarboxylic acid composition or adding after tetracarboxylic acid composition is dispersed or dissolved in organic solvent; On the contrary, in solution tetracarboxylic acid composition being dispersed or dissolved in organic solvent, add the method for diamine component; Or alternately add the method etc. of tetracarboxylic acid composition and diamine component.Any one in these methods can be adopted.In addition, under the occasion adopting multiple diamine component or tetracarboxylic acid to become to assign to make it react respectively, can it be made to react under the state be pre-mixed, it also can be made to react successively respectively, can also make to react respectively and the low-molecular weight obtained carries out hybrid reaction to obtain polymkeric substance.Polymerization temperature now can be selected from the arbitrary temp within the scope of-20 ~ 150 DEG C, but the preferred scope of-5 ~ 100 DEG C.In addition, reaction can be carried out under arbitrary concentration, if but concentration is too low, and be difficult to obtain the polymkeric substance of high molecular, the viscosity of excessive concentration then reaction solution can become too high and be difficult to stir uniformly.Therefore, preferably 1 ~ 50 quality %, more preferably 5 ~ 30 quality %.Can carry out with high density in initial reaction stage, add organic solvent afterwards.
In the polyreaction of polyimide precursor, the total mole number of diamine component is preferably 0.8 ~ 1.2 with the ratio of the total mole number of tetracarboxylic acid composition.Identical with common polycondensation, this mol ratio is more close to 1.0, then the molecular weight of the polyimide precursor generated is larger.
Polyimide of the present invention obtains by making above-mentioned polyimide precursor closed loop, and in this polyimide, the closed loop rate (also referred to as imide rate) of acid amides acidic group does not need one to be decided to be 100%, at random can adjust according to purposes or object.
As the method making polyimide precursor imidization, the hot-imide of the solution of direct heating polyimide precursor can be exemplified or in the solution of polyimide precursor, add the catalysis imidization of catalyzer.
Temperature when making polyimide precursor carry out hot-imide is in the solution 100 ~ 400 DEG C, preferably 120 ~ 250 DEG C, preferably carries out while the water removing will generated by imidization reaction is to system.
The catalysis imidization of polyimide precursor, by adding basic catalyst and acid anhydrides in the solution of polyimide precursor, stirs and carries out at-20 ~ 250 DEG C, preferably 0 ~ 180 DEG C.The amount of basic catalyst is 0.5 ~ 30 mole times of acid amides acidic group, preferably 2 ~ 20 moles times, and the amount of acid anhydrides is 1 ~ 50 mole times of acid amides acidic group, preferably 3 ~ 30 moles times.As basic catalyst, pyridine, triethylamine, Trimethylamine 99, Tributylamine or trioctylamine etc. can be exemplified, wherein pyridine have for make reaction carry out for appropriateness alkalescence, therefore preferably.As acid anhydrides, diacetyl oxide, trimellitic acid 1,2-anhydride or pyromellitic dianhydride etc. can be exemplified, wherein, use during diacetyl oxide and be easy to carry out reacting the purifying after terminating, therefore preferably.Adopt the imide rate of catalysis imidization can be controlled by adjustment catalytic amount and temperature of reaction, reaction times.
When reclaiming polyimide precursor or the polyimide of generation from the reaction soln of polyimide precursor or polyimide, reaction soln is put in solvent and make it precipitate.As the solvent for precipitating, methyl alcohol, ethanol, Virahol, acetone, hexane, ethylene glycol butyl ether, heptane, methylethylketone, mibk, toluene, benzene, water etc. can be exemplified.After the polymkeric substance putting in solvent precipitation reclaims after filtration, can under normal or reduced pressure, carry out drying under normal temperature or heating.In addition, if the polymkeric substance that precipitation reclaims is dissolved in organic solvent again and the redeposition operation 2 ~ 10 times of reclaiming, then the impurity in polymkeric substance can be reduced.As solvent now, can exemplify alcohols, ketone or hydrocarbon etc., if adopt the solvent of more than three kinds therefrom selected, then purification efficiency improves further, therefore preferably.
The molecular weight of particular polymers of the present invention is under the occasion of the operability considered when being formed by its obtained resin coating or liquid crystal aligning film strength, film and film, the weight-average molecular weight utilizing GPC (gel permeation chromatography) to measure preferably 5000 ~ 1000000, more preferably 10000 ~ 150000.
The specific polysiloxane > of <
Specific polysiloxane as the present invention (C) composition is by comprising the organoalkoxysilane polycondensation of any one of the organoalkoxysilane shown in above-mentioned formula [A1], formula [A2] or formula [A3] and the polysiloxane obtained,
Organoalkoxysilane shown in formula of the present invention [A1] is the organoalkoxysilane shown in following formula [A1].
[changing 56]
(A 1) mSi(A 2) n(OA 3) p[A1]
In formula [A1], A 1represent aliphatic hydrocarbon, phenyl ring, cyclohexane ring, heterocycle or there is the organic radical of carbon number 8 ~ 35 of steroid structure.
In formula [A1], A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively.Wherein, the alkyl of preferred hydrogen atom or carbon number 1 ~ 3.
In formula [A1], A 3represent the alkyl of carbon number 1 ~ 5 respectively.Wherein, consider from reactive viewpoint of polycondensation, the alkyl of preferred carbon number 1 ~ 3.
In formula [A1], m represents the integer of 1 or 2.Wherein, from the viewpoint of synthesis, be preferably 1.
In formula [A1], n represents the integer of 0 ~ 2.
In formula [A1], p represents the integer of 0 ~ 3.Wherein, consider from reactive viewpoint of polycondensation, be preferably the integer of 1 ~ 3.Be more preferably 2 or 3.
In formula [A1], m+n+p is the integer of 4.
As the concrete example of the organoalkoxysilane shown in formula [A1], octyl group Trimethoxy silane can be exemplified, octyltri-ethoxysilane, decyl Trimethoxy silane, dodecyltrimethoxysilane, dodecyl triethoxysilane, hexadecyl trimethoxy silane, hexadecyl, amyl triethoxysilane, heptadecyl Trimethoxy silane, heptadecyltriethoxysilane, octadecyl trimethoxysilane, octadecyltriethoxy silane, nonadecyl Trimethoxy silane, nonadecyl triethoxyl silane, isooctyltriethoxysilane, styroyl triethoxyl silane, pentafluorophenyl group propyl trimethoxy silicane, between styryl ethyl trimethoxy silane, to styryl ethyl trimethoxy silane, 1-naphthyl-triethyoxy silicane alkane, 1-naphthyl Trimethoxy silane, the fluoro-n-octyl silane of triethoxy-1H, 1H, 2H, 2H-13, dimethoxydiphenyl silane, dimethoxymethylphenylsilane or triethoxyphenylsilan etc.
In addition, the organoalkoxysilane shown in following formula [A1-1] ~ formula [A1-32] can also be used.
[changing 57]
[changing 58]
[changing 59]
[changing 60]
[changing 61]
[changing 62]
[changing 63]
[changing 64]
[changing 65]
(in formula [A1-1] ~ formula [A1-18], R 1represent the alkyl of carbon number 1 ~ 5 respectively).
[changing 66]
(in formula [A1-19] ~ formula [A1-22], R 1represent the alkyl of carbon number 1 ~ 5 respectively, R 2represent-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CON (CH respectively 3)-,-N (CH 3) CO-,-OCH 2-,-CH 2o-,-COOCH 2-or-CH 2oCO-, R 3represent the alkyl of carbon number 1 ~ 12, alkoxyl group respectively, containing fluoroalkyl or fluoroalkoxy).
[changing 67]
(in formula [A1-23] ~ formula [A1-24], R 1represent the alkyl of carbon number 1 ~ 5 respectively, R 2represent-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CON (CH respectively 3)-,-N (CH 3) CO-,-OCH 2-,-CH 2o-,-COOCH 2-or-CH 2oCO-, R 3represent the alkyl of carbon number 1 ~ 12, alkoxyl group respectively, containing fluoroalkyl, fluoroalkoxy, fluorine-based, cyano group, trifluoromethyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl).
[changing 68]
[changing 69]
(in formula [A1-25] ~ formula [A1-31], R 1represent the alkyl of carbon number 1 ~ 5 respectively, R 2represent-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CON (CH respectively 3)-,-N (CH 3) CO-,-OCH 2-,-CH 2o-,-COOCH 2-or-CH 2oCO-, R 3represent the alkyl of carbon number 1 ~ 12, alkoxyl group respectively, containing fluoroalkyl or fluoroalkoxy).
[changing 70]
(in formula [A1-32], R 1represent the alkyl of carbon number 1 ~ 5 respectively, B 4the alkyl of the carbon number 3 ~ 20 that expression can be replaced by fluorine atoms, B 3represent Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, B 2represent that Sauerstoffatom or COO-* (are wherein with key and the B of " * " 3connect), B 1represent that Sauerstoffatom or COO-* (are wherein with the key of " * " and (CH 2) a 2connect).In addition, a 1represent the integer of 0 or 1, a 2represent the integer of 2 ~ 10, a 3represent the integer of 0 or 1).
Operability when organoalkoxysilane shown in above-mentioned formula [A1] can be formed according to resin coating or liquid crystal aligning film strength or these films, make the characteristic of the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc. in addition, use a kind or two or more is used in combination.
Organoalkoxysilane shown in formula of the present invention [A2] is the organoalkoxysilane shown in following formula [A2].
[changing 71]
(B 1) mSi(B 2) n(OB 3) p[A2]
In formula [A2], B 1represent the organic radical with the carbon number 2 ~ 12 of vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl.Wherein, from the viewpoint of obtaining difficulty, preferred vinyl, epoxy group(ing), amino, methacryloyl, acryl or urea groups.More preferably methacryloyl, acryl or urea groups.
In formula [A2], B 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively.Wherein, the alkyl of preferred hydrogen atom or carbon number 1 ~ 3.
In formula [A2], B 3represent the alkyl of carbon number 1 ~ 5 respectively.Wherein, consider from reactive viewpoint of polycondensation, the alkyl of preferred carbon number 1 ~ 3.
In formula [A2], m represents the integer of 1 or 2.Wherein, from the viewpoint of synthesis, be preferably 1.
In formula [A2], n represents the integer of 0 ~ 2.
In formula [A2], p represents the integer of 0 ~ 3.Wherein, consider from reactive viewpoint of polycondensation, the preferably integer of 1 ~ 3.More preferably 2 or 3.
In formula [A2], m+n+p is the integer of 4.
As the concrete example of the organoalkoxysilane shown in formula [A2], allyltriethoxysilane can be exemplified, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, between styryl ethyl triethoxysilane, to styryl ethyl triethoxysilane, between styrylmethyl triethoxyl silane, to styrylmethyl triethoxyl silane, 3-(N-styrylmethyl-2-aminoethylamino) propyl trimethoxy silicane, diethoxy (3-glycidyloxypropyl) methyl-monosilane, 3-glycidyloxypropyl (dimethoxy) methyl-monosilane, 3-glycidyloxypropyl Trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-(2-aminoethylamino) dimethylamine oxygen butyldimethylsilyl, 3-(2-aminoethylamino) propyl-triethoxysilicane, 3-(2-aminoethylamino) propyl trimethoxy silicane, 3-aminopropyl diethoxymethylsilane, APTES, 3-TSL 8330, trimethoxy [3-(phenyl amino) propyl group] silane, 3-mercaptopropyi (dimethoxy) methyl-monosilane, (3-mercaptopropyi) triethoxyl silane, (3-mercaptopropyi) Trimethoxy silane, isocyanic acid 3-(triethoxysilyl) propyl diester, methacrylic acid 3-(triethoxysilyl) propyl diester, methacrylic acid 3-(trimethoxysilyl) propyl diester, vinylformic acid 3-(triethoxysilyl) propyl diester, vinylformic acid 3-(trimethoxysilyl) propyl diester, methacrylic acid 3-(triethoxysilyl) ethyl ester, methacrylic acid 3-(trimethoxysilyl) ethyl ester, vinylformic acid 3-(triethoxysilyl) ethyl ester, vinylformic acid 3-(trimethoxysilyl) ethyl ester, methacrylic acid 3-(triethoxysilyl) methyl ester, methacrylic acid 3-(trimethoxysilyl) methyl ester, vinylformic acid 3-(triethoxysilyl) methyl ester, vinylformic acid 3-(trimethoxysilyl) methyl ester, γ-ureidopropyltriethoxysilane, γ-ureido-propyl Trimethoxy silane, γ-ureido-propyl tripropoxy silane, (R)-N-1-phenylethyl-N '-triethoxysilylpropyltetrasulfide urea, (R)-N-1-phenylethyl-N '-trimethoxy-silylpropyl urea, two [3-(trimethoxysilyl) propyl group] urea, two [3-(tripropoxy-sil(ic)ane base) propyl group] urea, 1-[3-(trimethoxysilyl) propyl group] urea etc.
Operability when organoalkoxysilane shown in above-mentioned formula [A2] can be formed according to resin coating or liquid crystal aligning film strength or these films, make the characteristic of the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc. in addition, use a kind or two or more is used in combination.
Organoalkoxysilane shown in formula of the present invention [A3] is the organoalkoxysilane shown in following formula [A3].
[changing 72]
(D 1) nSi(OD 2) 4-n[A3]
In formula [A3], D 1represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, its can by halogen atom, nitrogen-atoms, Sauerstoffatom, sulphur atom replace.Wherein, the alkyl of preferred hydrogen atom or carbon number 1 ~ 3.
In formula [A3], D 2represent the alkyl of carbon number 1 ~ 5.Wherein, consider from reactive viewpoint of polycondensation, the alkyl of preferred carbon number 1 ~ 3.
In formula [A3], n represents the integer of 0 ~ 3.
As the concrete example of the organoalkoxysilane shown in formula [A3], tetramethoxy-silicane can be exemplified, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, methyl tripropoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethoxy diethylsilane, dibutoxy dimethylsilane, (chloromethyl) triethoxyl silane, 3-chloropropyl dimethoxymethylsilane, 3-chloropropyl triethoxysilane, 2-cyano ethyl triethoxyl silane, trimethoxy (3, 3, 3-trifluoro propyl) silane, hexyl Trimethoxy silane or 3-trimethoxy-silylpropyl chlorine etc.
In above-mentioned formula [A3], be the organoalkoxysilane of 0 as n, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes can be exemplified.
Operability when organoalkoxysilane shown in above-mentioned formula [A3] can be formed according to resin coating or liquid crystal aligning film strength or these films, make the characteristic of the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc. in addition, use a kind or two or more is used in combination.
Specific polysiloxane of the present invention is by comprising the organoalkoxysilane polycondensation of any one of the organoalkoxysilane shown in above-mentioned formula [A1], formula [A2] or formula [A3] and the polysiloxane that obtains, but preferably by comprising the organoalkoxysilane polycondensation of multiple described organoalkoxysilane and the polysiloxane that obtains.Namely, can exemplify by comprising above-mentioned formula [A1] and formula [A2] 2 kinds, the organoalkoxysilane polycondensation of above-mentioned formula [A1] and formula [A3] 2 kinds or above-mentioned formula [A2] and [A3] 2 kinds and the polysiloxane obtained, can also be by comprising the organoalkoxysilane polycondensation of above-mentioned formula [A1], formula [A2] and formula [A3] 3 kinds and the polysiloxane obtained.Wherein, preferably comprise above-mentioned formula [A1] and formula [A2] 2 kinds, above-mentioned formula [A1] and formula [A3] 2 kinds or comprise the organoalkoxysilane of above-mentioned formula [A1], formula [A2] and formula [A3] 3 kinds.
Above-mentioned formula [A1], formula [A2] or the organoalkoxysilane shown in formula [A3] are for obtaining specific polysiloxane of the present invention.
Organoalkoxysilane shown in formula [A1] is preferably 1 ~ 40 % by mole in whole organoalkoxysilane, is more preferably 1 ~ 30 % by mole.In addition, the organoalkoxysilane shown in formula [A2] is preferably 1 ~ 70 % by mole in whole organoalkoxysilane, is more preferably 1 ~ 60 % by mole.Moreover the organoalkoxysilane shown in formula [A3] is preferably 1 ~ 99 % by mole in whole organoalkoxysilane, is more preferably 1 ~ 80 % by mole.
The method obtaining specific polysiloxane used in the present invention is not particularly limited.Specific polysiloxane in the present invention obtains by making the organoalkoxysilane of any one comprising the organoalkoxysilane shown in above-mentioned formula [A1], formula [A2] or formula [A3] be polymerized in organic solvent, or makes the multiple organoalkoxysilane in above-mentioned formula [A1], formula [A2], the organoalkoxysilane shown in formula [A3] be polymerized in organic solvent and obtain.In addition, specific polysiloxane of the present invention is dissolved in the solution acquisition of organic solvent equably after can be used as and making organoalkoxysilane polycondensation.
The method of specific polysiloxane polycondensation of the present invention is not particularly limited.Wherein, such as can exemplify organoalkoxysilane is hydrolyzed the method for polycondensation in specific solvent of the present invention, alcoholic solvent or glycolic solvents.Now, hydrolysis condensation reaction can be partial hydrolysis also can be complete hydrolysis.Under the occasion of complete hydrolysis, add the water of 0.5 times mole of whole alkoxyl group in organoalkoxysilane in theory, but be usually preferably added beyond the excessive water of 0.5 times mole.In order to obtain specific polysiloxane of the present invention, the water yield used in said hydrolyzed polycondensation suitably can be selected according to object, but is preferably 0.5 ~ 2.0 times of molar weight of all alkoxyl groups in organoalkoxysilane.
In addition, in order to reach the object of facilitation of hydrolysis polycondensation, usually the acidic cpds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, toxilic acid or fumaric acid can be used, the basic cpds such as ammonia, methylamine, ethamine, thanomin or triethylamine, or the catalyzer of the metal-salt of hydrochloric acid, sulfuric acid or nitric acid etc. etc.In addition, also facilitation of hydrolysis polycondensation is carried out by carrying out heating to the solution being dissolved with organoalkoxysilane further.Now, suitably can select according to object Heating temperature and heat-up time.Such as, can exemplify and heat at 50 DEG C, stir 24 hours, then the condition that waits of heated and stirred 1 hour under reflux.
In addition, as other polycondensation method, the method for polycondensation after the mixture heating to organoalkoxysilane, organic solvent and oxalic acid can be exemplified, is carried out.Specifically following method: add oxalic acid in advance in specific solvent of the present invention or alcoholic solvent and after making the solution of oxalic acid, by the method that this solution mixes with organoalkoxysilane under warmed-up state.Now, the amount for the oxalic acid of above-mentioned reaction is preferably 0.2 ~ 2.0 mole relative to alkoxyl group 1 mole whole in organoalkoxysilane.In addition, this reaction can be carried out at solution temperature 50 ~ 180 DEG C, but in order to not cause the evaporation or volatilization etc. of solvent, preferably carries out dozens of minutes ~ tens hour under reflux.
Obtain in the polycondensation of specific polysiloxane of the present invention, when using the organoalkoxysilane shown in multiple above-mentioned formula [A1], formula [A2] and formula [A3], the mixture that multiple organoalkoxysilane can be used to be pre-mixed reacts, and also can react while adding multiple organoalkoxysilane successively.
As the solvent of the polycondensation for organoalkoxysilane, as long as the solvent of energy dissolvane TMOS is not particularly limited.In addition, even can not the solvent of dissolvane TMOS, as long as then also can be able to adopt by dissolvane TMOS while the polycondensation of organoalkoxysilane is carried out.As solvent used in polycondensation, usually, produce alcohol in order to the polycondensation by organoalkoxysilane, alcoholic solvent, glycolic solvents, glycol ethers solvent or the organic solvent good with the intermiscibility of alcohol can be adopted.As the concrete example of this kind solvent used in polycondensation, methyl alcohol can be exemplified, ethanol, propylene glycol, the alcoholic solvent of butanols or Pyranton etc., ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-PD, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, Isosorbide-5-Nitrae-pentanediol, 1,5-PD, 2,4-pentanediol, the glycolic solvents of 2,3-pentanediol or 1,6-hexylene glycol etc., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol dipropyl ether, dibutyl ethylene glycol ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, the glycol ethers solvent of propylene glycol dipropyl ether or propylene glycol dibutyl ether etc., METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, gamma-butyrolactone, DMF, N,N-dimethylacetamide, methyl-sulphoxide, tetramethylurea (TMU), the organic solvent that HMPA or meta-cresol etc. are good with alcohol intermiscibility.
Wherein, from modulation composition of the present invention or the aligning agent for liquid crystal employing said composition, preferably use specific solvent of the present invention.In addition, in the present invention, when polycondensation, above-mentioned solvent can use a kind or two or more is used in combination.
The polymeric solution of the specific polysiloxane obtained by aforesaid method, the Siliciumatom that the whole organoalkoxysilanes as raw material input have is converted into SiO 2and the concentration (SiO obtained 2converted score) preferably at below 20 quality %.Wherein, preferred 5 ~ 15 quality %.By selecting any concentration in this concentration range, the generation of gel in solution can be suppressed, the polycondensation solution of uniform specific polysiloxane can be obtained.
In the present invention, can using the polycondensation solution of specific polysiloxane that obtained by aforesaid method directly as the solution of the specific polysiloxane of the present invention (C) composition, also can as required and using the polycondensation solution of the specific polysiloxane obtained by aforesaid method solution as the specific polysiloxane of the present invention (C) composition after concentrating, add solvent cut, being replaced into other solvent.
Adding solvent (also referred to as interpolation solvent) used when above-mentioned solvent dilutes can be solvent used in polycondensation or specific solvent of the present invention, can also be other solvent.Be not particularly limited as long as these interpolation solvents can dissolve specific polysiloxane equably, a kind or any can be used to select two or more to use.Add solvent as this type of, except solvent used in above-mentioned polycondensation, the ketones solvent of acetone, methylethylketone or mibk etc. can be exemplified, the esters solvent etc. of methyl acetate, ethyl acetate or ethyl lactate etc.
In the present invention, before the specific polysiloxane of (C) composition mixes with the particular polymers of (B) composition, preferably the alcohol produced during specific polysiloxane polycondensation is distilled removing under normal or reduced pressure.
< composition aligning agent for liquid crystal >
Composition of the present invention or the aligning agent for liquid crystal employing said composition are the coating solutions for the formation of resin coating or liquid crystal orientation film (being also referred to as resin coating), are the coating solutions for the formation of resin coating comprising specific solvent, particular polymers and specific polysiloxane.Wherein, composition or the Inventive polymers employed in the aligning agent for liquid crystal of said composition represent particular polymers and specific polysiloxane.
Composition of the present invention or employ in the aligning agent for liquid crystal of said composition, the content of specific polysiloxane is preferably 0.1 ~ 90 mass parts relative to particular polymers composition 100 mass parts.Wherein, from the viewpoint of the stability of composition or aligning agent for liquid crystal, be more preferably 1 ~ 70 mass parts relative to particular polymers 100 mass parts.Be particularly preferably 5 ~ 60 mass parts.
Composition of the present invention or employ in the aligning agent for liquid crystal of said composition, whole component of polymer can be all Inventive polymers, also can be mixed with other polymkeric substance in addition in Inventive polymers.Now, the content of other polymkeric substance in addition can be 0.5 quality % ~ 15 quality %, the preferably 1 quality % ~ 10 quality % of Inventive polymers.As other polymkeric substance in addition, the polyimide precursor or polyimide that do not use above-mentioned diamine compound, the 2nd diamine compound or the specific tetracarboxylic acid composition with carboxyl can be exemplified.And then the polymkeric substance beyond polyimide precursor or polyimide specifically can exemplified by acrylic polymkeric substance, methacrylate polymer, polystyrene or polymeric amide etc.
Composition of the present invention or the organic solvent employed in the aligning agent for liquid crystal of said composition form uniform resin coating from the viewpoint of by coating, and the content of organic solvent is preferably 70 ~ 99.9 quality %.This content can carry out appropriate change according to the thickness of target resin coating or liquid crystal orientation film.
Composition of the present invention or the whole organic solvents employed in organic solvent used in the aligning agent for liquid crystal of said composition can be all specific solvents of the present invention, also can be mixed with other organic solvent in addition in organic solvent of the present invention.Now, specific solvent of the present invention is preferably 50 ~ 100 quality % of whole solvents contained in composition or aligning agent for liquid crystal.Wherein, preferred 55 ~ 100 quality %.More preferably 55 ~ 95 quality %.
As other organic solvent in addition, as long as the organic solvent that can dissolve particular polymers and specific polysiloxane is not particularly limited.Its concrete example is listed below.
Such as, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, methyl-sulphoxide, gamma-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methylethylketone, pimelinketone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone etc.
Wherein, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone or gamma-butyrolactone (above also referred to as (D) composition) is preferably used.
These (D) compositions are preferably composition or employ 1 ~ 50 quality % of whole organic solvents contained in the aligning agent for liquid crystal of said composition.Wherein, preferred 1 ~ 40 quality %.More preferably 1 ~ 30 quality %, further preferred 5 ~ 30 quality %.
Composition of the present invention or employ the aligning agent for liquid crystal of said composition can in the scope not damaging effect of the present invention, use film and the organic solvent of surface smoothness, i.e. poor solvent of the resin coating after the aligning agent for liquid crystal coating improving composition further or employ said composition or liquid crystal orientation film.
The concrete example improving resin coating or the film of liquid crystal orientation film and the poor solvent of surface smoothness is listed below:
Such as, ethanol, Virahol, n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, primary isoamyl alcohol, tertiary amyl alcohol, 3-methyl-2-butanols, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-ethyl-n-butyl alcohol, 1-heptanol, 2-enanthol, 3-enanthol, 1-octanol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, hexalin, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1, 2 methyl cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butyleneglycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2-ethyl-1, 3-hexylene glycol, dipropyl ether, dibutyl ether, two hexyl ethers, two alkane, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, dibutyl ethylene glycol ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-heptanone, dipropyl ketone, acetic acid 3-ethoxybutyl ester, acetic acid 1-methyl amyl ester, acetic acid 2-ethyl-butyl ester, acetic acid 2-(ethyl hexyl) ester, ethylene glycol acetate, glycol diacetate, Texacar PC, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl oxide, ethylene glycol ether, 2-(hexyloxy) ethanol, furfuryl alcohol, Diethylene Glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, Diethylene Glycol isopropyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monobutyl ether, 1-(Butoxyethoxy) propyl alcohol, propylene glycol methyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, DPE, Tripropylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol acetate, glycol diacetate, diethylene glycol monoethyl ether acetic ester, butyl carbitol acetate, 2-(2-ethoxy ethoxy) ethylhexoate, Diethylene Glycol acetic ester, triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, the organic solvent that the surface tension of the solvent of n-butyl lactate or isoamyl lactate etc. is low.
Wherein, preferred use 1-hexanol, hexalin, 1,2-ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, Diethylene Glycol isopropyl ether or diethylene glycol monobutyl ether (above also referred to as (E) composition).
These (E) compositions are preferably composition or employ 1 ~ 50 quality % of whole organic solvents contained in the aligning agent for liquid crystal of said composition.Wherein, preferred 1 ~ 45 quality %.More preferably 5 ~ 45 quality %, further preferred 5 ~ 40 quality %.
Composition of the present invention or employ in the aligning agent for liquid crystal of said composition, in the scope not damaging effect of the present invention, also can import the cross-linked compound with epoxy group(ing), isocyanate group, oxetanyl or cyclocarbonate radical, there is at least a kind of substituent cross-linked compound being selected from hydroxyl, hydroxyalkyl and low-grade alkoxy alkyl, or there is the cross-linked compound of polymerizability unsaturated link(age).These substituting groups or the polymerizability unsaturated link(age) of more than 2 must be had in cross-linked compound.
As the cross-linked compound with epoxy group(ing) or isocyanate group, such as bisphenol acetone glycidyl ether can be exemplified, novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, the amino diphenylene of four glycidyl group, four glycidyl group m-xylene diamine, two (amino-ethyl) hexanaphthene of four glycidyl group-1,3-, tetraphenyl glycidyl ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro ethanoyl diglycidylether, two (1-(2,3-glycidoxy)-1-trifluoromethyl-2,2, the 2-trifluoromethyl) benzene of 1,3-, two (2, the 3-glycidoxy) octafluorobiphenyl of 4,4-, triglycidyl group p-aminophenol, four glycidyl group m-xylene diamine, 2-(4-(2,3-glycidoxy) phenyl)-2-(4-(1, two (the 4-(2 of 1-, 3-glycidoxy) phenyl) ethyl) phenyl) propane or 1, two (4-(1-(the 4-(2 of 3-, 3-epoxy group(ing) propoxy-) phenyl)-1-(4-(1-(4-(2,3-glycidoxy phenyl)-1-methylethyl) phenyl) ethyl) phenoxy group)-2-propyl alcohol etc.
As the cross-linked compound with oxetanyl, it is the cross-linked compound with the oxetanyl shown at least 2 following formula [4].
[changing 73]
Specifically, be the cross-linked compound shown in following formula [4-1] ~ formula [4-11].
[changing 74]
(in formula [4-1], n represents the integer of 1 ~ 3).
[changing 75]
[changing 76]
[changing 77]
(in formula [4-7], n represents the integer of 1 ~ 3; In formula [4-8], n represents the integer of 1 ~ 3, and in formula [4-9], n represents the integer of 1 ~ 100).
[changing 78]
(in formula [4-11], n represents the integer of 1 ~ 10).
As the cross-linked compound with cyclocarbonate radical, it is the cross-linked compound with the cyclocarbonate radical shown at least 2 following formula [5].
[changing 79]
Specifically, be the cross-linked compound shown in following formula [5-1] ~ formula [5-37].
[changing 80]
[changing 81]
[changing 82]
[changing 83]
[changing 84]
[changing 85]
[changing 86]
[changing 87]
[changing 88]
[changing 89]
[changing 90]
[changing 91]
(in formula [5-24], n represents the integer of 1 ~ 10; In formula [5-25], n represents the integer of 1 ~ 10).
[changing 92]
[changing 93]
[changing 94]
[changing 95]
[changing 96]
(in formula [5-36], n represents the integer of 1 ~ 100; In formula [5-37], n represents the integer of 1 ~ 10).
Also can exemplify the polysiloxane with at least a kind of structure shown in following formula [5-38] ~ [5-40].
[changing 97]
(in formula [5-38] ~ [5-40], R 1, R 2, R 3, R 4and R 5the separately alkyl of the structure shown in expression [5], hydrogen atom, hydroxyl, carbon number 1 ~ 10, alkoxyl group, aliphatics ring or aromatic ring, at least 1 is the structure shown in formula [5]).
More specifically, the compound of following formula [5-41] and formula [5-42] can be exemplified.
[changing 98]
(in formula [5-42], n represents the integer of 1 ~ 10).
As having at least a kind of substituent cross-linked compound being selected from hydroxyl and alkoxyl group, such as can exemplify the aminoresin with hydroxyl or alkoxyl group, such as melamine resin, urea-formaldehyde resin, guanamine resin, glycolurilformaldehyde resins, succinic diamide-formaldehyde resin or ethylene urea-formaldehyde resin etc.Specifically, amino hydrogen atom can be used by methylol or alkoxy methyl or the melamine derivative that be instead of by methylol and alkoxy methyl, benzoguanamine derivative or glycoluril.This melamine derivative or benzoguanamine derivative also can exist with dimer or trimerical form.They are better on average have methylol or the alkoxy methyl of more than 3 less than 6 relative to every 1 triazine ring.
As the example of this type of melamine derivative or benzoguanamine derivative, every 1 triazine ring as commercially available product can be exemplified on average by MX-750 that 3.7 methoxymethyies instead of, MW-30 that every 1 triazine ring on average be instead of by 5.8 methoxymethyies (being Sanwa Chemical Co., Ltd (three and ケ ミ カ Le society) system above) and サ イ メ Le 300, 301, 303, 350, 370, 771, 325, 327, 703, the methoxymethylated trimeric cyanamide of 712 grades, サ イ メ Le 235, 236, 238, 212, 253, the methoxymethylated butoxymethyl trimeric cyanamide of 254 grades, サ イ メ Le 506, the butoxymethyl trimeric cyanamide of 508 grades, the carboxylic methoxymethylated isobutoxymethyl trimeric cyanamide of サ イ メ Le 1141 and so on, the methoxymethylated ethoxyl methyl benzoguanamine of サ イ メ Le 1123 and so on, the methoxymethylated butoxymethyl benzoguanamine of サ イ メ Le 1123-10 and so on, the butoxymethyl benzoguanamine of サ イ メ Le 1128 and so on, the carboxylic methoxymethylated ethoxyl methyl benzoguanamine (being Mitsui cyanamide Co., Ltd. (Mitsui サ イ ア Na ミ De society) system above) of サ イ メ Le 1125-80 and so on.As the example of glycoluril, the methoxyl group methylolation glycoluril etc. of methylolation glycoluril of the butoxymethyl glycoluril of サ イ メ Le 1170 and so on, サ イ メ Le 1172 and so on etc., パ ウ ダ ー リ Application Network 1174 and so on can be exemplified.
As benzene or the benzene phenoloid with hydroxyl or alkoxyl group, such as 1 can be exemplified, 3,5-tri-(methoxymethyl) benzene, 1,2,4-tri-(i-propoxymethyl) benzene, Isosorbide-5-Nitrae-bis-(sec-butoxymethyl) benzene, 2,6-dihydroxymethyl p-tert-butylphenols etc.
More specifically, the cross-linked compound shown in formula [6-1] ~ formula [6-48] that International Publication publication WO2011/132751 (2011.10.27 is open) 62nd ~ 66 pages records can be exemplified.
As the cross-linked compound with polymerizability unsaturated link(age), such as, there is in the molecule that can exemplify poly-(methyl) acrylate of trimethylolpropane tris (methyl) acrylate, three (methyl) acrylate, pentaerythritol, five (methyl) vinylformic acid dipentaerythritol ester, three (methyl) acryloyloxyethoxy TriMethylolPropane(TMP) or glycerine polyglycidyl ether etc. the cross-linked compound of 3 polymerizability unsaturated groups, further, two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid TEG ester, polyoxyethylene glycol two (methyl) acrylate, two (methyl) vinylformic acid propylene glycol ester, polypropylene glycol two (methyl) acrylate, two (methyl) vinylformic acid butanediol ester, two (methyl) vinylformic acid DOPCP, oxyethane bisphenol A-type two (methyl) acrylate, propylene oxide bisphenol type two (methyl) acrylate, two (methyl) vinylformic acid 1,6-hexylene glycol ester, two (methyl) glycerol acrylate, two (methyl) acrylate, pentaerythritol, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl glyceryl ether two (methyl) acrylate, there is in o-phthalic acid diglycidyl ester two (methyl) acrylate or hydroxy new pentane acid neopentyl glycol two (methyl) acrylate equimolecular the cross-linked compound of 2 polymerizability unsaturated groups, and, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxybutyl, (methyl) vinylformic acid 2-phenoxy group-2-hydroxy propyl ester, phthalic acid 2-(methyl) acryloxy-2-hydroxy propyl ester, (methyl) vinylformic acid 3-chlorine-2-hydroxyl propyl ester, glycerine list (methyl) acrylate, there is in the molecule of 2-(methyl) acryloyl-oxyethyl phosphoric acid ester or N-methylol (methyl) acrylamide etc. the cross-linked compound of 1 polymerizability unsaturated group.
The compound represented with following formula [7] can also be used.
[changing 99]
(in formula [7], E 1represent the group being selected from cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus or phenanthrene ring, E 2represent the group being selected from following formula [7a] or formula [7b], n represents the integer of 1 ~ 4).
[changing 100]
Above-claimed cpd is an example of cross-linked compound, is not limited to this.In addition, composition of the present invention or to employ cross-linked compound used in the aligning agent for liquid crystal of said composition can be a kind, also can of more than two kindsly combine.
Composition of the present invention or the content employing the cross-linked compound in the aligning agent for liquid crystal of said composition are preferably 0.1 ~ 150 mass parts relative to whole component of polymer 100 mass parts.Presenting target effect to make crosslinking reaction carry out, is more preferably 0.1 ~ 100 mass parts relative to whole component of polymer 100 mass parts, especially most preferably 1 ~ 50 mass parts.
As promoting the Charger transfer in liquid crystal orientation film after adopting the aligning agent for liquid crystal employing the present composition to make liquid crystal orientation film, promoting also can add the nitrogen heterocyclic ring amine compound shown in formula [M1] ~ [M156] that International Publication publication WO2011/132751 (2011.10.27 is open) 69th ~ 73 pages records by the compound of the electric charge release of the liquid crystal cell using this liquid crystal orientation film.This amine compound directly adds in composition also harmless, but preferably to make concentration with suitable solvent be add after the solution of 0.1 quality % ~ 10 quality %, preferably 1 quality % ~ 7 quality % again.As this solvent, as long as the organic solvent that can dissolve above-mentioned polymkeric substance is not particularly limited.
Composition of the present invention or employ said composition aligning agent for liquid crystal in the scope not damaging effect of the present invention, the resin coating after the aligning agent for liquid crystal coating improving composition or employ said composition or the film uniformity of liquid crystal orientation film and the compound of surface smoothness can be used.Also can use the compound etc. of the adaptation improving resin coating or liquid crystal orientation film and substrate.
As raising resin coating or the film uniformity of liquid crystal orientation film and the compound of surface smoothness, fluorine class tensio-active agent, siloxane type surfactants, nonionic surfactant etc. can be exemplified.
More specifically, such as エ Off ト ッ プ EF301 can be exemplified, EF303, EF352 (being Tuo Kaimu product Co., Ltd. (ト ー ケ system プ ロ ダ クツ society) system above), メ ガ Off ァ ッ Network F171, F173, R-30 (being Dainippon Ink and Chemicals, Inc (large Japanese イ Application キ society) system above), Off ロ ラ ー De FC430, FC431 (being Sumitomo 3M Co., Ltd. (Sumitomo ス リ ー エ system society) system above), ア サ ヒ ガ ー De AG710, サ ー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (being Asahi Glass Co., Ltd (Asahi Glass society) system above) etc.The usage rate of these tensio-active agents, relative to whole component of polymer 100 mass parts contained in composition or aligning agent for liquid crystal, is preferably 0.01 ~ 2 mass parts, is more preferably 0.01 ~ 1 mass parts.
As the concrete example of compound of adaptation that can improve resin coating or liquid crystal orientation film and substrate, the compound containing functional silanes shown below and the compound containing epoxy group(ing) can be exemplified.
Such as, 3-TSL 8330 can be exemplified, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTES of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) hexanaphthene of 1,3-or N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane etc.
Use can improve and the compound of adaptation of substrate when, preferably relative to composition or employ said composition aligning agent for liquid crystal in contained by whole component of polymer 100 mass parts be 0.1 ~ 30 mass parts, be more preferably 1 ~ 20 mass parts.If less than 0.1 mass parts, the effect that adaptation improves cannot be expected, if more than 30 mass parts, sometimes composition or employ said composition aligning agent for liquid crystal storage stability be deteriorated.
Composition of the present invention or employ in the aligning agent for liquid crystal of said composition, except above-mentioned poor solvent, cross-linked compound, raising resin coating or the film uniformity of liquid crystal orientation film and the compound of surface smoothness and make resin coating or liquid crystal orientation film and substrate closely sealed compound except, in the scope not damaging effect of the present invention, also can add dielectric medium and the conducting material of the object for reaching the electrical characteristic such as the specific inductivity that changes resin coating or liquid crystal orientation film and electroconductibility.
< resin coating >
Composition of the present invention is coated on substrate, after burning till, can be used as resin coating and uses.As substrate now used, according to target devices, the plastic base etc. of glass substrate, silicon wafer, vinylformic acid substrate and polycarbonate substrate etc. can be used.The coating process of composition is not particularly limited, but the method that industrial usual employing is undertaken by dip coating, rolling method, slot coated method, spin-coating method, spraying method, silk screen printing, offset printing, flexographic printing or ink jet method etc., these methods can use according to object.
Coated by composition after on substrate, the heating unit by hot-plate, heat-circulation type stove or IR (infrared rays) type stove etc. makes solvent evaporate and forms resin coating at 50 ~ 250 DEG C, preferably 80 ~ 200 DEG C, more preferably 80 ~ 150 DEG C.The thickness of the resin coating after burning till can be adjusted to 0.01 ~ 100 μm according to object.
< liquid crystal orientation film liquid crystal display device >
The aligning agent for liquid crystal employing the present composition is coated on substrate, after burning till, after carrying out orientation process by friction treatment or rayed etc., can be used as liquid crystal orientation film and use.In addition, when for vertical orientated purposes etc., even if do not carry out orientation process can be used as liquid crystal orientation film use yet.As substrate now used, as long as the high substrate of the transparency is not particularly limited, except glass substrate, the plastic base etc. of vinylformic acid substrate or polycarbonate substrate etc. also can be used.From the viewpoint of work simplification, preferably use the substrate of the ITO electrode etc. be formed with for liquid crystal drive.In addition, in reflection type liquid crystal display element, if be only limitted to one-sided substrate, also can use the opaque substrates such as silicon wafer, also can use the material of the reflected light such as aluminium as electrode now.
The coating process of aligning agent for liquid crystal is not particularly limited, but the method that industrial usual employing is undertaken by silk screen printing, offset printing, flexographic printing or ink jet method etc.As other coating processes, also have dip coating, rolling method, slot coated method, spin-coating method or spraying method etc., these methods can be used according to object.
Aligning agent for liquid crystal is coated after on substrate, at 50 ~ 250 DEG C, preferably 80 ~ 200 DEG C, more preferably 80 ~ 150 DEG C, make solvent evaporate by heating units such as hot-plate, heat-circulation type stove, IR (infrared rays) type stoves and form liquid crystal orientation film.If the thickness of the liquid crystal orientation film after burning till is blocked up, unfavorable in the power consumption of liquid crystal display device, if cross thin, the reliability of liquid crystal display device declines sometimes, is therefore preferably 5 ~ 300nm, is more preferably 10 ~ 100nm.When making liquid crystal horizontal alignment or tilted alignment, by friction, polarized UV rays irradiation etc., process is implemented to the liquid crystal orientation film after burning till.
Liquid crystal display device of the present invention, after obtaining the substrate of band liquid crystal orientation film by aforesaid method by the aligning agent for liquid crystal of present embodiment, is made the liquid crystal display device of liquid crystal cell by known method.
As the making method of liquid crystal cell, following method can be illustrated: namely, prepare a pair substrate being formed with liquid crystal orientation film, the liquid crystal orientation film of one piece of substrate scatters spacer, be in the mode of inner side by another block baseplate-laminating with liquid crystal aligning face, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with spacer after, baseplate-laminating is carried out the method etc. sealed.
Liquid crystal orientation film of the present invention is also preferred for by possessing the liquid crystal display device having liquid crystal layer between a pair substrate of electrode and form, manufacture through following operation, this operation is: between a pair substrate, configuration packet carries out the liquid-crystal composition of the polymerizable compound be polymerized containing at least one party utilized in active energy beam and heat, applies voltage while by the irradiation of active energy beam and add at least one party hankered and make polymerizable compound be polymerized between electrode.Here, as active energy beam, preferred ultraviolet.As ultraviolet, wavelength is 300 ~ 400nm, preferably 310 ~ 360nm.Under the occasion of being polymerized is carried out in utilization heating, Heating temperature is 40 ~ 120 DEG C, preferably 60 ~ 80 DEG C.In addition, also can carry out ultraviolet irradiation and heating simultaneously.
Above-mentioned liquid crystal display device controls the tilt angle of liquid crystal molecule by PSA (Polymer SustainedAlignment, polymer stabilizing orientation) mode.In PSA mode, a small amount of photopolymerizable compound, such as photopolymerization monomer is mixed in advance in liquid crystal material, after assembling liquid crystal cell, to photopolymerizable compound irradiation ultraviolet radiation etc. under the state of voltage liquid crystal layer being applied to regulation, the polymkeric substance generated is utilized to control the tilt angle of liquid crystal molecule.The state of orientation of liquid crystal molecule when polymkeric substance generates also can be remembered after removal of the voltage, therefore by controlling the electric field etc. formed in liquid crystal layer, can adjust the tilt angle of liquid crystal molecule.In addition, in PSA mode, do not need friction treatment, be therefore applicable to the formation being difficult to the liquid crystal layer being controlled the vertical orientating type of tilt angle by friction treatment.
Namely, liquid crystal display device of the present invention by with aforesaid method by aligning agent for liquid crystal of the present invention obtain band liquid crystal orientation film substrate after, make liquid crystal cell, by ultraviolet irradiation and add at least one party hankered and make polymerizable compound be polymerized, thus the orientation of control liquid crystal molecule.
If exemplify an example of the liquid crystal cell making PSA mode, following method can be exemplified: namely, prepare a pair substrate being formed with liquid crystal orientation film, the liquid crystal orientation film of one piece of substrate scatters spacer, be in the mode of inner side by another block baseplate-laminating with liquid crystal aligning face, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with spacer after, baseplate-laminating is carried out the method etc. sealed.
Can mix in liquid crystal and carry out by heating or irradiation ultraviolet radiation the polymerizable compound that is polymerized.As polymerizable compound, the compound of the polymerizability unsaturated group such as acrylate-based or methacrylate based with more than 1 can be exemplified in molecule.Now, polymerizable compound is preferably 0.01 ~ 10 mass parts relative to liquid crystal composition 100 mass parts, more preferably 0.1 ~ 5 mass parts.If polymerizable compound is less than 0.01 mass parts, then polymerizable compound is not polymerized and cannot carries out the tropism control of liquid crystal, if more than 10 mass parts, then unreacted polymerizable compound increases and causes the burning screen characteristics of liquid crystal display device to decline.
After making liquid crystal cell, by apply liquid crystal cell to exchange or direct current voltage, to heat or irradiation ultraviolet radiation and polymerizable compound is polymerized on one side.By this, the orientation of liquid crystal molecule can be controlled.
And, aligning agent for liquid crystal of the present invention also can perform well in liquid crystal display device, this liquid crystal display device by possess between a pair substrate of electrode, there is liquid crystal layer and form and through following operation obtain: namely, between a pair substrate, configuration packet carries out the liquid crystal orientation film of the polymerizable group be polymerized containing at least one party utilized in active energy beam and heat, between electrode, apply voltage.Here, as active energy beam, preferred ultraviolet.As ultraviolet, wavelength is 300 ~ 400nm, preferably 310 ~ 360nm.Under the occasion of being polymerized is carried out in utilization heating, Heating temperature is 40 ~ 120 DEG C, preferably 60 ~ 80 DEG C.In addition, also can carry out ultraviolet irradiation and heating simultaneously.
At least one party in active energy beam and heat is utilized and the liquid crystal orientation film of the polymerizable group be polymerized in order to obtain to comprise, the method of adding the compound containing this polymerizable group in aligning agent for liquid crystal can be exemplified, and use the method for the component of polymer containing polymerizable group.Aligning agent for liquid crystal of the present invention contains to have and utilizes heat or ultraviolet irradiation and the specific compound at the double bond position of reacting, so by ultraviolet irradiation and can add the orientation that at least one party hankered controls liquid crystal molecule.
If exemplify the example that liquid crystal cell makes, following method can be exemplified: namely, prepare a pair substrate being formed with liquid crystal orientation film, the liquid crystal orientation film of one piece of substrate scatters spacer, be in the mode of inner side by another block baseplate-laminating with liquid crystal aligning face, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with spacer after, baseplate-laminating is carried out the method etc. sealed.
After making liquid crystal cell, by the voltage to liquid crystal cell applying interchange or direct current, while heating or irradiation ultraviolet radiation, the orientation of liquid crystal molecule can be controlled by this.
The liquid crystal display device that use as above aligning agent for liquid crystal of the present invention is made excellent in reliability, is applicable to the LCD TV etc. of large picture and high-resolution.
Embodiment
Below, the present invention will be described in more detail to exemplify embodiment, but the present invention is not limited to this.
Abbreviation used in synthesis example, embodiment and comparative example is as follows.
(there is the diamine compound of carboxyl)
A1:3,5-diaminobenzoic acid (diamine compound shown in following formula [A1])
A2:2,5-diaminobenzoic acid (diamine compound shown in following formula [A2])
[changing 101]
(the 2nd diamine compound)
B1:1,3-diamino-4-[4-(trans-4-n-heptyl cyclohexyl) phenoxy group] benzene (diamine compound shown in following formula [B1])
B2:1,3-diamino-4-[4-(trans-4-n-heptyl cyclohexyl) phenoxymethyl] benzene (diamine compound shown in following formula [B2])
B3:1,3-diamino-4-{4-[trans-4-(trans-4-n-pentyl cyclohexyl) cyclohexyl] phenoxy group } benzene (diamine compound shown in following formula [B3])
B4: the diamine compound shown in following formula [B4]
B5:1,3-diamino-4-(octadecane oxygen base) benzene (diamine compound shown in following formula [B5])
B6: the diamine compound shown in following formula [B6]
[changing 102]
[changing 103]
[changing 104]
(other diamine compound)
C1: Ursol D (diamine compound shown in following formula [C1])
C2: mphenylenediamine (diamine compound shown in following formula [C2])
[changing 105]
(tetracarboxylic acid composition)
D1:1,2,3,4-tetramethylene tetracarboxylic dianhydride (tetracarboxylic dianhydride shown in following formula [D1])
D2: two rings [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride (tetracarboxylic dianhydride shown in following formula [D2])
D3: the tetracarboxylic dianhydride shown in following formula [D3]
D4: the tetracarboxylic dianhydride shown in following formula [D4]
[changing 106]
(alkoxy silane monomer)
MPMS:3-methacryloxypropyl trimethoxy silane (alkoxy silane monomer shown in formula of the present invention [A2])
UPS:3-ureidopropyltriethoxysilane (alkoxy silane monomer shown in formula of the present invention [A2])
TEOS: tetraethoxysilane (alkoxy silane monomer shown in formula of the present invention [A3])
((A) of the present invention composition (specific solvent))
PGME: propylene glycol monomethyl ether (solvent shown in formula of the present invention [1a-1])
MCS: ethylene glycol monomethyl ether (solvent shown in formula of the present invention [1b-1])
ECS: ethylene glycol monoethyl ether (solvent shown in formula of the present invention [1b-2])
PCS: ethylene glycol ether (solvent shown in formula of the present invention [1b-3])
[changing 107]
((D) of the present invention composition (other organic solvent))
NMP:N-N-methyl-2-2-pyrrolidone N-
NEP:N-ethyl-2-pyrrolidone
γ-BL: gamma-butyrolactone
((E) of the present invention composition (other organic solvent))
BCS: ethylene glycol monobutyl ether
(molecular weight determination of polyimide precursor and polyimide)
Polyimide precursor in synthesis example and the molecular weight of polyimide use normal temperature gel permeation chromatography (GPC) device (GPC-101) (Showa Denko K. K (Showa Electricity work society) system) and post (KD-803, KD-805) (Shodex Co., Ltd. (Shodex society) system) to measure in accordance with the following methods.
Column temperature: 50 DEG C
Elutriant: N, N'-dimethyl formamide (as additive, lithiumbromide hydrate (LiBrH2O) is 30mmol/L, phosphoric anhydride crystallization (o-phosphoric acid) is 30mmol/L, tetrahydrofuran (THF) (THF) is 10ml/L (liter)).
Flow velocity: 1.0ml/ minute
Calibration curve making standard test specimen: TSK standard polyethylene oxide (molecular weight is about 900000,150000,100000 and 30000) ((East ソ ー society of TOSOH Co., Ltd) is made) and polyoxyethylene glycol (molecular weight is about 12000,4000 and 1000) (Polymer Laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) system).
(mensuration of the imide rate of polyimide)
The imide rate of the polyimide in synthesis example measures as follows.Polyimide powder 20mg is joined NMR (nucleus magnetic resonance) stopple coupon (NMR stopple coupon specification, φ (wasteland's science Co., Ltd. (wasteland's science society) system), add deuterated dimethyl sulfoxide (DMSO-d6,0.05 quality %TMS (tetramethylsilane) mixture) (0.53ml), apply ultrasonic wave and make it dissolve completely.This solution NMR determinator (JNW-ECA500) (NEC Dan Ding Co., Ltd. (Japanese Electricity デ ー タ system society) system) is determined to the proton N MR of 500MHz.Imide rate is tried to achieve as follows: the proton coming from unconverted structure before and after imidization is decided to be standard proton, uses the peak integrated value of this proton and the proton peak integrated value of the NH base from amido acid that occurs near 9.5 ~ 10.0ppm to be tried to achieve by following formula.
Imide rate (%)=(1-α x/y) × 100
In above formula, x is the proton peak integrated value of the NH base from amido acid, and y is the peak integrated value of reference proton, and when α is polyamic acid (imide rate is 0%), reference proton is relative to the number ratio of NH matrix of an amido acid.
[synthesis as the particular polymers (polyimide precursor and polyimide) of the present invention (B) composition]
< synthesis example 1>
By D1 (3.12g, 15.9mmol), A1 (2.42g, 15.9mmol) mixing in PGME (49.9g), makes it react 8 hours in 40 DEG C, obtains the polyamic acid solution (1) of resin solid content concentration 10.0 quality %.The number-average molecular weight of this polyamic acid is 10100, and weight-average molecular weight is 23500.
< synthesis example 2>
By D2 (8.42g, 33.7mmol), A2 (6.40g, 42.1mmol) mixing in NMP (27.7g), after making it react 5 hours in 80 DEG C, add D1 (1.65g, 8.41mmol) with NMP (22.2g), make it react 6 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (6.52g), the pyridine (5.05g) as imidization catalyst, make it react 4 hours in 90 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (2).The imide rate of this polyimide is 55%, and number-average molecular weight is 12200, and weight-average molecular weight is 33000.
< synthesis example 3>
By D2 (1.82g, 7.27mmol), B1 (2.30g, 6.04mmol), A1 (0.92g, 6.05mmol) mixing in PGME (29.7g), after making it react 5 hours in 80 DEG C, add D1 (0.95g, 4.84mmol) with PGME (24.3g), make it react 8 hours in 40 DEG C, obtain the polyamic acid solution (3) of resin solid content concentration 10.0 quality %.The number-average molecular weight of this polyamic acid is 12500, and weight-average molecular weight is 34100.
< synthesis example 4>
By D2 (3.83g, 15.3mmol), B1 (4.86g, 12.8mmol), A1 (1.94g, 12.8mmol) mixing in NMP (20.8g), after making it react 5 hours in 80 DEG C, add D1 (2.00g, 10.2mmol) with NMP (17.0g), make it react 6 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (5.16g), the pyridine (4.00g) as imidization catalyst, make it react 2 hours in 80 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (4).The imide rate of this polyimide is 61%, and number-average molecular weight is 15200, and weight-average molecular weight is 38300.
< synthesis example 5>
By D2 (6.12g, 24.5mmol), B1 (4.66g, 12.2mmol), A1 (2.33g, 15.3mmol), C1 (0.33g, 3.05mmol) mixing in NMP (24.2g), after making it react 5 hours in 80 DEG C, add D1 (1.20g, 6.12mmol) and NMP (19.8g), make it react 6 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (5.33g), the pyridine (4.13g) as imidization catalyst, make it react 2 hours in 80 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (5).The imide rate of this polyimide is 58%, and number-average molecular weight is 16100, and weight-average molecular weight is 39100.
< synthesis example 6>
By D2 (4.91g, 19.6mmol), B2 (3.32g, 8.41mmol), A1 (2.13g, 14.0mmol), B6 (1.14g, 5.61mmol) mixing in NMP (21.7g), after making it react 5 hours in 80 DEG C, add D1 (1.65g, 8.41mmol) and NMP (17.8g), make it react 6 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (5.50g), the pyridine (4.25g) as imidization catalyst, make it react 3 hours in 80 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (6).The imide rate of this polyimide is 51%, and number-average molecular weight is 17900, and weight-average molecular weight is 41200.
< synthesis example 7>
By D2 (5.06g, 20.2mmol), B3 (3.75g, 8.67mmol), A2 (2.63g, 17.3mmol), C2 (0.31g, 2.87mmol) mixing in NMP (22.2g), after making it react 5 hours in 80 DEG C, add D1 (1.70g, 8.67mmol) and NMP (18.2g), make it react 6 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (5.64g), the pyridine (4.38g) as imidization catalyst, make it react 3 hours in 80 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (7).The imide rate of this polyimide is 60%, and number-average molecular weight is 18900, and weight-average molecular weight is 42900.
< synthesis example 8>
By D2 (6.28g, 25.1mmol), B4 (2.32g, 4.71mmol), A1 (4.06g, 26.7mmol) mixing in NMP (22.9g), after making it react 6 hours in 80 DEG C, add D1 (1.23g, 6.27mmol) with NMP (18.7g), make it react 6 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (5.77g), the pyridine (4.47g) as imidization catalyst, make it react 3.5 hours in 80 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (8).The imide rate of this polyimide is 45%, and number-average molecular weight is 15100, and weight-average molecular weight is 36500.
< synthesis example 9>
By D3 (6.51g, 29.0mmol), B1 (3.32g, 8.72mmol), A1 (3.09g, 20.3mmol) mixing in NMP (38.8g), make it react 5 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (5.74g), the pyridine (4.45g) as imidization catalyst, make it react 3 hours in 80 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (9).The imide rate of this polyimide is 60%, and number-average molecular weight is 13100, and weight-average molecular weight is 36200.
< synthesis example 10>
By D3 (6.54g, 29.2mmol), B5 (3.30g, 8.76mmol), B6 (1.19g, 5.85mmol), A2 (2.22g, 14.6mmol) mixing in NMP (39.7g), make it react 5 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (5.62g), the pyridine (4.36g) as imidization catalyst, make it react 3 hours in 80 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (10).The imide rate of this polyimide is 55%, and number-average molecular weight is 12100, and weight-average molecular weight is 32900.
< synthesis example 11>
By D4 (5.17g, 17.2mmol), B2 (3.40g, 8.62mmol), C2 (0.47g, 4.35mmol), A2 (2.40g, 15.8mmol) mixing in NMP (22.6g), after making it react 5 hours in 80 DEG C, add D1 (2.25g, 11.5mmol) and NMP (18.5g), make it react 5.5 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (6.45g), the pyridine (3.35g) as imidization catalyst, make it react 1.5 hours in 40 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (11).The imide rate of this polyimide is 59%, and number-average molecular weight is 19100, and weight-average molecular weight is 40600.
< synthesis example 12>
By D4 (4.06g, 13.5mmol), B1 (3.09g, 8.12mmol), B6 (1.65g, 8.12mmol), A1 (1.64g, 10.8mmol) mixes, after making it react 5 hours in 80 DEG C in NMP (21.6g), add D1 (2.65g, 13.5mmol) with NMP (17.7g), make it react 5.5 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (6.33g), the pyridine (3.27g) as imidization catalyst, make it react 1.5 hours in 40 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (12).The imide rate of this polyimide is 55%, and number-average molecular weight is 17800, and weight-average molecular weight is 39100.
< synthesis example 13>
By D1 (2.85g, 14.5mmol), A1 (2.21g, 14.5mmol) mixing in NMP (15.2g), makes it react 8 hours in 40 DEG C, obtains the polyamic acid solution (13) of resin solid content concentration 25.0 quality %.The number-average molecular weight of this polyamic acid is 18100, and weight-average molecular weight is 35200.
< synthesis example 14>
By D2 (4.11g, 16.4mmol), B1 (5.22g, 13.7mmol), A1 (2.09g, 13.7mmol) mixing in NMP (22.4g), after making it react 5 hours in 80 DEG C, add D1 (2.15g, 11.0mmol) and NMP (18.3g), make it react 6 hours in 40 DEG C, obtain the polyamic acid solution (14) of resin solid content concentration 25.0 quality %.The number-average molecular weight of this polyamic acid is 19100, and weight-average molecular weight is 45800.
< synthesis example 15>
By D2 (4.02g, 16.1mmol), B1 (5.09g, 13.4mmol), C1 (1.45g, 13.4mmol) mixing in NMP (20.9g), after making it react 5 hours in 80 DEG C, add D1 (2.10g, 10.7mmol) and NMP (17.1g), make it react 5.5 hours in 40 DEG C, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution (40.0g) of gained, add NMP with after being diluted to 6 quality %, add diacetyl oxide (5.40g), the pyridine (4.18g) as imidization catalyst, make it react 3 hours in 80 DEG C.This reaction soln is put in methyl alcohol (650ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (15).The imide rate of this polyimide is 60%, and number-average molecular weight is 16000, and weight-average molecular weight is 39200.
Particular polymers of the present invention (imide precursor and polyimide) is shown in table 1.
[table 1]
* 1: polyamic acid.
[synthesis of the alkoxy silane monomer shown in formula of the present invention [A1]]
< synthesis example 16>
[changing 108]
In the 500ml four-hole boiling flask possessing magnetic stirring apparatus, drop into compound (1) (30.0g), salt of wormwood (25.2g), DMF (120g), drip allyl bromide 98 (22.1g) in 25 DEG C.Then, stir 11 hours in 50 DEG C.With ethyl acetate (500g) dilute reaction solution, then pure water (200g) is used to clean organic phase 3 times.Make organic phase dry with sodium sulfate, after organic phase being filtered, concentrate drying is carried out to filtrate, obtain compound (2) and (must measure: 34.8g, yield: 100%).
1H-NMR(400MHz，CDCl 3，δppm)：0.90(3H，t，J＝7.2Hz,3H)，
0.99-1.09(2H，m)1.18-1.46(11H，m)，1.84-1.89(4H，m)，
2.37-2.44(1H，m)，4.51(2H，dt，J＝5.4Hz，1.6Hz)，
5.26(1H，dq，J＝10.6Hz，1.6Hz)，5.40(1H，dq，J＝17.2Hz，1.6Hz)，
6.07(1H，ddd，J＝17.2Hz，10.6Hz，5.4Hz)，
6.83(2H，dd，J＝8.8Hz，2.9Hz)，7.10(2H，dd，J＝8.8Hz，2.9Hz).
In the 300ml four-hole boiling flask possessing magnetic stirring apparatus, drop into compound (2) (20.0g), toluene (120g), stir in 25 DEG C.Then, after adding Karst catalyzer (xylene solution of the 0.1mol/L of platinum (0)-1,1,3,3-tetramethyl disiloxane title complex) (700 μ l), Trimethoxy silane (12.4ml) is dripped.After stirring 29 hours in 25 DEG C, concentrate drying is carried out to reaction solution, obtain crude product.Underpressure distillation is carried out to this crude product, outside temperature: distillate under the condition of 245 DEG C/pressure: 0.8torr, obtain the alkoxy silane monomer (A) shown in formula of the present invention [A1] and (must measure: 12.2g, yield: 43%).
1H-NMR(400MHz，CDCl 3，δppm)：0.76-0.82(2H，m)，
0.89(3H，t，J＝7.2Hz)，0.98-1.08(2H，m)，1.18-1.45(11H，m)，
1.84-1.93(6H，m)，2.36-2.43(1H，m)，3.58(9H，s)，
3.91(2H，t，J＝6.8Hz)，6.81(2H，d，J＝8.8Hz)，
7.08(2H，d，J＝8.8Hz).
[synthesis as the specific polysiloxane of the present invention (C) composition]
< synthesis example 17>
In 200ml tetra-mouthfuls of reaction flasks that thermometer and return line are housed, to be mixed in PGME (28.3g), TEOS (32.5g), synthesis example 16 obtained alkoxy silane monomer (A) (4.10g), MPMS (7.45g) and be modulated into the solution of alkoxy silane monomer.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using PGME (14.2g), water (10.8g), the solution that modulates as oxalic acid (0.70g) mixing of catalyzer, then stir 30 minutes in 25 DEG C.Afterwards, use oil bath reflux after 30 minutes, adding the UPS content modulated in advance is the methanol solution (1.20g) of 92 quality % and the mixing solutions of PGME (0.90g).After refluxing 30 minutes, naturally cooling obtains SiO again 2converted score is the polysiloxane solution (1) of 12 quality %.
< synthesis example 18>
In 200ml tetra-mouthfuls of reaction flasks that thermometer and return line are housed, to be mixed in MCS (28.3g), TEOS (32.5g), synthesis example 16 obtained alkoxy silane monomer (A) (4.10g), MPMS (7.45g) and be modulated to the solution of alkoxy silane monomer.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using MCS (14.2g), water (10.8g), the solution that modulates as oxalic acid (0.70g) mixing of catalyzer, then stir 30 minutes in 25 DEG C.Afterwards, use oil bath reflux after 30 minutes, adding the UPS content modulated in advance is the methanol solution (1.20g) of 92 quality % and the mixing solutions of MCS (0.90g).After refluxing 30 minutes, naturally cooling obtains SiO again 2converted score is the polysiloxane solution (2) of 12 quality %.
< synthesis example 19>
In 200ml tetra-mouthfuls of reaction flasks that thermometer and return line are housed, to be mixed in ECS (28.3g), TEOS (32.5g), synthesis example 16 obtained alkoxy silane monomer (A) (4.10g), MPMS (7.45g) and be modulated into the solution of alkoxy silane monomer.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using ECS (14.2g), water (10.8g), the solution that modulates as oxalic acid (0.70g) mixing of catalyzer, then stir 30 minutes in 25 DEG C.Afterwards, use oil bath reflux after 30 minutes, adding the UPS content modulated in advance is the methanol solution (1.20g) of 92 quality % and the mixing solutions of ECS (0.90g).After refluxing 30 minutes, naturally cooling obtains SiO again 2converted score is the polysiloxane solution (3) of 12 quality %.
< synthesis example 20>
In 200ml tetra-mouthfuls of reaction flasks that thermometer and return line are housed, to be mixed in PCS (28.3g), TEOS (32.5g), synthesis example 16 obtained alkoxy silane monomer (A) (4.10g), MPMS (7.45g) and be modulated into the solution of alkoxy silane monomer.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using PCS (14.2g), water (10.8g), the solution that modulates as oxalic acid (0.70g) mixing of catalyzer, then stir 30 minutes in 25 DEG C.Afterwards, use oil bath reflux after 30 minutes, adding the UPS content modulated in advance is the methanol solution (1.20g) of 92 quality % and the mixing solutions of PCS (0.90g).After refluxing 30 minutes, naturally cooling obtains SiO again 2converted score is the polysiloxane solution (4) of 12 quality %.
< synthesis example 21>
In 200ml tetra-mouthfuls of reaction flasks that thermometer and return line are housed, to be mixed in PGME (25.4g), TEOS (20.0g), synthesis example 16 obtained alkoxy silane monomer (A) (8.20g), MPMS (19.9g) and be modulated into the solution of alkoxy silane monomer.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using PGME (12.7g), water (10.8g), the solution that modulates as oxalic acid (1.10g) mixing of catalyzer, then stir 30 minutes in 25 DEG C.Afterwards, use oil bath reflux after 30 minutes, adding the UPS content modulated in advance is the methanol solution (1.20g) of 92 quality % and the mixing solutions of PGME (0.90g).After refluxing 30 minutes, naturally cooling obtains SiO again 2converted score is the polysiloxane solution (5) of 12 quality %.
< synthesis example 22>
In 200ml tetra-mouthfuls of reaction flasks that thermometer and return line are housed, to be mixed in PGME (29.2g), TEOS (38.8g), synthesis example 16 obtained alkoxy silane monomer (A) (4.10g) and to be modulated into the solution of alkoxy silane monomer.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using PGME (14.6g), water (10.8g), the solution that modulates as oxalic acid (0.50g) mixing of catalyzer, then stir 30 minutes in 25 DEG C.Afterwards, use oil bath reflux after 30 minutes, adding the UPS content modulated in advance is the methanol solution (1.20g) of 92 quality % and the mixing solutions of PGME (0.90g).After refluxing 30 minutes, naturally cooling obtains SiO again 2converted score is the polysiloxane solution (6) of 12 quality %.
< synthesis example 23>
In 200ml tetra-mouthfuls of reaction flasks that thermometer and return line are housed, be mixed into PGME (31.6g), TEOS (41.7g) and be modulated into the solution of alkoxy silane monomer.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using PGME (15.8g), water (10.8g), the solution that modulates as oxalic acid (0.20g) mixing of catalyzer, then stir 30 minutes in 25 DEG C.Afterwards, use oil bath reflux after 60 minutes, naturally cooling obtains SiO 2converted score is the polysiloxane solution (7) of 12 quality %.
Specific polysiloxane (polysiloxane solution) of the present invention is shown in table 2.
[table 2]
[manufacture of composition of the present invention and aligning agent for liquid crystal]
The Production Example of composition is described in following embodiment 1 ~ embodiment 27, comparative example 1 ~ comparative example 7.In addition, these compositions are also for the evaluation of aligning agent for liquid crystal.
Composition of the present invention and aligning agent for liquid crystal are shown in table 3 ~ table 5.
Use composition obtained in examples and comparative examples of the present invention or aligning agent for liquid crystal, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [evaluation of the ink-jet application of aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell], [evaluation (common structure cell) of liquid crystal aligning], [making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning] and [evaluation of voltage retention].Its condition is as described below.
[evaluation of the coating of composition and aligning agent for liquid crystal]
Pressure filtration is carried out to the membrane filter that composition fine pore obtained in examples and comparative examples of the present invention is 1 μm, uses the solution obtained therefrom to carry out the evaluation of coating.Coating uses spin coater (1H-D7) (three large bamboo hat with a conical crown and broad brim Co., Ltd. (ミ カ サ society) system).Coating is by spin coating on the ito surface of the substrate with 30 × 40mmITO electrode cleaned with pure water and IPA (Virahol) (long 40mm × wide 30mm, thick 0.7mm), from be applied to predrying till time be 30 seconds, predryingly carry out under 80 DEG C of heating condition of 5 minutes on hot plate.
Then, the evaluation of the pore of gained resin coating is carried out.The evaluation of the pore of resin coating is undertaken by visual observation resin coating under sodium vapor lamp.Specifically count the stomatal number that resin coating is identified, stomatal number more at least this evaluation is more excellent.
In addition, obtained in examples and comparative examples of the present invention composition can be used for aligning agent for liquid crystal.Therefore, the result of the coating of obtained in the present embodiment and comparative example resin coating is also as the result of the printing of liquid crystal orientation film.
The stomatal number of resin coating (liquid crystal orientation film) obtained in embodiment shown in table 6 ~ table 8 and comparative example.
[evaluation of the ink-jet application of aligning agent for liquid crystal]
With the membrane filter that fine pore is 1 μm, pressure filtration is carried out to aligning agent for liquid crystal (16) obtained in aligning agent for liquid crystal (9) obtained in embodiments of the invention 9 and embodiment 16, uses the solution obtained therefrom to carry out the evaluation of ink-jet application.Ink-jet application machine uses HIS-200 (Hitachi's device counts Co., Ltd. (Hitachi プ ラ Application ト テ Network ノ ロ ジ ー society) system).Coating is by ITO (tin indium oxide) the evaporation substrate cleaned with pure water and IPA (Virahol), surface covered be 70 × 70mm, injector spacing is 0.423mm, sweep span is 0.5mm, surface covered is 40mm/ second, from be applied to predrying till time be 60 seconds, predryingly carry out in 70 DEG C of heating condition of 5 minutes on hot plate.
The evaluation of the pore of gained liquid crystal orientation film is carried out under the condition identical with the evaluation of the coating of aligning agent for liquid crystal [composition with].
The stomatal number of liquid crystal orientation film obtained in embodiment shown in table 6 and table 7.
[making (common structure cell) of liquid crystal cell]
Pressure filtration is carried out to the membrane filter that aligning agent for liquid crystal fine pore obtained in examples and comparative examples of the present invention is 1 μm, use the solution obtained therefrom, spin coating on the ito surface of the substrate with 30 × 40mmITO electrode cleaned with pure water and IPA (Virahol) (long 40mm × wide 30mm, thick 0.7mm), obtains in 100 DEG C of heat treated 5 minutes the ito substrate that thickness is the band polyimide liquid crystal direct action membrane of 100nm on hot plate.To the coated surface roller footpath of this ito substrate be 120mm friction gear and use artificial silk cloth roller rotating speed be 1000rpm, roller gait of march is 50mm/ second, intrusion carries out friction treatment under being the condition of 0.1mm.
Prepare the ito substrate of two pieces of band liquid crystal orientation films, inner side is in and the mode clipping the spacer of 6 μm is assembled to make liquid crystal orientation film, printing and sealing agent (XN-1500T, Mitsui Chemicals, Inc (Mitsui Chemicals society) makes).Then, after fitting to make the liquid crystal orientation film mode relative with another block substrate, negative crystal born of the same parents are made by within 90 minutes, being cured in 120 DEG C of heat treated in thermal cycling type cleaning stove by sealing agent.Adopt decompression injection method to inject liquid crystal in this negative crystal born of the same parents, inlet sealing is obtained liquid crystal cell (common structure cell).
In addition, in the liquid crystal cell using aligning agent for liquid crystal (28) ~ aligning agent for liquid crystal (30) obtained in aligning agent for liquid crystal (1) ~ aligning agent for liquid crystal (3) obtained in embodiment 1 ~ embodiment 3, comparative example 1 ~ comparative example 3, use nematic liquid crystal (MLC-2003) (Merck & Co., Inc. (メ ルク society) system).
In addition, using aligning agent for liquid crystal (4) ~ aligning agent for liquid crystal (8) obtained in embodiment 4 ~ embodiment 8, aligning agent for liquid crystal (10) ~ aligning agent for liquid crystal (15) obtained in embodiment 10 ~ embodiment 15, in the liquid crystal cell of aligning agent for liquid crystal (the 31) ~ aligning agent for liquid crystal (34) obtained in aligning agent for liquid crystal (17) ~ aligning agent for liquid crystal (27) obtained in embodiment 17 ~ embodiment 27 and comparative example 4 ~ comparative example 7, use nematic liquid crystal (MLC-6608) (Merck Japanese firm (メ Le Network ジ ャ パ Application society) system).
[evaluation (common structure cell) of liquid crystal aligning]
Liquid crystal cell obtained in above-mentioned [making (common structure cell) of liquid crystal cell] is used to carry out the evaluation of liquid crystal aligning.The evaluation of liquid crystal aligning observes liquid crystal cell with polarizing microscope (ECLIPSEE600WPOL, Nikon Corp. (ニ コ Application society) makes), confirms there is No yield point defect.Specifically the liquid crystal cell having no orientation defect is decided to be in this evaluation excellence (showing to be good in table 6 ~ table 8).
The result of the liquid crystal aligning obtained in embodiment shown in table 6 ~ table 8 and comparative example.
[making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning]
To aligning agent for liquid crystal (7) obtained in embodiment 7, aligning agent for liquid crystal (12) obtained in embodiment 12, the aligning agent for liquid crystal (26) obtained in aligning agent for liquid crystal (14) obtained in embodiment 14 and embodiment 26 carries out pressure filtration with the membrane filter that fine pore is 1 μm, use the solution obtained therefrom, at the center cleaned with pure water and IPA (Virahol) with the substrate (long 40mm × wide 30mm of the ITO electrode of 10mm × 40mm, thick 0.7mm) and center be the substrate (long 40mm × wide 30mm of the ITO electrode of 20 μm with the pattern spacing of 10mm × 10mm, thick 0.7mm) ito surface on spin coating, the polyimide coating film that thickness is 100nm is obtained on hot plate in 100 DEG C of heat treated 5 minutes.After having cleaned this coated surface with pure water, in thermal cycling type cleaning stove, obtain the substrate being with liquid crystal orientation film in 100 DEG C of heat treated 15 minutes.
By the substrate of this band liquid crystal orientation film to make liquid crystal orientation film be in inner side and the mode clipping the spacer of 6 μm assembles, with sealing agent by bonding around and make negative crystal born of the same parents.Decompression injection method is adopted to inject liquid crystal to this negative crystal born of the same parents, inlet sealing is obtained liquid crystal cell, this liquid crystal is the liquid crystal being mixed into the polymerizable compound (1) shown in following formula and obtaining in nematic liquid crystal (MLC-6608) (Merck Japanese firm system), and polymerizable compound (1) is 0.3 quality % relative to nematic liquid crystal (MLC-6608) 100 quality %.
[changing 109]
For the liquid crystal cell of gained, apply the voltage exchanging 5V, while use the metal halide lamp that illumination is 60mW, the wavelength of shielding below 350nm, carrying out converts with 365nm counts 20J/cm 2uviolizing, obtain the liquid crystal cell (PSA structure cell) that is under control of liquid crystal aligning direction.It is 50 DEG C to the temperature in irradiating unit during liquid crystal cell irradiation ultraviolet radiation.
The response speed of the liquid crystal before determining the uviolizing of this liquid crystal cell and after uviolizing.Response speed measures from transmissivity 90% to the T90 → T10 of transmissivity 10%.
PSA structure cell obtained in embodiment is compared with the liquid crystal cell before uviolizing, and the response speed of the liquid crystal cell after uviolizing accelerates, and the differently-oriented directivity therefore confirming liquid crystal is controlled.In addition, for arbitrary liquid crystal cell by using the observation of polarizing microscope (ECLIPSE E600WPOL) (Nikon Corp.), liquid crystal orientation equably is all confirmed.
[evaluation of voltage retention]
At the temperature of 80 DEG C, liquid crystal cell obtained in above-mentioned [making (common structure cell) of liquid crystal cell] is applied to the voltage 60 μ s of 1V, voltage after measuring 16.67ms and after 50ms, can keep voltage how much illustrating as voltage retention (also becoming VHR).In addition, measure and use voltage retention determinator (VHR-1) (Toyo Corp. (East Yang テ Network ニ カ society) system), at voltage: ± 1V, pulse width: 60 μ s, frame period: carry out under the imposing a condition of 16.67ms or 50ms.
The voltage retention obtained in embodiment shown in table 9 and comparative example.
< embodiment 1>
The resin solid content concentration obtained in the synthetic method by synthesis example 1 is in polyamic acid solution (1) (12.0g) of 10.0 quality %, adds PGME (10.5g), stirs 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 23 2converted score is polysiloxane solution (7) (2.50g) of 12 quality %, obtains composition (1) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (1) also as aligning agent for liquid crystal (1) for evaluate.
Use composition (1) and the aligning agent for liquid crystal (1) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 2>
The resin solid content concentration obtained in the synthetic method by synthesis example 1 is in polyamic acid solution (1) (10.5g) of 10.0 quality %, add PGME (10.5g), γ-BL (1.27g), stir 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 23 2converted score is polysiloxane solution (7) (4.71g) of 12 quality %, obtains composition (2) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (2) also as aligning agent for liquid crystal (2) for evaluate.
Use composition (2) and the aligning agent for liquid crystal (2) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 3>
In polyimide powder (2) (1.34g) that the synthetic method by synthesis example 2 is obtained, add PGME (28.0g), NMP (4.20g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 23 2converted score is polysiloxane solution (7) (11.2g) of 12 quality %, obtains composition (3) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (3) also as aligning agent for liquid crystal (3) for evaluate.
Use composition (3) and the aligning agent for liquid crystal (3) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 4>
The resin solid content concentration obtained in the synthetic method by synthesis example 3 is in polyamic acid solution (3) (13.5g) of 10.0 quality %, adds PGME (11.8g), stirs 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 21 2converted score is polysiloxane solution (5) (2.81g) of 12 quality %, obtains composition (4) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (4) also as aligning agent for liquid crystal (4) for evaluate.
Use composition (4) and the aligning agent for liquid crystal (4) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell], [evaluation (common structure cell) of liquid crystal aligning] and [evaluation of voltage retention] under these conditions.
< embodiment 5>
The resin solid content concentration obtained in the synthetic method by synthesis example 3 is in polyamic acid solution (3) (8.50g) of 10.0 quality %, add PGME (10.1g), γ-BL (2.66g), stir 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 17 2converted score is polysiloxane solution (1) (7.08g) of 12 quality %, obtains composition (5) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (5) also as aligning agent for liquid crystal (5) for evaluate.
Use composition (5) and the aligning agent for liquid crystal (5) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 6>
The resin solid content concentration obtained in the synthetic method by synthesis example 3 is in polyamic acid solution (3) (15.0g) of 10.0 quality %, add PGME (3.56g), γ-BL (2.61g), BCS (5.22g), stir 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 21 2converted score is polysiloxane solution (5) (1.39g) of 12 quality %, obtains composition (6) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (6) also as aligning agent for liquid crystal (6) for evaluate.
Use composition (6) and the aligning agent for liquid crystal (6) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 7>
In polyimide powder (4) (1.65g) that the synthetic method by synthesis example 4 is obtained, add PGME (35.0g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 17 2converted score is polysiloxane solution (1) (9.17g) of 12 quality %, obtains composition (7) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (7) also as aligning agent for liquid crystal (7) for evaluate.
Use composition (7) and the aligning agent for liquid crystal (7) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell], [evaluation (common structure cell) of liquid crystal aligning], [making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning] and [evaluation of voltage retention] under these conditions.
< embodiment 8>
In polyimide powder (4) (1.33g) that the synthetic method by synthesis example 4 is obtained, add PCS (23.6g), γ-BL (8.33g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 20 2converted score is polysiloxane solution (4) (11.1g) of 12 quality %, obtains composition (8) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (8) also as aligning agent for liquid crystal (8) for evaluate.
Use composition (8) and the aligning agent for liquid crystal (8) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 9>
In polyimide powder (4) (1.00g) that the synthetic method by synthesis example 4 is obtained, add PCS (36.8g), γ-BL (11.0g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 20 2converted score is polysiloxane solution (4) (8.33g) of 12 quality %, obtains composition (9) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (9) also as aligning agent for liquid crystal (9) for evaluate.
Use the aligning agent for liquid crystal (9) of gained, carry out under these conditions [evaluation of the ink-jet application of aligning agent for liquid crystal].
< embodiment 10>
In polyimide powder (4) (1.23g) that the synthetic method by synthesis example 4 is obtained, add PCS (14.7g), γ-BL (4.28g), BCS (12.9g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 20 2converted score is polysiloxane solution (4) (12.5g) of 12 quality %, obtains composition (10) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (10) also as aligning agent for liquid crystal (10) for evaluate.
Use composition (10) and the aligning agent for liquid crystal (10) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 11>
In polyimide powder (5) (2.10g) that the synthetic method by synthesis example 5 is obtained, add MCS (20.8g), NEP (6.17g), BCS (10.3g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 18 2converted score is polysiloxane solution (2) (4.38g) of 12 quality %, obtains composition (11) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (10) also as aligning agent for liquid crystal (11) for evaluate.
Use composition (11) and the aligning agent for liquid crystal (11) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 12>
In polyimide powder (5) (2.55g) that the synthetic method by synthesis example 5 is obtained, add PGME (24.6g), γ-BL (13.3g), BCS (4.44g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 22 2converted score is polysiloxane solution (6) (2.36g) of 12 quality %, obtains composition (12) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (12) also as aligning agent for liquid crystal (12) for evaluate.
Use composition (12) and the aligning agent for liquid crystal (12) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell], [evaluation (common structure cell) of liquid crystal aligning] and [making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning] under these conditions.
< embodiment 13>
In polyimide powder (6) (1.35g) that the synthetic method by synthesis example 6 is obtained, add PGME (32.4g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 21 2converted score is polysiloxane solution (5) (11.3g) of 12 quality %, obtains composition (13) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (13) also as aligning agent for liquid crystal (13) for evaluate.
Use composition (13) and the aligning agent for liquid crystal (13) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 14>
In polyimide powder (6) (2.10g) that the synthetic method by synthesis example 6 is obtained, add PGME (33.2g), γ-BL (4.11g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 23 2converted score is polysiloxane solution (7) (4.38g) of 12 quality %, obtains composition (14) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (14) also as aligning agent for liquid crystal (14) for evaluate.
Use composition (14) and the aligning agent for liquid crystal (14) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell], [evaluation (common structure cell) of liquid crystal aligning] and [making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning] under these conditions.
< embodiment 15>
In polyimide powder (6) (1.75g) that the synthetic method by synthesis example 6 is obtained, add PCS (21.9g), NEP (7.83g), BCS (3.92g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 20 2converted score is polysiloxane solution (4) (6.25g) of 12 quality %, obtains composition (15) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (15) also as aligning agent for liquid crystal (15) for evaluate.
Use composition (15) and the aligning agent for liquid crystal (15) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 16>
In polyimide powder (6) (1.05g) that the synthetic method by synthesis example 6 is obtained, add PCS (25.7g), NEP (8.27g), BCS (4.14g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 20 2converted score is polysiloxane solution (4) (3.75g) of 12 quality %, obtains composition (16) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (16) also as aligning agent for liquid crystal (16) for evaluate.
Use the aligning agent for liquid crystal (16) of gained, carry out under these conditions [evaluation of the ink-jet application of aligning agent for liquid crystal].
< embodiment 17>
In polyimide powder (7) (2.11g) that the synthetic method by synthesis example 7 is obtained, add ECS (20.9g), NMP (8.26g), BCS (8.26g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 19 2converted score is polysiloxane solution (3) (4.40g) of 12 quality %, obtains composition (17) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (17) also as aligning agent for liquid crystal (17) for evaluate.
Use composition (17) and the aligning agent for liquid crystal (17) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 18>
In polyimide powder (8) (2.55g) that the synthetic method by synthesis example 8 is obtained, add PGME (37.9g), γ-BL (4.44g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 22 2converted score is polysiloxane solution (6) (2.36g) of 12 quality %, obtains composition (18) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (18) also as aligning agent for liquid crystal (18) for evaluate.
Use composition (18) and the aligning agent for liquid crystal (18) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 19>
In polyimide powder (8) (1.75g) that the synthetic method by synthesis example 8 is obtained, add MCS (27.8g), γ-BL (1.96g), BCS (3.92g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 18 2converted score is polysiloxane solution (2) (6.25g) of 12 quality %, obtains composition (19) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (19) also as aligning agent for liquid crystal (19) for evaluate.
Use composition (19) and the aligning agent for liquid crystal (19) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 20>
In polyimide powder (9) (1.35g) that the synthetic method by synthesis example 9 is obtained, add PGME (26.5g), γ-BL (3.85g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 21 2converted score is polysiloxane solution (5) (9.20g) of 12 quality %, obtains composition (20) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (20) also as aligning agent for liquid crystal (20) for evaluate.
Use composition (20) and the aligning agent for liquid crystal (20) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 21>
In polyimide powder (9) (1.77g) that the synthetic method by synthesis example 9 is obtained, add PCS (22.2g), γ-BL (7.92g), BCS (3.96g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 20 2converted score is polysiloxane solution (4) (6.32g) of 12 quality %, obtains composition (21) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (21) also as aligning agent for liquid crystal (21) for evaluate.
Use composition (21) and the aligning agent for liquid crystal (21) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 22>
In polyimide powder (10) (1.65g) that the synthetic method by synthesis example 10 is obtained, add PCS (23.3g), NMP (9.94g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 20 2converted score is polysiloxane solution (4) (7.40g) of 12 quality %, obtains composition (22) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (22) also as aligning agent for liquid crystal (22) for evaluate.
Use composition (22) and the aligning agent for liquid crystal (22) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 23>
In polyimide powder (11) (1.95g) that the synthetic method by synthesis example 11 is obtained, add PGME (30.8g), γ-BL (3.82g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 17 2converted score is polysiloxane solution (1) (4.06g) of 12 quality %, obtains composition (23) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (23) also as aligning agent for liquid crystal (23) for evaluate.
Use composition (23) and the aligning agent for liquid crystal (23) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 24>
In polyimide powder (11) (1.90g) that the synthetic method by synthesis example 11 is obtained, add PGME (32.3g), γ-BL (4.25g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 22 2converted score is polysiloxane solution (6) (6.79g) of 12 quality %, obtains composition (24) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (24) also as aligning agent for liquid crystal (24) for evaluate.
Use composition (24) and the aligning agent for liquid crystal (24) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 25>
In polyimide powder (11) (2.23g) that the synthetic method by synthesis example 11 is obtained, add PCS (25.4g), γ-BL (3.88g), BCS (7.76g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 20 2converted score is polysiloxane solution (4) (2.06g) of 12 quality %, obtains composition (25) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (25) also as aligning agent for liquid crystal (25) for evaluate.
Use composition (25) and the aligning agent for liquid crystal (25) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< embodiment 26>
In polyimide powder (12) (1.22g) that the synthetic method by synthesis example 12 is obtained, add PGME (25.5g), γ-BL (3.82g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 21 2converted score is polysiloxane solution (5) (10.2g) of 12 quality %, obtains composition (26) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (26) also as aligning agent for liquid crystal (26) for evaluate.
Use composition (26) and the aligning agent for liquid crystal (26) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell], [evaluation (common structure cell) of liquid crystal aligning] and [making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning] under these conditions.
< embodiment 27>
In polyimide powder (12) (2.50g) that the synthetic method by synthesis example 12 is obtained, add MCS (28.4g), γ-BL (2.18g), BCS (10.9g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 18 2converted score is polysiloxane solution (2) (2.31g) of 12 quality %, obtains composition (27) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (27) also as aligning agent for liquid crystal (27) for evaluate.
Use composition (27) and the aligning agent for liquid crystal (27) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< comparative example 1>
The resin solid content concentration obtained in the synthetic method by synthesis example 13 is in polyamic acid solution (13) (7.70g) of 25.0 quality %, adds NMP (28.4g), stirs 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 23 2converted score is polysiloxane solution (7) (4.01g) of 12 quality %, obtains composition (28) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (28) also as aligning agent for liquid crystal (28) for evaluate.
Use composition (28) and the aligning agent for liquid crystal (28) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< comparative example 2>
The resin solid content concentration obtained in the synthetic method by synthesis example 13 is in polyamic acid solution (13) (7.75g) of 25.0 quality %, adds γ-BL (28.6g), stirs 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 23 2converted score is polysiloxane solution (7) (4.04g) of 12 quality %, obtains composition (29) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (29) also as aligning agent for liquid crystal (29) for evaluate.
Use composition (29) and the aligning agent for liquid crystal (29) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< comparative example 3>
The resin solid content concentration obtained in the synthetic method by synthesis example 13 is in polyamic acid solution (13) (6.50g) of 25.0 quality %, add NMP (17.6g), BCS (6.36g), stir 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 23 2converted score is polysiloxane solution (7) (3.39g) of 12 quality %, obtains composition (30) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (30) also as aligning agent for liquid crystal (30) for evaluate.
Use composition (30) and the aligning agent for liquid crystal (30) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< comparative example 4>
The resin solid content concentration obtained in the synthetic method by synthesis example 14 is in polyamic acid solution (14) (8.12g) of 25.0 quality %, adds NMP (29.9g), stirs 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 21 2converted score is polysiloxane solution (5) (4.23g) of 12 quality %, obtains composition (31) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (31) also as aligning agent for liquid crystal (31) for evaluate.
Use composition (31) and the aligning agent for liquid crystal (31) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] and [evaluation of voltage retention] under these conditions.
< comparative example 5>
The resin solid content concentration obtained in the synthetic method by synthesis example 14 is in polyamic acid solution (14) (8.10g) of 25.0 quality %, add NMP (21.9g), BCS (7.93g), stir 1 hour in 25 DEG C.In this solution, add by the obtained SiO of the synthetic method of synthesis example 21 2converted score is polysiloxane solution (5) (4.22g) of 12 quality %, obtains composition (32) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (32) also as aligning agent for liquid crystal (32) for evaluate.
Use composition (32) and the aligning agent for liquid crystal (32) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] under these conditions.
< comparative example 6>
In polyimide powder (4) (1.65g) that the synthetic method by synthesis example 4 is obtained, add NMP (35.0g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the obtained SiO of the synthetic method of synthesis example 17 2converted score is polysiloxane solution (1) (9.17g) of 12 quality %, obtains composition (33) in 25 DEG C of stirrings 2 hours.Confirming in said composition the exception having no muddy or precipitate generation etc., is uniform solution.In addition, said composition (33) also as aligning agent for liquid crystal (33) for evaluate.
Use composition (33) and the aligning agent for liquid crystal (33) of gained, carry out [evaluation of the coating of composition and aligning agent for liquid crystal], [making (common structure cell) of liquid crystal cell] and [evaluation (common structure cell) of liquid crystal aligning] and [evaluation of voltage retention] under these conditions.
< comparative example 7>
In polyimide powder (15) (1.55g) that the synthetic method by synthesis example 15 is obtained, add PGME (32.9g), within 24 hours, make it dissolve in 70 DEG C of stirrings.Find in solution that the dissolving of polyimide powder remains, then stir 12 hours in 70 DEG C, but polyimide powder still fails to dissolve completely.
Therefore, composition (34) and aligning agent for liquid crystal (34) cannot be made.
[table 3]
* 2: represent the ratio shared by polymkeric substance in composition (aligning agent for liquid crystal).
[table 4]
* 3: represent the ratio shared by polymkeric substance in composition (aligning agent for liquid crystal).
[table 5]
* 4: represent the ratio shared by polymkeric substance in composition (aligning agent for liquid crystal).
* 5: represent solvent composition contained in polysiloxane solution.
[table 6]
Composition Aligning agent for liquid crystal Particular polymers Specific polysiloxane Stomatal number Liquid crystal aligning
Embodiment 1 Composition (1) Aligning agent for liquid crystal (1) Polyamic acid solution (1) Polysiloxane solution (7) < 3 Well
Embodiment 2 Composition (2) Aligning agent for liquid crystal (2) Polyamic acid solution (1) Polysiloxane solution (7) < 3 Well
Embodiment 3 Composition (3) Aligning agent for liquid crystal (3) Polyimide powder (2) Polysiloxane solution (7) < 3 Well
Embodiment 4 Composition (4) Aligning agent for liquid crystal (4) Polyamic acid solution (3) Polysiloxane solution (5) < 3 Well
Embodiment 5 Composition (5) Aligning agent for liquid crystal (5) Polyamic acid solution (3) Polysiloxane solution (1) < 3 Well
Embodiment 6 Composition (6) Aligning agent for liquid crystal (6) Polyamic acid solution (3) Polysiloxane solution (5) < 3 Well
Embodiment 7 Composition (7) Aligning agent for liquid crystal (7) Polyimide powder (4) Polysiloxane solution (1) < 3 Well
Embodiment 8 Composition (8) Aligning agent for liquid crystal (8) Polyimide powder (4) Polysiloxane solution (4) < 3 Well
Embodiment 9 Composition (9) Aligning agent for liquid crystal (9) Polyimide powder (4) Polysiloxane solution (4) < 3 －
Embodiment 10 Composition (10) Aligning agent for liquid crystal (10) Polyimide powder (4) Polysiloxane solution (4) < 3 Well
Embodiment 11 Composition (11) Aligning agent for liquid crystal (11) Polyimide powder (5) Polysiloxane solution (2) < 3 Well
Embodiment 12 Composition (12) Aligning agent for liquid crystal (12) Polyimide powder (5) Polysiloxane solution (6) < 3 Well
Embodiment 13 Composition (13) Aligning agent for liquid crystal (13) Polyimide powder (6) Polysiloxane solution (5) < 3 Well
Embodiment 14 Composition (14) Aligning agent for liquid crystal (14) Polyimide powder (6) Polysiloxane solution (7) < 3 Well
Embodiment 15 Composition (15) Aligning agent for liquid crystal (15) Polyimide powder (6) Polysiloxane solution (4) < 3 Well
[table 7]
Composition Aligning agent for liquid crystal Particular polymers Specific polysiloxane Stomatal number Liquid crystal aligning
Embodiment 16 Composition (16) Aligning agent for liquid crystal (16) Polyimide powder (6) Polysiloxane solution (4) < 3 －
Embodiment 17 Composition (17) Aligning agent for liquid crystal (17) Polyimide powder (7) Polysiloxane solution (3) < 3 Well
Embodiment 18 Composition (18) Aligning agent for liquid crystal (18) Polyimide powder (8) Polysiloxane solution (6) < 3 Well
Embodiment 19 Composition (19) Aligning agent for liquid crystal (19) Polyimide powder (8) Polysiloxane solution (2) < 3 Well
Embodiment 20 Composition (20) Aligning agent for liquid crystal (20) Polyimide powder (9) Polysiloxane solution (5) < 3 Well
Embodiment 21 Composition (21) Aligning agent for liquid crystal (21) Polyimide powder (9) Polysiloxane solution (4) < 3 Well
Embodiment 22 Composition (22) Aligning agent for liquid crystal (22) Polyimide powder (10) Polysiloxane solution (4) < 3 Well
Embodiment 23 Composition (8) Aligning agent for liquid crystal (8) Polyimide powder (11) Polysiloxane solution (1) < 3 Well
Embodiment 24 Composition (24) Aligning agent for liquid crystal (24) Polyimide powder (11) Polysiloxane solution (6) < 3 Well
Embodiment 25 Composition (25) Aligning agent for liquid crystal (25) Polyimide powder (11) Polysiloxane solution (4) < 3 Well
Embodiment 26 Composition (26) Aligning agent for liquid crystal (26) Polyimide powder (12) Polysiloxane solution (5) < 3 Well
Embodiment 27 Composition (27) Aligning agent for liquid crystal (27 Polyimide powder (12) Polysiloxane solution (2) < 3 Well
[table 8]
Composition Aligning agent for liquid crystal Particular polymers Specific polysiloxane Stomatal number Liquid crystal aligning
Comparative example 1 Composition (28) Aligning agent for liquid crystal (28) Polyamic acid solution (13) Polysiloxane solution (7) 25 *8
Comparative example 2 Composition (29) Aligning agent for liquid crystal (29) Polyamic acid solution (13) Polysiloxane solution (7) 27 *8
Comparative example 3 Composition (30) Aligning agent for liquid crystal (30) Polyamic acid solution (13) Polysiloxane solution (7) 14 *7
Comparative example 4 Composition (31) Aligning agent for liquid crystal (31) Polyamic acid solution (14) Polysiloxane solution (5) 31 *8
Comparative example 5 Composition (32) Aligning agent for liquid crystal (32) Polyamic acid solution (14) Polysiloxane solution (5) 18 *7
Comparative example 6 Composition (33) Aligning agent for liquid crystal (33) Polyimide powder (4) Polysiloxane solution (1) 30 *8
Comparative example 7 Composition (34) Aligning agent for liquid crystal (34) Polyimide powder (15) Polysiloxane solution (1) *6 *6
* 6: polyimide powder does not dissolve completely, cannot modulation group compound and aligning agent for liquid crystal.
* 7: orientation defect confirmation has 15 ~ 24.
* 8: orientation defect confirmation has more than 25.
[table 9]
From the above results, the composition of embodiments of the invention, compared with the composition of comparative example, is presented the uniform coating of the pore do not produced with shrinkage cavity when coating substrate.Specifically, it is the comparison when using the composition of identical polyimide precursor or solvent-soluble type polyimide, i.e. the comparing of embodiment 1 and comparative example 1, comparative example 2 or comparative example 3, comparing of embodiment 4 and comparative example 4 or comparative example 5, and the comparing of embodiment 7 and comparative example 6.
In addition, the liquid crystal aligning process of the present composition is employed and obtained liquid crystal orientation film have also been obtained identical result.Specifically, it is the comparison when using the aligning agent for liquid crystal of identical polyimide precursor or solvent-soluble type polyimide, i.e. the comparing of embodiment 1 and comparative example 1, comparative example 2 or comparative example 3, comparing of embodiment 4 and comparative example 4 or comparative example 5, and the comparing of embodiment 7 and comparative example 6.Particularly when have employed in diamine component the aligning agent for liquid crystal of the diamine compound that uses and there is side chain and the polyimide precursor that obtains or solvent-soluble type polyimide, also with the above-mentioned uniform coating presenting the pore do not produced with shrinkage cavity in the same manner.
And, in the evaluation of the liquid crystal aligning of liquid crystal cell, by employ the aligning agent for liquid crystal of the present composition and obtained liquid crystal cell with by employing the aligning agent for liquid crystal of comparative example composition and compared with obtained liquid crystal cell, have no the orientation defect caused by pore, uniform liquid crystal aligning can be obtained.Specifically, it is the comparison when using the aligning agent for liquid crystal of identical polyimide precursor or solvent-soluble type polyimide, i.e. the comparing of embodiment 1 and comparative example 1, comparative example 2 or comparative example 3, comparing of embodiment 4 and comparative example 4 or comparative example 5, and the comparing of embodiment 7 and comparative example 6.
In addition, in the evaluation of voltage retention, by employ the aligning agent for liquid crystal of the present composition and obtained liquid crystal cell with by employing the aligning agent for liquid crystal of comparative example composition and compared with obtained liquid crystal cell, presenting high numerical value.Specifically, be the comparison when using the aligning agent for liquid crystal of identical polyimide precursor or solvent-soluble type polyimide, i.e. the comparing of embodiment 4 and comparative example 4, and the comparing of embodiment 7 and comparative example 6.
[utilizing feasibility in industry]
The resin coating of the uniform coating presenting the pore do not produced with shrinkage cavity can be obtained when composition of the present invention is coated with on substrate.In addition, the aligning agent for liquid crystal employing the present composition also can obtain identical result.
In addition, aligning agent for liquid crystal of the present invention can obtain the liquid crystal cell not producing the orientation defect caused by the pore with shrinkage cavity.The aligning agent for liquid crystal particularly employing the diamine compound that to use in diamine component and have side chain and the polyimide precursor that obtains or solvent-soluble type polyimide also can obtain identical result.
In addition, aligning agent for liquid crystal of the present invention is also useful for the liquid crystal display device switched between the transmissive state (also referred to as vitreous state) and scattering state of liquid crystal, the liquid crystal display device that namely have employed the dispersed liquid crystal (PDLC (Polymer Dispersed Liquid Crystal)) of polymer or macromolecule network type liquid crystal (PNLC (Polymer Network Liquid Crystal)).
Particularly for be vitreous state when not applying voltage, apply voltage time be that the counter-rotative type element of scattering state is useful.This counter-rotative type element for use sheet glass and the plastic base such as PET (polyethylene terephthalate) and vinylformic acid substrate be shown as the liquid-crystal display of object and control light through being useful with the light-regulating window of the vehicles such as the light-regulating window covered, light shadowing elements, automobile and the backboard etc. of transparent display.
And, even if aligning agent for liquid crystal easy fired of the present invention also can present high voltage holding ratio.
Thus, there is the excellent in reliability of the liquid crystal display device of the liquid crystal orientation film obtained by aligning agent for liquid crystal of the present invention, be applicable to the LCD TV etc. of large picture and high-resolution, the liquid crystal display device for TN element, STN element, TFT liquid crystal cell, particularly vertical orientating type is useful.
And the liquid crystal orientation film obtained by aligning agent for liquid crystal of the present invention is for must the liquid crystal display device of irradiation ultraviolet radiation also be useful when making liquid crystal display device.Namely, to having between a pair substrate of electrode that liquid crystal layer is formed, the liquid crystal display device that manufactures through following operation is also useful possessing, this operation is: between described a pair substrate, configuration packet is containing the liquid-crystal composition of the polymerizable compound utilizing at least one party of active energy beam and heat to be polymerized, and applies voltage while make described polymerizable compound be polymerized between above-mentioned electrode; And to having between a pair substrate of electrode that liquid crystal layer is formed, the liquid crystal display device that manufactures through following operation is also useful possessing, this operation is: between described a pair substrate, configuration packet is containing the liquid crystal orientation film of the polymerizable group utilizing at least one party of active energy beam and heat to be polymerized, and applies voltage while make described polymerizable group be polymerized between above-mentioned electrode.

Claims (21)

1. a composition, is characterized in that, comprises following (A) composition, (B) composition and (C) composition,
(A) composition: at least one solvent being selected from following formula [1a] or formula [1b],
In formula [1a], X 1represent the alkyl of carbon number 1 ~ 3, in formula [1b], X 2represent the alkyl of carbon number 1 ~ 3,
(B) composition: at least one polymkeric substance being selected from polyimide precursor or the polyimide being reacted by the diamine component and tetracarboxylic dianhydride's composition that comprise the diamine compound with carboxyl and obtained,
(C) composition: by comprising the organoalkoxysilane polycondensation of any one of the organoalkoxysilane shown in following formula [A1], formula [A2] or formula [A3] and the polysiloxane obtained,
[changing 2]
(A 1) mSi(A 2) n(OA 3) p[A1]
In formula [A1], A 1represent aliphatic hydrocarbon, phenyl ring, cyclohexane ring, heterocycle or there is the organic radical of carbon number 8 ~ 35 of steroid structure, A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, A 3represent the alkyl of carbon number 1 ~ 5 respectively, m represents the integer of 1 or 2, and n represents the integer of 0 ~ 2, and p represents the integer of 0 ~ 3, and m+n+p is 4,
[changing 3]
(B 1) mSi(B 2) n(OB 3) p[A2]
In formula [A2], B 1represent the organic radical with the carbon number 2 ~ 12 of vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl, B 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, B 3represent the alkyl of carbon number 1 ~ 5 respectively, m represents the integer of 1 or 2, and n represents the integer of 0 ~ 2, and p represents the integer of 0 ~ 3, and m+n+p is 4,
[changing 4]
(D 1) nSi(OD 2) 4-n[A3]
In formula [A3], D 1represent the alkyl of hydrogen atom or carbon number 1 ~ 5 respectively, D 2represent the alkyl of carbon number 1 ~ 5, n represents the integer of 0 ~ 3.
2. composition as claimed in claim 1, is characterized in that, described (A) composition is 50 ~ 100 quality % of whole solvents contained in composition.
3. composition as claimed in claim 1 or 2, is characterized in that, the diamine compound with carboxyl of described (B) composition for having the diamine compound of the structure shown in following formula [2],
[changing 5]
-(CH 2) a-COOH [2]
In formula [2], a represents the integer of 0 ~ 4.
4. composition as claimed in claim 1 or 2, is characterized in that, the diamine compound with carboxyl of described (B) composition for having the diamine compound of the structure shown in following formula [2a],
In formula [2a], a represents the integer of 0 ~ 4, and n represents the integer of 1 ~ 4.
5. the composition as described in claim 3 or 4, is characterized in that, described in there is carboxyl diamine compound be in whole diamines used in described (B) composition 20 % by mole ~ 100 % by mole.
6. the composition according to any one of Claims 1 to 5, is characterized in that, the diamine component of described (B) composition comprises the diamine compound of at least one being selected from the structure shown in following formula [2b],
In formula [2b], Y represents the structure of following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5], and m represents the integer of 1 ~ 4,
In formula [2b-1], a represents the integer of 0 ~ 4,
In formula [2b-2], Y 1represent singly-bound ,-(CH 2) a-,-O-,-CH 2o-,-COO-or-OCO-, wherein a is the integer of 1 ~ 15; Y 2represent singly-bound or-(CH 2) b-, wherein b is the integer of 1 ~ 15; Y 3represent singly-bound ,-(CH 2) c-,-O-,-CH 2o-,-COO-or-OCO-, wherein c is the integer of 1 ~ 15; Y 4represent the bivalent cyclic base being selected from phenyl ring, cyclohexane ring or heterocycle, or there is the divalent organic base of carbon number 12 ~ 25 of steroid skeleton, any hydrogen atom in above-mentioned cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; Y 5represent the bivalent cyclic base being selected from phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom in these cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; N represents the integer of 0 ~ 4; Y 6what represent the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18 contains fluoroalkyl, the alkoxyl group of carbon number 1 ~ 18 or the fluoroalkoxy of carbon number 1 ~ 18,
In formula [2b-3], Y 7represent the alkyl of carbon number 8 ~ 22,
In formula [2b-4], Y 8and Y 9separately represent the alkyl of carbon number 1 ~ 6,
In formula [2b-5], Y 10represent the alkyl of carbon number 1 ~ 8.
7. the composition according to any one of claim 1 ~ 6, is characterized in that, tetracarboxylic dianhydride's composition of described (B) composition is the compound shown in following formula [3],
In formula [3], Z 1represent the group being selected from least one structure of following formula [3a] ~ formula [3j],
In formula [3a], Z 2~ Z 5represent hydrogen atom, methyl, chlorine atom or phenyl ring, each other can identical also can be different, in formula [3g], Z 6and Z 7represent hydrogen atom or methyl, each other can identical also can be different.
8. the composition according to any one of claim 1 ~ 7, it is characterized in that, the organoalkoxysilane shown in formula [A2] of described (C) composition is for being selected from allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, methacrylic acid 3-(triethoxysilyl) propyl diester, the at least one of vinylformic acid 3-(trimethoxysilyl) propyl diester or methacrylic acid 3-(trimethoxysilyl) propyl diester.
9. the composition according to any one of claim 1 ~ 7, it is characterized in that, the organoalkoxysilane shown in formula [A2] of described (C) composition is for being selected from least one of 3-glycidoxypropyl (dimethoxy) methyl-monosilane, 3-glycidoxypropyl (diethoxy) methyl-monosilane, 3-glycidoxypropyltrimethoxy base silane or 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane.
10. the composition according to any one of claim 1 ~ 9, is characterized in that, the polysiloxane of described (C) composition is the polysiloxane obtained by the organoalkoxysilane polycondensation shown in described formula [A1], formula [A2] and formula [A3].
11. compositions according to any one of claim 1 ~ 10, is characterized in that, containing at least one solvent as the METHYLPYRROLIDONE of (D) composition, N-ethyl-2-pyrrolidone or gamma-butyrolactone.
12. compositions according to any one of claim 1 ~ 11, it is characterized in that, containing 1-hexanol, hexalin, 1 as (E) composition, the at least one solvent of 2-ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, Diethylene Glycol isopropyl ether or diethylene glycol monobutyl ether.
13. resin coatings, is characterized in that, the composition according to any one of claim 1 ~ 12 obtains.
14. aligning agent for liquid crystal, is characterized in that, the composition according to any one of claim 1 ~ 12 obtains.
15. liquid crystal orientation films, is characterized in that, use the aligning agent for liquid crystal described in claim 14 to obtain.
16. liquid crystal orientation films, is characterized in that, use the aligning agent for liquid crystal described in claim 14 to be obtained by ink jet method.
17. liquid crystal display device, is characterized in that, have the liquid crystal orientation film described in claim 15 or 16.
18. liquid crystal orientation films as described in claim 15 or 16, it is characterized in that, for possessing the liquid crystal display device that there is between a pair substrate of electrode liquid crystal layer and form, manufacture through following operation, this operation is: between described a pair substrate, configuration packet is containing the liquid-crystal composition of the polymerizable compound utilizing at least one party of active energy beam and heat to be polymerized, and applies voltage while make described polymerizable compound be polymerized between above-mentioned electrode.
19. liquid crystal display device, is characterized in that, have liquid crystal orientation film according to claim 18.
20. liquid crystal orientation films as described in claim 15 or 16, it is characterized in that, for possessing the liquid crystal display device that there is between a pair substrate of electrode liquid crystal layer and form, manufacture through following operation, this operation is: between described a pair substrate, configuration packet is containing the liquid crystal orientation film of the polymerizable group utilizing at least one party of active energy beam and heat to be polymerized, and applies voltage while make described polymerizable group be polymerized between above-mentioned electrode.
21. liquid crystal display device, is characterized in that, have liquid crystal orientation film according to claim 20.
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