CN104884533A - 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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CN104884533A
CN104884533A CN201380066234.XA CN201380066234A CN104884533A CN 104884533 A CN104884533 A CN 104884533A CN 201380066234 A CN201380066234 A CN 201380066234A CN 104884533 A CN104884533 A CN 104884533A
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liquid crystal
composition
formula
carbon number
represent
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CN104884533B (en
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三木德俊
桥本淳
巴幸司
片山雅章
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • G02F1/133719—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films with coupling agent molecules, e.g. silane
    • 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
    • G02F1/133723—Polyimide, polyamide-imide

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Physics & Mathematics (AREA)
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Abstract

(1) A composition containing component (A), component (B), and component (C), described below. Component (A): A solvent indicated by formula [1]. (In formula [1], X1 indicates a C1-4 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 specified alkoxysilane (img file='DDA0000740375460000011. TIF' wi='845' he='173' /).

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 use the liquid crystal display device of this liquid crystal orientation film.
Background technology
The resin coating formed by organic materialss such as macromolecular materials is conceived to the difficulty and insulating property etc. that are formed, in electron device, be widely used as interlayer dielectric and protective membrane etc.Wherein, in the liquid crystal display device be known as display device, the resin coating formed by organic materials is used as liquid crystal orientation film.
In recent years, liquid crystal display device is by practical in the LCD TV of large picture and the mobile purposes (display section of digital camera and mobile phone) of high-resolution widely.With this situation, compared with the past, substrate used maximizes, and the concavo-convex change of substrate jump is large.Under these circumstances, from the angle of display characteristic, for large substrate and jump, still require to be coated with formation liquid crystal orientation film equably.In the production process of this liquid crystal orientation film, substrate is coated with the aligning agent for liquid crystal of polyamic acid or solvent-soluble polyimide (also referred to as resin), industrial general employing flexographic printing process or ink-jet application method etc. are carried out.At this moment, in the solvent of aligning agent for liquid crystal, except the METHYLPYRROLIDONE (also referred to as NMP) or gamma-butyrolactone (γ-BL) etc. as the good solvent (also referred to as good solvent) of resin dissolves, in order to improve the film of liquid crystal orientation film, be also mixed with the ethylene glycol monobutyl ether etc. (reference example is as patent documentation 1) as the low solvent (also referred to as poor solvent) of resin dissolves.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2-37324 publication
Summary of the invention
Invent technical problem to be solved
Liquid crystal orientation film is by burning till film after aligning agent for liquid crystal is coated substrate and being formed.At this moment, in order to improve the film (also referred to as coating) of liquid crystal orientation film, that is, suppressing the generation with the pore repelled, requiring to improve aligning agent for liquid crystal to the infiltration spread of substrate.This is same with the in the past used aligning agent for liquid crystal comprising polyimide-based polymer, for the aligning agent for liquid crystal requirement too comprising polyimide-based polymer and polysiloxane.
In the aligning agent for liquid crystal that the polymers soln obtained by making polyimide-based polymer be dissolved in NMP or the γ-BL as the solvent usually adopted and polysiloxane obtain, the intermiscibility of the polysiloxane that NMP and the γ-BL that polarity is high is high with hydrophobicity is poor, when said composition is coated substrate, liquid crystal orientation film easily produces the pore with repelling.That is, in the past comprise in the aligning agent for liquid crystal of polyimide-based polymer and polysiloxane, easily produce the orientation defect with stomatal limiting value.
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; so except liquid crystal orientation film, be also used to the interlayer dielectric and protective membrane etc. in other electron device.For these films, also need the coating improving resin coating, that is, suppress the generation with the pore repelled on resin coating.
So, the object of the present invention is to provide the composition having above-mentioned characteristic concurrently.That is, the object of the present invention is to provide the composition comprising polyimide-based polymer and polysiloxane that can suppress the generation with the pore repelled when forming resin coating.
In addition, the present invention also aims to provide the aligning agent for liquid crystal employing above-mentioned composition that can suppress the generation with the pore repelled when forming liquid crystal orientation film.
In addition, the present invention also aims to provide the liquid crystal orientation film adapting to above-mentioned requirements.That is, its object is to provide the liquid crystal orientation film of the orientation defect that can suppress with stomatal limiting value.
In addition, the present invention also aims to provide the liquid crystal display device possessing the liquid crystal orientation film adapting to above-mentioned requirements.
The technical scheme that technical solution problem adopts
Present inventor has performed and conscientiously study, found that comprise the solvent with ad hoc structure, that the composition being selected from polyimide precursor that the diamine component that makes to comprise the diamine compound with carboxyl and tetracarboxylic acid composition react and obtain or at least one polymkeric substance of polyimide and the polysiloxane of ad hoc structure states object aspect is in realization very effective, thus completes the present invention.
That is, the present invention includes following technology contents.
(1) composition, is characterized in that, comprises following (A) composition, (B) composition and (C) composition:
(A) composition: the solvent represented with following formula [1],
In formula [1], X 1represent the alkyl of carbon number 1 ~ 4;
(B) composition: at least one polymkeric substance being selected from polyimide precursor that the diamine component that makes to comprise the diamine compound with carboxyl and tetracarboxylic dianhydride's composition react and obtain or polyimide;
(C) composition: make to comprise the organoalkoxysilane polycondensation of any one in the organoalkoxysilane represented with 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, hexamethylene ring, heterocycle or there is the organic group 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 wherein, m+n+p is 4,
[changing 3]
(B 1) mSi(B 2) n(OB 3) p[A2]
In formula [A2], B 1represent the organic group 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 wherein, 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), is characterized in that, 50 ~ 100 quality % of the whole solvents of described (A) composition contained by composition.
(3) composition as described in above-mentioned (1) or above-mentioned (2), is characterized in that, the diamine compound with carboxyl of described (B) composition is the diamine compound with the structure represented with 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 above-mentioned (2), is characterized in that, the diamine compound with carboxyl of described (B) composition is the diamine compound of the structure represented with following formula [2a],
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 above-mentioned (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) composition as described in any one in above-mentioned (1) ~ above-mentioned (5), it is characterized in that, the diamine component of described (B) composition comprises at least one diamine compound being selected from the structure represented with 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], and Y 1for representing singly-bound ,-(CH 2) a-,-O-,-CH 2o-,-COO-or-OCO-, a is the integer of 1 ~ 15, Y 2represent singly-bound or-(CH 2) b-, b is the integer of 1 ~ 15, Y 3represent singly-bound ,-(CH 2) c-,-O-,-CH 2o-,-COO-or-OCO-, c is the integer of 1 ~ 15, Y 4represent the divalent organic group of the divalent cyclic group being selected from phenyl ring, hexamethylene ring or heterocycle or the carbon number 12 ~ 25 with steroid skeleton, arbitrary hydrogen atom on described 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 divalent cyclic group being selected from phenyl ring, hexamethylene ring or heterocycle, arbitrary hydrogen atom on these cyclic groups 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 is 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], and 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 as described in any one in above-mentioned (1) ~ above-mentioned (6), is characterized in that, tetracarboxylic dianhydride's composition of described (B) composition is the compound represented with following formula [3],
In formula [3], Z 1for being selected from the group of at least one structure of following formula [3a] ~ formula [3j],
In formula [3a], Z 2~ Z 5represent hydrogen atom, methyl, chlorine atom or phenyl ring, may be the same or different respectively, in formula [3g], Z 6and Z 7represent hydrogen atom or methyl, may be the same or different respectively.
(8) composition as described in any one in above-mentioned (1) ~ above-mentioned (7), it is characterized in that, the organoalkoxysilane represented with formula [A2] of described (C) composition is for being selected from allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, 3-(triethoxysilicane alkyl) propyl methacrylate, the at least one of 3-(Trimethoxy silane base) propyl acrylate or 3-(Trimethoxy silane base) propyl methacrylate.
(9) composition as described in any one in above-mentioned (1) ~ above-mentioned (7), it is characterized in that, the organoalkoxysilane represented with formula [A2] of described (C) composition is for being selected from least one of 3-glycidoxypropyl group (dimethoxy) methyl-monosilane, 3-glycidoxypropyl group (diethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane or 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane.
(10) composition as described in any one in above-mentioned (1) ~ above-mentioned (9), it is characterized in that, the polysiloxane that the polysiloxane of described (C) composition obtains for making the described organoalkoxysilane polycondensation that represents with formula [A1], formula [A2] and formula [A3].
(11) composition as described in any one in above-mentioned (1) ~ above-mentioned (10), it is characterized in that, as (D) composition, comprise at least one solvent in METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone or gamma-butyrolactone.
(12) composition as described in any one in above-mentioned (1) ~ above-mentioned (11), it is characterized in that, as (E) composition, comprise 1-hexanol, hexalin, 1, at least one solvent in 2-ethylene glycol, 1,2-PD, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, glycol isopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether.
(13) resin coating, is characterized in that, is obtained by the composition described in any one in above-mentioned (1) ~ above-mentioned (12).
(14) aligning agent for liquid crystal, is characterized in that, is obtained by the composition described in any one in above-mentioned (1) ~ above-mentioned (12).
(15) liquid crystal orientation film, is characterized in that, uses the aligning agent for liquid crystal described in above-mentioned (14) and obtains.
(16) liquid crystal orientation film, is characterized in that, uses the aligning agent for liquid crystal described in above-mentioned (14) to be obtained by ink jet method.
(17) liquid crystal display device, is characterized in that, has above-mentioned (15) or the liquid crystal orientation film described in above-mentioned (16).
(18) liquid crystal orientation film as described in above-mentioned (15) or above-mentioned (16), it is characterized in that, for there is liquid crystal layer between a pair substrate possessing electrode and the liquid crystal display device made through following operation, this operation is: between described a pair substrate, configuration packet is containing the liquid-crystal composition of the polymerizable compound by least one party in active energy beam and heat polymerization, alively makes described polymerizable compound be polymerized to executing between described electrode simultaneously.
(19) liquid crystal display device, is characterized in that, has the liquid crystal orientation film described in above-mentioned (18).
(20) liquid crystal orientation film as described in above-mentioned (15) or above-mentioned (16), it is characterized in that, for there is liquid crystal layer between a pair substrate possessing electrode and the liquid crystal display device made through following operation, this operation is: between described a pair substrate, configuration packet is containing the liquid crystal orientation film of the polymerizable group by least one party in active energy beam and heat polymerization, alively makes described polymerizable group be polymerized to executing between described electrode simultaneously.
(21) liquid crystal display device, is characterized in that, has the liquid crystal orientation film described in above-mentioned (20).
The effect of invention
The solvent with ad hoc structure, the composition being selected from polyimide precursor that the diamine component that makes to comprise the diamine compound with carboxyl and tetracarboxylic dianhydride's composition react and obtain or at least one polymkeric substance of polyimide and the polysiloxane of ad hoc structure of comprising of the present invention, when coating on substrate, can suppress the generation with the pore repelled on resin coating.
In addition, the aligning agent for liquid crystal formed by composition of the present invention, when coating on substrate, can suppress the generation with the pore repelled on liquid crystal orientation film.Therefore, the liquid crystal display device with thus obtained liquid crystal orientation film becomes the liquid crystal display device not having orientation defect.
Embodiment
The present inventor conscientiously studies the following discovery of rear acquisition, completes the present invention.
The present invention be comprise following (A) composition, resin coating, the liquid crystal orientation film using this aligning agent for liquid crystal to obtain and the liquid crystal display device with this liquid crystal orientation film that the composition of (B) composition and (C) composition, aligning agent for liquid crystal, use said composition obtain.
(A) composition: the solvent (also referred to as specific solvent) represented with following formula [1].
In formula [1], X 1represent 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 that the diamine component that makes to comprise the diamine compound with carboxyl and tetracarboxylic dianhydride's composition react and obtain or polyimide.
(C) composition: make to comprise the organoalkoxysilane polycondensation of any one in the organoalkoxysilane represented with 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, hexamethylene ring, heterocycle or there is the organic group 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 wherein, m+n+p is 4.
[changing 13]
(B 1) mSi(B 2) n(OB 3) p[A2]
In formula [A2], B 1represent the organic group 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 wherein, m+n+p is 4.
[changing 14]
(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.
Specific solvent of the present invention is compared with NMP with the γ-BL equal solvent being generally used for the composition with polyimide-based polymer, and the surface tension as solvent is lower.Therefore, use the infiltration spread of composition to substrate of specific solvent higher.Therefore, the generation with the pore repelled on resin coating can be suppressed.
In addition, in composition of the present invention, even if mix the polymers soln of specific polysiloxane or specific polysiloxane in the polymers soln obtained to making particular polymers be dissolved in specific solvent, because specific solvent is not the solvent that polarity is high as NMP and γ-BL etc., therefore the intermiscibility of the polymers soln of solvent and specific polysiloxane or specific polysiloxane is high.Therefore, when said composition is coated substrate, the generation with the pore repelled on resin coating can be suppressed.
Based on above reason, composition of the present invention, when coating substrate, can suppress the defects such as the pore with repulsion formation on resin coating.In addition, the aligning agent for liquid crystal obtained by composition of the present invention also can obtain above-mentioned effect based on same reason.
Below, embodiments of the present invention are described in detail.
< specific solvent >
Specific solvent as (A) of the present invention composition is the solvent represented with following formula [1].
In formula [1], X 1represent the alkyl of carbon number 1 ~ 4.
Specifically, the structure represented with following formula [1-1] ~ formula [1-6] can be exemplified.
Wherein, from boiling point and the angle obtaining difficulty of solvent, be better formula [1-1] or formula [1-2].
Specific solvent of the present invention strengthens the effect of above-mentioned raising to the infiltration spread of substrate, is therefore preferably 50 ~ 100 quality % of the whole solvents contained by aligning agent for liquid crystal of composition or use said composition.Wherein, be better 55 ~ 100 quality %.Be more preferably 55 ~ 95 quality %.
In whole solvents contained by aligning agent for liquid crystal of composition or use said composition, the amount of specific solvent of the present invention is more, then effect of the present invention, the i.e. coating solution infiltration spread to substrate is higher, can obtain the better resin coating of coating or liquid crystal orientation film.
< particular polymers >
Particular polymers as (B) of the present invention composition is be selected from least one polymkeric substance that the diamine component that makes to comprise the diamine compound with carboxyl and tetracarboxylic acid composition react polyimide precursor or the polyimide obtained.
Polyimide precursor is the structure represented with following formula [A].
In formula [A], R 1be 4 valency organic groups, R 2for there is the divalent organic group of carboxyl, A 1and A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 8, can be identical or different respectively, A 3and A 4represent alkyl or the ethanoyl of hydrogen atom, carbon number 1 ~ 5, can be identical or different respectively, n represents positive integer.
As described diamine component, it is the diamine compound in molecule with 2 primary aminos or secondary amino group; 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.
Because by the diamine compound with carboxyl represented with following formula [C] and the tetracarboxylic dianhydride represented using following formula [B] being obtained more easily as raw material, particular polymers of the present invention is better the polyamic acid formed by the structural formula of the repeating unit represented with following formula [D] or the polyimide making this polyamic acid imidization and obtain.
In formula [B] and formula [C], R 1and R 2identical with the definition in formula [A].
In formula [D], R 1and R 2identical with the definition in formula [A].
In addition, also by common synthetic method to the A shown in drawing-in system [A] in the polymkeric substance of the formula [D] obtained in above-mentioned 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 represented with following formula [2].
[changing 20]
-(CH 2) a-COOH [2]
In formula [2], a represents the integer of 0 ~ 4.Wherein, from the angle obtaining the difficulty of difficulty and synthesis of raw material, it is better the integer of 0 or 1.
As the diamine compound with the structure represented with formula [2], the structure that the following formula [2a] stated represents specifically can be exemplified.
In formula [2a], a represents the integer of 0 ~ 4.Wherein, from the angle obtaining the difficulty of difficulty and synthesis of raw material, be better 0 or 1.
In formula [2a], n represents the integer of 1 ~ 4.Wherein, from the angle of the difficulty of synthesis, be better 1.
The method manufacturing the diamine compound represented with formula [2a] of the present invention is not particularly limited, and as preferred method, can exemplify method as described below.
As an example, after the dinitro matrix compounds that the diamine compound represented represents with following formula [2a-A] by synthesis, reduce its nitro and be converted into amino to obtain with formula [2a].
In formula [2a-A], a represents the integer of 0 ~ 4, and n represents the integer of 1 ~ 4.
The method of the dinitrobenzene of the dinitro matrix compounds that reduction represents with formula [2a-A] is not particularly limited, and usually has the method using palladium carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminum oxide or platinum sulfide carbon etc. to make it react as catalyzer under hydrogen, hydrazine or hydrogenchloride condition in ethyl acetate, toluene, tetrahydrofuran (THF), diox or alcoholic solvent equal solvent.
As the diamine compound with carboxyl of the present invention, the structure represented with following formula [2a-1] ~ formula [2a-4] also can be exemplified.
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 angle of the difficulty of synthesis, be better singly-bound ,-CH 2-,-C (CH 3) 2-,-O-,-CO-,-NH-,-N (CH 3)-,-CONH-,-NHCO-,-COO-or-OCO-.Be 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 2better 1 or 2.
In formula [2a-2], m 3and m 4represent the integer of 1 ~ 5 respectively.Wherein, from the angle of the difficulty of synthesis, be better 1 or 2.
In formula [2a-3], A 2represent straight chain or the branched alkyl groups of carbon number 1 ~ 5.Wherein, be better the straight chained alkyl of carbon number 1 ~ 3.
In formula [2a-3], m 5represent the integer of 1 ~ 5.Wherein, be better 1 or 2.
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, be better singly-bound ,-CH 2-,-C (CH 3) 2-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH 2o-,-OCH 2-,-COO-or-OCO-.Be 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 angle of the difficulty of synthesis, be better 1.
The diamine compound with carboxyl of the present invention is better 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, make liquid crystal orientation film time the characteristic such as orientation, voltage retention, Accumulating charge of liquid crystal, use one or more used in combination.
< the 2nd diamine compound >
In diamine component for the preparation of particular polymers of the present invention, as the 2nd diamine compound, the diamine compound (also referred to as the 2nd diamine compound) represented with following formula [2b] can be used.
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,
In formula [2b-1], a represents the integer of 0 ~ 4.Wherein, from the angle obtaining the difficulty of difficulty and synthesis of raw material, it is better the integer of 0 or 1.
In formula [2b-2], Y 1represent singly-bound ,-(CH 2) a-,-O-,-CH 2o-,-COO-or-OCO-, a is the integer of 1 ~ 15.Wherein, from the angle obtaining the difficulty of difficulty and synthesis of raw material, be better singly-bound ,-(CH 2) a-,-O-,-CH 2o-or-COO-, a are the integer of 1 ~ 15.Be more preferably singly-bound ,-(CH 2) a-,-O-,-CH 2o-or-COO-, a are the integer of 1 ~ 10.
In formula [2b-2], Y 2represent singly-bound or-(CH 2) b-, b is the integer of 1 ~ 15.Wherein, be better singly-bound or-(CH 2) b-, b is the integer of 1 ~ 10.
In formula [2b-2], Y 3represent singly-bound ,-(CH 2) c-,-O-,-CH 2o-,-COO-or-OCO-, c is the integer of 1 ~ 15.Wherein, from the angle of the difficulty of synthesis, be better singly-bound ,-(CH 2) c-,-O-,-CH 2o-or-COO-, c are the integer of 1 ~ 15.Be more preferably singly-bound ,-(CH 2) c-,-O-,-CH 2o-or-COO-, c are the integer of 1 ~ 10.
In formula [2b-2], Y 4for being selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the arbitrary hydrogen atom on these cyclic groups 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.In addition, Y 4it can be the divalent organic group of the organic group being selected from the carbon number 12 ~ 25 with steroid skeleton.Wherein, from the angle of difficulty of synthesis, be better phenyl ring, hexamethylene ring or there is the organic group of carbon number 12 ~ 25 of steroid skeleton.
In formula [2b-2], Y 5represent the divalent cyclic group being selected from phenyl ring, hexamethylene ring or heterocycle, the arbitrary hydrogen atom on these cyclic groups 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, be better phenyl ring or hexamethylene ring.
In formula [2b-2], n represents the integer of 0 ~ 4.Wherein, from the angle obtaining the difficulty of difficulty and synthesis of raw material, be better 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, be better the alkyl of 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.Be 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.
As 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 6with the preferably combination of n, the combination same with (2-1) ~ (2-629) disclosed in the table 6 ~ table 47 of 13 of International Publication publication WO2011/132751 (2011.10.27 is open) ~ 34 can be exemplified.In each table of International Publication publication, the Y in the present invention 1~ Y 6illustrate as Y1 ~ Y6, Y1 ~ Y6 can be replaced 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 represented with formula [2b] of the present invention is not particularly limited, and as preferred method, can exemplify method as described below.
As an example, after the dinitro matrix compounds that the diamine compound represented represents with following formula [2b-A] by synthesis, reduce its nitro and be converted into amino to obtain with formula [2b].
In formula [2b-A], Y represents the substituting group of at least one structure of the above-mentioned formula [2b-1] that is selected from, 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 dinitrobenzene of the dinitro matrix compounds that reduction represents with formula [2b-A] is not particularly limited, and usually has the method using palladium carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminum oxide or platinum sulfide carbon etc. to make it react as catalyzer under hydrogen, hydrazine or hydrogenchloride condition in ethyl acetate, toluene, tetrahydrofuran (THF), diox or alcoholic solvent equal solvent.
Below, exemplify the concrete structure of the 2nd diamine compound represented with formula [2b] of the present invention, but be not limited in these examples.
Namely, as the 2nd diamine compound represented with formula [2b], except mphenylenediamine, 2,4-dimethyl-m-phenylenediamines, 2,6-diaminotoluenes, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamino benzylalcohols, 2,4-diamino benzylalcohols, 4, outside 6-diamino resorcin, also can exemplify the diamine compound of the structure represented with following formula [2b-6] ~ [2b-46].
In formula [2b-6] ~ [2b-9], A 1represent the alkyl of carbon number 1 ~ 22 or contain fluoroalkyl.
In formula [2b-34] ~ formula [2b-36], R 1represent-O-,-OCH 2-,-CH 2o-,-COOCH 2-or CH 2oCO-, R 2for the alkyl of carbon number 1 ~ 22, alkoxyl group, containing fluoroalkyl or fluoroalkoxy.
In formula [2b-37] ~ formula [2b-39], R 3represent-COO-,-OCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-or-CH 2-, R 4for the alkyl of carbon number 1 ~ 22, alkoxyl group, containing fluoroalkyl or fluoroalkoxy.
In formula [2b-40] and formula [2b-41], R 5for-COO-,-OCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-,-CH 2-or-O-, R 6for fluorine-based, cyano group, trifluoromethyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl.
In formula [2b-42] and formula [2b-43], R 7represent the alkyl of carbon number 3 ~ 12.For the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene, be better trans-isomer(ide) respectively.
In formula [2b-44] and formula [2b-45], R 8represent the alkyl of carbon number 3 ~ 12.For the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene, be better trans-isomer(ide) respectively.
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 Sauerstoffatom or-COO-*, wherein, the key of band " * " and B 3in conjunction with, B 1represent Sauerstoffatom or-COO-*, wherein, key and the (CH of band " * " 2) a 2in conjunction with.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.
In 2nd diamine compound of the present invention, the substituting group Y employed in formula [2b] is the hydrophobicity that the composition of the diamine compound of the structure represented with formula [2b-2] can improve resin coating.In addition, when making liquid crystal orientation film, the tilt angle of liquid crystal can be improved.At this moment, in order to improve these effects, in above-mentioned diamine compound, be better use the diamine compound represented with formula [2b-28] ~ formula [2b-39] or formula [2b-42] ~ formula [2b-46].Be more preferably the diamine compound represented with formula [2b-24] ~ formula [2b-39] or formula [2b-42] ~ formula [2b-46].In addition, in order to improve these effects further, these diamine compounds are better more than 5 % by mole less than 80 % by mole of whole diamine component.From the angle of composition and the coating of aligning agent for liquid crystal and the electrical characteristic as liquid crystal orientation film, these diamine compounds are more preferably more than 5 % by mole less than 60 % by mole of whole diamine component.More than 10 % by mole less than 60 % by mole of particularly preferably 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, make liquid crystal orientation film time the characteristic such as orientation, voltage retention, Accumulating charge of liquid crystal, use one or more used in combination.
Other diamine compound of < >
In particular polymers of the present invention, only otherwise destroy effect of the present invention, except the diamine compound in the molecule that represents with formula [2a], formula [2a-1] ~ formula [2a-4] with carboxyl and the 2nd diamine compound represented with formula [2b], other diamine compound (also referred to as other diamine compound) can be used as diamine component.
Below, exemplify the object lesson of other diamine compound, but be not limited in these examples.
That is, as other diamine compound, 4,4'-benzidine can be exemplified, 3,3'-dimethyl-4,4'-benzidine, 3,3'-dimethoxy-4 ', 4'-benzidine, 3,3'-dihydroxyl-4,4'-benzidine, 3,3'-dicarboxyl-4,4'-benzidine, fluoro-4, the 4'-benzidines of 3,3'-bis-, 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'-diamino-diphenyl ether, 3,3'-diamino-diphenyl ether, 3,4'-diamino-diphenyl ether, 2,2'-diamino-diphenyl ether, 2,3'-diamino-diphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4'-diamino diphenyl sulfide, 3,3'-diamino diphenyl sulfide, 4,4'-diamino-diphenyl amine, 3,3'-diamino-diphenyl amine, 3,4'-diamino-diphenyl amine, 2,2'-diamino-diphenyl amine, 2,3'-diamino-diphenyl amine, 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'-diamino benzophenone, 3,3'-diamino benzophenone, 3,4'-diamino benzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2'-diamino benzophenone, 2,3'-diamino benzophenone, 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) phthalic ester, two (3-aminophenyl) phthalic ester, 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), two (4-aminophenyl) phthalic diamide of N, N'-, two (3-aminophenyl) phthalic diamide of N, N'-, two (4-aminophenyl) isophtalamide of N, N'-, two (3-aminophenyl) isophtalamide of N, N'-, two (4-aminophenyl) anthracene of 9,10-, two (4-amino-benzene oxygen) sulfobenzide of 4,4'-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2'-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2'-, two (4-aminophenyl) HFC-236fa of 2,2'-, two (3-aminophenyl) HFC-236fa of 2,2'-, two (3-amino-4-aminomethyl phenyl) HFC-236fa of 2,2'-, two (4-aminophenyl) propane of 2,2'-, two (3-aminophenyl) propane of 2,2'-, two (3-amino-4-aminomethyl phenyl) propane of 2,2'-, 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-, two (3-amino-benzene oxygen) heptane of 1,7-, 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, the aromatic diamines such as 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, also can exemplify two amine side chains have alkyl, containing fluoroalkyl, aromatic nucleus, aliphatics ring or heterocycle diamine compound and there is the diamine compound etc. that the large ring-type formed by them replaces body.Specifically, can the diamine compound that represents with following formula [DA1] ~ formula [DA13] of example.
In formula [DA1] ~ formula [DA6], A 1represent-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-, A 2represent the straight-chain of the straight-chain of carbon number 1 ~ 22 or the alkyl of branch-like or carbon number 1 ~ 22 or branch-like containing fluoroalkyl.
In formula [DA7], p represents the integer of 1 ~ 10.
Only otherwise destroy effect of the present invention, as other diamine compound, the diamine compound represented with following formula [DA8] ~ formula [DA13] can also be used.
In formula [DA10], m represents the integer of 0 ~ 3, and in formula [DA13], n represents the integer of 1 ~ 5.
In addition, only otherwise destroy effect of the present invention, the diamine compound represented with following formula [DA14] can also be used.
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) the divalent organic group 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-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, as other diamine compound, the diamine compound represented with following formula [DA15] and formula [DA16] also can be used.
Other above-mentioned diamine compound also can particular polymers according to the present invention to the coating of the solvability of solvent and composition, make liquid crystal orientation film time the characteristic such as orientation, voltage retention, Accumulating charge of liquid crystal, use one or more used in combination.
< tetracarboxylic dianhydride composition >
As the tetracarboxylic acid composition for the preparation of particular polymers of the present invention, the tetracarboxylic dianhydride or its tetracarboxylic acid derivatives (also referred to as specific tetracarboxylic dianhydride's composition) that represent with following formula [3] can be exemplified.
In formula [3], Z 1for being selected from the group of at least one structure of following formula [3a] ~ formula [3j].
In formula [3a], Z 2~ Z 5represent hydrogen atom, methyl, chlorine atom or phenyl ring, may be the same or different respectively.
In formula [3g], Z 6, Z 7represent hydrogen atom or methyl, may be the same or different respectively.
As specific tetracarboxylic dianhydride's composition of the present invention formula [3] shown in structure in, from the angle of difficulty of the difficulty of synthesis and polymerisation reactivity when manufacturing polymkeric substance, Z 1it is better the structure represented with formula [3a], formula [3c], formula [3d], formula [3e], formula [3f] or formula [3g].Be more preferably the structure represented with formula [3a], formula [3e], formula [3f] or formula [3g], particularly preferably formula [3e], formula [3f] or formula [3g].
Specific tetracarboxylic dianhydride's composition of the present invention is better more than 1 % by mole in whole tetracarboxylic acid composition.Be more preferably more than 5 % by mole, 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 in whole tetracarboxylic dianhydride's composition more than 20 % by mole, required effect can be obtained.It is better more than 30 % by mole.In addition, tetracarboxylic dianhydride's composition can be all specific tetracarboxylic dianhydride's composition of the structure of formula [3e], formula [3f] or formula [3g].
In particular polymers of the present invention, only otherwise destroy effect of the present invention, other tetracarboxylic dianhydride's composition except specific tetracarboxylic dianhydride's composition can be used.
As other tetracarboxylic dianhydride's composition, 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'-sulfobenzide tetracarboxylic acid, 3, 4, 9, 10-tetracarboxylic acid or 1, 3-phenylbenzene-1, 2, 3, 4-cyclobutanetetracarboxylic.
Specific tetracarboxylic acid composition and other tetracarboxylic acid composition also can particular polymers according to the present invention to the coating of the solvability of solvent and composition, make liquid crystal orientation film time the characteristic such as orientation, voltage retention, Accumulating charge of liquid crystal, use one or more used in combination.
The manufacture method > of < particular polymers
In the present invention, the method for synthesis particular polymers is not particularly limited.Usually, diamine component and tetracarboxylic dianhydride's composition is made to react and obtain.Generally make at least one tetracarboxylic dianhydride composition being selected from tetracarboxylic dianhydride and derivative thereof react with the diamine component comprising one or more diamine compounds, obtain polyamic acid.Specifically, the diamine compound polycondensation of tetracarboxylic dianhydride and primary amine or secondary amine can be used and obtain polyamic acid method, make the diamine compound of tetracarboxylic acid and primary amine or secondary amine carry out dehydrating polycondensation reaction and obtain the method for polyamic acid or make the diamine compound polycondensation of dicarboxylic acid two carboxylic acid halides and primary amine or secondary amine and obtain the method for polyamic acid.
In order to obtain polyamic acid alkyl ester, the method for the diamine compound polycondensation of the method for the tetracarboxylic acid that can use the esterification of carboxyl dialkyl group and the diamine compound polycondensation of primary amine or secondary amine, dicarboxylic acid two carboxylic acid halides made the esterification of carboxyl dialkyl group and primary amine or secondary amine or the method being ester by the converting carboxylate groups of polyamic acid.
In order to obtain polyimide, above-mentioned polyamic acid or polyamic acid alkyl ester closed loop can be used and form the method for polyimide.
The reaction of diamine component and tetracarboxylic dianhydride's composition makes diamine component and tetracarboxylic dianhydride's composition react in organic solvent usually.As the organic solvent at this moment used, as long as maybe can dissolve the solvent of the polyimide precursor of generation as the specific solvent of (A) of the present invention composition, be not particularly limited.
As the solvent beyond specific solvent of the present invention, following solvent can be exemplified.
Namely, N can be exemplified, dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, methyl-sulphoxide, gamma-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, pimelinketone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone etc.
They can be used alone, also can be used in combination.In addition, even the solvent that polyimide precursor dissolves cannot be made, in the scope that the polyimide precursor generated can not be separated out, can be mixed in above-mentioned solvent and use.In addition, the moisture in organic solvent hinders polyreaction, also can cause the polyimide precursor hydrolysis generated, so organic solvent is better use the solvent after dehydrating.
When diamine component and tetracarboxylic acid composition are reacted in organic solvent, following method can be exemplified: stir and make diamine component be dispersed or dissolved in organic solvent and the solution that obtain, tetracarboxylic dianhydride's composition is direct or carry out the method for adding after being dispersed or dissolved in organic solvent; Otherwise, in the solution obtained to making tetracarboxylic dianhydride be dispersed or dissolved in organic solvent, add the method for diamine component; By the method etc. that tetracarboxylic dianhydride's composition and diamine component alternately add.Any one method wherein can be used.In addition, diamine component or tetracarboxylic dianhydride's composition use multiple when carrying out reacting 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 hybrid reaction obtained and obtain polymkeric substance.At this moment polymerization temperature can select the arbitrary temp of-20 DEG C ~ 150 DEG C, is better in the scope of-5 DEG C ~ 100 DEG C.In addition, reaction can be carried out under arbitrary concentration, if but concentration is too low, then and be difficult to obtain the polymkeric substance of high molecular, if excessive concentration, then the viscosity of reaction solution is too high and be difficult to stir.Therefore, be better 1 ~ 50 quality %, be more preferably 5 ~ 30 quality %.Initial reaction stage can carry out in higher concentrations, then add organic solvent.
In the polyreaction of polyimide precursor, the ratio of the total mole number of diamine component and the total mole number of tetracarboxylic dianhydride's composition is better 0.8 ~ 1.2.Same 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 is the polyimide making described polyimide precursor closed loop and obtain, in this polyimide, the closed loop rate (also referred to as imide rate) of acid amides acidic group is not necessary for 100%, at random can adjust according to purposes or object.
As the method making polyimide precursor imidization, can exemplify direct-fired for the solution of polyimide precursor hot-imide or the catalysis imidization adding catalyzer in the solution of polyimide precursor.
Make polyimide precursor in the solution hot-imide time temperature be 100 DEG C ~ 400 DEG C, being better 120 DEG C ~ 250 DEG C, is better carry out while being expelled to outside system by the water generated by imidization reaction.
The catalysis imidization of polyimide precursor by adding basic catalyst and acid anhydrides in the solution of polyimide precursor, at-20 ~ 250 DEG C, preferably can stir and carrying out at 0 ~ 180 DEG C.The amount of basic catalyst is mole to count 0.5 ~ 30 times of acid amides acidic group, preferably 2 ~ 20 times, and the amount of acid anhydrides is mole to count 1 ~ 50 times of acid amides acidic group, preferably 3 ~ 30 times.As basic catalyst, can exemplify pyridine, triethylamine, Trimethylamine 99, Tributylamine or trioctylamine etc., wherein pyridine has the alkalescence for making reaction carry out appropriateness, 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 dropped in solvent and make it precipitate.As the solvent for precipitating, methyl alcohol, ethanol, Virahol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, benzene, water etc. can be exemplified.The polymkeric substance putting into precipitation in solvent after filtered and recycled, can carry out drying in normal temperature or heating under normal or reduced pressure.In addition, if the polymkeric substance repeating to make precipitation reclaim is dissolved in organic solvent and the redeposition operation 2 ~ 10 times of reclaiming again, then the impurity in polymkeric substance can be reduced.As solvent now, can exemplify such as alcohols, ketone or hydro carbons etc., if use the solvent being selected from more than 3 kinds of these solvents, then purification efficiency improves further, therefore preferably.
When considering operability when the resin coating that obtained by it or liquid crystal aligning film strength, film are formed and film, the molecular weight of particular polymers of the present invention is to pass through GPC (gel permeation chromatography, Gel Permeation Chromatography) to haggle over be 5000 ~ 1000000 to the weight-average molecular weight that measures of method, is more preferably 10000 ~ 150000.
The specific polysiloxane > of <
As the specific polysiloxane of (C) of the present invention composition for making to comprise the organoalkoxysilane polycondensation of any one in the organoalkoxysilane that represents with described formula [A1], formula [A2] or formula [A3] and the polysiloxane obtained.
The organoalkoxysilane represented with formula [A1] of the present invention is the organoalkoxysilane represented with following formula [A1].
[changing 55]
(A 1) mSi(A 2) n(OA 3) p[A1]
In formula [A1], A 1for aliphatic hydrocarbon, phenyl ring, hexamethylene ring, heterocycle or the organic group of carbon number 8 ~ 35 with steroid structure.
In formula [A1], A 2be respectively the alkyl of hydrogen atom or carbon number 1 ~ 5.Wherein, be better the alkyl of hydrogen atom or carbon number 1 ~ 3.
In formula [A1], A 3be respectively the alkyl of carbon number 1 ~ 5.Wherein, from reactive angle of polycondensation, it is better the alkyl of carbon number 1 ~ 3.
In formula [A1], m is the integer of 1 or 2.Wherein, from the angle of synthesis, be better 1.
In formula [A1], n is the integer of 0 ~ 2.
In formula [A1], p is the integer of 0 ~ 3.Wherein, from reactive angle of polycondensation, it is better the integer of 1 ~ 3.Be more preferably 2 or 3.
In formula [A1], m+n+p is 4.
As the object lesson of the organoalkoxysilane represented with 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, triethoxy-1H, 1H, 2H, 2H-ten trifluoro n-octyl silane, dimethoxydiphenyl silane, dimethoxymethylphenylsilane or triethoxyphenylsilan etc.
In addition, the organoalkoxysilane represented with following formula [A1-1] ~ formula [A1-32] can also be used.
In formula [A1-1] ~ formula [A1-18], R 1represent the alkyl of carbon number 1 ~ 5 respectively.
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.
In formula [A1-23] and 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.
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.
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 Sauerstoffatom or-COO-*, wherein, the key of band " * " and B 3in conjunction with, B 1represent Sauerstoffatom or COO-*, wherein, key and the (CH of band " * " 2) a 2in conjunction with.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 above-mentioned organoalkoxysilane represented with formula [A1] can, according to resin coating or liquid crystal aligning film strength and operability when forming these films and the characteristic such as liquid crystal aligning, voltage retention, Accumulating charge when making liquid crystal orientation film, use one or more used in combination.
The organoalkoxysilane represented with formula [A2] of the present invention is the organoalkoxysilane represented with following formula [A2].
[changing 70]
(B 1) mSi(B 2) n(OB 3) p[A2]
In formula [A2], B 1for having the organic group of the carbon number 2 ~ 12 of vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl.Wherein, from the angle of the difficulty obtained, be better vinyl, epoxy group(ing), amino, methacryloyl, acryl or urea groups.Be more preferably methacryloyl, acryl or urea groups.
In formula [A2], B 2be respectively the alkyl of hydrogen atom or carbon number 1 ~ 5.Wherein, be better the alkyl of hydrogen atom or carbon number 1 ~ 3.
In formula [A2], B 3be respectively the alkyl of carbon number 1 ~ 5.Wherein, from reactive angle of polycondensation, it is better the alkyl of carbon number 1 ~ 3.
In formula [A2], m is the integer of 1 or 2.Wherein, from the angle of synthesis, be better 1.
In formula [A2], n is the integer of 0 ~ 2.
In formula [A2], p is the integer of 0 ~ 3.Wherein, from reactive angle of polycondensation, it is better the integer of 1 ~ 3.Be more preferably 2 or 3.
In formula [A2], m+n+p is 4.
As the object lesson of the organoalkoxysilane represented with 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-glycidoxypropyl group) methyl-monosilane, 3-glycidoxypropyl group (dimethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane, 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, 3-(triethoxysilicane alkyl) propylisocyanate, methacrylic acid-3-(triethoxysilicane alkyl) propyl diester, methacrylic acid-3-(Trimethoxy silane base) propyl diester, vinylformic acid-3-(triethoxysilicane alkyl) propyl diester, vinylformic acid-3-(Trimethoxy silane base) propyl diester, methacrylic acid-3-(triethoxysilicane alkyl) ethyl ester, methacrylic acid-3-(Trimethoxy silane base) ethyl ester, vinylformic acid-3-(triethoxysilicane alkyl) ethyl ester, vinylformic acid-3-(Trimethoxy silane base) ethyl ester, methacrylic acid-3-(triethoxysilicane alkyl) methyl ester, methacrylic acid-3-(Trimethoxy silane base) methyl ester, vinylformic acid-3-(triethoxysilicane alkyl) methyl ester, vinylformic acid-3-(Trimethoxy silane base) methyl ester, γ-ureidopropyltriethoxysilane, γ-ureido-propyl Trimethoxy silane, γ-ureido-propyl tripropoxy silane, (R)-N-1-phenylethyl-N'-tri-ethoxy silylpropyl urea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropyl urea, two [3-(Trimethoxy silane base) propyl group] urea, two [3-(tripropoxy silylation) propyl group] urea, 1-[3-(Trimethoxy silane base) propyl group] urea etc.
The above-mentioned organoalkoxysilane represented with formula [A2] can, according to resin coating or liquid crystal aligning film strength and operability when forming these films and the characteristic such as liquid crystal aligning, voltage retention, Accumulating charge when making liquid crystal orientation film, use one or more used in combination.
The organoalkoxysilane represented with formula [A3] of the present invention is the organoalkoxysilane represented with following formula [A3].
[changing 71]
(D 1) nSi(OD 2) 4-n[A3]
In formula [A3], D 1be respectively the alkyl of hydrogen atom or carbon number 3 ~ 5, they can be replaced by halogen atom, nitrogen-atoms, Sauerstoffatom, sulphur atom.Wherein, be better the alkyl of hydrogen atom or carbon number 1 ~ 3.
In formula [A3], D 2be respectively the alkyl of carbon number 1 ~ 5.Wherein, from reactive angle of polycondensation, it is better the alkyl of carbon number 1 ~ 3.
In formula [A3], n is the integer of 0 ~ 3.
As the object lesson of the organoalkoxysilane represented with 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-r-chloropropyl trimethoxyl silane etc.
In above-mentioned formula [A3], be the organoalkoxysilane of 0 as n, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes etc. can be exemplified.
The above-mentioned organoalkoxysilane represented with formula [A3] can, according to resin coating or liquid crystal aligning film strength and operability when forming these films and the characteristic such as liquid crystal aligning, voltage retention, Accumulating charge when making liquid crystal orientation film, use one or more used in combination.
Specific polysiloxane of the present invention, for making to comprise the organoalkoxysilane polycondensation of any one in the organoalkoxysilane that represents with described formula [A1], formula [A2] or formula [A3] and the polysiloxane obtained, is better make to comprise the organoalkoxysilane polycondensation of multiple described organoalkoxysilane and the polysiloxane obtained.Namely, the organoalkoxysilane of 2 kinds making to comprise described formula [A1] and formula [A2], described formula [A1] and formula [A3] or described formula [A2] and formula [A3] can be exemplified, and the polysiloxane comprising this 3 kinds the organoalkoxysilane polycondensation of described formula [A1], formula [A2] and formula [A3] and obtain.Wherein, be better comprise described formula [A1] and formula [A2], described formula [A1] and formula [A3] the organoalkoxysilane of 2 kinds or comprise described formula [A1], formula [A2] and this organoalkoxysilane of 3 kinds of formula [A3].
The organoalkoxysilane represented with described formula [A1], formula [A2] or formula [A3] is used to obtain specific polysiloxane of the present invention.
The organoalkoxysilane represented with formula [A1] is better 1 ~ 40 % by mole in whole organoalkoxysilanes, is more preferably 1 ~ 30 % by mole.
In addition, the organoalkoxysilane represented with formula [A2] is better 1 ~ 70 % by mole in whole organoalkoxysilanes, is more preferably 1 ~ 60 % by mole.
In addition, the organoalkoxysilane represented with formula [A3] is better 1 ~ 99 % by mole in whole organoalkoxysilanes, is more preferably 1 ~ 80 % by mole.
Obtain the method being used for specific polysiloxane of the present invention to be not particularly limited.Specific polysiloxane in the present invention obtains by the organoalkoxysilane polycondensation of any one that makes to comprise in the organoalkoxysilane that represents with described formula [A1], formula [A2] or formula [A3], or makes the multiple organoalkoxysilane in the organoalkoxysilane that represents with described formula [A1], formula [A2] or formula [A3] be polymerized in organic solvent and obtain.In addition, specific polysiloxane of the present invention as by organoalkoxysilane polycondensation and uniform dissolution in organic solvent solution and obtain.
The method that specific polysiloxane of the present invention carries out polycondensation is not particularly limited.Wherein, can exemplify and such as make organoalkoxysilane be hydrolyzed in specific solvent of the present invention, alcoholic solvent or glycolic solvents the method for polycondensation.At this moment, in adjustment composition of the present invention or aligning agent for liquid crystal, be better use specific solvent of the present invention.
Hydrolysis condensation reaction can be partial hydrolysis, also can be complete hydrolysis.When complete hydrolysis, adding the water of 0.5 times of molar weight of the whole alkoxyl groups in organoalkoxysilane in theory, is better the water of the amount being added beyond 0.5 times of molar weight usually.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, is better 0.5 ~ 2.5 times of molar weight of the whole alkoxyl groups in organoalkoxysilane.
In addition, in order to facilitation of hydrolysis polycondensation, 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 such as the metal-salt of hydrochloric acid, nitric acid or nitric acid etc.In addition, also the solution of organoalkoxysilane is had to carry out facilitation of hydrolysis polycondensation by heating for dissolving.At this moment, suitably can select according to object Heating temperature and heat-up time.Such as, can exemplify in 50 DEG C of heated and stirred condition such as heated and stirred 1 hour under reflux after 24 hours.
In addition, as other method of polycondensation, the mixture of heating organoalkoxysilane, organic solvent and oxalic acid can be exemplified to carry out the method for polycondensation.Specifically, be in specific solvent of the present invention or alcoholic solvent, add oxalic acid in advance and after making the solution of oxalic acid, the method for mixed oxyalkyl silane under the state of this solution of heating.At this moment, the amount of the oxalic acid used in above-mentioned reaction is better 0.2 ~ 2.0 mole relative to the whole alkoxyl groups in organoalkoxysilane 1 mole.In addition, this reaction can be carried out under solution temperature is the condition of 50 ~ 180 DEG C, is better under the evaporation that solvent does not occur and the condition be vaporized, to carry out several tens minutes under reflux to tens of hours.
Obtain in the polycondensation of specific polysiloxane of the present invention, when using the multiple organoalkoxysilane represented with described formula [A1], formula [A2] and formula [A3], can use and multiple organoalkoxysilane to be pre-mixed and the mixture obtained reacts, also can react while adding multiple organoalkoxysilane successively.
As the solvent used in the polycondensation of organoalkoxysilane, as long as the solvent of dissolvane TMOS, be not particularly limited.In addition, even do not dissolve the solvent of organoalkoxysilane, as long as the solvent that can dissolve while the polycondensation of organoalkoxysilane is carried out.As the solvent used in polycondensation, because the polycondensation of usual organoalkoxysilane can generate alcohol, alcoholic solvent, glycolic solvents, glycol ethers solvent or the organic solvent good with the intermiscibility of alcohol therefore can be used.As the object lesson of the solvent used in such polycondensation, the alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol, butanols or Pyranton can be exemplified, ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-PD, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-PD, 2,4-pentanediols, 2, the glycolic solvents such as 3-pentanediol or 1,6-hexylene glycol, 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 solvents such as propylene glycol dipropyl ether or propylene glycol dibutyl ether, the organic solvent that METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, gamma-butyrolactone, DMF, N,N-dimethylacetamide, methyl-sulphoxide, tetramethyl-urea, HMPA or meta-cresol etc. are good with the intermiscibility of alcohol.
Wherein, in the aligning agent for liquid crystal adjusting composition of the present invention or use said composition, be better use specific solvent of the present invention.In addition, in the present invention, what can use in above-mentioned solvent during polycondensation is one kind or two or more used in combination.
In the polymeric solution of the specific polysiloxane obtained by aforesaid method, the Siliciumatom that the whole organoalkoxysilanes added as raw material have is scaled SiO 2and the concentration obtained is (also referred to as SiO 2converted score) be better below 20 quality %.Wherein, be better 5 ~ 15 quality %.By selecting arbitrary concentration in this concentration range, the generation of the gel in solution can be suppressed, obtaining the polycondensation solution of uniform specific polysiloxane.
In the present invention, can using the polycondensation solution of specific polysiloxane that obtained by above-mentioned method directly as the solution of the specific polysiloxane of (C) of the present invention composition, also can as required the polycondensation solution of the specific polysiloxane obtained by above-mentioned method is concentrated or solubilizing agent dilution or after being replaced as other solvent as the solution of the specific polysiloxane of (C) composition.
The solvent (also referred to as interpolation solvent) used when adding above-mentioned solvent cut can be the solvent used in polycondensation, specific solvent of the present invention and other solvent.As long as this interpolation solvent can the specific polysiloxane of uniform dissolution, be not particularly limited, one kind or two or more use can be selected arbitrarily.As such interpolation solvent, except the solvent used in above-mentioned polycondensation, also can exemplify the ketones solvents such as acetone, methyl ethyl ketone or methyl iso-butyl ketone (MIBK), the esters solvents etc. such as methyl acetate, ethyl acetate or ethyl lactate.
In the present invention, the specific polysiloxane of (C) composition is better before mixing with the particular polymers of (B) composition, is heated up in a steamer under normal or reduced pressure the alcohol generated during the polycondensation of specific polysiloxane.
< composition and aligning agent for liquid crystal >
The aligning agent for liquid crystal of composition of the present invention or use said composition is the coating solution for the formation of resin coating or liquid crystal orientation film (being also referred to as resin coating), is the coating solution for the formation of the resin coating comprising specific solvent, particular polymers and specific polysiloxane.Wherein, composition or use said composition aligning agent for liquid crystal in polymkeric substance of the present invention represent particular polymers and specific polysiloxane.
The content of the specific polysiloxane in the aligning agent for liquid crystal of composition of the present invention or use said composition is better 0.1 ~ 90 mass parts relative to particular polymers composition 100 mass parts.Wherein, from the angle of the stability of composition or aligning agent for liquid crystal, 1 ~ 70 mass parts is more preferably relative to particular polymers 100 mass parts.Particularly preferably 5 ~ 60 mass parts.
All component of polymer in the aligning agent for liquid crystal of composition of the present invention or use said composition can be all polymkeric substance of the present invention, also can be mixed with other polymkeric substance in addition in particular polymers of the present invention.At this moment, the content of other polymkeric substance is in addition 0.5 quality % ~ 15 quality % of polymkeric substance of the present invention, is better 1 quality % ~ 10 quality %.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.In addition, also can exemplify the polymkeric substance except polyimide precursor and polyimide, be specially acrylate copolymer, methacrylate polymer, polystyrene or polymeric amide etc.
From the viewpoint being formed uniform resin coating by coating, the content of the organic solvent in the aligning agent for liquid crystal of composition of the present invention or use said composition is better 70 ~ 99.9 quality %.Its content can according to the target film thickness of resin coating or liquid crystal orientation film and appropriate change.
Whole organic solvents in the organic solvent used in the aligning agent for liquid crystal of composition of the present invention or use said composition can be all specific solvent of the present invention, also can be mixed with other solvent in addition in organic solvent of the present invention.At this moment, specific solvent of the present invention is better 50 ~ 100 quality % of composition or the whole solvents contained by aligning agent for liquid crystal.Wherein, be better 55 ~ 100 quality %.Be more preferably 55 ~ 95 quality %.
As other organic solvent in addition, as long as the organic solvent that particular polymers and specific polysiloxane can be made to dissolve, be not particularly limited.Below, its object lesson is exemplified.
Such as, N can be exemplified, dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, methyl-sulphoxide, gamma-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, pimelinketone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone etc.
Wherein, be better use METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone or gamma-butyrolactone (above also referred to as (D) composition).
These (D) compositions are better 1 ~ 50 quality % of composition or the whole organic solvents contained by aligning agent for liquid crystal using said composition.Wherein, be better 1 ~ 40 quality %.Be more preferably 1 ~ 30 quality %, be more preferably 5 ~ 30 quality % further.
Only otherwise destroy effect of the present invention, organic solvent, poor solvent that the film of composition of the present invention or resin coating when using the aligning agent for liquid crystal of said composition can use coating composition or use the aligning agent for liquid crystal of said composition or liquid crystal orientation film and surface smoothness improve.
Below, the object lesson of the poor solvent of the film making resin coating or liquid crystal orientation film and surface smoothness raising is exemplified.
Such as, ethanol can be exemplified, 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-ethandiol, 1,2-PD, 1,3-PD, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 2,3-butanediol, 1,5-PD, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexylene glycol, dipropyl ether, dibutyl ether, two hexyl ethers, dioxane, 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 methyl ethyl ether, dibutyl ethylene glycol ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-heptanone, dipropyl ketone, 3-ethoxybutyl acetic ester, 1-methyl amyl acetic ester, 2-ethyl-butyl acetic ester, 2-ethylhexyl acetate, ethylene glycol acetate, glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol list isoamyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ether, 2-(hexyloxy) ethanol, furfuryl alcohol, Diethylene Glycol, propylene glycol, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, diethylene 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, propylene glycol acetate list ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methylethyl ester, 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, n-butyl lactate or isoamyl lactate etc. have the organic solvent of low surface tension.
Wherein, better use 1-hexanol, hexalin, 1,2-ethylene glycol, 1,2-PD, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, glycol isopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether (above also referred to as (E) composition).
These (E) compositions are better 1 ~ 50 quality % of composition or the whole organic solvents contained by aligning agent for liquid crystal using said composition.Wherein, be better 1 ~ 45 quality %.Be more preferably 5 ~ 45 quality %, be more preferably 5 ~ 40 quality % further.
In the aligning agent for liquid crystal of composition of the present invention or use said composition, in the scope not destroying effect of the present invention, also can import the cross-linked compound with epoxy group(ing), isocyanate group, oxetanyl or cyclic carbonate group, 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 and polymerizability unsaturated link(age) must have more than 2 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, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl group isocyanuric acid ester, benzene stretched by four glycidyl group amino connection, four glycidyl group m-xylene diamine, two (amino-ethyl) hexanaphthene of tetracarboxylic acid peroxy-1,3-, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bis-phenol hexafluoro ethanoyl diglycidyl ether, 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-glycidoxy) phenyl)-1-(4-(1-(4-(2,3-glycidoxy) phenyl)-1-methylethyl) phenyl) ethyl) phenoxy group)-2-propyl alcohol etc.
The cross-linked compound with oxetanyl is the cross-linked compound at least with the oxetanyl that 2 represent with following formula [4].
Be specially the cross-linked compound represented with following formula [4-1] ~ formula [4-11].
In formula [4-1], n represents the integer of 1 ~ 3.
In formula [4-7], n represents the integer of 1 ~ 3, and in formula [4-8], n represents the integer of 1 ~ 3, and in formula [4-9], n represents the integer of 1 ~ 100.
In formula [4-11], n represents the integer of 1 ~ 10.
As the cross-linked compound with cyclic carbonate group, it is the cross-linked compound at least with the cyclic carbonate group that 2 represent with following formula [5].
Be specially the cross-linked compound represented with following formula [5-1] ~ formula [5-37].
In formula [5-24], n represents the integer of 1 ~ 10, and in formula [5-25], n represents the integer of 1 ~ 10.
In formula [5-36], n represents the integer of 1 ~ 100, and in formula [5-37], n represents the integer of 1 ~ 10.
In addition, the polysiloxane with at least a kind of structure shown in following formula [5-38] ~ formula [5-40] can also be exemplified.
In formula [5-38] ~ formula [5-40], R 1, R 2, R 3, R 4and R 5separately represent the structure, hydrogen atom, hydroxyl, the alkyl of carbon number 1 ~ 10, alkoxyl group, aliphatics ring or the aromatic ring that represent with formula [5], at least 1 is the structure represented with formula [5].
More particularly, following formula [5-41] and the compound of formula [5-42] can be exemplified.
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, the aminoresin such as with hydroxyl or alkoxyl group can be exemplified, such as melamine resin, urea resin, guanamine resin, glycolurilformaldehyde resins, succinic diamide-formaldehyde resin or ethene urea-formaldehyde resins etc.Specifically, amino hydrogen atom can be used by methylol or alkoxy methyl or melamine derivative, benzo guanamine derivative or glycoluril that both replaces.This melamine derivative or benzo guanamine derivative also can dimer or the existence of trimerical form.These compounds are better methylol or the alkoxy methyls that every 1 triazine ring on average has more than 3 less than 6.
As the example of such melamine derivative or benzo guanamine derivative, the MX-750 that every 1 triazine ring as commercially available product on average has 3.7 methoxymethyies to replace can be exemplified, MW-30 that every 1 triazine ring on average has 5.8 methoxymethyies to replace (being Sanwa Chemical Co., Ltd (three and ケ ミ カ Le society) system above), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, the methoxymethylated trimeric cyanamides such as 712, Cymel 235, 236, 238, 212, 253, the methoxymethylated butoxymethyl trimeric cyanamides such as 254, Cymel 506, the butoxymethyl trimeric cyanamides such as 508, the carboxylic methoxymethylated isobutoxymethyl trimeric cyanamides such as Cymel 1141, the methoxymethylated ethoxyl methyl benzo guanamines such as Cymel 1123, the methoxymethylated butoxymethyl benzo guanamines such as Cymel 1123-10, the butoxymethyl benzo guanamines such as Cymel 1128, the carboxylic methoxymethylated ethoxyl methyl benzo guanamines such as Cymel 1125-80 (being Mitsui cyanamide Co., Ltd. (Mitsui サ イ ア Na ミ De society) system above).In addition, as the example of glycoluril, the methoxyl group methylolation glycolurils etc. such as the methylolation such as butoxymethyl glycoluril, Cymel 1172 glycoluril, POWDERLINK 1174 such as Cymel 1170 can be exemplified.
As benzene or the phenoloid with hydroxyl or alkoxyl group, such as 1 can be exemplified, 3,5-tri-(methoxymethyl) benzene, 1,2,4-tri-(i-propoxymethyl) benzene, 1,4-two (sec-butoxymethyl) benzene or 2,6-bishydroxymethyl p-tert-butylphenol etc.
More particularly, the cross-linked compound represented with formula [6-1] ~ formula [6-48] published in 62 pages ~ 66 pages of International Publication publication WO2011/132751 (2011.10.27 is open) can be exemplified.
As the cross-linked compound with polymerizability unsaturated link(age), such as trimethylolpropane tris (methyl) acrylate can be exemplified, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, there is in three (methyl) acryloyloxyethoxy TriMethylolPropane(TMP) or the many glycidyl ethers of glycerine many (methyl) acrylate equimolecular the cross-linked compound of 3 polymerizability unsaturated groups, and ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxyethane-bisphenol A-type two (methyl) acrylate, propylene oxide-bisphenol type two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, glycerine two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, ethylene glycol diglycidyl base ether two (methyl) acrylate, diethylene glycol diglycidyl glyceryl ether two (methyl) acrylate, there is in phthalic acid diglycidyl ester two (methyl) acrylate or hydroxyl trimethylacetic acid DOPCP two (methyl) acrylate equimolecular the cross-linked compound of 2 polymerizability unsaturated groups, also have 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, 2-phenoxy group-2-hydroxypropyl (methyl) acrylate, 2-(methyl) acryloxy-2-hydroxypropyl phthalate, 3-chlorine-2-hydroxyl propyl group (methyl) acrylate, glycerine list (methyl) acrylate, there is in 2-(methyl) acryloyl-oxyethyl phosphoric acid ester or N-methylol (methyl) acrylamide equimolecular the cross-linked compound of 1 polymerizability unsaturated group.
In addition, the compound represented with following formula [7] can also be used.
In formula [7], E 1represent the group being selected from hexamethylene ring, the own ring of dicyclo, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus or phenanthrene ring, E 2represent and be selected from following formula [7a] or the group of formula [7b], n represents the integer of 1 ~ 4.
Above-claimed cpd is an example of cross-linked compound, is not limited in these compounds.In addition, the cross-linked compound used in the aligning agent for liquid crystal of composition of the present invention or use said composition can be a kind, also can two or more combination.
The content of the cross-linked compound in the aligning agent for liquid crystal of composition of the present invention or use said composition is better 0.1 ~ 150 mass parts relative to whole component of polymer 100 mass parts.Playing target effect to make crosslinking reaction carry out, being more preferably 0.1 ~ 100 mass parts relative to whole component of polymer 100 mass parts, particularly preferably 1 ~ 50 mass parts.
When making liquid crystal orientation film to use the aligning agent for liquid crystal of composition of the present invention, moving as the electric charge promoted in liquid crystal orientation film and promote to use the compound removing electric charge of the liquid crystal cell of this liquid crystal orientation film, is better the nitrogen heterocyclic ring amine compound represented with formula [M1] ~ formula [M156] published in 69 pages ~ 73 pages of interpolation International Publication publication WO2011/132751 (2011.10.27 is open).This amine compound can directly make an addition in composition, preferably with suitable solvent be adjusted to concentration 0.1 quality % ~ 10 quality %, be better 1 quality % ~ 7 quality % solution after add.As this solvent, as long as make the organic solvent of above-mentioned polymer dissolution, be not particularly limited.
Only otherwise destroy effect of the present invention, the compound that the homogeneity of the thickness of composition of the present invention or resin coating when using the aligning agent for liquid crystal of said composition can use coating composition or use the aligning agent for liquid crystal of said composition or liquid crystal orientation film and surface smoothness improve.In addition, the compound etc. that the adaptation of resin coating or liquid crystal orientation film and substrate also can be used to improve.
As the compound that the homogeneity and surface smoothness that make the thickness of resin coating or liquid crystal orientation film improve, fluorine class tensio-active agent, siloxane type surfactants, nonionic surfactant etc. can be exemplified.
More particularly, such as eftop EF301 can be exemplified, EF303, EF352 (being Tuo Kaimu goods Co., Ltd. (ト ー ケ system プ ロ ダ クツ society) system above), MEGAFACE F171, F173, R-30 (being Dainippon Ink. & Chemicals Inc (large Japanese イ Application キ society) system above), Fluorad FC430, FC431 (being Sumitomo 3M Co., Ltd. (Sumitomo ス リ ー エ system society) system above), AashiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (being Asahi Glass Co., Ltd (Asahi Glass society) system above) etc.The usage ratio of these tensio-active agents is better 0.01 ~ 2 mass parts relative to whole component of polymer 100 mass parts contained by composition or aligning agent for liquid crystal, is more preferably 0.01 ~ 1 mass parts.
As the object lesson of the compound making the adaptation of resin coating or liquid crystal orientation film and substrate improve, the compound containing functional silanes shown below or 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-tri-ethoxy silylpropyl diethylenetriamine, N-trimethoxysilylpropyl diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilicane alkyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-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 diglycidyl base ether, polyethylene glycol diglycidyl base ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexylene glycol diglycidyl ether, glycerine diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N', N'-four glycidyl group m-xylene diamine, two (N, N-diglycidyl amino methyl) hexanaphthene or N, N, N', N'-four glycidyl group-4, the 4'-diaminodiphenyl-methane etc. of 1,3-.
When the compound using these to make resin coating or liquid crystal orientation film and substrate closely sealed, its usage quantity relative to composition or use said composition aligning agent for liquid crystal contained by whole component of polymer 100 mass parts be better 0.1 ~ 30 mass parts, be more preferably 1 ~ 20 mass parts.If lower than 0.1 mass parts, then cannot expect the effect that adaptation improves; If higher than 30 mass parts, then the storage stability of the aligning agent for liquid crystal of composition or use said composition may be deteriorated.
In the liquid crystal aligning process of composition of the present invention or use said composition, except above-mentioned poor solvent, cross-linked compound, the compound that the homogeneity of the thickness of resin coating or liquid crystal orientation film and surface smoothness are improved and make itself and substrate closely sealed compound except, as long as in the scope not destroying effect of the present invention, dielectric medium or the conducting material of the electrical specification such as specific inductivity and electroconductibility for changing resin coating or liquid crystal orientation film can be added.
< resin coating >
Composition of the present invention can coated on substrate and after burning till, use as resin coating.As the substrate now used, according to the device as target, the plastic bases etc. such as glass substrate, silicon wafer, vinylformic acid substrate and polycarbonate substrate also can be used.The coating process of composition is not particularly limited, the method that industrial usual employing is undertaken by pickling process, 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.
Composition is coated after on substrate, by the heater meanses such as hot-plate, thermal cycling type baking oven or IR (infrared rays) type baking oven 50 ~ 300 DEG C, be better 80 ~ 250 DEG C solvent evaporated, thus can be made into resin coating.The thickness of the resin coating after burning till can be adjusted to 0.01 ~ 100 μm according to object.
< liquid crystal orientation film and liquid crystal display device >
Use the aligning agent for liquid crystal of composition of the present invention coating on substrate and after burning till, to carry out orientation process by friction treatment or illumination etc., thus use as liquid crystal orientation film.In addition, when vertical orientated purposes etc., also can be used as liquid crystal orientation film when not carrying out orientation process and use.As the substrate now used, as long as the substrate that the transparency is high, be not particularly limited, glass substrate and the plastic base etc. such as vinylformic acid substrate and polycarbonate substrate 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 the liquid crystal display device of reflection-type, can adopt the opaque substrates such as silicon wafer by the substrate only in side, the electrode in this situation also can use the material of the reflected light such as aluminium.
The coating process of aligning agent for liquid crystal is not particularly limited, the method that industrial usual employing is undertaken by silk screen printing, offset printing, flexographic printing or ink jet method etc.As other coating process, also have dip coating, rolling method, slot coated, 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, by the heater meanses such as hot-plate, thermal cycling type baking oven or IR (infrared rays) type baking oven 50 ~ 300 DEG C, be better 80 ~ 250 DEG C solvent evaporated, thus can be made into liquid crystal orientation film.For the thickness of the liquid crystal orientation film after burning till, if excessive, be then disadvantageous in the current consumption of liquid crystal display device, if too small, then the reliability of liquid crystal display device may reduce, so be better 5 ~ 300nm, is more preferably 10 ~ 100nm.When making liquid crystal horizontal alignment or tilted alignment, the liquid crystal orientation film after burning till is processed by friction or polarized UV rays irradiation etc.
Liquid crystal display device of the present invention, after being with the substrate of liquid crystal orientation film by aforesaid method by aligning agent for liquid crystal acquisition of the present invention, making liquid crystal cell, thus make liquid crystal display device by known method.
As the making method of liquid crystal cell, can the following method of example: prepare a pair substrate being formed with liquid crystal orientation film, the liquid crystal orientation film of one piece of substrate scatters spacer, and the mode being positioned at inner side with liquid crystal aligning face bonds another block substrate, and decompression injects liquid crystal and the method for sealing; Or after the liquid crystal aligning face dropping liquid crystalline substance being scattered with spacer, the method etc. that adhesive base plate carrying out seals.
In addition, aligning agent for liquid crystal of the present invention is also preferred for having liquid crystal layer between a pair substrate possessing electrode and the liquid crystal display device made through following operation: between a pair substrate, configuration packet is containing the liquid-crystal composition of the polymerizable compound by least one party in active energy beam and heat polymerization, alively by irradiating active energy beam and adding at least one method of hankering, polymerizable compound is polymerized to executing between electrode simultaneously.Here, as active energy beam, it is better ultraviolet.As ultraviolet, wavelength is 300 ~ 400nm, is better 310 ~ 360nm.When adopting the polymerization of heating, Heating temperature is 40 ~ 120 DEG C, is better 60 ~ 80 DEG C.In addition, ultraviolet irradiation and heating can be carried out simultaneously.
Above-mentioned liquid crystal display device controls the tilt angle of liquid crystal molecule by PSA (Polymer Sustained Alignment, polymer stabilizing orientation) mode.For 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 applying assigned voltage to liquid crystal layer, by the tilt angle of the polymer controls liquid crystal molecule of generation.The state of orientation of liquid crystal molecule during generation polymkeric substance also can be remembered after removal of the voltage, so the electric field etc. by controlling to be formed at liquid crystal layer adjusts the tilt angle of liquid crystal molecule.In addition, PSA mode does not need friction treatment, so be suitable for the formation being difficult to the vertical alignment-type liquid crystal layer being controlled tilt angle by friction treatment.
Namely, in liquid crystal display device of the present invention, liquid crystal cell can be made after being with the substrate of liquid crystal orientation film by above-mentioned method by aligning agent for liquid crystal acquisition of the present invention, by ultraviolet irradiation with add at least one method of hankering and be polymerized by polymerizable compound, thus control the orientation of liquid crystal molecule.
If the example that the liquid crystal cell exemplifying PSA mode makes, following method can be exemplified: preparation is formed with a pair substrate of liquid crystal orientation film, one piece of substrate scatters spacer, and the mode being positioned at inner side with liquid crystal aligning face bonds another block substrate, and decompression injects liquid crystal and the method for sealing; Or the method etc. that adhesive base plate after the liquid crystal aligning face dropping liquid crystalline substance being scattered with spacer carrying out seals.
The polymerizable compound be polymerized by heating or uviolizing is mixed in liquid crystal.As polymerizable compound, the compound with more than 1 the polymerizability unsaturated group such as acrylate-based or methacrylate based can be exemplified in molecule.At this moment, polymerizable compound is better 0.01 ~ 10 mass parts relative to 100 mass parts liquid crystal compositions, is 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 is many, and the sintering adhesion characteristics of liquid crystal display device declines.
After making liquid crystal cell, liquid crystal cell is applied to the voltage of interchange or direct current, polymerizable compound is polymerized by heating or irradiation ultraviolet radiation simultaneously.Take this, the orientation of liquid crystal molecule can be controlled.
In addition, aligning agent for liquid crystal of the present invention is also preferred for having liquid crystal layer between a pair substrate possessing electrode and the liquid crystal display device made through following operation: between described a pair substrate, configuration packet is containing the liquid crystal orientation film of the polymerizable group by least one party's polymerization in active energy beam and heat, between electrode, apply voltage.Here, as active energy beam, it is better ultraviolet.As ultraviolet, wavelength is 300 ~ 400nm, is better 310 ~ 360nm.When adopting the polymerization of heating, Heating temperature is 40 ~ 120 DEG C, is better 60 ~ 80 DEG C.In addition, ultraviolet irradiation and heating can be carried out simultaneously.
In order to obtain the liquid crystal orientation film of the polymerizable group comprised by least one party's polymerization in active energy beam and heat, the method of adding in aligning agent for liquid crystal and comprising the compound of this polymerizable group can be exemplified, or use the method comprising the component of polymer of polymerizable group.Aligning agent for liquid crystal of the present invention comprises the specific compound with the double bond position of being reacted by heat or uviolizing, therefore by uviolizing with add the orientation that at least one party hankered controls liquid crystal molecule.
An example of liquid crystal cell is made if exemplify, following method can be exemplified: preparation is formed with a pair substrate of liquid crystal orientation film, one piece of substrate scatters spacer, and the mode being positioned at inner side with liquid crystal aligning face bonds another block substrate, and decompression injects liquid crystal and the method for sealing; Or the method etc. that adhesive base plate after the liquid crystal aligning face dropping liquid crystalline substance being scattered with spacer carrying out seals.
After making liquid crystal cell, by heating or irradiation ultraviolet radiation while voltage liquid crystal cell being applied to interchange or direct current, the orientation of liquid crystal molecule can be controlled.
As mentioned above, the reliability of the liquid crystal display device using aligning agent for liquid crystal of the present invention to make is good, can perform well in the LCD TV etc. of large picture, high-resolution.
Embodiment
Below exemplify embodiment and more specific description is carried out to the present invention, but the present invention is not limited in these embodiments.
The abbreviation used in composition-seies, embodiment and comparative example is as follows.
(there is the diamine compound of carboxyl)
A1:3,5-diaminobenzoic acid (diamine compound represented with following formula [A1])
A2:2,5-diaminobenzoic acid (diamine compound represented with following formula [A2])
(the 2nd diamine compound)
B1:1,3-diamino-4-[4-(trans-4-n-heptyl cyclohexyl) phenoxy group] benzene (diamine compound represented with following formula [B1])
B2:1,3-diamino-4-[4-(trans-4-n-heptyl cyclohexyl) phenoxymethyl] benzene (diamine compound represented with following formula [B2])
B3:1,3-diamino-4-{4-[trans-4-(trans-4-n-pentyl cyclohexyl) cyclohexyl] phenoxy group } benzene (diamine compound represented with following formula [B3])
B4: the diamine compound represented with following formula [B4]
B5:1,3-diamino-4-octadecane oxygen base benzene (diamine compound represented with following formula [B5])
B6: the diamine compound represented with following formula [B6]
(other diamine compound)
C1: Ursol D (diamine compound represented with following formula [C1])
C2: mphenylenediamine (diamine compound represented with following formula [C2])
(tetracarboxylic acid composition)
D1:1,2,3,4-tetramethylene tetracarboxylic dianhydride (tetracarboxylic dianhydride represented with following formula [D1])
D2: two rings [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride (tetracarboxylic dianhydride represented with following formula [D2])
D3: the tetracarboxylic dianhydride represented with following formula [D3]
D4: the tetracarboxylic dianhydride represented with following formula [D4]
(alkoxy silane monomer)
MPMS:3-methacryloxypropyl trimethoxy silane (alkoxy silane monomer represented with formula [A2] of the present invention)
UPS:3-ureidopropyltriethoxysilane (alkoxy silane monomer represented with formula [A2] of the present invention)
TEOS: tetraethoxysilane (alkoxy silane monomer represented with formula [A3] of the present invention)
((A) of the present invention composition (specific solvent))
DEME: diethylene glycol monomethyl ether (solvent represented with formula [1-1] of the present invention)
DEEE: diethylene glycol monoethyl ether (solvent represented with formula [1-2] of the present invention)
((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)
The molecular weight of the polyimide precursor in synthesis example and polyimide uses normal temperature gel permeation chromatography (GPC) device (GPC-101) (Showa Denko K. K (Showa Electricity work society) system), post (KD-803, KD-805) (Xiao De Ces Co., Ltd (Shodex society) system), measures as follows.
Column temperature: 50 DEG C
Elutriant: N, N'-dimethyl formamide (as additive, lithiumbromide monohydrate (LiBrH 2o) be 30mmol/L (liter), phosphoric acid anhydrous crystal (o-phosphoric acid) is 30mmol/L, and tetrahydrofuran (THF) (THF) is 10mL/L)
Flow velocity: 1.0ml/ minute
Calibration curve making standard model: TSK standard polyethylene oxide (molecular weight: about 900000,150000,100000 and 30000) ((East ソ ー society of TOSOH Co., Ltd) system) and polyoxyethylene glycol (molecular weight 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.20mg polyimide powder is added NMR (nucleus magnetic resonance) sample hose (wasteland's science Co., Ltd. (wasteland's science society) NMR sampling tube standard type φ 5 processed), add 0.53mL deuterated dimethyl sulfoxide (DMSO-d6,0.05 quality %TMS melange), apply ultrasonic wave and make it dissolve completely.By NMR tester (JNW-ECA500) (NEC De Tamu Co., Ltd. (Japanese Electricity デ ー タ system society) system) the proton N MR to this measured in solution 500MHz.For imide rate, to derive from the proton of unchanged structure before and after imidization for reference proton, use the integrated value at the peak of this proton and appear at the integrated value deriving from the peak of the NH base of amido acid near 9.5ppm ~ 10.0ppm, try to achieve imide rate by following formula.
Imide rate (%)=(1-α x/y) 100
In above formula, x is the proton peak integrated value of the NH base deriving from amido acid, and y is the peak integrated value of reference proton, relative to the number ratio of the reference proton of NH matrix of 1 amido acid when α is polyamic acid (imide rate is 0%).
" synthesis as the particular polymers (polyimide precursor and polyimide) of (B) of the present invention composition "
< synthesis example 1 >
By D1 (3.55g, 18.1mmol), A1 (2.75g, 18.1mmol) mixing in DEEE (56.7g), 40 DEG C of reactions 8 hours, obtains the polyamic acid solution (1) of resin solid content concentration 10.0 quality %.The number-average molecular weight of this polyamic acid is 12100, and weight-average molecular weight is 27100.
< synthesis example 2 >
By D2 (9.34g, 37.3mmol), A2 (7.10g, 46.7mmol) mixing in NMP (30.1g), 80 DEG C of reactions after 5 hours, add D1 (1.83g, 9.33mmol) with NMP (24.7g), 40 DEG C of reactions 6 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (6.52g), pyridine (5.05g) as imidization catalyst, 90 DEG C of reactions 4 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (2).The imide rate of this polyimide is 54%, and number-average molecular weight is 13400, and weight-average molecular weight is 34500.
< synthesis example 3 >
By D2 (2.11g, 8.43mmol), B1 (2.67g, 7.02mmol), A1 (1.07g, 7.03mmol) mixing in DEEE (34.4g), after 5 hours, D1 (1.10g, 5.61mmol) and DEEE (28.1g) is added 80 DEG C of reactions, 40 DEG C of reactions 8 hours, obtain the polyamic acid solution (3) of resin solid content concentration 10.0 quality %.The number-average molecular weight of this polyamic acid is 12900, and weight-average molecular weight is 35500.
< synthesis example 4 >
By D2 (4.06g, 16.2mmol), B1 (5.14g, 13.5mmol), A1 (2.06g, 13.5mmol) mixing in NMP (22.1g), after 5 hours, D1 (2.12g, 10.8mmol) and NMP (18.1g) is added 80 DEG C of reactions, 40 DEG C of reactions 6 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (5.16g), pyridine (4.00g) as imidization catalyst, 80 DEG C of reactions 2 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (4).The imide rate of this polyimide is 60%, and number-average molecular weight is 14300, and weight-average molecular weight is 37100.
< synthesis example 5 >
By D2 (6.02g, 24.1mmol), B1 (4.58g, 12.0mmol), A1 (2.29g, 15.1mmol), C1 (0.33g, 3.05mmol) mixes, 80 DEG C of reactions after 5 hours in NMP (23.8g), add D1 (1.18g, 6.02mmol) with NMP (19.4g), 40 DEG C of reactions 6 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (5.33g), pyridine (4.13g) as imidization catalyst, 80 DEG C of reactions 2 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (5).The imide rate of this polyimide is 58%, and number-average molecular weight is 15100, and weight-average molecular weight is 37800.
< synthesis example 6 >
By D2 (5.42g, 21.7mmol), B2 (3.66g, 9.28mmol), A1 (2.35g, 15.4mmol), B6 (1.26g, 6.20mmol) mixes, 80 DEG C of reactions after 5 hours in NMP (23.9g), add D1 (1.82g, 9.28mmol) with NMP (19.6g), 40 DEG C of reactions 6 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (5.50g), pyridine (4.25g) as imidization catalyst, 80 DEG C of reactions 3 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (6).The imide rate of this polyimide is 50%, and number-average molecular weight is 18500, and weight-average molecular weight is 42700.
< synthesis example 7 >
By D2 (5.51g, 22.0mmol), B3 (4.08g, 9.43mmol), A2 (2.87g, 18.9mmol), C2 (0.34g, 3.14mmol) mixes, 80 DEG C of reactions after 5 hours in NMP (24.2g), add D1 (1.85g, 9.43mmol) with NMP (19.8g), 40 DEG C of reactions 6 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (5.64g), pyridine (4.38g) as imidization catalyst, 80 DEG C of reactions 3 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (7).The imide rate of this polyimide is 60%, and number-average molecular weight is 18500, and weight-average molecular weight is 42200.
< synthesis example 8 >
By D2 (6.63g, 26.5mmol), B4 (2.45g, 4.97mmol), A1 (4.29g, 28.2mmol) mixing in NMP (24.2g), after 6 hours, D1 (1.30g, 6.63mmol) and NMP (19.8g) is added 80 DEG C of reactions, 40 DEG C of reactions 6 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (5.77g), pyridine (4.47g) as imidization catalyst, 80 DEG C of reactions 3.5 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (8).The imide rate of this polyimide is 47%, and number-average molecular weight is 16600, and weight-average molecular weight is 38100.
< synthesis example 9 >
By D3 (7.00g, 31.2mmol), B1 (3.57g, 9.38mmol), A1 (3.33g, 21.9mmol) mixing in NMP (41.7g), 40 DEG C of reactions 5 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (5.74g), pyridine (4.45g) as imidization catalyst, 80 DEG C of reactions 3 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (9).The imide rate of this polyimide is 62%, and number-average molecular weight is 13900, and weight-average molecular weight is 37800.
< synthesis example 10 >
By D3 (7.00g, 31.2mmol), B5 (3.53g, 9.37mmol), B6 (1.27g, 6.25mmol), A2 (2.38g, 15.6mmol) mixing in NMP (42.5g), 40 DEG C of reactions 5 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (5.62g), pyridine (4.36g) as imidization catalyst, 80 DEG C of reactions 3 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (10).The imide rate of this polyimide is 55%, and number-average molecular weight is 14500, and weight-average molecular weight is 34100.
< synthesis example 11 >
By D4 (5.28g, 17.6mmol), B2 (3.47g, 8.79mmol), C2 (0.48g, 4.44mmol), A2 (2.45g, 16.1mmol) mixes, 80 DEG C of reactions after 5 hours in NMP (23.1g), add D1 (2.30g, 11.7mmol) with NMP (18.9g), 40 DEG C of reactions 5.5 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (6.45g), pyridine (3.35g) as imidization catalyst, 40 DEG C of reactions 1.5 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (11).The imide rate of this polyimide is 57%, and number-average molecular weight is 17100, and weight-average molecular weight is 39600.
< synthesis example 12 >
By D4 (4.36g, 14.5mmol), B1 (3.32g, 8.72mmol), B6 (1.77g, 8.71mmol), A1 (1.77g, 11.6mmol) mixes, 80 DEG C of reactions after 5 hours in NMP (23.2g), add D1 (2.85g, 14.5mmol) with NMP (19.0g), 40 DEG C of reactions 5.5 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (6.33g), pyridine (3.27g) as imidization catalyst, 40 DEG C of reactions 1.5 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (12).The imide rate of this polyimide is 55%, and number-average molecular weight is 18100, and weight-average molecular weight is 39500.
< synthesis example 13 >
By D1 (2.90g, 14.8mmol), A1 (2.25g, 14.8mmol) mixing in NMP (15.5g), 40 DEG C of reactions 8 hours, obtains the polyamic acid solution (13) of resin solid content concentration 25.0 quality %.The number-average molecular weight of this polyamic acid is 18300, and weight-average molecular weight is 35500.
< synthesis example 14 >
By D2 (4.21g, 16.8mmol), B1 (5.34g, 14.0mmol), A1 (2.13g, 14.0mmol) mixing in NMP (22.9g), after 5 hours, D1 (2.20g, 11.2mmol) and NMP (18.7g) is added 80 DEG C of reactions, 40 DEG C of reactions 6 hours, obtain the polyamic acid solution (14) of resin solid content concentration 25.0 quality %.The number-average molecular weight of this polyamic acid is 19500, and weight-average molecular weight is 46800.
< synthesis example 15 >
By D2 (4.50g, 18.0mmol), B1 (5.70g, 15.0mmol), C1 (1.62g, 15.0mmol) mixing in NMP (23.4g), after 5 hours, D1 (2.35g, 12.0mmol) and NMP (19.1g) is added 80 DEG C of reactions, 40 DEG C of reactions 5.5 hours, obtain the polyamic acid solution of resin solid content concentration 25.0 quality %.
In the polyamic acid solution obtained (40.0g), add NMP dilution was after 6 quality %, adds diacetyl oxide (5.40g), pyridine (4.18g) as imidization catalyst, 80 DEG C of reactions 3 hours.This reaction soln is dropped in methyl alcohol (650mL), the throw out of filtering separation gained.By this throw out washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (15).The imide rate of this polyimide is 60%, and number-average molecular weight is 16100, and weight-average molecular weight is 39800.
Particular polymers of the present invention (polyimide precursor and polyimide) is shown in table 1.
[table 1]
* 1: polyamic acid.
" synthesis of the alkoxy silane monomer represented with formula [A1] of the present invention "
< synthesis example 16 >
To possess magnetic stirring apparatus 500ml four-hole boiling flask in add compound (1) (30.0g), salt of wormwood (25.2g), DMF (120g), at room temperature drip allyl bromide 98 (22.1g).Then, stir 11 hours at 50 DEG C.Reaction solution ethyl acetate (500g) dilution, cleans 3 times by organic phase pure water (200g).Make organic phase dry with sodium sulfate, after being filtered, by filtrate concentrate drying, obtain compound (2) (receipts amount: 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, add compound (2) (20.0g), toluene (120g), at room temperature stir.Then, after adding Karst catalyzer (the 0.1mol/L xylene solution of platinum (0)-1,1,3,3-tetramethyl disiloxane complex compound) (700 μ l), Trimethoxy silane (12.4ml) is dripped.At room temperature stir after 29 hours, by reaction solution concentrate drying, obtain raw product.By its underpressure distillation, temperature in addition: the condition of 245 DEG C/pressure: 0.8 holder makes it distillate, and obtains alkoxy silane monomer (A) (receipts amount: 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 (C) of the present invention composition "
< synthesis example 17 >
In the four mouthfuls of reaction flasks of 200ml possessing thermometer and return line, mix alkoxy silane monomer (A) (4.10g), the MPMS (7.45g) that obtain in DEME (28.3g), TEOS (32.5g), synthesis example 16, make the solution of alkoxy silane monomer.Be pre-mixed DEME (14.2g), water (10.8g), the solution made as the oxalic acid (0.70g) of catalyzer at 25 DEG C with dripping in 30 points of this solution of clockwise, then stir 30 minutes at 25 DEG C.Then, with oil bath heating, after refluxing 30 minutes, adding previously prepared UPS content is the methanol solution (1.20g) of 92 quality % and the mixing solutions of DEME (0.90g).Let cool after refluxing again 30 minutes, obtain SiO 2converted score is the polysiloxane solution (1) of 12 quality %.
< synthesis example 18 >
In the four mouthfuls of reaction flasks of 200ml possessing thermometer and return line, mix alkoxy silane monomer (A) (4.10g), the MPMS (7.45g) that obtain in DEEE (28.3g), TEOS (32.5g), synthesis example 16, make the solution of alkoxy silane monomer.Be pre-mixed DEEE (14.2g), water (10.8g), the solution made as the oxalic acid (0.70g) of catalyzer at 25 DEG C with dripping in 30 points of this solution of clockwise, then stir 30 minutes at 25 DEG C.Then, with oil bath heating, after refluxing 30 minutes, adding previously prepared UPS content is the methanol solution (1.20g) of 92 quality % and the mixing solutions of DEEE (0.90g).Let cool after refluxing again 30 minutes, obtain SiO 2converted score is the polysiloxane solution (2) of 12 % by weight.
< synthesis example 19 >
In the four mouthfuls of reaction flasks of 200ml possessing thermometer and return line, mix alkoxy silane monomer (A) (8.20g), the MPMS (19.9g) that obtain in DEEE (25.4g), TEOS (20.0g), synthesis example 16, make the solution of alkoxy silane monomer.Be pre-mixed DEEE (12.7g), water (10.8g), the solution made as the oxalic acid (1.10g) of catalyzer at 25 DEG C with dripping in 30 points of this solution of clockwise, then stir 30 minutes at 25 DEG C.Then, with oil bath heating, after refluxing 30 minutes, adding previously prepared UPS content is the methanol solution (1.20g) of 92 quality % and the mixing solutions of DEEE (0.90g).Let cool after refluxing again 30 minutes, obtain SiO 2converted score is the polysiloxane solution (3) of 12 % by weight.
< synthesis example 20 >
Mix alkoxy silane monomer (A) (4.10g) that obtain in DEEE (29.2g), TEOS (38.8g), synthesis example 16 in the four mouthfuls of reaction flasks of 200ml possessing thermometer and return line, make the solution of alkoxy silane monomer.Be pre-mixed DEEE (14.6g), water (10.8g), the solution made as the oxalic acid (0.50g) of catalyzer at 25 DEG C with dripping in 30 points of this solution of clockwise, then stir 30 minutes at 25 DEG C.Then, with oil bath heating, after refluxing 30 minutes, adding previously prepared UPS content is the methanol solution (1.20g) of 92 quality % and the mixing solutions of DEEE (0.90g).Let cool after refluxing again 30 minutes, obtain SiO 2converted score is the polysiloxane solution (4) of 12 % by weight.
< synthesis example 21 >
In the four mouthfuls of reaction flasks of 200ml possessing thermometer and return line, mix DEEE (31.6g), TEOS (41.7g), make the solution of alkoxy silane monomer.Be pre-mixed DEEE (15.8g), water (10.8g), the solution made as the oxalic acid (0.20g) of catalyzer at 25 DEG C with dripping in 30 points of this solution of clockwise, then stir 30 minutes at 25 DEG C.Then, let cool after refluxing 60 minutes with oil bath heating, obtain SiO 2converted score is the polysiloxane solution (5) of 12 % by weight.
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 "
In following embodiment 1 ~ embodiment 27, comparative example 1 ~ comparative example 7, record the Production Example of composition.In addition, these compositions are also used to 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 the composition or aligning agent for liquid crystal that obtain in examples and comparative examples of the present invention, carry out " evaluation of the printing 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 " and " making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning ".Its condition is as described below.
" evaluation of the printing of composition and aligning agent for liquid crystal "
Use the solution membrane filter pressure filtration of the composition fine pore 1 μm obtained in examples and comparative examples of the present invention obtained, carry out the evaluation of printing.Printing press uses Simple printing press S15 type (Nissha Printing Co., Ltd (description printing society of Japan) system).Be printed on the chromium evaporation substrate that cleaned with pure water and IPA (Virahol) with printing area be 80 × 80mm, squeegee pressure is 0.2mm, discard that substrate is 5 pieces, printing to the pre-dried time is 90 seconds, predrying be that 70 DEG C of conditions of 5 minutes are carried out on hot plate.
Then, the evaluation of the pore of the resin coating of gained has been carried out.The evaluation of the pore of resin coating is undertaken by visual inspection resin coating under sodium vapor lamp.Specifically, the quantity of the pore that counting resin coating confirms, the quantity of pore is fewer, then this evaluation is better.
The composition obtained in examples and comparative examples of the present invention can be used for aligning agent for liquid crystal.Therefore, the result of the printing of the resin coating obtained in the present embodiment and comparative example is also as the result of the printing of liquid crystal orientation film.
The quantity of the pore of the 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 composition and aligning agent for liquid crystal "
Use the solution membrane filter pressure filtration of the aligning agent for liquid crystal (16) obtained in the aligning agent for liquid crystal obtained in embodiments of the invention 9 (9) and embodiment 16 fine pore 1 μm obtained, carry out the evaluation of ink-jet application.Ink-jet application machine uses HIS-200 (Hitachi Koko Co., Ltd (Hitachi プ ラ Application ト テ Network ノ ロ ジ ー society) system).Be coated on ITO (tin indium oxide) the evaporation substrate that cleaned with pure water and IPA (Virahol) with surface covered be 70 × 70mm, injector spacing is 0.423mm, sweep span is 0.5mm, surface covered is 40mm/ second, be applied to the pre-dried time be 60 seconds, predrying be that 70 DEG C of conditions of 5 minutes are carried out on hot plate.
The evaluation of the pore of the liquid crystal orientation film of gained has been carried out with the condition same with " evaluation of the printing of composition and aligning agent for liquid crystal ".
The quantity of the pore of the resin coating (liquid crystal orientation film) obtained in embodiment shown in table 6 ~ table 8.
" making (common structure cell) of liquid crystal cell "
Use the solution membrane filter pressure filtration of the aligning agent for liquid crystal fine pore 1 μm obtained in examples and comparative examples of the present invention obtained, be spun on the substrate (vertical 40mm × horizontal 30mm of the band ITO electrode of the 30mm × 40mm cleaned with pure water and IPA (Virahol), thick 0.7mm) ito surface, on hot plate in 100 DEG C of heat treated 5 minutes, again in thermal cycling type cleaning oven in 220 DEG C of heat treated 30 minutes, obtain the ito substrate of the polyimide liquid crystal direct action membrane of band thickness 100nm.With the condition of roller rotating speed 1000rpm, roller gait of march 50mm/ second, the amount of pushing 0.1mm, friction treatment is carried out to the coated surface of this ito substrate by the friction gear artificial silk cloth of roller footpath 120mm.
Prepare the ito substrate of the band liquid crystal orientation film of 2 pieces of gained, the spacer that the mode being positioned at inner side with liquid crystal aligning face clips 6 μm combines, printing and sealing agent (XN-1500T) (Mitsui Chemicals, Inc (Mitsui Chemicals society) system).Then, after bonding with another block substrate and liquid crystal aligning face mode in opposite directions, sealing agent is solidified in 150 DEG C of heat treated 90 minutes in thermal cycling type cleaning oven, makes negative crystal born of the same parents.Inject liquid crystal to this negative crystal born of the same parents by decompression injection method, inlet is sealed, obtain liquid crystal cell (common structure cell).
In the liquid crystal cell of aligning agent for liquid crystal (the 28) ~ aligning agent for liquid crystal (30) obtained in aligning agent for liquid crystal (the 1) ~ aligning agent for liquid crystal (3) obtained in use embodiment 1 ~ embodiment 3, comparative example 1 ~ comparative example 3, liquid crystal uses nematic liquid crystal (MLC-2003) (Merck Japanese firm (メ Le Network ジ ャ パ Application society) system).
In addition, use aligning agent for liquid crystal (the 4) ~ aligning agent for liquid crystal (8) obtained in embodiment 4 ~ embodiment 8, the aligning agent for liquid crystal (10) obtained in embodiment 10 ~ embodiment 15 ~ aligning agent for liquid crystal (15), in the liquid crystal cell of aligning agent for liquid crystal (the 31) ~ aligning agent for liquid crystal (34) obtained in the aligning agent for liquid crystal (17) obtained in embodiment 17 ~ embodiment 27 ~ aligning agent for liquid crystal (27) and comparative example 4 ~ comparative example 7, liquid crystal uses nematic liquid crystal (MLC-6608) (Merck Japanese firm system).
" evaluation (common structure cell) of liquid crystal aligning "
The 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.For liquid crystal aligning, observe liquid crystal cell with polarizing microscope (ECLIPSE E600WPOL) (Nikon Corp. (ニ コ Application society) system), confirm the presence or absence of orientation defect.Specifically, the sample having no defect regards as good in this evaluation (being expressed as 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 "
Use the solution membrane filter pressure filtration of the aligning agent for liquid crystal (26) obtained in the aligning agent for liquid crystal (14) obtained in the aligning agent for liquid crystal (12) obtained in the aligning agent for liquid crystal obtained in embodiment 7 (7), embodiment 12, embodiment 14 and embodiment 26 fine pore 1 μm obtained, clean with pure water and IPA (Virahol).Be spun on the substrate (vertical 40mm × horizontal 30mm of center with the ITO electrode of the pattern spacing 20 μm of 10 × 10mm, thick 0.7mm) and center with the substrate (vertical 40mm × horizontal 30mm of the ITO electrode of 10 × 40mm, thick 0.7mm) ito surface, on hot plate in 100 DEG C of heat treated 5 minutes, again in thermal cycling type cleaning oven in 220 DEG C of heat treated 30 minutes, obtain the polyimide coating film of thickness 100nm.After pure water cleaning coated surface, in 100 DEG C of heat treated 15 minutes in thermal cycling type cleaning oven, obtain the substrate of band liquid crystal orientation film.
For the substrate of this band liquid crystal orientation film, the spacer that the mode being positioned at inner side with liquid crystal aligning face clips 6 μm combines, with sealing agent, surrounding is bonding, makes negative crystal born of the same parents.By in nematic liquid crystal (MLC-6608) (Merck Japanese firm system) being that the liquid crystal that polymerizable compound (1) that the ratio mixing of 0.3 quality % represents with following formula obtain injects this negative crystal born of the same parents by the injection method that reduces pressure relative to the nematic liquid crystal (MLC-6608) of 100 quality %, again inlet is sealed, obtain liquid crystal cell.
For the liquid crystal cell of gained, while the voltage applying interchange 5V, use the metal halide lamp of illumination 60mW, the wavelength of shielding below 350nm, carries out being scaled 20J/cm with 365nm 2uviolizing, obtain the liquid crystal cell (PSA structure cell) that the differently-oriented directivity of liquid crystal obtains controlling.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 the uviolizing of this liquid crystal cell and after uviolizing is measured.For response speed, determine the T90 → T10 of transmissivity 90% to transmissivity 10%.
For the PSA structure cell obtained in embodiment, compared with the liquid crystal cell before uviolizing, the fast response time of the liquid crystal cell after uviolizing, so confirm that the differently-oriented directivity of liquid crystal is controlled.In addition, all liquid crystal cell are all by adopting the observation of polarizing microscope (ECLIPSE E600WPOL) (Nikon Corp.'s system) to confirm the even orientation of liquid crystal.
< embodiment 1 >
Add DEEE (10.9g) in polyamic acid solution (1) (12.5g) of the resin solid content concentration 10.0 quality % obtained to the synthetic method by synthesis example 1, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 21 in this solution obtains 2converted score is polysiloxane solution (5) (2.60g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (1).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 2 >
Add DEEE (12.4g), γ-BL (1.51g) in polyamic acid solution (1) (12.5g) of the resin solid content concentration 10.0 quality % obtained to the synthetic method by synthesis example 1, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 21 in this solution obtains 2converted score is polysiloxane solution (5) (5.61g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (2).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 3 >
In polyimide powder (2) (1.55g) that the synthetic method by synthesis example 2 obtains, add DEEE (32.3g), NMP (4.86g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 21 in this solution obtains 2converted score is polysiloxane solution (5) (12.9g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (3).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 4 >
Add DEEE (12.3g) in polyamic acid solution (3) (14.0g) of the resin solid content concentration 10.0 quality % obtained to the synthetic method by synthesis example 3, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 19 in this solution obtains 2converted score is polysiloxane solution (3) (2.92g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (4).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 5 >
Add DEEE (10.7g), γ-BL (2.82g) in polyamic acid solution (3) (9.00g) of the resin solid content concentration 10.0 quality % obtained to the synthetic method by synthesis example 3, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 17 in this solution obtains 2converted score is polysiloxane solution (1) (7.50g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (5).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 6 >
Add DEEE (3.67g), γ-BL (2.70g), BCS (5.40g) in polyamic acid solution (3) (15.5g) of the resin solid content concentration 10.0 quality % obtained to the synthetic method by synthesis example 3, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 19 in this solution obtains 2converted score is polysiloxane solution (3) (1.44g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (6).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 7 >
In polyimide powder (4) (1.70g) that the synthetic method by synthesis example 4 obtains, add DEEE (36.1g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (9.44g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (7).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 8 >
In polyimide powder (4) (1.40g) that the synthetic method by synthesis example 4 obtains, add DEEE (24.8g), γ-BL (8.77g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (11.7g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (8).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 9 >
In polyimide powder (4) (1.00g) that the synthetic method by synthesis example 4 obtains, add DEEE (36.8g), γ-BL (11.0g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (8.33g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (9).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.Said composition (9) also as aligning agent for liquid crystal (9) for evaluate.
The aligning agent for liquid crystal (9) of gained is used to carry out " evaluation of the ink-jet application of aligning agent for liquid crystal " with above-mentioned condition.
< embodiment 10 >
In polyimide powder (4) (1.35g) that the synthetic method by synthesis example 4 obtains, add DEEE (16.1g), γ-BL (4.70g), BCS (14.1g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 20 in this solution obtains 2converted score is polysiloxane solution (4) (13.8g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (10).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 11 >
In polyimide powder (5) (2.25g) that the synthetic method by synthesis example 5 obtains, add DEME (22.3g), NEP (6.61g), BCS (11.0g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 17 in this solution obtains 2converted score is polysiloxane solution (1) (4.69g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (11).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.Said composition (11) 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 printing 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 " with above-mentioned condition.
< embodiment 12 >
In polyimide powder (5) (2.60g) that the synthetic method by synthesis example 5 obtains, add DEEE (25.0g), γ-BL (13.6g), BCS (4.53g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (2.41g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (12).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 13 >
In polyimide powder (6) (1.40g) that the synthetic method by synthesis example 6 obtains, add DEEE (33.6g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (11.7g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (13).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 14 >
In polyimide powder (6) (2.10g) that the synthetic method by synthesis example 6 obtains, add DEME (33.2g), γ-BL (4.11g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 17 in this solution obtains 2converted score is polysiloxane solution (1) (4.38g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (14).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 15 >
In polyimide powder (6) (1.85g) that the synthetic method by synthesis example 6 obtains, add DEEE (23.2g), NEP (8.28g), BCS (4.14g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (6.61g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (15).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 16 >
In polyimide powder (6) (1.10g) that the synthetic method by synthesis example 6 obtains, add DEEE (26.9g), NEP (8.67g), BCS (4.33g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (3.93g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (16).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.Said composition (16) also as aligning agent for liquid crystal (16) for evaluate.
The aligning agent for liquid crystal (16) of gained is used to carry out " evaluation of the ink-jet application of aligning agent for liquid crystal " with above-mentioned condition.
< embodiment 17 >
In polyimide powder (7) (2.10g) that the synthetic method by synthesis example 7 obtains, add DEME (20.8g), NMP (8.23g), BCS (8.23g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 17 in this solution obtains 2converted score is polysiloxane solution (1) (4.38g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (17).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 18 >
In polyimide powder (8) (2.50g) that the synthetic method by synthesis example 8 obtains, add DEEE (37.1g), γ-BL (4.35g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 19 in this solution obtains 2converted score is polysiloxane solution (3) (2.31g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (18).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 19 >
In polyimide powder (8) (1.80g) that the synthetic method by synthesis example 8 obtains, add DEEE (28.6g), γ-BL (2.01g), BCS (4.03g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 20 in this solution obtains 2converted score is polysiloxane solution (4) (6.43g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (19).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 20 >
In polyimide powder (9) (1.30g) that the synthetic method by synthesis example 9 obtains, add DEEE (25.5g), γ-BL (3.70g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (8.86g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (20).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 21 >
In polyimide powder (9) (1.70g) that the synthetic method by synthesis example 9 obtains, add DEME (21.3g), γ-BL (7.61g), BCS (3.80g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 17 in this solution obtains 2converted score is polysiloxane solution (1) (6.07g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (21).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 22 >
In polyimide powder (10) (1.70g) that the synthetic method by synthesis example 10 obtains, add DEEE (24.0g), NMP (10.2g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 21 in this solution obtains 2converted score is polysiloxane solution (5) (7.63g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (22).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 23 >
In polyimide powder (11) (2.05g) that the synthetic method by synthesis example 11 obtains, add DEEE (32.4g), γ-BL (4.01g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 19 in this solution obtains 2converted score is polysiloxane solution (3) (4.27g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (23).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 24 >
In polyimide powder (11) (1.80g) that the synthetic method by synthesis example 11 obtains, add DEME (30.6g), γ-BL (4.03g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 17 in this solution obtains 2converted score is polysiloxane solution (1) (6.43g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (24).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 25 >
In polyimide powder (11) (2.20g) that the synthetic method by synthesis example 11 obtains, add DEEE (25.0g), γ-BL (3.83g), BCS (7.66g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (2.04g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (25).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 26 >
In polyimide powder (12) (1.20g) that the synthetic method by synthesis example 12 obtains, add DEEE (25.0g), γ-BL (3.76g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 20 in this solution obtains 2converted score is polysiloxane solution (4) (10.0g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (26).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< embodiment 27 >
In polyimide powder (12) (2.50g) that the synthetic method by synthesis example 12 obtains, add DEEE (28.4g), γ-BL (2.18g), BCS (10.9g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 19 in this solution obtains 2converted score is polysiloxane solution (3) (2.31g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (27).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< comparative example 1 >
Add NMP (29.5g) in polyamic acid solution (13) (8.00g) of the resin solid content concentration 25.0 quality % obtained to the synthetic method by synthesis example 13, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 21 in this solution obtains 2converted score is polysiloxane solution (5) (4.17g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (28).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< comparative example 2 >
Add γ-BL (29.7g) in polyamic acid solution (13) (8.05g) of the resin solid content concentration 25.0 quality % obtained to the synthetic method by synthesis example 13, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 21 in this solution obtains 2converted score is polysiloxane solution (5) (4.19g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (29).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< comparative example 3 >
Add NMP (17.7g), BCS (6.41g) in polyamic acid solution (13) (6.55g) of the resin solid content concentration 25.0 quality % obtained to the synthetic method by synthesis example 13, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 21 in this solution obtains 2converted score is polysiloxane solution (5) (3.41g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (30).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< comparative example 4 >
Add NMP (29.9g) in polyamic acid solution (14) (8.10g) of the resin solid content concentration 25.0 quality % obtained to the synthetic method by synthesis example 14, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 19 in this solution obtains 2converted score is polysiloxane solution (3) (4.22g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (31).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< comparative example 5 >
Add NMP (21.7g), BCS (7.83g) in polyamic acid solution (14) (8.00g) of the resin solid content concentration 25.0 quality % obtained to the synthetic method by synthesis example 14, stir 1 hour at 25 DEG C.The SiO that the synthetic method being added with synthesis example 19 in this solution obtains 2converted score is polysiloxane solution (3) (4.17g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (32).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< comparative example 6 >
In polyimide powder (4) (1.70g) that the synthetic method by synthesis example 4 obtains, add NMP (36.1g), within 24 hours, make it dissolve 70 DEG C of stirrings.The SiO that the synthetic method being added with synthesis example 18 in this solution obtains 2converted score is polysiloxane solution (2) (9.44g) of 12 quality %, stirs 2 hours at 25 DEG C, obtains composition (33).Said composition has no the abnormal conditions such as the generation of muddiness or precipitate, confirms as uniform solution.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 printing 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 " with above-mentioned condition.
< comparative example 7 >
In polyimide powder (15) (1.50g) that the synthetic method by synthesis example 15 obtains, add DEEE (31.8g), within 24 hours, make it dissolve 70 DEG C of stirrings.Find in solution that the dissolving of polyimide powder remains, therefore stirred 12 hours at 70 DEG C further, but failed polyimide powder to dissolve completely.
Therefore, composition (34) and aligning agent for liquid crystal (34) cannot be prepared.
[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 the solvent composition contained by polysiloxane solution.
[table 6]
[table 7]
[table 8]
* 6: polyimide powder does not dissolve completely, composition and aligning agent for liquid crystal cannot be prepared.
* 7: confirm 15 ~ 24 orientation defects.
* 8: the orientation defect confirming more than 25.
From the above results, the composition of embodiments of the invention is compared with the composition of comparative example, and when coating substrate, display does not produce the uniform film with the pore repelled.Specifically, the comparison of the composition using same polyimide precursor or solvent-soluble type polyimide, that is, the comparative example 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, also obtain same result by the liquid crystal orientation film using the aligning agent for liquid crystal of composition of the present invention to obtain.Specifically, it is the comparison of the aligning agent for liquid crystal using same polyimide precursor or solvent-soluble type polyimide, namely, the comparative example 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.Especially, even the aligning agent for liquid crystal of the polyimide precursor using diamine component to adopt the diamine compound with side chain to obtain or solvent-soluble type polyimide, the uniform film not producing pore is also shown as described above.
In addition, in the evaluation of the liquid crystal aligning of liquid crystal cell, compared with the liquid crystal cell obtained by the liquid crystal cell using the aligning agent for liquid crystal of composition of the present invention to obtain and the aligning agent for liquid crystal by the composition using comparative example, have no the orientation defect produced with pore, obtain uniform liquid crystal aligning.Specifically, it is the comparison of the aligning agent for liquid crystal using same polyimide precursor or solvent-soluble type polyimide, namely, the comparative example 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.
The possibility of industrial utilization
Composition of the present invention, when coating substrate, can obtain the resin coating that display does not produce the uniform film with the pore repelling formation.In addition, even use the aligning agent for liquid crystal of composition of the present invention, also same result can be obtained.
In addition, aligning agent for liquid crystal of the present invention can obtain the liquid crystal cell not producing the orientation defect caused with the pore repelling formation.Especially, even the aligning agent for liquid crystal of the polyimide precursor using diamine component to adopt the diamine compound with side chain to obtain or solvent-soluble type polyimide, also same result can be obtained.
In addition, aligning agent for liquid crystal of the present invention is for the liquid crystal display device carrying out switching between the transmissive state (also referred to as vitreous state) and scattering state of liquid crystal, namely adopt the liquid crystal display device of polymer dispersion type liquid crystal (PDLC (Polymer Dispersed Liquid Crystal)) or polymer grid liquid crystal (PNLC (Polymer Network Liquid Crystal)) also useful.
Especially, to transparent state when not applying voltage, apply voltage time be that reverse (reverse) type element of scattering state is useful.This reversal element is for the liquid-crystal display to be shown as object using glass substrate and the plastic base such as PET (polyethylene terephthalate) or vinylformic acid substrate, and the light-regulating window of the vehicles and the backboard of transparent display etc. such as light-regulating window, optical shutter element, car that control the transmission of light and shielding are useful.
Therefore, the reliability with the liquid crystal display device of the liquid crystal orientation film obtained by aligning agent for liquid crystal of the present invention is good, the LCD TV etc. of large picture and high-resolution can be performed well in, can be used for the liquid crystal display device of TN element, STN element, TFT liquid crystal cell, particularly vertical orientating type.
In addition, the liquid crystal orientation film obtained by aligning agent for liquid crystal of the present invention needs the liquid crystal display device of irradiation ultraviolet radiation also useful for when making liquid crystal display device.Namely, for between a pair substrate possessing electrode, there is liquid crystal layer and useful through the liquid crystal display device that following operation is obtained, this operation is: between described a pair substrate, configuration packet is containing the liquid-crystal composition of the polymerizable compound by least one party in active energy beam and heat polymerization, is polymerized executing the alive polymerizable compound that makes between described electrode simultaneously; And between a pair substrate possessing electrode, there is liquid crystal layer and useful through the liquid crystal display device that following operation is obtained, this operation is: between described a pair substrate, configuration packet is containing the liquid crystal orientation film of the polymerizable group by least one party in active energy beam and heat polymerization, is polymerized executing the alive polymerizable group that makes between described electrode simultaneously.

Claims (21)

1. composition, is characterized in that, comprises following (A) composition, (B) composition and (C) composition:
(A) composition: the solvent represented with following formula [1],
[changing 1]
In formula [1], X 1represent the alkyl of carbon number 1 ~ 4;
(B) composition: at least one polymkeric substance being selected from polyimide precursor that the diamine component that makes to comprise the diamine compound with carboxyl and tetracarboxylic dianhydride's composition react and obtain or polyimide;
(C) composition: make to comprise the organoalkoxysilane polycondensation of any one in the organoalkoxysilane represented with 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, hexamethylene ring, heterocycle or there is the organic group 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 wherein, m+n+p is 4,
[changing 3]
(B 1) mSi(B 2) n(OB 3) p[A2]
In formula [A2], B 1represent the organic group 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 wherein, 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, 50 ~ 100 quality % of the whole solvents of described (A) composition contained by composition.
3. composition as claimed in claim 1 or 2, is characterized in that, the diamine compound with carboxyl of described (B) composition is the diamine compound with the structure represented with 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 is the diamine compound of the structure represented with following formula [2a],
[changing 6]
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 as described in any one in Claims 1 to 5, is characterized in that, the diamine component of described (B) composition comprises at least one diamine compound being selected from the structure represented with 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], and Y 1for representing singly-bound ,-(CH 2) a-,-O-,-CH 2o-,-COO-or-OCO-, a is the integer of 1 ~ 15, Y 2represent singly-bound or-(CH 2) b-, b is the integer of 1 ~ 15, Y 3represent singly-bound ,-(CH 2) c-,-O-,-CH 2o-,-COO-or-OCO-, c is the integer of 1 ~ 15, Y 4represent the divalent organic group of the divalent cyclic group being selected from phenyl ring, hexamethylene ring or heterocycle or the carbon number 12 ~ 25 with steroid skeleton, arbitrary hydrogen atom on described 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 divalent cyclic group being selected from phenyl ring, hexamethylene ring or heterocycle, arbitrary hydrogen atom on these cyclic groups 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 is 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], and 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 as described in any one in claim 1 ~ 6, is characterized in that, tetracarboxylic dianhydride's composition of described (B) composition is the compound represented with following formula [3],
[changing 9]
In formula [3], Z 1for being selected from the group of at 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, may be the same or different respectively, in formula [3g], Z 6and Z 7represent hydrogen atom or methyl, may be the same or different respectively.
8. the composition as described in any one in claim 1 ~ 7, it is characterized in that, the organoalkoxysilane represented with formula [A2] of described (C) composition is for being selected from allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, 3-(triethoxysilicane alkyl) propyl methacrylate, the at least one of 3-(Trimethoxy silane base) propyl acrylate or 3-(Trimethoxy silane base) propyl methacrylate.
9. the composition as described in any one in claim 1 ~ 7, it is characterized in that, the organoalkoxysilane represented with formula [A2] of described (C) composition is for being selected from least one of 3-glycidoxypropyl group (dimethoxy) methyl-monosilane, 3-glycidoxypropyl group (diethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane or 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane.
10. the composition as described in any one in claim 1 ~ 9, it is characterized in that, the polysiloxane that the polysiloxane of described (C) composition obtains for making the described organoalkoxysilane polycondensation that represents with formula [A1], formula [A2] and formula [A3].
11. compositions as described in any one in claim 1 ~ 10, is characterized in that, as (D) composition, comprise at least one solvent in METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone or gamma-butyrolactone.
12. compositions as described in any one in claim 1 ~ 11, it is characterized in that, as (E) composition, comprise 1-hexanol, hexalin, 1, at least one solvent in 2-ethylene glycol, 1,2-PD, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, glycol isopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether.
13. resin coatings, is characterized in that, are obtained by the composition described in any one in claim 1 ~ 12.
14. aligning agent for liquid crystal, is characterized in that, are obtained by the composition described in any one in claim 1 ~ 12.
15. liquid crystal orientation films, is characterized in that, use the liquid crystal aligning agent 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 there is liquid crystal layer between a pair substrate possessing electrode and the liquid crystal display device made through following operation, this operation is: between described a pair substrate, configuration packet is containing the liquid-crystal composition of the polymerizable compound by least one party in active energy beam and heat polymerization, alively makes described polymerizable compound be polymerized to executing between described electrode simultaneously.
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 there is liquid crystal layer between a pair substrate possessing electrode and the liquid crystal display device made through following operation, this operation is: between described a pair substrate, configuration packet is containing the liquid crystal orientation film of the polymerizable group by least one party in active energy beam and heat polymerization, alively makes described polymerizable compound be polymerized to executing between described electrode simultaneously.
21. liquid crystal display device, is characterized in that, have liquid crystal orientation film according to claim 20.
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