CN105814141A - Composition, treatment agent for liquid crystal alignment, liquid crystal alignment film, and liquid crystal display element - Google Patents

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

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CN105814141A
CN105814141A CN201480067004.XA CN201480067004A CN105814141A CN 105814141 A CN105814141 A CN 105814141A CN 201480067004 A CN201480067004 A CN 201480067004A CN 105814141 A CN105814141 A CN 105814141A
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liquid crystal
formula
carbon number
represent
composition
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CN105814141B (en
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三木徳俊
桥本淳
若林晓子
保坂和義
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Nissan Chemical Corp
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    • 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
    • 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
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

The present invention provides a composition that contains: a component (A) that is a solvent that is represented by formula [A] (in the formula, X1 and X2 each independently represent an alkyl group having 1-3 carbon atoms and X3 and X4 each independently represent an alkyl group having 1-3 carbon atoms),and a component (B) that is at least one polymer selected from among polyimide precursors and polyimides.

Description

Compositions, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element
Technical field
The present invention relates to the compositions for forming polyimide film, represent the aligning agent for liquid crystal of element, this aligning agent for liquid crystal liquid crystal orientation film obtained for manufacturing liquid crystal and employ the liquid crystal of this liquid crystal orientation film and represent element.
Background technology
Formed easness, the insulating properties etc. of the film formed by organic materials such as macromolecular materials receive much concern, and it is widely used as the interlayer dielectric in electronic equipment, protecting film etc..Wherein, the liquid crystal being widely known by the people as expression equipment represents in element, organic material the organic membrane formed is used as liquid crystal orientation film.
In recent years, liquid crystal represents that element is extensively practically applicable to the mobile purposes expression part of mobile phone (digital camera) of the LCD TV of big picture, high-resolution.Accompanying with this, compared with the past, the substrate used maximizes, and then concavo-convex the becoming larger of substrate height difference.In this condition, from characteristic viewpoint, for large substrate, difference in height, it is desirable to coating of liquid crystalline alignment films equably.In the manufacturing process of this liquid crystal orientation film, when the aligning agent for liquid crystal employing the polyimides based polymer (also referred to as resin) such as polyamic acid, solvent-soluble polyimide (also referred to as polyimides) is coated substrate, industrial carry out typically by flexible printing method, ink-jet application method etc..Now, in the solvent of aligning agent for liquid crystal, on the basis of the METHYLPYRROLIDONE (also referred to as NMP) of solvent (also referred to as good solvent) excellent as resin dissolubility, gamma-butyrolacton (also referred to as γ-BL) etc., in order to improve the film of liquid crystal orientation film, ethylene glycol monobutyl ether being also mixed with the solvent (also referred to as poor solvent) low as resin dissolubility etc. (referring for example to patent documentation 1).
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2-37324 publication
Summary of the invention
The problem that invention to solve
The organic membrane (also referred to as polyimide film) of polyimides system, except being widely used in liquid crystal orientation film, is also widely used in the interlayer dielectric in electronic equipment, protecting film etc..Identically with the situation of liquid crystal orientation film, it is possible to formed by the compositions (also referred to as coating solution) of the solution comprising polyimide precursor and polyamic acid or polyimides.Further, for other electronic equipment, the film improving polyimide film is also required that.That is, the film improving polyimide film is effective for suppressing the defect produced with coating.
It addition, employ obtain with the diamine compound with side chain polyamic acid, polyimides aligning agent for liquid crystal high due to the hydrophobicity at side chain position, therefore there is the tendency that the film of liquid crystal orientation film reduces.Especially, when producing pin hole, making liquid crystal when representing element when obtaining uniform coating, namely with shrinking, this part becomes expression defect.Therefore, in order to obtain uniform film, it is necessary to increase the coating solution combined amount for the high poor solvent of the moistening autgmentability of substrate.But, the ability dissolving polyamic acid, polyimides of poor solvent, when therefore mixing in a large number, there is the problem that resin precipitates out.
And, in recent years, employ liquid crystal represent element towards the mobile purposes such as smart mobile phone, mobile phone, in these purposes, in order to ensure expression face as much as possible, carry out sealant that is bonding and that use in order to make liquid crystal represent between the substrate of element and be present in the position close to end of liquid crystal orientation film.Therefore, when the film of the end of liquid crystal orientation film reduces, the end of liquid crystal orientation film is not when being straight line or when being in the state of this end protuberance, liquid crystal orientation film bonding with sealant (also referred to as closely sealed) effect step-down, the characterization of element, reliability reduce to make liquid crystal represent.
And then, employing in compositions or the aligning agent for liquid crystal of polyimides, the boiling point of NMP, γ-BL as solvent wherein used is high, therefore, when making the polyimide film such as interlayer dielectric, protecting film and liquid crystal orientation film, it is necessary at high temperature burn till.Therefore, from the view point of cut down cost of energy, when making these polyimide films and liquid crystal orientation film, it is desirable to burn till at low temperatures.
Thus, it is an object of the invention to, it is provided that have the compositions of above-mentioned characteristic concurrently.That is, it is an object of the invention to, it is provided that can suppress to produce the compositions of the film also excellence of pin hole, its end with shrinking when forming polyimide film.Now, purpose also resides in, even if carrying out at low temperatures burning till the compositions also being able to make polyimide film.
It addition, for the aligning agent for liquid crystal employing the present composition, it is provided that can suppress to produce the aligning agent for liquid crystal of the film also excellence of pin hole and then its end with shrinking when forming liquid crystal orientation film.Especially, it is provided that even with the aligning agent for liquid crystal of the polyamic acid obtained with the diamine compound with side chain, polyimides, the aligning agent for liquid crystal that their characteristic is also excellent.And then, it is provided that even if burning till with low temperature when making liquid crystal orientation film, liquid crystal represents the aligning agent for liquid crystal that the electrical characteristics of element, especially voltage retention (also referred to as VHR) are also excellent.
And, it is provided that the polyimide film obtained by foregoing, foregoing liquid crystal the aligning agent liquid crystal orientation film obtained and there is the liquid crystal of foregoing liquid crystal alignment films represent element.
For solving the scheme of problem
Present inventor has performed further investigation, found that: the compositions comprising the solvent with ad hoc structure and at least one polymer in polyimide precursor or polyimides is extremely effective for realizing above-mentioned purpose, thus completing the present invention.
That is, the present invention has following purport.
(1) a kind of compositions, it contains:
(A) composition: the solvent shown in following formula [A]；And
(B) composition: at least one polymer in polyimide precursor and polyimides.
(in formula, X1And X2Represent the alkyl of carbon number 1～3, X independently of one another3And X4Represent the alkyl of carbon number 1～3 independently of one another).
(2) compositions according to above-mentioned (1), wherein, the solvent of aforementioned (A) composition is the solvent shown in following formula [A-1].
(3) compositions according to above-mentioned (1) or above-mentioned (2), wherein, aforementioned (B) composition be the diamine compound of at least one structure having in structure shown in following formula [1-1] and formula [1-2] is obtained for the part of raw material, at least one polymer in polyimide precursor and polyimides.
(in formula, Y1Represent selected from singly-bound ,-(CH2)a-(a is the integer of 1～15) ,-O-,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) at least one binding groups in CO-,-COO-and-OCO-；Y2Represent singly-bound or-(CH2)b-(b is the integer of 1～15)；Y3Represent selected from singly-bound ,-(CH2)c-(c is the integer of 1～15) ,-O-,-CH2At least one binding groups in O-,-COO-and-OCO-；Y4The divalent organic group of the bivalent cyclic group representing at least one ring in phenyl ring, cyclohexane ring and heterocycle or the carbon number 17～51 with steroid skeleton, any hydrogen atom on aforementioned cyclic group is optionally by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, the replacing containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom of carbon number 1～3；Y5Representing the bivalent cyclic group of at least one ring in phenyl ring, cyclohexane ring and heterocycle, any hydrogen atom on these cyclic groups is optionally by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, the replacing containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom of carbon number 1～3；N represents the integer of 0～4；Y6Represent selected from the alkyl of carbon number 1～22, the thiazolinyl of carbon number 2～22, carbon number 1～22 containing at least one in fluoroalkyl, the alkoxyl of carbon number 1～22 and the fluoroalkoxy of carbon number 1～22)；
-Y7-Y8[1-2]
(in formula, Y7Represent selected from singly-bound ,-O-,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) at least one binding groups in CO-,-COO-and-OCO-；Y8Represent the alkyl of carbon number 8～22 or carbon number 6～18 containing fluoroalkyl)
(4) compositions according to above-mentioned (3), wherein, having the diamine compound of structure shown in previously described formula [1-1] and formula [1-2] is the diamine compound shown in following formula [1a].
(in formula, Y represents at least one structure in structure shown in previously described formula [1-1] and formula [1-2], and m represents the integer of 1～4)
(5) compositions according to any one of above-mentioned (1)～above-mentioned (4), wherein, the polymer of aforementioned (B) composition be the diamine compound of at least one substituent group having in carboxyl (COOH yl) and hydroxyl (OH yl) is obtained for the part of raw material, at least one polymer in polyimide precursor and polyimides.
(6) compositions according to above-mentioned (5), wherein, the diamine compound with aforementioned carboxyl and hydroxyl is the diamine compound shown in following formula [2a].
{ in formula, A represents the substituent group of at least one structure in following formula [2-1] and formula [2-2], and m represents the integer of 1～4 }
-(CH2)a-COOH[2-1]-(CH2)b-OH[2-2]
(in formula [2-1], a represents the integer of 0～4；In formula [2-2], b represents the integer of 0～4)
(7) compositions according to any one of above-mentioned (1)～above-mentioned (6), wherein, the polymer of aforementioned (B) composition be the diamine compound shown in following formula [3a] is obtained for the part of raw material, at least one polymer in polyimide precursor and polyimides.
(in formula, B1Represent selected from-O-,-NH-,-N (CH3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)-and-N (CH3) at least one binding groups in CO-；B2Represent at least one in singly-bound, the divalent group of aliphatic hydrocarbon of carbon number 1～20, the divalent group of non-aromatic ring type hydrocarbon and the divalent group of aromatic hydrocarbon；B3Represent selected from singly-bound ,-O-,-NH-,-N (CH3)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-、-N(CH3) CO-and-O (CH2)mAt least one binding groups in-(m is the integer of 1～5)；B4Represent nitrogen heterocycle；N represents the integer of 1～4)
(8) compositions according to above-mentioned (7), wherein, is the B in previously described formula [3a]1Represent-CONH-, B2Represent the alkylidene of carbon number 1～5, B3Represent singly-bound, B4Represent the diamine compound that imidazole radicals or pyridine radicals, n represent 1.
(9) compositions according to any one of above-mentioned (1)～above-mentioned (8), wherein, the polymer of aforementioned (B) composition be the tetracarboxylic compound shown in following formula [4] is obtained for the part of raw material, at least one polymer in polyimide precursor and polyimides.
{ in formula, Z represents the group of at least one structure in following formula [4a]～formula [4k] }
(in formula [4a], Z1～Z4Represent hydrogen atom, methyl, chlorine atom or phenyl independently of one another；In formula [4g], Z5And Z6Represent hydrogen atom or methyl independently of one another)
(10) compositions according to any one of above-mentioned (1)～above-mentioned (9), wherein, the polymer of aforementioned (B) composition is at least one polymer in polyamic acid Arrcostab and polyimides.
(11) compositions according to any one of above-mentioned (1)～above-mentioned (10), wherein, as (C) composition, containing at least one solvent in METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone and gamma-butyrolacton.
(12) compositions according to any one of above-mentioned (1)～above-mentioned (11), wherein, as (D) composition, containing selected from 1-hexanol, Hexalin, 1, at least one solvent in solvent shown in 2-ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dimethyl ether and following formula [D-1]～formula [D-3].
(in formula [D-1], D1Represent the alkyl of carbon number 1～3；In formula [D-2], D2Represent the alkyl of carbon number 1～3；In formula [D-3], D3Represent the alkyl of carbon number 1～4)
(13) compositions according to any one of above-mentioned (1)～above-mentioned (12), wherein, compositions comprises at least one cross-linked compound being selected from cross-linked compound: there is the cross-linked compound of epoxy radicals, NCO, oxetanylmethoxy or cyclocarbonate radical；There is the cross-linked compound of at least one substituent group in the group selecting free hydroxyl, hydroxy alkyl and low-grade alkoxy alkyl composition；And, there is the cross-linked compound of polymerism unsaturated bond.
(14) compositions according to any one of above-mentioned (1)～above-mentioned (13), wherein, aforementioned (A) composition is 5～70 mass % that the solvent comprised in compositions is overall.
(15) compositions according to any one of above-mentioned (11)～above-mentioned (14), wherein, aforementioned (C) composition is 40～80 mass % that the solvent comprised in compositions is overall.
(16) compositions according to any one of above-mentioned (12)～above-mentioned (15), wherein, aforementioned (D) composition is 1～50 mass % that the solvent comprised in compositions is overall.
(17) compositions according to any one of above-mentioned (1)～above-mentioned (16), wherein, aforementioned (B) composition is 0.1 mass %～30 mass % in the composition.
(18) a kind of polyimide film, it is that the compositions according to any one of above-mentioned (1)～above-mentioned (17) obtains.
(19) a kind of aligning agent for liquid crystal, it is that the compositions according to any one of above-mentioned (1)～above-mentioned (17) obtains.
(20) a kind of liquid crystal orientation film, it is to use aligning agent for liquid crystal described in above-mentioned (19) to obtain.
(21) a kind of liquid crystal orientation film, it is to use the aligning agent for liquid crystal described in above-mentioned (19) to be obtained by ink-jet method.
(22) a kind of liquid crystal represents element, and it has the liquid crystal orientation film described in above-mentioned (20) or above-mentioned (21).
(23) liquid crystal orientation film according to above-mentioned (20) or above-mentioned (21), it is characterized in that, it is used to have liquid crystal layer between a pair substrate possessing electrode and the liquid crystal that manufactures via following operation represents element: configure liquid-crystal composition between aforementioned a pair substrate, described liquid-crystal composition comprises at least one utilizing active energy beam and hanker and carries out the polymerizable compound being polymerized, while make aforementioned polymeric compound polymerization to applying voltage limit between former electrodes.
(24) a kind of liquid crystal represents element, it is characterised in that it has the liquid crystal orientation film described in above-mentioned (23).
(25) liquid crystal orientation film according to above-mentioned (20) or above-mentioned (21), it is characterized in that, it is used to have liquid crystal layer between a pair substrate possessing electrode and the liquid crystal that manufactures via following operation represents element: configure liquid crystal orientation film between aforementioned a pair substrate, described liquid crystal orientation film comprises at least one utilizing active energy beam and hanker and carries out the polymerizable group being polymerized, while make aforementioned polymeric radical polymerisation to applying voltage limit between former electrodes.
(26) a kind of liquid crystal represents element, it is characterised in that it has the liquid crystal orientation film described in above-mentioned (25).
The effect of invention
The compositions comprising the solvent with ad hoc structure and at least one polymer in polyimide precursor or polyimides of the present invention can be produced on when forming polyimide film and adjoint contraction can be suppressed to produce the polyimide film of the film also excellence of pin hole, its end.Now, it also is able to make polyimide film even if carrying out at low temperatures burning till.
It addition, for the aligning agent for liquid crystal employing the present composition, it is provided that can suppress to produce the aligning agent for liquid crystal of the film also excellence of pin hole and then its end with shrinking when forming liquid crystal orientation film.Especially, it is provided that even with the aligning agent for liquid crystal of the polyamic acid obtained with the diamine compound with side chain, polyimides, the aligning agent for liquid crystal that their characteristic is also excellent.And then, it is provided that even if burning till with low temperature when making liquid crystal orientation film, liquid crystal represents the aligning agent for liquid crystal that the electrical characteristics of element, especially voltage retention (VHR) are also excellent.
It addition, by the compositions of the present invention is used as aligning agent for liquid crystal, using the teaching of the invention it is possible to provide can suppress to produce the liquid crystal orientation film of the film also excellence of pin hole and then its end with shrinking.Especially, even with the aligning agent for liquid crystal of the polyamic acid obtained with the diamine compound with side chain, polyimides, it is also possible to provide the liquid crystal orientation film of these excellents.And then, using the teaching of the invention it is possible to provide even if burning till with low temperature when making liquid crystal orientation film, liquid crystal represents the liquid crystal orientation film that the electrical characteristics of element, especially voltage retention (VHR) are also excellent.Thus, the liquid crystal with the liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention represents the excellent in reliability of element, can be suitably employed in the LCD TV of big picture and high-resolution, middle-size and small-size auto-navigation system, smart mobile phone etc..
Accompanying drawing explanation
Fig. 1 is the linear schematic diagram in end of the polyimide film coating glass substrate.
Fig. 2 is the schematic diagram of the end protuberance of the polyimide film coating glass substrate.
Detailed description of the invention
It is described in detail below for the present invention.
The present invention is containing following (A) composition and the compositions of (B) composition, aligning agent for liquid crystal, uses this aligning agent for liquid crystal and the liquid crystal orientation film that obtains and the liquid crystal with this liquid crystal orientation film represent element.
(A) composition: the solvent (also referred to as specific solvent) shown in following formula [A].
(in formula [A], X1And X2Represent the alkyl of carbon number 1～3, X independently of one another3And X4Represent the alkyl of carbon number 1～3 independently of one another).
(B) composition: at least one polymer (also referred to as particular polymers) in polyimide precursor and polyimides.
The specific solvent of the present invention can be used as the solvent (also referred to as good solvent) that the polyimides based polymer such as polyimide precursor and polyimides can be made to dissolve, and then, also it is improved the effect of the film of polyimide film and liquid crystal orientation film.That is, compared with the NMP being generally used for good solvent, the specific solvent of the present invention is low as the surface tension of solvent, therefore, employs the coating solution of specific solvent compared with the coating solution not using it, and coating solution uprises for the moistening autgmentability of substrate.Thus, when making polyimide film and liquid crystal orientation film, the end rectilinearity of these films uprises.And then, owing to coating solution uprises for the moistening autgmentability of substrate, therefore can also suppress to produce pin hole with shrinking.
And then, compared with NMP, γ-BL being typically used as good solvent, the boiling point of the specific solvent of the present invention is low.Therefore, can burn till with low temperature when making polyimide film and liquid crystal orientation film.Therefore, even if especially can obtain burning till with low temperature when making liquid crystal orientation film, liquid crystal represents the liquid crystal orientation film also excellent for VHR of element.
Further, (B) composition of the present invention is at least one polymer in polyimide precursor or polyimides.Wherein, when the compositions of the present invention is used for aligning agent for liquid crystal to make liquid crystal orientation film, at least one polymer (also referred to as particular polymers) selected from polyimide precursor or polyimides in is preferably used, and described polymer has at least one side chain (being also referred to collectively as particular side chain structure) in structure shown in following formula [1-1] and formula [1-2].
(in formula [1-1], Y1Represent selected from singly-bound ,-(CH2)a-(a is the integer of 1～15) ,-O-,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) at least one binding groups in CO-,-COO-and-OCO-；Y2Represent singly-bound or-(CH2)b-(b is the integer of 1～15)；Y3Represent selected from singly-bound ,-(CH2)c-(c is the integer of 1～15) ,-O-,-CH2At least one binding groups in O-,-COO-and-OCO-；Y4The divalent organic group of the bivalent cyclic group representing at least one ring in phenyl ring, cyclohexane ring and heterocycle or the carbon number 17～51 with steroid skeleton, any hydrogen atom on aforementioned cyclic group is optionally by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, the replacing containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom of carbon number 1～3；Y5Representing the bivalent cyclic group of at least one ring in phenyl ring, cyclohexane ring and heterocycle, any hydrogen atom on these cyclic groups is optionally by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, the replacing containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom of carbon number 1～3；N represents the integer of 0～4；Y6Represent selected from the alkyl of carbon number 1～22, the thiazolinyl of carbon number 2～22, carbon number 1～22 containing at least one in fluoroalkyl, the alkoxyl of carbon number 1～22 and the fluoroalkoxy of carbon number 1～22).
-Y7-Y8[1-2]
(in formula [1-2], Y7Represent selected from singly-bound ,-O-,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) at least one binding groups in CO-,-COO-and-OCO-；Y8Represent the alkyl of carbon number 8～22 or carbon number 6～18 containing fluoroalkyl).
Wherein, the particular side chain structure shown in previously described formula [1-1] possesses at pendant moiety: phenyl ring, cyclohexyl ring or heterocycle bivalent cyclic group or have the divalent organic group of carbon number 17～51 of steroid skeleton.The divalent organic group of the bivalent cyclic group of these phenyl ring, cyclohexyl ring or heterocycle or the carbon number 17～51 with steroid skeleton demonstrates upright and outspoken structure.Thus, the heat stability at side chain position improves, it is suppressed that by burning till and the decomposition at side chain position that causes when making liquid crystal orientation film, it is possible to obtain the excellent liquid crystal orientation film of VHR.
From the view point of above, even if the compositions comprising specific solvent and at least one polymer in polyimide precursor or polyimides of the present invention becomes film excellence and carries out at low temperatures burning till the compositions also being able to form polyimide film.
It addition, the aligning agent for liquid crystal obtained by the compositions of the present invention can obtain the liquid crystal orientation film that film is excellent.And then, it is possible to even if burning till with low temperature when obtaining making liquid crystal orientation film, liquid crystal represents the liquid crystal orientation film also excellent for VHR of element.Therefore, by using this liquid crystal orientation film, using the teaching of the invention it is possible to provide the liquid crystal that characterization is excellent and reliability is high represents element.
And, the aligning agent for liquid crystal obtained by the compositions comprising specific solvent and at least one polymer in the polyimide precursor with the particular side chain structure shown in previously described formula [1-1] or polyimides of the present invention can obtain the liquid crystal orientation film that foregoing advantages is more excellent, even if burning till with low temperature when can access making liquid crystal orientation film, liquid crystal represents the liquid crystal orientation film also excellent for VHR of element.Therefore, by using this liquid crystal orientation film, using the teaching of the invention it is possible to provide the liquid crystal that characterization is more excellent and reliability is higher represents element.
Hereinafter, embodiments of the present invention are further described.
<specific solvent>
The specific solvent of the present invention is the solvent shown in following formula [A].
In formula [A], X1And X2Represent the alkyl (such as, methyl, ethyl, propyl group or isopropyl) of carbon number 1～3 independently of one another, it is preferable that represent methyl or ethyl, it is particularly preferred to represent methyl.
In formula [A], X3And X4Represent the alkyl (such as, methyl, ethyl, propyl group or isopropyl) of carbon number 1～3 independently of one another, it is preferable that represent methyl or ethyl, it is particularly preferred to represent methyl.
Specifically, it is preferred to the material shown in following formula [A-1].
In order to improve the above-mentioned coating solution moistening autgmentability for substrate further, it is preferable that the amount of the specific solvent of the present invention is 5～80 mass % that the solvent comprised in compositions and aligning agent for liquid crystal is overall.Wherein, it is preferred to 5～75 mass %.It is more preferably 5～70 mass %, more preferably 10～60 mass %.
Among solvent entirety in compositions and aligning agent for liquid crystal, the amount of the specific solvent of the present invention is more many, then the effect of the present invention, i.e. coating solution become more high for the moistening autgmentability of substrate, it is possible to obtain the excellent polyimide film of film and liquid crystal orientation film.
<particular polymers>
(B) composition of the present invention and particular polymers are at least one polymer in polyimide precursor and polyimides (being also referred to collectively as polyimides based polymer).Wherein, the polyimides based polymer of the present invention is preferably the polyimide precursor or polyimides that make diamine component react and to obtain with tetrabasic carboxylic acid composition.
Polyimide precursor is the structure shown in following formula [a].
(in formula [a], R1For quadrivalent organic radical group；R2For divalent organic group；A1And A2Represent the alkyl of hydrogen atom or carbon number 1～5 independently of one another；A3And A4Represent hydrogen atom, the alkyl of carbon number 1～5 or acetyl group independently of one another；N represents positive integer).
As aforementioned diamine component, the diamine compound with 2 primary amino radicals or secondary amino group can be listed in molecule.
It addition, as aforementioned tetrabasic carboxylic acid composition, tetracarboxylic compound, tetracarboxylic dianhydride, tetrabasic carboxylic acid two acetyl halide compound, tetrabasic carboxylic acid dialkyl compound or tetrabasic carboxylic acid dialkyl two acetyl halide compound can be listed.
In order to obtain the A in formula [a]1And A2Polyamic acid for hydrogen atom, it is possible to obtain by making the diamine compound in previous molecular with 2 primary amino radicals or secondary amino group react with tetracarboxylic compound or tetracarboxylic anhydride.
In order to obtain the A in formula [a]1And A2Polyamic acid Arrcostab for the alkyl of carbon number 1～5, it is possible to by making aforementioned diamine compound react obtain with tetrabasic carboxylic acid two acetyl halide compound, tetrabasic carboxylic acid dialkyl compound or tetrabasic carboxylic acid dialkyl two acetyl halide compound.Alternatively, it is also possible to the A shown in the formula [a] in the polyamic acid utilizing preceding method to obtain1And A2Import the alkyl of carbon number 1～5.
The polyimides based polymer of the present invention be preferably will the diamine compound of at least one particular side chain structure having in structure shown in following formula [1-1] and formula [1-2] be used for the part of raw material and obtain, at least one polymer in polyimide precursor and polyimides.
In formula [1-1], Y1Represent selected from singly-bound ,-(CH2)a-(a is the integer of 1～15) ,-O-,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) at least one binding groups in CO-,-COO-and-OCO-.Wherein, from the view point of raw material availability, synthesis easness, it is preferred to singly-bound ,-(CH2)a-(a is the integer of 1～15) ,-O-,-CH2O-or-COO-.It is more preferably singly-bound ,-(CH2)a-(a is the integer of 1～10) ,-O-,-CH2O-or-COO-.
In formula [1-1], Y2Represent singly-bound or-(CH2)b-(b is the integer of 1～15).Wherein, it is preferred to singly-bound or-(CH2)b-(b is the integer of 1～10).
In formula [1-1], Y3Represent selected from singly-bound ,-(CH2)c-(c is the integer of 1～15) ,-O-,-CH2At least one binding groups in O-,-COO-and-OCO-.Wherein, from the view point of synthesize easness, it is preferred to singly-bound ,-(CH2)c-(c is the integer of 1～15) ,-O-,-CH2O-or-COO-.It is more preferably singly-bound ,-(CH2)c-(c is the integer of 1～10) ,-O-,-CH2O-or-COO-.
In formula [1-1], Y4For the bivalent cyclic group of at least one ring in phenyl ring, cyclohexane ring and heterocycle, any hydrogen atom on these cyclic groups is optionally by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, the replacing containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom of carbon number 1～3.And then, Y4The divalent organic group having in the organic group of the carbon number 17～51 of steroid skeleton can be chosen from.Wherein, from the view point of synthesis easness, it is preferred to the bivalent cyclic group of phenyl ring or cyclohexane ring or there is the divalent organic group of carbon number 17～51 of steroid skeleton.
In formula [1-1], Y5Representing the bivalent cyclic group of at least one ring in phenyl ring, cyclohexane ring and heterocycle, any hydrogen atom on these cyclic groups is optionally by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, the replacing containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom of carbon number 1～3.Wherein, it is preferred to phenyl ring or cyclohexane ring.
In formula [1-1], n represents the integer of 0～4.Wherein, from the view point of raw material availability, synthesis easness, it is preferred to 0～3.It is more preferably 0～2.
In formula [1-1], Y6Represent selected from the alkyl of carbon number 1～22, the thiazolinyl of carbon number 2～22, carbon number 1～22 containing at least one in fluoroalkyl, the alkoxyl of carbon number 1～22 and the fluoroalkoxy of carbon number 1～22.Wherein, it is preferred to the alkyl of carbon number 1～18, the thiazolinyl of carbon number 2～18, carbon number 1～10 the fluoroalkoxy containing fluoroalkyl, the alkoxyl of carbon number 1～18 or carbon number 1～10.It is more preferably the alkoxyl of the alkyl of carbon number 1～12, the thiazolinyl of carbon number 2～12 or carbon number 1～12.It is particularly preferably the alkyl of carbon number 1～9 or the alkoxyl of carbon number 1～9.
As the Y in formula [1-1]1～Y6With the preferred compositions of n, can list and the combination that (2-1)～(2-629) is identical disclosed in the table 6～table 47 of 13 pages～34 pages of International Publication publication the 2011/132751st (2011.10.27 is open).It should be noted that in each table of International Publication publication, the Y in the present invention1～Y6It is illustrated as Y1～Y6, but Y1～Y6 can be regarded as Y1～Y6.Additionally, in (2-605) disclosed in each table of International Publication publication～(2-629), the organic group of the carbon number 17～51 with steroid skeleton in the present invention is illustrated as the organic group of the carbon number 12～25 with steroid skeleton, but the organic group with the carbon number 12～25 of steroid skeleton can be regarded as the organic group of the carbon number 17～51 with steroid skeleton.
-Y7-Y8[1-2]
In formula [1-2], Y7Represent selected from singly-bound ,-O-,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) at least one binding groups in CO-,-COO-and-OCO-.Wherein, it is preferred to singly-bound ,-O-,-CH2O-、-CONH-、-CON(CH3)-or-COO-.It is more preferably singly-bound ,-O-,-CONH-or-COO-.
In formula [1-2], Y8Represent the alkyl of carbon number 8～22 or carbon number 6～18 containing fluoroalkyl.Wherein, it is preferred to the alkyl of carbon number 8～18.
As the particular side chain structure of the present invention, from the view point of high and stable liquid crystal vertical-tropism can be obtained, it is preferred to use the structure shown in formula [1-1].
For the method that the particular side chain structure of the present invention is directed into particular polymers, it does not have be particularly limited to, it is preferable that the diamine compound with particular side chain structure is used for diamine component.
Specifically, it is preferred to use the diamine compound (also referred to as particular side chain diamine compound) shown in following formula [1a].At this time it is also possible to use the diamine compound that amino is secondary amino group in following formula [1a].
In formula [1a], Y represents at least one structure in structure shown in previously described formula [1-1] and formula [1-2].It should be noted that Y during Y expression [1-1] in formula [1a]1～Y6Described above with the preferred compositions of n.
In formula [1a], m represents the integer of 1～4.Wherein, it is preferred to 1.
It is the diamine compound of secondary amino group that the concrete example of the particular side chain diamine compound of the present invention can list the such as diamine compound shown in following formula [1a-1]～formula [1a-34] and their amino.
(in formula [1a-1]～formula [1a-3], R1、R3And R5Represent-O-,-OCH independently of one another2-、-CH2O-、-COOCH2-or-CH2OCO-；In formula [1a-1]～formula [1a-3], R2、R4And R6Represent the straight-chain of carbon number 1～22 or branched alkyl, the straight-chain of carbon number 1～22 or branched alkoxyl, the straight-chain of carbon number 1～22 or the branched fluoroalkoxy containing fluoroalkyl or carbon number 1～22 independently of one another).
(in formula [1a-4]～formula [1a-6], R1、R3And R5Represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH independently of one another2-、-CH2OCO-、-CH2O-、-OCH2-or-CH2-；In formula [1a-4]～formula [1a-6], R2、R4And R6Represent the straight-chain of carbon number 1～22 or branched alkyl, the straight-chain of carbon number 1～22 or branched alkoxyl, the straight-chain of carbon number 1～22 or the branched fluoroalkoxy containing fluoroalkyl or carbon number 1～22 independently of one another).
(formula [1a-7] and in formula [1a-8], R1And R3Represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH independently of one another2-、-CH2OCO-、-CH2O-、-OCH2-、-CH2-,-O-or-NH-；R2And R4Represent fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl independently of one another).
(formula [1a-9] and in formula [1a-10], R1And R2Represent straight-chain or branched alkyl, the cis-trans isomerization of the Isosorbide-5-Nitrae-cyclohexylene respectively transisomer of carbon number 3～12 independently of one another).
(formula [1a-11] and in formula [1a-12], R1And R2Represent straight-chain or branched alkyl, the cis-trans isomerization of the Isosorbide-5-Nitrae-cyclohexylene respectively transisomer of carbon number 3～12 independently of one another).
(in formula [1a-13], A4For the straight-chain of carbon number 3～20 being optionally replaced by fluorine atoms or branched alkyl；A3For 1,4-cyclohexylene or 1,4-phenylene；A2For oxygen atom or-COO-* (wherein, the key of labelling " * " and A3It is bonded)；A1For oxygen atom or-COO-* (wherein, the key of labelling " * " and (CH2)a2) be bonded).It addition, a1It it is the integer of 0 or 1；a2It it is the integer of 2～10；a3It is the integer of 0 or 1).
(in formula [1a-32]～formula [1a-35], A1～A4Represent the alkyl of carbon number 1～22 independently of one another or containing fluoroalkyl).
In previously described formula [1a-1]～[1a-21], [1a-24]～[1a-35], it is particularly preferred to the particular side chain diamine compound of structure is formula [1a-1]～formula [1a-6], formula [1a-9]～formula [1a-13] or formula [1a-24]～formula [1a-31].
Particular side chain diamine compound in the particular polymers of the present invention is preferably 10 moles of overall more than % of diamine component and 80 moles of below %.It is particularly preferably 70 moles of below % of 10 moles of more than %.
The particular side chain diamine compound of the present invention also dependent on the particular polymers dissolubility in a solvent of the present invention, compositions and aligning agent for liquid crystal coating, make liquid crystal orientation film time liquid crystal aligning, voltage retention, the characteristic such as accumulated charge and use a kind or mix two or more and use.
The particular polymers of the present invention is preferably the polymer obtained by the diamine compound of at least one substituent group having in carboxyl (COOH yl) and hydroxyl (OH yl) for diamine component.
Specifically, it is preferred to use the diamine compound shown in following formula [2a].At this time it is also possible to use the diamine compound that amino is secondary amino group in following formula [2a].
In formula [2a], A represents the substituent group of at least one structure in following formula [2-1] and formula [2-2].
-(CH2)a-COOH[2-1]-(CH2)b-OH[2-2]
In formula [2-1], a represents the integer of 0～4.
In formula [2-2], b represents the integer of 0～4.
In formula [2a], m represents the integer of 1～4.
More specifically, 2,4-diaminophenols, 3,5-diaminophenols, 3,5-diaminourea benzylalcohols, 2,4-diaminourea benzylalcohols, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acids, 2,5-diaminobenzoic acids or 3,5-diaminobenzoic acids can be listed.Wherein, it is preferred to 2,4-diaminobenzoic acids, 2,5-diaminobenzoic acids or 3,5-diaminobenzoic acids.
Alternatively, it is also possible to use the diamine compound shown in following formula [2a-1]～formula [2a-4] and their diamine compound that amino is secondary amino group.
(in formula [2a-1], A1Represent selected from singly-bound ,-CH2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3)-and-N (CH3) at least one binding groups in CO-, m1And m2Represent integer and the m of 0～4 independently of one another1+m2Represent the integer of 1～4；In formula [2a-2], m3And m4Represent the integer of 1～5 independently of one another；In formula [2a-3], A2Represent the straight chain of carbon number 1～5 or the alkyl of branch, m5Represent the integer of 1～5；In formula [2a-4], A3And A4Represent independently of one another selected from singly-bound ,-CH2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3)-and-N (CH3) at least one binding groups in CO-, m6Represent the integer of 1～4).
The diamine compound of at least one substituent group having in carboxyl (COOH yl) and hydroxyl (OH yl) in the particular polymers of the present invention is preferably 10 moles of overall more than % of diamine component and 80 moles of below %.It is particularly preferably 10 moles of more than % and 70 moles of below %.
The diamine compound of at least one substituent group having in carboxyl (COOH yl) and hydroxyl (OH yl) of the present invention can according to the coating of the particular polymers of present invention dissolubility in a solvent, compositions and aligning agent for liquid crystal, make liquid crystal orientation film time liquid crystal aligning, voltage retention, the characteristic such as accumulated charge and use a kind or mix two or more and use.
The particular polymers of the present invention is preferably used has the nitrogenous heterocyclic diamine compound shown in following formula [3a] and their diamine compound that amino is secondary amino group.
In formula [3a], B1Represent selected from-O-,-NH-,-N (CH3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)-and-N (CH3) at least one binding groups in CO-.Wherein, it is preferred to-O-,-NH-,-CONH-,-NHCO-,-CH2O-、-OCO-、-CON(CH3)-or-N (CH3) CO-, this is because be readily synthesized diamine compound.It is more preferably-O-,-NH-,-CONH-,-NHCO-,-CH2O-,-OCO-or-CON (CH3)-.It is particularly preferably-O-,-CONH-or-CH2O-。
In formula [3a], B2Represent at least one in singly-bound, the divalent group of aliphatic hydrocarbon of carbon number 1～20, the divalent group of non-aromatic ring type hydrocarbon and the divalent group of aromatic hydrocarbon.The divalent group of the aliphatic hydrocarbon of carbon number 1～20 can be straight-chain, it is also possible to for branched.Furthermore it is also possible to have unsaturated bond.Wherein, it is preferred to the alkylidene of carbon number 1～10.Additionally, as the concrete example of non-aromatic hydrocarbon, cyclopropane ring, Tetramethylene. ring, Pentamethylene. ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring icosane ring, three ring icosane rings, three ring docosane rings, norbornane ring, decahydro naphthalene nucleus, norborene ring or diamantane (obsolete) ring etc. can be listed.Wherein, it is preferred to cyclopropane ring, Tetramethylene. ring, Pentamethylene. ring, cyclohexane ring, cycloheptane ring, norborene ring or diamantane (obsolete) ring.As the concrete example of aromatic hydrocarbyl, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring or that alkene ring non-etc. can be listed.Wherein, it is preferred to phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring or anthracene nucleus.
As the preferred B in formula [3a]2, for the divalent group of singly-bound, the alkylidene of carbon number 1～10 or at least one ring in cyclopropane ring, Tetramethylene. ring, Pentamethylene. ring, cyclohexane ring, cycloheptane ring, norborene ring, diamantane (obsolete) ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring and anthracene nucleus.Wherein, it is preferred to the divalent group of singly-bound, the alkylidene of carbon number 1～5 or cyclohexane ring or phenyl ring.
In formula [3a], B3Represent selected from singly-bound ,-O-,-NH-,-N (CH3)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-、-N(CH3) CO-and-O (CH2)mAt least one binding groups in-(m is the integer of 1～5).Wherein, it is preferred to singly-bound ,-O-,-COO-,-OCO-or-O (CH2)m-(m is the integer of 1～5).It is more preferably singly-bound ,-O-,-OCO-or-O (CH2)m-(m is the integer of 1～5).
In formula [3a], B4For nitrogen heterocycle, it it is the heterocyclic group containing at least one structure in following formula [3a-1], formula [3a-2] and formula [3a-3].
(in formula [3a-3], Z11Represent the alkyl of carbon number 1～5).
More specifically, pyrrole ring, imidazole ring, azoles ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, diazole ring or acridine ring etc. can be listed.Wherein, it is preferred to pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring or benzimidazole ring.It is more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring.It addition, the B in formula [3a]3Preferably it is bonded to B4Not adjacent with the structure of formula [3a-1], formula [3a-2] and formula [3a-3] annular atoms comprised.
In formula [3a], n is the integer of 1～4, from its reactive viewpoint with tetrabasic carboxylic acid composition, it is preferred to 1 or 2.
B in formula [3a]1～B4Particularly preferred combination with n is B1Represent-CONH-, B2Represent the alkylidene of carbon number 1～5, B3Represent singly-bound, B4Represent the diamine compound that imidazole ring or pyridine ring, n represent 1.
Two amino (-NH in formula [3a]2) bonding position do not limit.Specifically, relative to the binding groups (-B of side chain1-), can list on phenyl ring 2,3 position, 2,4 position, 2,5 position, the position of 2,6, the position of 3,4 or 3,5 position.Wherein, from synthesizing polyamides acid reactive viewpoint time, it is preferred to the position of 2,4, the position of 2,5 or 3,5 position.When being additionally contemplates that easiness when synthesizing diamine compound, more preferably the position of 2,4 or the position of 2,5.
The nitrogenous heterocyclic diamine compound that has shown in previously described formula [3a] in the particular polymers of the present invention is preferably 10 moles of overall more than % of diamine component and 80 moles of below %.It is particularly preferably 10 moles of more than % and 70 moles of below %.
Shown in the previously described formula [3a] of the present invention have nitrogenous heterocyclic diamine compound also can according to the coating of the particular polymers of present invention dissolubility in a solvent, compositions and aligning agent for liquid crystal, make liquid crystal orientation film time liquid crystal aligning, voltage retention, the characteristic such as accumulated charge and use a kind or mix two or more and use.
In the particular polymers of the present invention, in the scope not damaging effect of the present invention, as other diamine compound, it is possible to use the diamine compound shown in following formula [a-1]～formula [a-13] and their diamine compound that amino is secondary amino group.
(in formula [a-1], A1And A3Represent independently of one another selected from-COO-,-OCO-,-CONH-,-NHCO-,-CH2-, at least one binding groups in-O-,-CO-and-NH-, A2Represent the straight-chain of the straight-chain of carbon number 1～22 or branched alkyl or carbon number 1～22 or branched containing fluoroalkyl；In formula [a-2], A4And A6Represent independently of one another selected from-COO-,-OCO-,-CONH-,-NHCO-,-CH2-, at least one binding groups in-O-,-CO-and-NH-, A5Represent the straight-chain of the straight-chain of carbon number 1～22 or branched alkyl or carbon number 1～22 or branched containing fluoroalkyl).
(in formula [a-3], A1And A3Represent independently of one another selected from-COO-,-OCO-,-CONH-,-NHCO-,-CH2-, at least one binding groups in-O-,-CO-and-NH-, A2Represent the straight-chain of the straight-chain of carbon number 1～22 or branched alkyl or carbon number 1～22 or branched containing fluoroalkyl；In formula [a-4], A4And A6Represent independently of one another selected from-COO-,-OCO-,-CONH-,-NHCO-,-CH2-, at least one binding groups in-O-,-CO-and-NH-, A5Represent the straight-chain of the straight-chain of carbon number 1～22 or branched alkyl or carbon number 1～22 or branched containing fluoroalkyl).
(in formula [a-5], A1And A3Represent independently of one another selected from-COO-,-OCO-,-CONH-,-NHCO-,-CH2-, at least one binding groups in-O-,-CO-and-NH-, A2Represent the straight-chain of the straight-chain of carbon number 1～22 or branched alkyl or carbon number 1～22 or branched containing fluoroalkyl；In formula [a-6], A4And A6Represent independently of one another selected from-COO-,-OCO-,-CONH-,-NHCO-,-CH2-, at least one binding groups in-O-,-CO-and-NH-, A5Represent the straight-chain of the straight-chain of carbon number 1～22 or branched alkyl or carbon number 1～22 or branched containing fluoroalkyl).
(in formula [a-7], p represents the integer of 1～10).
(in formula [a-12], R1Represent the alkyl of hydrogen atom or carbon number 1～5；In formula [a-13], n represents the integer of 1～10).
And then, as other diamine compound, it is possible to use following diamine compound and their diamine compound that amino is secondary amino group.
nullSpecifically，P-phenylenediamine can be listed、2,3,5,6-tetramethyl-para-phenylene diamine、2,5-dimethyl-p-phenylenediamine、M-diaminobenzene.、2,4-dimethyl-m-phenylenediamine、2,5-diaminotoluene、2,6-diaminotoluene、4,4 '-benzidine、3,3 '-dimethyl-4,4 '-benzidine、3,3 '-dimethoxy-4 ',4 '-benzidine、3,3 '-dihydroxy-4,4 '-benzidine、3,3 '-dicarboxyl-4,4 '-benzidine、3,3 '-two fluoro-4,4 '-benzidine、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、Double; two (4-aminophenyl) silane、Double; two (3-aminophenyl) silane、Dimethyl-bis-(4-aminophenyl) silane、Dimethyl-bis-(3-aminophenyl) silane、4,4 '-phenothiazine、3,3 '-phenothiazine、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 '-diaminobenzophenone、3,3 '-diaminobenzophenone、3,4 '-diaminobenzophenone、1,4-diaminonaphthalene、2,2 '-diaminobenzophenone、2,3 '-diaminobenzophenone、1,5-diaminonaphthalene、1,6-diaminonaphthalene、1,7-diaminonaphthalene、1,8-diaminonaphthalene、2,5-diaminonaphthalene、2,6-diaminonaphthalene、2,7-diaminonaphthalene、2,8-diaminonaphthalene、1,Double; two (4-aminophenyl) ethane of 2-、1,Double; two (3-aminophenyl) ethane of 2-、1,Double; two (4-aminophenyl) propane of 3-、1,Double; two (3-aminophenyl) propane of 3-、1,Double; two (4-aminophenyl) butane of 4-、1,Double; two (3-aminophenyl) butane of 4-、Double; two (3,5-diethyl-4-aminophenyl) methane、1,Double; two (4-amino-benzene oxygen) benzene of 4-、1,Double; two (4-amino-benzene oxygen) benzene of 3-、1,Double; two (4-aminophenyl) benzene of 4-、1,Double; two (4-aminophenyl) benzene of 3-、1,Double; two (4-aminobenzyl) benzene of 4-、1,Double; two (4-amino-benzene oxygen) benzene of 3-、4,4’-[1,4-phenylene double; two (methylene)] diphenylamines、4,4’-[1,3-phenylene double; two (methylene)] diphenylamines、3,4’-[1,4-phenylene double; two (methylene)] diphenylamines、3,4’-[1,3-phenylene double; two (methylene)] diphenylamines、3,3’-[1,4-phenylene double; two (methylene)] diphenylamines、3,3’-[1,3-phenylene double; two (methylene)] diphenylamines、1,4-phenylene double; two [(4-aminophenyl) ketone]、1,4-phenylene double; two [(3-aminophenyl) ketone]、1,3-phenylene double; two [(4-aminophenyl) ketone]、1,3-phenylene double; two [(3-aminophenyl) ketone]、1,4-phenylene double; two (PABA ester)、1,4-phenylene double; two (3-Aminobenzoate)、1,3-phenylene double; two (PABA ester)、1,3-phenylene double; two (3-Aminobenzoate)、Double; two (4-aminophenyl) terephthalate、Double; two (3-aminophenyl) terephthalate、Double; two (4-aminophenyl) isophthalic acid ester、Double; two (3-aminophenyl) isophthalic acid ester、N,N’-(1,4-phenylene) double; two (4-aminobenzamides)、N,N’-(1,3-phenylene) double; two (4-aminobenzamides)、N,N’-(1,4-phenylene) double; two (3-ABs)、N,N’-(1,3-phenylene) double; two (3-ABs)、N,N '-bis-(4-aminophenyl) p dimethylamine、N,N '-bis-(3-aminophenyl) p dimethylamine、N,N '-bis-(4-aminophenyl) m-xylene diamine、N,N '-bis-(3-aminophenyl) m-xylene diamine、9,Double; two (4-aminophenyl) anthracene of 10-、4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide .s、2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane、2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa、2,2 '-bis-(4-aminophenyl) HFC-236fa、2,2 '-bis-(3-aminophenyl) HFC-236fa、2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa、2,2 '-bis-(4-aminophenyl) propane、2,2 '-bis-(3-aminophenyl) propane、2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane、1,Double; two (4-amino-benzene oxygen) propane of 3-、1,Double; two (3-amino-benzene oxygen) propane of 3-、1,Double; two (4-amino-benzene oxygen) butane of 4-、1,Double; two (3-amino-benzene oxygen) butane of 4-、1,Double; two (4-amino-benzene oxygen) pentane of 5-、1,Double; two (3-amino-benzene oxygen) pentane of 5-、1,Double; two (4-amino-benzene oxygen) hexane of 6-、1,Double; two (3-amino-benzene oxygen) hexane of 6-、1,Double; two (4-amino-benzene oxygen) heptane of 7-、1,7-(3-amino-benzene oxygen) heptane、1,Double; two (4-amino-benzene oxygen) octane of 8-、1,Double; two (3-amino-benzene oxygen) octane of 8-、1,Double; two (4-amino-benzene oxygen) nonane of 9-、1,Double; two (3-amino-benzene oxygen) nonane of 9-、1,10-(4-amino-benzene oxygen) decane、1,10-(3-amino-benzene oxygen) decane、1,11-(4-amino-benzene oxygen) hendecane、1,11-(3-amino-benzene oxygen) hendecane、1,12-(4-amino-benzene oxygen) dodecane、1,The aromatic diamine compounds such as 12-(3-amino-benzene oxygen) dodecane、Double; two (4-aminocyclohexyl) methane、The ester ring type diamine compounds such as double; two (4-amino-3-methylcyclohexyl) methane；1,3-diaminopropanes, 1,4-diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1, the aliphatic diamine compounds such as 11-diamino undecane, 1,12-diamino dodecane.
Other diamine compound of the present invention also dependent on the particular polymers dissolubility in a solvent of the present invention, compositions and aligning agent for liquid crystal coating, make liquid crystal orientation film time liquid crystal aligning, voltage retention, the characteristic such as accumulated charge and use a kind or mix two or more and use.
As being used for making the particular polymers i.e. tetrabasic carboxylic acid composition of these polyimides based polymers of the present invention, it is preferred to use the tetracarboxylic dianhydride shown in following formula [4].Now, it is possible not only to the tetracarboxylic dianhydride shown in use formula [4], it is also possible to use its tetracarboxylic acid derivatives and tetrabasic carboxylic acid, tetrabasic carboxylic acid two acetyl halide compound, tetrabasic carboxylic acid dialkyl compound or tetrabasic carboxylic acid dialkyl two acetyl halide compound (also the tetracarboxylic dianhydride shown in formula [4] and derivant thereof being referred to as specific tetrabasic carboxylic acid composition).
(in formula [4], Z represents at least one structure in structure shown in following formula [4a]～formula [4k]).
In formula [4a], Z1～Z4Represent hydrogen atom, methyl, ethyl, propyl group, chlorine atom or phenyl independently of one another.
In formula [4g], Z5And Z6Represent hydrogen atom or methyl independently of one another.
Among Z in formula [4], from the view point of polymerisation reactivity easness when synthesis easness, manufacture polymer, it is preferred to the tetracarboxylic dianhydride of structure shown in formula [4a], formula [4c]～formula [4g] or formula [4k] and tetracarboxylic acid derivatives thereof.It is more preferably the structure shown in formula [4a] or formula [4e]～formula [4g].It is particularly preferably tetracarboxylic dianhydride and the tetracarboxylic acid derivatives thereof of structure shown in [4a], formula [4e] or formula [4f].
Specific tetrabasic carboxylic acid composition in the particular polymers of the present invention is preferably 1 mole of %～100 mole % in 100 moles of % of whole tetrabasic carboxylic acid compositions.Wherein, it is preferred to 5 moles of %～95 mole %.It is more preferably 20 moles of %～80 mole %.
The specific tetrabasic carboxylic acid composition of the present invention also dependent on the particular polymers dissolubility in a solvent of the present invention, compositions and aligning agent for liquid crystal coating, make liquid crystal orientation film time liquid crystal aligning, voltage retention, the characteristic such as accumulated charge and use a kind or mix two or more and use.
In the particular polymers of the present invention, in the scope not damaging effect of the present invention, it is possible to use other tetrabasic carboxylic acid composition beyond specific tetrabasic carboxylic acid composition.As other tetrabasic carboxylic acid composition, tetracarboxylic compound described below, tetracarboxylic dianhydride, tetrabasic carboxylic acid two acetyl halide compound, tetrabasic carboxylic acid dialkyl compound or tetrabasic carboxylic acid dialkyl two acetyl halide compound can be listed.
nullNamely，As other tetrabasic carboxylic acid composition，1 can be listed,2,5,6-naphthalene tetracarboxylic acid、1,4,5,8-naphthalene tetracarboxylic acid、1,2,5,6-anthracene tetrabasic carboxylic acid、3,3’,4,4 '-biphenyltetracarboxyacid acid、2,3,3’,4-biphenyltetracarboxyacid acid、Double; two (3,4-dicarboxyphenyi) ether、3,3’,4,4 '-benzophenone tetrabasic carboxylic acid、Double; two (3,4-dicarboxyphenyi) sulfone、Double; two (3,4-dicarboxyphenyi) methane、2,2-double; two (3,4-dicarboxyphenyi) propane、1,1,1,3,3,3-hexafluoro-2,2-double; two (3,4-dicarboxyphenyi) propane、Double; two (3,4-dicarboxyphenyi) dimethylsilane、Double; two (3,4-dicarboxyphenyi) diphenyl silane、2,3,4,5-pyridine tetrabasic carboxylic acid、2,6-double; two (3,4-dicarboxyphenyi) pyridine、3,3’,4,4 '-sulfobenzide. tetrabasic carboxylic acid、3,4,9,10-tetrabasic carboxylic acid or 1,3-diphenyl-1,2,3,4-Tetramethylene. tetrabasic carboxylic acid etc..
Other tetrabasic carboxylic acid composition of the present invention also dependent on the particular polymers dissolubility in a solvent of the present invention, compositions and aligning agent for liquid crystal coating, make liquid crystal orientation film time liquid crystal aligning, voltage retention, the characteristic such as accumulated charge and use a kind or mix two or more and use.
<manufacture method of particular polymers>
In the present invention, it is not particularly limited for making the particular polymers i.e. method of these polyimides based polymers.Diamine component is generally made to react with tetrabasic carboxylic acid composition and obtain.In general, can list: the method that at least one tetrabasic carboxylic acid composition in the group making the derivant of the free tetracarboxylic dianhydride of choosing and tetrabasic carboxylic acid thereof form reacts with the diamine component comprising one or more diamine compounds and obtains polyamic acid.Specifically, it is possible to use following method: make tetracarboxylic dianhydride and primary diamines compound or secondary diamine compounds polycondensation and obtain the method for polyamic acid, make tetrabasic carboxylic acid and primary diamines compound or secondary diamine compounds generation dehydrating polycondensation react and obtain the method for polyamic acid or the method making tetrabasic carboxylic acid two acetyl halide compound and primary diamines compound or secondary diamine compounds polycondensation and obtaining polyamic acid.
In order to obtain polyamic acid Arrcostab, it is possible to use following method: the method making tetrabasic carboxylic acid and primary diamines compound or the secondary diamine compounds polycondensation being esterified by carboxylic acid group's dialkyl group, the method making tetrabasic carboxylic acid two acetyl halide compound and primary diamines compound or the secondary diamine compounds polycondensation being esterified by carboxylic acid group's dialkyl group or the method converting the carboxyl of polyamic acid to ester.
In order to obtain polyimides, it is possible to use make foregoing polyamides acid or polyamic acid Arrcostab closed loop and the method for making polyimides.
About the reaction of diamine component Yu tetrabasic carboxylic acid composition, diamine component and tetrabasic carboxylic acid composition is generally made to carry out in a solvent.As the solvent now used, it is possible to use the specific solvent of the present invention, as long as the solvent dissolving the polyimide precursor generated just is not particularly limited.The following concrete example listing the solvent that reaction uses, but it is not limited to these examples.
Include, for example out METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone or gamma-butyrolacton, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolinone.It addition, when the solvent solubility of polyimide precursor is high, it is possible to use the solvent shown in butanone, Ketohexamethylene, Ketocyclopentane, 4-hydroxy-4-methyl-2-pentanone or following formula [D-1]～formula [D-3].
(in formula [D-1], D1Represent the alkyl of carbon number 1～3；In formula [D-2], D2Represent the alkyl of carbon number 1～3；In formula [D-3], D3Represent the alkyl of carbon number 1～4).
These solvents can be used alone, it is also possible to mixing uses.And then, even the solvent of insoluble polyimide precursor, in the scope that the polyimide precursor generated will not precipitate out, it is also possible to mixing uses to aforementioned solvents.It addition, the moisture in solvent can hinder polyreaction, will also become the reason making the polyimide precursor generated be hydrolyzed, therefore solvent uses preferably in after dehydrate.
When making diamine component and tetrabasic carboxylic acid composition react in a solvent, following method can be listed: stirring makes diamine component be dispersed or dissolved in the solution of solvent, directly add tetrabasic carboxylic acid composition or make it disperse or dissolve to solvent the method added；Otherwise, the method adding diamine component to making tetrabasic carboxylic acid composition be dispersed or dissolved in the solution of solvent；Alternately add the method etc. of diamine component and tetrabasic carboxylic acid composition, it is possible to use the either method in these.It addition, when using multiple diamine component or tetrabasic carboxylic acid composition to react respectively, it is possible to react when being pre-mixed, it is also possible to react successively respectively, it is also possible to be the low-molecular weight generation hybrid reaction of individually reaction and make polymer.Polymerization temperature now can select the arbitrary temp of-20 DEG C～150 DEG C, it is preferred to the scope of-5 DEG C～100 DEG C.It addition, reaction can carry out with any concentration, but when concentration is too low, it is difficult to obtaining the polymer of high molecular, during excessive concentration, the viscosity of reactant liquor becomes too high, is difficult to uniform stirring.It is therefore preferable that be 1～50 mass %, be more preferably 5～30 mass %.Can react and initially carry out with high concentration, add thereafter solvent.
In the polyreaction of polyimide precursor, the ratio of the total mole number of diamine component and the total mole number of tetrabasic carboxylic acid composition is preferably 0.8～1.2.In the same manner as common polycondensation reaction, this mol ratio is closer to 1.0, then the molecular weight of the polyimide precursor generated becomes more big.
The polyimides of the present invention is make aforementioned polyimide precursor closed loop and the polyimides that obtains, and in this polyimides, the closed loop rate (also referred to as acid imide rate) of amide acidic group must be not necessarily 100%, it is possible to arbitrarily adjusts according to purposes, purpose.
As the method making polyimide precursor carry out imidizate, can list: by direct-fired for the solution of polyimide precursor hot-imide or to the catalysis imidizate adding catalyst in the solution of polyimide precursor.
Temperature when making polyimide precursor carry out hot-imide in the solution is 100 DEG C～400 DEG C, is preferably 120 DEG C～250 DEG C, it is preferred that be expelled to outside system by the water generated in imidization reaction, while carrying out hot-imide.
The catalysis imidizate of polyimide precursor can pass through to add base catalyst and anhydride in the solution of polyimide precursor, with-20 DEG C～250 DEG C, preferably carry out with 0 DEG C～180 DEG C stirrings.The amount of base catalyst is 0.5 mole of amide acidic group times～30 moles times, is preferably 2 moles times～20 moles times, the amount of anhydride is amide acidic group 1 mole times～50 moles times, be preferably 3 moles times～30 moles times.As base catalyst, can listing pyridine, triethylamine, trimethylamine, tri-n-butylamine or trioctylamine etc., wherein, pyridine has the alkalescence of appropriateness for advancing reaction, so preferably.As anhydride, acetic anhydride, trihemellitic acid acid anhydride or PMA etc. can be listed, wherein, when using acetic anhydride, react the purification after terminating and become easy, so preferably.Acid imide rate based on catalysis imidizate can be controlled by adjustment catalytic amount and reaction temperature, response time.
When reclaiming the polyimide precursor generated or polyimides from the reaction solution of polyimide precursor or polyimides, it is possible to reaction solution is fed in solvent and makes it precipitate.As the solvent for precipitating, methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, butanone, methyl iso-butyl ketone (MIBK), toluene, benzene, water etc. can be listed.The polymer being fed into solvent and make it precipitate is after being recovered by filtration, it is possible to carry out normal temperature drying or heat drying under normal or reduced pressure.It addition, the polymer making precipitation reclaim is dissolved in again solvent and precipitates the operation of recovery again when repeating 2 times～10 times, it is possible to reduce the impurity in polymer.As solvent now, can listing such as alcohols, ketone or hydrocarbon etc., when using more than 3 kinds solvents among these, purification efficiency improves further, so preferably.
<compositions/aligning agent for liquid crystal>
The compositions of the present invention and the aligning agent for liquid crystal employing it are for forming polyimide film and the coating solution of liquid crystal orientation film (being also referred to collectively as resin coating), are the coating solutions for forming resin coating containing specific solvent and particular polymers.
The particular polymers of the present invention can use any polyimides based polymer in polyamic acid, polyamic acid Arrcostab and polyimides.Wherein, it is preferred to polyamic acid Arrcostab or polyimides.It is more preferably polyimides.
Whole component of polymer in the compositions of the present invention and aligning agent for liquid crystal can be entirely the particular polymers of the present invention.At this time it is also possible to the particular polymers of the present invention being mixed with two or more.It addition, particular polymers can also be mixed with other polymer in addition.As polymer in addition, cellulose-based polymer, acrylic polymer, methacrylic polymer, polystyrene, polyamide or polysiloxanes etc. can be listed.Now, the content of other polymer in addition is 0.5 mass parts～30 mass parts relative to particular polymers 100 mass parts of the present invention.Wherein, it is preferred to 1 mass parts～20 mass parts.
It addition, using the compositions of the present invention as aligning agent for liquid crystal form liquid crystal orientation film time, particular polymers is preferably used the particular polymers with the particular side chain structure shown in previously described formula [1-1] of the present invention.Wherein, it is preferred to use, employ the particular polymers of the particular side chain diamine compound shown in formula [1a] with the particular side chain structure shown in formula [1-1].Especially, need the liquid crystal orientation film of the pattern of liquid crystal pretilt angle about for TN (twisted nematic (TwistedNematic)) pattern, VA (vertical orientated (VerticalAlignment)) pattern etc., employ the particular polymers of particular side chain diamine compound preferably.It addition, at this point it is possible to the particular polymers employing particular side chain diamine compound is mixed use with the particular polymers not using particular side chain diamine compound.Now, the content not using the particular polymers of particular side chain diamine compound is preferably 10 mass parts～300 mass parts relative to particular polymers 100 mass parts employing particular side chain diamine compound.Especially, it is preferred to 20 mass parts～200 mass parts.
About the solvent in the compositions of the present invention and aligning agent for liquid crystal, from the view point of form uniform resin overlay film by being coated with, the content of solvent is preferably 70～99.9 mass %.This content suitably can change according to the target film thickness of polyimide film and liquid crystal orientation film.
It addition, as solvent now, it is possible to it is entirely the specific solvent of the present invention, it is also possible to use simultaneously and dissolve the solvent of particular polymers of the present invention, i.e. good solvent.The following concrete example listing good solvent, but it is not limited to these examples.
It is such as N, dinethylformamide, N, N-dimethyl acetylamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone, butanone, Ketohexamethylene, Ketocyclopentane or 4-hydroxy-4-methyl-2-pentanone etc..
Wherein, it is preferred to use METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone or gamma-butyrolacton (above also referred to as (C) composition).
These (C) compositions are preferably in compositions and aligning agent for liquid crystal 1～70 mass % that the solvent comprised is overall.Wherein, it is preferred to 5～65 mass %.It is more preferably 5～60 mass %, more preferably 10～60 mass %.
Aforementioned good solvent uses a kind or mixes two or more and use also dependent on the coating of the particular polymers dissolubility in a solvent of the present invention, compositions and aligning agent for liquid crystal.
In the compositions of the present invention and aligning agent for liquid crystal, in the scope not damaging effect of the present invention, it is also preferred that organic solvent that the film of resin coating when making coating composition and aligning agent for liquid crystal, surface smoothness improve, poor solvent.The following concrete example listing poor solvent, but it is not limited to these examples.
nullInclude, for example out ethanol、Isopropanol、N-butyl alcohol、2-butanol、Isobutanol、The tert-butyl alcohol、1-amylalcohol、2-amylalcohol、3-amylalcohol、2-methyl-1-butene alcohol、Isoamyl alcohol、Tert-pentyl alcohol、3-methyl-2-butanol、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-capryl alcohol、Sec-n-octyl alcohol、2-ethyl-1-hexanol、Hexalin、1 methyl cyclohexanol、2 methyl cyclohexanol、3 methyl cyclohexanol、1,2-ethylene glycol、1,2-propylene glycol、1,Ammediol、1,2-butanediol、1,3-butanediol、1,4-butanediol、2,3-butanediol、1,5-pentanediol、2-methyl-2,4-pentanediol、2-ethyl-1,3-hexanediol、Dipropyl ether、Butyl oxide、Two hexyl ethers、Dioxane、Glycol dimethyl ether、Ethylene glycol diethyl ether、Butyl cellosolve、1,2-butoxy ethane、Diethylene glycol dimethyl ether、Diethylene glycol diethyl ether、Diethylene glycol MEE、Dibutyl ethylene glycol ether、2 pentanone、Propione、Methyl-n-butyl ketone、2-heptanone、Dipropyl ketone、3-ethoxybutyl acetas、1-methyl amyl acetas、2-ethyl-butyl acetas、2-ethylhexyl acetate、Ethylene glycol acetate、Ethylene acetate、Propylene carbonate、Ethylene carbonate、2-(methoxymethoxy) ethanol、Ethylene glycol monobutyl ether、Ethylene glycol list isoamyl oxide、Ethylene glycol monohexylether、2-(hexyloxy) ethanol、Furfuryl alcohol、Diethylene glycol、Propylene glycol、Propylene glycol monobutyl ether、1-(Butoxyethoxy) propanol、Propylene glycol methyl ether acetate、Dipropylene glycol、Dipropylene glycol monomethyl ether、DPE、Dimethyl ether、Tripropylene glycol monomethyl Ether、Ethylene glycol monomethyl ether acetate、Ethylene glycol monoethylether acetate、Ethylene glycol monomethyl ether acetate、Ethylene glycol acetate、Ethylene acetate、Diethylene glycol monoethyl ether acetas、Butyl carbitol acetate、2-(2-ethoxy ethoxy) ethylhexoate、Diethylene glycol acetas、Triethylene glycol、Triethylene glycol monomethyl ether、Triethylene glycol ethyl ether、Methyl acetate、Ethyl acetate、N-butyl acetate、Acetic acid dihydroxypropane single-ether、Methyl pyruvate、Ethyl pyruvate、3-methoxy methyl propionate、3-ethoxy-propionic acid Methylethyl、3-methoxypropionate、3-ethoxy-propionic acid、3-methoxypropionic acid、3-methoxy propyl propyl propionate、3-methoxy propyl acid butyl ester、Methyl lactate、Ethyl lactate、Lactic acid n-propyl ester、N-butyl lactate、Isoamyl lactate、Or the solvent etc. shown in previously described formula [D-1]～formula [D-3].
Wherein, be preferably used 1-hexanol, Hexalin, 1, solvent (above also referred to as (D) composition) shown in 2-ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dimethyl ether or previously described formula [D-1]～formula [D-3].
These (D) compositions are preferably in compositions and aligning agent for liquid crystal 10～80 mass % that the solvent comprised is overall.Wherein, it is preferred to 10～70 mass %.It is more preferably 20～70 mass %, more preferably 20～60 mass %.
Aforementioned poor solvent uses a kind or mixes two or more and use also dependent on the coating of the particular polymers dissolubility in a solvent of the present invention, compositions and aligning agent for liquid crystal.
The compositions of the present invention and aligning agent for liquid crystal preferably import following cross-linked compound: there is the cross-linked compound of epoxy radicals, NCO, oxetanylmethoxy or cyclocarbonate radical；There is the cross-linked compound of at least one substituent group in hydroxyl, hydroxy alkyl and low-grade alkoxy alkyl；Or, there is the cross-linked compound of polymerism unsaturated bond.These substituent groups, polymerism unsaturated bond need there are more than 2 in cross-linked compound.
nullAs the cross-linked compound with epoxy radicals or NCO，Include, for example out bisphenol acetone glycidyl ether、Phenol novolac epoxy resins、Cresol novolac epoxy、Triglycidyl group isocyanuric acid ester、Four glycidyl group aminobphenyl、Four glycidyl group m-xylene diamine、Four glycidyl group-1,Double; two (amino-ethyl) hexamethylene of 3-、Tetraphenyl glycidyl ether ethane、Trisphenyl glycidyl ether ethane、Bis-phenol hexafluoro acetyl group diglycidyl ether、1,Double; two (the 1-(2 of 3-,3-glycidoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl) benzene、4,4-double; two (2,3-glycidoxy) octafluorobiphenyl、Triglycidyl group para-aminophenol、Four glycidyl group m-xylene diamine、2-(4-(2,3-glycidoxy) phenyl)-2-(4-(1,Double; two (the 4-(2 of 1-,3-glycidoxy) phenyl) ethyl) phenyl) propane or 1,Double; 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-propanol etc..
The cross-linked compound with oxetanylmethoxy is the cross-linked compound with the oxetanylmethoxy shown at least 2 following formula [4A].
Specifically, the cross-linked compound shown in 58～59 disclosed formulas [4a]～formula [4k] of International Publication publication the 2011/132751st (2011.10.27 is open) can be listed.
As the cross-linked compound with cyclocarbonate radical, for having the cross-linked compound of the cyclocarbonate radical shown at least 2 following formula [5A].
Specifically, the cross-linked compound shown in 76～82 disclosed formulas [5-1]～formula [5-42] of International Publication publication the 2012/014898th (2012.2.2 is open) can be listed.
Cross-linked compound as at least one substituent group having in the group selecting free hydroxyl and alkoxyl composition, include, for example out the amino resins with hydroxyl or alkoxyl, for instance melamine resin, carbamide resin, guanamine resin, glycolurilformaldehyde resins, succinamide-formaldehyde resin or ethylene urea-formaldehyde resins etc..Specifically, it is possible to use the hydrogen atom of amino is by methylol or alkoxy methyl or melamine derivative, benzoguanamine derivant or glycoluril that both replaces.This melamine derivative or benzoguanamine derivant can also exist with dimer or trimerical form.They preferably every 1 triazine ring there is methylol or the alkoxy methyl of average more than 3 and less than 6.
Example as this melamine derivative or benzoguanamine derivant, every 1 triazine ring that can list commercially available product replaces the MX-750 having average 3.7 methoxies, every 1 triazine ring replaces the MW-30 (above for Sanwa Chemical Co., Ltd's system) having average 5.8 methoxies, the methoxymethylated melamine such as CYMEL300,301,303,350,370,771,325,327,703,712；The methoxymethylated butoxymethyl melamines such as CYMEL235,236,238,212,253,254；CYMEL506, the butoxymethyl melamines such as 508；The carboxylic methoxymethylated isobutoxymethyl melamine of CYMEL1141 etc；The methoxymethylated ethoxyl methyl benzoguanamine of CYMEL1123 etc；The methoxymethylated butoxymethyl benzoguanamine of CYMEL1123-10 etc；The butoxymethyl benzoguanamine of CYMEL1128 etc；The carboxylic methoxymethylated ethoxyl methyl benzoguanamine (being MitsuiCytecLtd system above) of CYMEL1125-80 etc.It addition, as the example of glycoluril, the methoxyl group methylolation glycoluril etc. of methylolation glycoluril that can list the butoxymethyl glycoluril of CYMEL1170 etc, CYMEL1172 etc etc., Powderlink1174 etc.
As benzene or the phenoloid with hydroxyl or alkoxyl, for instance 1,3 can be listed, 5-tri-(methoxy) benzene, 1,2,4-tri-(i-propoxymethyl) benzene, 1,4-double; two (sec-butoxymethyl) benzene or 2,6-bishydroxymethyl p-t-butyl phenols etc..
More specifically, can list that 62 pages～66 pages of International Publication publication the 2011/132751st (2011.10.27 is open) are disclosed, the cross-linked compound shown in formula [6-1]～formula [6-48].
As the cross-linked compound with polymerism unsaturated bond, for instance the cross-linked compound in poly-(methyl) the acrylate equimolecular of trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyloxyethoxy trimethylolpropane or glycerol polyglycidyl ether with 3 polymerism unsaturated groups can be listed；nullAnd then，Ethylene glycol bisthioglycolate (methyl) acrylate、Diethylene glycol two (methyl) acrylate、TEG two (methyl) acrylate、Polyethylene Glycol two (methyl) acrylate、Propylene glycol two (methyl) acrylate、Polypropylene glycol two (methyl) acrylate、Butanediol two (methyl) acrylate、Neopentyl glycol two (methyl) acrylate、Oxirane bisphenol A-type two (methyl) acrylate、Expoxy propane bisphenol type two (methyl) acrylate、1,6-hexanediol two (methyl) acrylate、Glycerol two (methyl) acrylate、Tetramethylolmethane two (methyl) acrylate、Ethylene glycol diglycidyl ether two (methyl) acrylate、Diethylene glycol diglycidyl glycerin ether two (methyl) acrylate、There is in o-phthalic acid diglycidyl ester two (methyl) acrylate or 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate equimolecular the cross-linked compound of 2 polymerism unsaturated groups；And, there is in (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 2-phenoxy group-2-hydroxy propyl ester, 2-(methyl) acryloxy-2-hydroxypropyl phthalate, (methyl) acrylic acid 3-chlorine-2-hydroxyl propyl ester, glycerol list (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl phosphate ester or N-methylol (methyl) acrylamide equimolecular the cross-linked compound etc. of 1 polymerism unsaturated group.
And, it is possible to use the compound shown in following formula [7A].
(in formula [7A], E1Represent at least one in cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus and phenanthrene ring, E2Representing the group in following formula [7a] or formula [7b], n represents the integer of 1～4).
Above-claimed cpd is an example of cross-linked compound, but is not limited to them.It addition, the cross-linked compound used in the compositions of the present invention and aligning agent for liquid crystal can be a kind, it is also possible to combine two or more.
The content of the cross-linked compound in the compositions of the present invention and aligning agent for liquid crystal is preferably 0.1 mass parts～150 mass parts relative to whole component of polymer 100 mass parts.Wherein, target effect is shown in order to make cross-linking reaction advance, relative to whole component of polymer 100 mass parts, it is preferred to 0.1 mass parts～100 mass parts.It is more preferably 1 mass parts～50 mass parts.
In the compositions of the present invention and aligning agent for liquid crystal, in the scope not damaging effect of the present invention, it is possible to use the compound that the film thickness uniformity of resin coating when making coating composition and aligning agent for liquid crystal, surface smoothness improve.
As the compound making the film thickness uniformity of resin coating, surface smoothness improve, fluorine system surfactant, silicone based surfactants, nonionic system surfactant etc. can be listed.
More specifically, for instance EftopEF301, EF303, EF352 (more than, TohkemproductsCorporation system) can be listed；MegafacF171, F173, R-30 (more than, big Japanese ink Co., Ltd. system)；FluoradFC430, FC431 (more than, Sumitomo3MLimited system)；AsahiGuardAG710, SurflonS-382, SC101, SC102, SC103, SC104, SC105, SC106 (more than, Asahi Glass Co., Ltd's system) etc..
The usage ratio of these surfactants is preferably 0.01 mass parts～2 mass parts relative to whole component of polymer 100 mass parts contained in compositions and aligning agent for liquid crystal, is more preferably 0.01 mass parts～1 mass parts.
And then, in the compositions of the present invention and aligning agent for liquid crystal, as promoting the electric charge in resin coating to move, promote the compound of the de-electric charge of element, it is also possible to add that 69 pages～73 pages of International Publication publication the 2011/132751st (2011.10.27 is open) are disclosed, the nitrogen heterocyclic ring amines shown in formula [M1]～formula [M156].This amines can be added directly in compositions and aligning agent for liquid crystal, it is preferred that adds after making, with suitable solvent, the solution that concentration is 0.1 mass %～10 mass %, preferably 1 mass %～7 mass % again.As this solvent, as long as dissolve the solvent of above-mentioned particular polymers, just it is not particularly limited.
In the compositions of the present invention and aligning agent for liquid crystal, except the compound of above-mentioned lean solvent, cross-linked compound, the film thickness uniformity making resin coating and/or surface smoothness raising and the compound of the de-electric charge of promotion, as long as in the scope not damaging effect of the present invention, it is also possible to add for changing the dielectric substance of electrical characteristics, the conductive materials such as the dielectric constant of resin coating, electric conductivity.
<polyimide film>
The compositions of the present invention can be coated on substrate and burn till, and is then used as polyimide film.As the substrate now used, according to target device, it is possible to use plastic bases etc. such as glass substrate, silicon wafer, acrylic compounds substrate, polycarbonate substrate or PET (polyethylene terephthalate) substrates.Furthermore it is also possible to polyimide film is directly used as film substrate.The coating process of compositions is not particularly limited, and industrial is generally the method utilizing infusion process, rolling method, slot coated method, spin-coating method, spraying process, silk screen printing, hectographic printing, flexible printing or ink-jet method etc. to carry out.They can use these methods according to purpose.
After being coated on substrate by compositions, it is possible to use the heater meanses such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven, solvent is made to evaporate at 50～300 DEG C, preferably in 80～250 DEG C, thus making polyimide film.When the compositions employing specific solvent of the present invention, even if also being able to make polyimide film with 200 DEG C of temperature below.The thickness of the polyimide film after burning till can adjust according to purpose to 0.01～100 μm.
<liquid crystal orientation film/liquid crystal represents element>
Employ after the aligning agent for liquid crystal of the present composition can be coated on substrate and burn till, utilize brushing process, light irradiation etc. to carry out orientation process such that it is able to as liquid crystal orientation film.It addition, when vertical orientated purposes such as VA patterns, even if not carrying out orientation process to be also used as liquid crystal orientation film.As the substrate now used, as long as the high substrate of the transparency is just not particularly limited, except glass substrate, it is also possible to use the plastic bases etc. such as acrylic compounds substrate, polycarbonate substrate or PET (polyethylene terephthalate) substrate.From the view point of Simplified flowsheet, it is preferred to use be formed with the substrate of ITO (tin indium oxide) electrode etc. for driving liquid crystal.It addition, when representing element for the liquid crystal of reflection-type, if being only unilateral substrate, then the opaque substrates such as silicon wafer can also be used, as electrode now, it is possible to use aluminum etc. can reflect the material of light.
The coating process of aligning agent for liquid crystal is not particularly limited, the industrial method usually utilizing silk screen printing, hectographic printing, flexible printing or ink-jet method etc. to carry out.As other coating process, there are infusion process, rolling method, slot coated method, spin-coating method or spraying process etc., it is possible to use these methods according to purpose.
After aligning agent for liquid crystal is coated on substrate, utilize the heater meanses such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven, according to the solvent used in aligning agent for liquid crystal, with 30～300 DEG C, preferably make solvent evaporate with the temperature of 30～250 DEG C such that it is able to make liquid crystal orientation film.When the aligning agent for liquid crystal employing specific solvent of the present invention, even if also being able to make liquid crystal orientation film with 200 DEG C of temperature below.When the thickness of the liquid crystal orientation film after burning till is blocked up, representing in the power consumption of element it is disadvantageous at liquid crystal, when thickness is crossed thin, liquid crystal represents that the reliability of element reduces sometimes, it is thus preferred to is 5～300nm, is more preferably 10～150nm.When making liquid crystal horizontal alignment, tilted alignment, by brushing or polarized UV rays irradiation etc., the liquid crystal orientation film after burning till is processed.
Liquid crystal about the present invention represents element, is obtained with, after the substrate of liquid crystal orientation film, utilizing known method to make liquid crystal cells, thus making liquid crystal to represent element by the aligning agent for liquid crystal of the present invention by preceding method.
Manufacture method as liquid crystal cells, following method can be exemplified: prepare to be formed with a pair substrate of liquid crystal orientation film, the liquid crystal orientation film of single substrate spreads sept, being pasted on another substrate by liquid crystal orientation film in the way of inner side, liquid crystal the method carrying out sealing are injected in decompression；Or, after being scattered with the liquid crystal aligning face dropping liquid crystalline substance of sept, adhesive substrate also carries out the method etc. sealed.
And then, the aligning agent for liquid crystal of the present invention is also preferably used for having liquid crystal layer between a pair substrate possessing electrode and the liquid crystal that manufactures via following operation represents element: configure liquid-crystal composition between a pair substrate, described liquid-crystal composition comprises at least one utilizing active energy beam and hanker and carries out the polymerizable compound being polymerized, to applying voltage between electrode and by irradiating active energy beam and adding at least one hankered and make polymerizable compound be polymerized.Herein, as active energy beam, it is suitably for ultraviolet.As ultraviolet, wavelength is 300～400nm, is preferably 310～360nm.When being polymerized by heating, heating-up temperature is 40～120 DEG C, is preferably 60～80 DEG C.It addition, ultraviolet irradiation and heating can carry out simultaneously.
Foregoing liquid crystal represents that element utilizes PSA (PolymerSustainedAlignment) mode to control the pre-dumping of liquid crystal molecule.In PSA mode, in liquid crystal material, it is mixed into a small amount of photopolymerizable compound in advance, is such as mixed into photopolymerization monomer, after assembling liquid crystal cells, when liquid crystal layer is applied assigned voltage, to photopolymerizable compound irradiation ultraviolet radiation etc., utilize the pre-dumping of the polymer controls liquid crystal molecule generated.Even if the state of orientation of liquid crystal molecule when generating polymer is also remembered after removing voltage, therefore by controlling the electric field etc. formed in liquid crystal layer, it is possible to adjust the pre-dumping of liquid crystal molecule.It addition, in PSA mode, it is not necessary to brushing processes, and is thus suitable for the formation being difficult to be processed the vertical alignment-type liquid crystal layer controlling pre-dumping by brushing.
Namely, liquid crystal in the present invention represents in element, preceding method is utilized to be obtained with after the substrate of liquid crystal orientation film by the aligning agent for liquid crystal of the present invention, make liquid crystal cells, utilize ultraviolet irradiation and add at least one hankered and make polymerizable compound be polymerized such that it is able to the orientation of control liquid crystal molecule.
If listing an example of the liquid crystal cells making PSA mode, then can list following method: prepare to be formed with a pair substrate of liquid crystal orientation film, the liquid crystal orientation film of single substrate spreads sept, being pasted on another substrate by liquid crystal orientation film in the way of inner side, liquid crystal the method sealed are injected in decompression；Or, after dripping liquid crystal on the liquid crystal aligning face spread sept, adhesive substrate also carries out the method etc. sealed.
The polymerizable compound being polymerized because of heat, ultraviolet radiation is mixed in liquid crystal.As polymerizable compound, the compound with more than 1 the polymerism unsaturated group such as acrylate-based, methacrylate based can be listed in molecule.Now, polymerizable compound is preferably 0.01～10 mass parts relative to liquid crystal composition 100 mass parts, more preferably 0.1～5 mass parts.When polymerizable compound is less than 0.01 mass parts, polymerizable compound will not be polymerized and the orientation of uncontrollable liquid crystal, and during more than 10 mass parts, the after image characteristic that unreacted polymerizable compound becomes many, liquid crystal represents element reduces.
Make after liquid crystal cells, liquid crystal cells applied the voltage of exchange or direct current, while heat, irradiation ultraviolet radiation and make polymerizable compound be polymerized.Thereby, it is possible to control the orientation of liquid crystal molecule.
In addition, the aligning agent for liquid crystal of the present invention is also preferably used for having liquid crystal layer between a pair substrate possessing electrode and the liquid crystal that manufactures via following operation represents element, i.e. SC-PVA pattern: configure liquid crystal orientation film between aforementioned a pair substrate, described liquid crystal orientation film comprises at least one utilizing active energy beam and hanker and carries out the polymerizable group being polymerized, and applies voltage in-between the electrodes.Herein, as active energy beam, it is suitably for ultraviolet.As ultraviolet, wavelength is 300～400nm, is preferably 310～360nm.When utilizing heating to be polymerized, heating-up temperature is 40～120 DEG C, is preferably 60～80 DEG C.Furthermore it is possible to apply ultraviolet and heating simultaneously.
In order to obtain comprising the liquid crystal orientation film utilizing active energy beam and at least one hankered and carrying out the polymerizable group being polymerized, can list: method that the compound comprising this polymerizable group is added in aligning agent for liquid crystal, the method using the component of polymer comprising polymerizable group.
If listing an example of the liquid crystal cells making SC-PVA pattern, then can list following method: prepare to be formed with a pair substrate of the liquid crystal orientation film of the present invention, the liquid crystal orientation film of single substrate spreads sept, pasting another substrate by liquid crystal orientation film in the way of inner side, liquid crystal the method sealed are injected in decompression；Or, after dripping liquid crystal on the liquid crystal aligning face be scattered with sept, adhesive substrate also carries out the method etc. sealed.
After making liquid crystal cells, liquid crystal cells is applied the voltage of exchange or direct current, while heating, irradiation ultraviolet radiation such that it is able to control the orientation of liquid crystal molecule.
Operating as above, the aligning agent for liquid crystal of the present invention can form the liquid crystal orientation film that film is excellent, and then, burning till with low temperature when making liquid crystal orientation film even if can be formed, liquid crystal represents the electrical characteristics of element and the liquid crystal orientation film that VHR is also excellent.Thus, the liquid crystal with the liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention represents the excellent in reliability of element, can be suitably employed in the LCD TV of big picture and high-resolution, middle-size and small-size auto-navigation system, smart mobile phone etc..
Embodiment
It is exemplified below embodiment and further describes the present invention, but be not limited to them.
" abbreviation used in the synthesis example of the present invention, embodiment and comparative example "
The abbreviation used in synthesis example, embodiment and comparative example is as follows.
<for manufacturing the monomer of the polyimides based polymer of the present invention>
(the particular side chain diamine compound of the present invention)
A1:1,3-diaminourea-4-(4-(trans-4-n-heptyl cyclohexyl) phenoxy group) benzene (the particular side chain diamine compound with the particular side chain structure shown in formula [1-1] of the present invention)
A2:1,3-diaminourea-4-(4-(trans-4-n-heptyl cyclohexyl) phenoxymethyl) benzene (the particular side chain diamine compound with the particular side chain structure shown in formula [1-1] of the present invention)
A3:1,3-diaminourea-4-{4-(trans-4-(trans-4-n-pentyl cyclohexyl) cyclohexyl) phenoxy group } benzene (the particular side chain diamine compound with the particular side chain structure shown in formula [1-1] of the present invention)
A4: the diamine compound (the particular side chain diamine compound with the particular side chain structure shown in formula [1-1] of the present invention) shown in following formula [A4]
A5:1,3-diaminourea-4-octadecane oxygen base benzene (the particular side chain diamine compound with the particular side chain structure shown in formula [1-2] of the present invention)
(diamine compound shown in formula [2a] of the present invention)
B1:3,5-diaminobenzoic acid (diamine compound with carboxyl (COOH yl) shown in the formula [2a] of the present invention)
(diamine compound shown in formula [3a] of the present invention)
C1: diamine compound shown in following formula [C1] (shown in the formula [3a] of the present invention there is nitrogenous heterocyclic diamine compound)
C2: diamine compound shown in following formula [C2] (shown in the formula [3a] of the present invention there is nitrogenous heterocyclic diamine compound)
(other diamine compound)
D1: p-phenylenediamine
D2: m-diaminobenzene.
(specific tetrabasic carboxylic acid composition)
E1:1,2,3,4-Tetramethylene. tetracarboxylic dianhydride
E2: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
E3: the tetracarboxylic dianhydride shown in following formula [E3]
E4: the tetracarboxylic dianhydride shown in following formula [E4]
E5: the tetracarboxylic dianhydride shown in following formula [E5]
<cross-linked compound used in the present invention>
K1: the cross-linked compound shown in following formula [K1]
<specific solvent of the present invention>
S1: the solvent (specific solvent shown in formula [A-1] of the present invention) shown in following formula [S1]
<other solvent>
NMP:N-N-methyl-2-2-pyrrolidone N
NEP:N-ethyl-2-pyrrolidone
γ-BL: gamma-butyrolacton
BCS: ethylene glycol monobutyl ether
PB: propylene glycol monobutyl ether
EC: diethylene glycol monoethyl ether
DME: dimethyl ether
" mensuration of the molecular weight of the polyimides based polymer of the present invention "
Molecular weight about the polyimide precursor in synthesis example and polyimides, using room temperature gel permeation chromatography (GPC) device (GPC-101) (Showa Denko K. K's system), post (KD-803, KD-805) (Shodex company system), following operation measures.
Column temperature: 50 DEG C
Eluent: N, N '-dimethyl Methanamide is (as additive, lithium bromide monohydrate (LiBr H2O) for 30mmol/L (liter), phosphoric acid anhydrous crystalline (orthophosphoric acid) be 30mmol/L, oxolane (THF) be 10ml/L)
Flow velocity: 1.0ml/ minute
Standard curve making standard sample: TSK standard poly(ethylene oxide) (molecular weight: about 900000,150000,100000 and 30000) (TOSOH Co., Ltd's system) and Polyethylene Glycol (molecular weight: about 12000,4000 and 1000) (PolymerLaboratoriesLtd. system).
" mensuration of the acid imide rate of the polyimides of the present invention "
The acid imide rate of the polyimides in synthesis example operates as follows and measures.Polyimide powder 20mg is fed into NMR (nuclear magnetic resonance, NMR) sample cell (NMR sample cell specification, φ 5 (wasteland science Co., Ltd. system)), adds deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass %TMS (tetramethylsilane) melange) (0.53ml), make it be completely dissolved with ultrasound wave.Utilize the NMR measuring machine (JNW-ECA500) (JEOLDATUM company system) the proton N MR to this measured in solution 500MHz.The proton being derived from the structure not changed before and after imidizate is determined by acid imide rate as reference proton, uses the peak integrated value of this proton and the proton peak integrated value of the neighbouring NH base being derived from amic acid occurred of 9.5ppm～10.0ppm to utilize following formula to obtain.
Acid imide rate (%)=(1-α x/y) × 100
In above-mentioned formula, x is the proton peak integrated value of the NH base being derived from amic acid, y be the peak integrated value of reference proton, α is the number ratio relative to NH substrate 1 of amic acid of reference proton during polyamic acid (acid imide rate is 0%).
" synthesis of the polyimides based polymer of the present invention "
<synthesis example 1>
Mixing E1 (5.21g, 26.6mmol), A1 (5.12g, 13.5mmol) and B1 (2.05g, 13.5mmol) in S1 (37.1g), react 8 hours with 40 DEG C, thus obtaining the polyamic acid solution (1) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 25800, weight average molecular weight is 86900.
<synthesis example 2>
Mixing E2 (3.40g, 13.6mmol), B1 (4.19g, 27.6mmol) and D1 (0.74g, 6.89mmol) in S1 (24.7g), after reacting 5 hours with 80 DEG C, add E1 (4.00g, 20.4mmol) and S1 (12.3g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution (2) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 26200, weight average molecular weight is 86400.
<synthesis example 3>
After adding NMP in the polyamic acid solution (2) (30.0g) utilizing the synthetic method of synthesis example 2 to obtain and being diluted to 6 mass %, add acetic anhydride (3.95g) and pyridine (2.50g) as imidization catalyst, react 2 hours with 60 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (3) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 53%, and number-average molecular weight is 22100, weight average molecular weight is 60900.
<synthesis example 4>
Mixing E2 (3.96g, 15.8mmol), B1 (4.14g, 27.2mmol), C1 (0.39g, 1.60mmol) and D2 (0.35g, 3.20mmol) in NEP (24.2g), after reacting 5 hours with 80 DEG C, add E1 (3.10g, 15.8mmol) and NEP (12.1g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NEP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (4.40g) and pyridine (3.30g) as imidization catalyst, react 3.5 hours with 80 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (4) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 80%, and number-average molecular weight is 19900, weight average molecular weight is 55100.
<synthesis example 5>
Mixing E2 (3.22g, 12.9mmol), A2 (4.62g, 11.7mmol), B1 (1.78g, 11.7mmol) and D1 (0.28g, 2.60mmol) in S1 (24.8g), after reacting 5 hours with 80 DEG C, add E1 (2.52g, 12.9mmol) and S1 (12.4g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution (5) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 20900, weight average molecular weight is 72100.
<synthesis example 6>
After adding NMP in the polyamic acid solution (5) (30.0g) utilizing the synthetic method of synthesis example 5 to obtain and being diluted to 6 mass %, add acetic anhydride (3.95g) and pyridine (2.40g) as imidization catalyst, react 3.5 hours with 70 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (6) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 73%, and number-average molecular weight is 19900, weight average molecular weight is 53900.
<synthesis example 7>
Mixing E2 (1.31g, 5.23mmol), A3 (3.44g, 7.94mmol), C1 (2.57g, 10.6mmol) and D2 (0.86g, 7.94mmol) in NMP (24.5g), after reacting 5 hours with 80 DEG C, add E1 (4.10g, 20.9mmol) and NMP (12.3g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (4.50g) and pyridine (3.30g) as imidization catalyst, react 3.5 hours with 80 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (7) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 80%, and number-average molecular weight is 15900, weight average molecular weight is 43800.
<synthesis example 8>
Mixing E2 (1.23g, 4.91mmol), A2 (3.92g, 9.94mmol), C2 (2.58g, 9.94mmol) and D2 (0.54g, 4.97mmol) in NMP (24.2g), after reacting 5 hours with 80 DEG C, add E1 (3.85g, 19.6mmol) and NMP (12.1g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (3.85g) and pyridine (2.50g) as imidization catalyst, react 2 hours with 60 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (8) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 55%, and number-average molecular weight is 16900, weight average molecular weight is 46900.
<synthesis example 9>
Mixing E2 (2.55g, 10.2mmol), A4 (2.55g, 5.17mmol), B1 (0.39g, 2.58mmol), C2 (3.35g, 12.9mmol) and D2 (0.56g, 5.17mmol) in NEP (24.8g), after reacting 5 hours with 80 DEG C, add E1 (3.00g, 15.3mmol) and NEP (12.4g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NEP in gained polyamic acid solution (30.5g) and being diluted to 6 mass %, add acetic anhydride (3.95g) and pyridine (2.55g) as imidization catalyst, react 3 hours with 60 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (9) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 61%, and number-average molecular weight is 16000, weight average molecular weight is 44800.
<synthesis example 10>
Mixing E2 (1.20g, 4.78mmol), A5 (3.65g, 9.69mmol), C2 (2.51g, 9.69mmol) and D2 (0.52g, 4.84mmol) in NMP (23.3g), after reacting 5 hours with 80 DEG C, add E1 (3.75g, 19.1mmol) and NMP (11.6g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (3.80g) and pyridine (2.55g) as imidization catalyst, react 2 hours with 60 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (10) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 56%, and number-average molecular weight is 16200, weight average molecular weight is 48100.
<synthesis example 11>
Mixing E3 (7.50g, 33.5mmol), B1 (3.61g, 23.7mmol), C1 (0.41g, 1.69mmol) and D1 (0.92g, 8.47mmol) in NMP (37.3g), react 8 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (4.20g) and pyridine (3.10g) as imidization catalyst, react 2.5 hours with 80 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (11) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 75%, and number-average molecular weight is 19800, weight average molecular weight is 53900.
<synthesis example 12>
Mixing E3 (5.90g, 26.3mmol), A2 (4.21g, 10.7mmol), B1 (0.41g, 2.67mmol) and D2 (1.44g, 13.3mmol) in NMP (35.9g), react 8 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (4.50g) and pyridine (3.35g) as imidization catalyst, react 3.5 hours with 80 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (12) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 81%, and number-average molecular weight is 18200, weight average molecular weight is 51600.
<synthesis example 13>
Mixing E3 (5.50g, 24.5mmol), A4 (2.45g, 4.97mmol), B1 (0.19g, 1.24mmol), C2 (3.54g, 13.7mmol) and D2 (0.54g, 4.97mmol) in NMP (36.7g), react 8 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.5g) and being diluted to 6 mass %, add acetic anhydride (3.90g) and pyridine (2.60g) as imidization catalyst, react 3.5 hours with 60 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (13) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 65%, and number-average molecular weight is 18500, weight average molecular weight is 50200.
<synthesis example 14>
Mixing E4 (5.21g, 17.3mmol), A1 (4.60g, 12.1mmol), B1 (0.67g, 4.39mmol) and D1 (0.59g, 5.49mmol) in NEP (23.8g), after reacting 6 hours with 80 DEG C, add E1 (0.85g, 4.33mmol) and NEP (11.9g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NEP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (3.80g) and pyridine (2.50g) as imidization catalyst, react 2 hours with 60 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (14) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 55%, and number-average molecular weight is 16800, weight average molecular weight is 45300.
<synthesis example 15>
Mixing E4 (3.29g, 11.0mmol), A2 (3.51g, 8.88mmol), C1 (1.61g, 6.66mmol), C2 (1.15g, 4.44mmol) and D2 (0.24g, 2.22mmol) in NMP (23.9g), after reacting 6 hours with 80 DEG C, add E1 (2.15g, 11.0mmol) and NMP (12.0g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.1g) and being diluted to 6 mass %, add acetic anhydride (4.20g) and pyridine (3.15g) as imidization catalyst, react 2.5 hours with 80 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (15) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 73%, and number-average molecular weight is 15900, weight average molecular weight is 43800.
<synthesis example 16>
Mixing E5 (4.30g, 20.3mmol), A3 (3.89g, 8.98mmol), C2 (1.33g, 5.13mmol) and D2 (1.25g, 11.6mmol) in NMP (23.5g), after reacting 6 hours with 80 DEG C, add E1 (0.99g, 5.07mmol) and NMP (11.8g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (3.85g) and pyridine (2.40g) as imidization catalyst, react 2 hours with 60 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (16) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 51%, and number-average molecular weight is 15700, weight average molecular weight is 44500.
<synthesis example 17>
Mixing E5 (4.10g, 19.3mmol), B1 (4.47g, 29.4mmol) and D2 (0.35g, 3.26mmol) in NMP (24.3g), after reacting 6 hours with 80 DEG C, add E2 (3.22g, 12.9mmol) and NMP (12.1g), react 6 hours with 80 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (4.20g) and pyridine (3.20g) as imidization catalyst, react 2.5 hours with 80 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (17) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 73%, and number-average molecular weight is 16200, weight average molecular weight is 48100.
<synthesis example 18>
Mixing E5 (2.95g, 13.9mmol), A2 (3.71g, 9.39mmol), B1 (0.36g, 2.35mmol), C1 (1.14g, 4.70mmol), C2 (1.22g, 4.70mmol) and D1 (0.25g, 2.35mmol) in NEP (23.9g), after reacting 6 hours with 80 DEG C, add E2 (2.32g, 9.27mmol) and NEP (11.9g), react 6 hours with 80 DEG C, thus obtaining the polyamic acid solution that resin solid content concentration is 25 mass %.
After adding NMP in gained polyamic acid solution (30.0g) and being diluted to 6 mass %, add acetic anhydride (4.20g) and pyridine (3.20g) as imidization catalyst, react 2 hours with 80 DEG C.This reaction solution is fed in methanol (460ml), and leaching gained precipitate.This precipitate methanol is carried out, obtains polyimide powder (18) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 68%, and number-average molecular weight is 15500, weight average molecular weight is 45100.
<synthesis example 19>
Mixing E2 (3.10g, 12.4mmol), B1 (3.82g, 25.1mmol) and D1 (0.68g, 6.28mmol) in NMP (22.5g), after reacting 5 hours with 80 DEG C, add E1 (3.65g, 18.6mmol) and NMP (11.3g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution (19) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 27900, weight average molecular weight is 88900.
<synthesis example 20>
Mixing E2 (3.13g, 12.5mmol), A2 (4.49g, 11.4mmol), B1 (1.73g, 11.4mmol) and D1 (0.27g, 2.53mmol) in NMP (24.2g), after reacting 5 hours with 80 DEG C, add E1 (2.45g, 12.5mmol) and NMP (12.1g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution (20) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 22200, weight average molecular weight is 76900.
The polyimides based polymer of the present invention is shown in table 1 and table 2.
[table 1]
* 1: polyamic acid.
[table 2]
* 1: polyamic acid.
" compositions of the present invention and the manufacture of aligning agent for liquid crystal "
Following embodiment 1～embodiment 20, comparative example 1～comparative example 4 are recorded the manufacture example of compositions.It addition, these compositionss are additionally operable to the evaluation of aligning agent for liquid crystal.
The compositions of the present invention and aligning agent for liquid crystal are shown in table 3～table 5.
Use the compositions and aligning agent for liquid crystal that obtain in examples and comparative examples of the present invention, carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (normal cells) of voltage retention (VHR) ", " evaluation of the ink-jet application of aligning agent for liquid crystal ", " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning " and " making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning ".
" evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal "
Use the compositions obtained by the method for examples and comparative examples of the present invention, carry out the evaluation of the pin hole of polyimide film.Specifically, the membrane filter that these compositions apertures are 1 μm is carried out pressure filtration, unwashed Cr is deposited with substrate (vertical 100mm × horizontal 100mm, thickness 1.0mm) and prints.Printer uses Simple printing press S15 type (Nissha Printing Co., Ltd's system), printing area to be the scope of 80 × 80mm, squeegee pressure relative to substrate center be 0.2mm, disposable substrate be 5, from printing time to predrying be 90 seconds, predrying be 5 minutes with 70 DEG C on hot plate, lead and burn till in thermal cycle type cleaning baking oven with 160 DEG C for 15 minutes when carry out.
Thereafter, the pin hole quantity of the substrate of resulting tape polyimide film is confirmed.Specifically, this substrate with polyimide film of visualization under sodium vapor lamp, count the pin hole quantity on polyimide film.It should be noted that the quantity of pin hole is more few, then the precipitate in compositions is more few, is denoted as this evaluation excellent.
Table 6～table 8 illustrates the pin hole quantity obtained in embodiment and comparative example.
It should be noted that the compositions obtained in examples and comparative examples of the present invention can be used in aligning agent for liquid crystal.Therefore, the pin hole evaluation of the polyimide film of the compositions obtained in examples and comparative examples of the present invention also serves as the pin hole evaluation of liquid crystal orientation film.
" evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal "
It is used in aforementioned " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal " substrate with polyimide film obtained, carries out the evaluation of the end protuberance (evaluation also referred to as protuberance) of the evaluation of film end of polyimide film, the i.e. linear evaluation in the end of polyimide film (also referred to as linear evaluation) and polyimide film.
The linear evaluation in end of polyimide film is by carrying out relative to the polyimide film that print direction is right-hand end with observation by light microscope.More specifically, the length of (1) in Fig. 1 of observable polyimides film image and the A in the difference of (2), i.e. Fig. 1 under 25 times of multiplying powers of optical microscope is measured.Now, the image of whole polyimide films all obtains under same multiplying power.The length of this A is more short, then the end rectilinearity regarding as polyimide film is more excellent.
Evaluating by carrying out relative to the polyimide film that print direction is right-hand end with observation by light microscope of the end protuberance of polyimide film.Specifically, the length of the B in Fig. 2 of observable polyimides film image under 25 times of multiplying powers of optical microscope is measured.Now, whole polyimides film images all obtain under same multiplying power.The length of this B is more short, then the end protuberance regarding as polyimide film is more excellent.
Table 6～table 8 illustrates the length of the aforementioned A obtained in embodiment and comparative example and the length of B.
It should be noted that the compositions obtained in examples and comparative examples of the present invention may be used for aligning agent for liquid crystal.Therefore, the evaluation of the film end of the polyimide film obtained in the present embodiment and comparative example also serves as the evaluation of the film end of liquid crystal orientation film.
" evaluation (normal cells) of voltage retention (VHR) "
Use the aligning agent for liquid crystal obtained in examples and comparative examples of the present invention, carry out the evaluation of voltage retention (VHR).Specifically, the membrane filter that these aligning agent for liquid crystal apertures are 1 μm is carried out pressure filtration, be spun on the substrate with ITO electrode (vertical 40mm × horizontal 30mm, thickness 0.7mm) cleaned with pure water and IPA (isopropanol)) ito surface, with 80 DEG C of heat treated 3 minutes on hot plate, and clean baking oven with 160 DEG C of heat treated 15 minutes by thermal cycle type, thus obtaining the ito substrate with the liquid crystal orientation film that thickness is 100nm.Utilize the brushing device that roller diameter is 120mm, use artificial silk cloth, at roller rotating speed: 300rpm, roller pace: 20mm/ second, intrusion: when 0.4mm, the coated surface of this ito substrate is carried out brushing process.
Prepare the ito substrate of 2 resulting tape liquid crystal orientation films, clamp the sept of 6 μm with liquid crystal aligning face for inner side combine, the sealant of printing ultraviolet hardening.Then, after fitting with another substrate and the aspectant mode of liquid crystal aligning face, the process of sealant cures for making ultraviolet hardening is carried out, thus obtaining dummy cell.Specifically, using illumination is the metal halide lamp of 60mW, clips the wavelength of below 310nm, irradiates and is scaled 5J/cm with 365nm2Ultraviolet, thereafter, clean with 120 DEG C of heat treated 60 minutes in baking oven in thermal cycle type, thus obtaining dummy cell.Inject by reducing pressure in this dummy cell of normal direction and inject nematic liquid crystal, thus obtaining liquid crystal cells (normal cells).
It should be noted that employ aligning agent for liquid crystal (the 2)～aligning agent for liquid crystal (4) obtained by the method for embodiment 2～embodiment 4, liquid crystal in the liquid crystal cells of aligning agent for liquid crystal (21) that aligning agent for liquid crystal (12) that method by embodiment 12 obtains, aligning agent for liquid crystal (19) that method by embodiment 19 obtains, method by comparative example 1 obtain and the aligning agent for liquid crystal (22) that the method by comparative example 2 obtains employs MLC-2003 (MERCKCORPORATION system).
It addition, the liquid crystal employed in the liquid crystal cells of the aligning agent for liquid crystal obtained by the embodiment outside aforementioned and comparative example employs MLC-6608 (MERCKCORPORATION system).
At the temperature of 80 DEG C, gained liquid crystal cells is applied 1V voltage with 60 μ s, measure the voltage after 50ms, can keep voltage to which kind of degree being calculated as voltage retention (VHR).It should be noted that, measure and use voltage retention determinator (VHR-1) (TOYOCorporation system), at voltage (Voltage): ± 1V, pulse width (PulseWidth): 60 μ s, frame period (FlamePeriod): carry out under the setting of 50ms.
And then, the liquid crystal cells after the mensuration of VHR being terminated is keeping 720 hours in the high temperature groove of temperature 80 DEG C, again carry out the mensuration (after the keeping of high temperature groove) of VHR when same as described above.
About evaluation, on the basis of the VHR value after firm making liquid crystal cells, in high temperature groove, the VHR value after keeping is little relative to the reduction of the VHR value after just making liquid crystal cells, then regard as well.
Table 9～table 11 illustrates the value of the voltage retention (VHR) obtained in embodiment and comparative example.
" evaluation of the ink-jet application of aligning agent for liquid crystal "
Use aligning agent for liquid crystal (7) that the aligning agent for liquid crystal (4) obtained by the method for embodiments of the invention 4, method by embodiment 7 obtained and the aligning agent for liquid crystal (15) that the method by embodiment 15 obtains, carry out the evaluation of ink-jet application.Specifically, the membrane filter that these aligning agent for liquid crystal apertures are 1 μm is carried out pressure filtration, ink-jet application machine uses HIS-200 (HitachiPlantTechnologies, Ltd. system), it is deposited with on substrate at the ITO (tin indium oxide) cleaned with pure water and IPA, it is 70 × 70mm at spreading area, injector spacing is 0.423mm, sweep spacing is 0.5mm, coating speed is the 40mm/ second, from coating, the time to predrying is 60 seconds, predrying on hot plate with 70 DEG C for 5 minutes, main burning till is coated when cleaning baking oven with 160 DEG C for 15 minutes by thermal cycle type.
The substrate of visualization resulting tape liquid crystal orientation film under sodium vapor lamp, counts the pin hole quantity on liquid crystal orientation film, and the pin hole of the liquid crystal orientation film obtained in result any embodiment is all less than 5.It addition, any embodiment all can obtain the liquid crystal orientation film of film excellent in uniformity.
And then, use the substrate of resulting tape liquid crystal orientation film, when aforementioned " evaluation (normal cells) of voltage retention (VHR) ", carry out the evaluation of VHR (normal cells).
" making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning "
Use aligning agent for liquid crystal (9) that the aligning agent for liquid crystal (6) obtained by the method for embodiments of the invention 6, method by embodiment 9 obtained and the aligning agent for liquid crystal (14) that the method by embodiment 14 obtains, carry out the making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning.Specifically, the membrane filter that these aligning agent for liquid crystal apertures are 1 μm is carried out pressure filtration, it is spun on the ito surface of the substrate (vertical 40mm × horizontal 30mm, thickness 0.7mm) of the substrate (vertical 40mm × horizontal 30mm, thickness 0.7mm) of the ITO electrode of the pattern spacing 20 μm of the center band 10 × 10mm cleaned with pure water and IPA and the ITO electrode of center band 10 × 40mm, with 80 DEG C of heat treated 3 minutes on hot plate, and clean baking oven with 160 DEG C of heat treated 15 minutes by thermal cycle type, thus obtaining the substrate with the liquid crystal orientation film that thickness is 100nm.
Combine while these substrates with liquid crystal orientation film are clamped with liquid crystal aligning face for inner side the sept of 6 μm, around make dummy cell with sealant is bonding.Inject by reducing pressure in this dummy cell of normal direction and inject liquid crystal, described liquid crystal is to mix the polymerizable compound (1) shown in following formula relative to the mode that 100 mass % nematic liquid crystals (MLC-6608) (MERCKCORPORATION system) are 0.3 mass % with polymerizable compound (1) to obtain to nematic liquid crystal (MLC-6608), seals inlet and obtains liquid crystal cells.
While gained liquid crystal cells applies the voltage of exchange 5V, limit uses illumination to be the metal halide lamp of 60mW, clips the wavelength of below 350nm, irradiates and is scaled 20J/cm with 365nm2Ultraviolet, obtain the liquid crystal cells (PSA unit) that the differently-oriented directivity of liquid crystal is controlled.The temperature in irradiation unit during to liquid crystal cells irradiation ultraviolet radiation is 50 DEG C.
Measure before the ultraviolet radiation of this liquid crystal cells and the response speed of liquid crystal after ultraviolet radiation.Response speed measures the T90 → T10 from absorbance 90% to absorbance 10%.
Compared with the liquid crystal cells before ultraviolet radiation, the response speed of the PSA unit obtained in any embodiment liquid crystal cells after uv irradiation all accelerates, and the differently-oriented directivity therefore confirming liquid crystal is controlled.It addition, confirm by utilizing micropolariscope (ECLIPSEE600WPOL) (NIKON's system) to carry out observing: the arbitrarily liquid crystal orientation all equably of liquid crystal cells.
" making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning "
Use aligning agent for liquid crystal (9) that the aligning agent for liquid crystal (6) obtained by the method for embodiments of the invention 6, method by embodiment 9 obtained and the aligning agent for liquid crystal (14) that the method by embodiment 14 obtains, carry out the making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning.Specifically, add in these aligning agent for liquid crystal relative to the aforementioned shown polymerizable compound (1) that the whole component of polymer 100 mass % in aligning agent for liquid crystal is 2 mass %, stir 4 hours with 25 DEG C.Thereafter, the membrane filter that gained aligning agent for liquid crystal aperture is 1 μm is carried out pressure filtration, it is spun on the ito surface of the substrate (vertical 40mm × horizontal 30mm, thickness 0.7mm) of the substrate (vertical 40mm × horizontal 30mm, thickness 0.7mm) of the ITO electrode of the pattern spacing 20 μm of the center band 10 × 10mm cleaned with pure water and IPA and the ITO electrode of center band 10 × 40mm, with 80 DEG C of heat treated 3 minutes on hot plate, and clean baking oven with 160 DEG C of heat treated 15 minutes by thermal cycle type, thus obtaining the substrate with the liquid crystal orientation film that thickness is 100nm.
Combine while these substrates with liquid crystal orientation film are clamped with liquid crystal aligning face for inner side the sept of 6 μm, around make dummy cell with sealant is bonding.Inject by reducing pressure in this dummy cell of normal direction and inject nematic liquid crystal (MLC-6608) (MERCKCORPORATION system), seal inlet and obtain liquid crystal cells.
While gained liquid crystal cells applies the voltage of exchange 5V, limit uses illumination to be the metal halide lamp of 60mW, clips the wavelength of below 350nm, irradiates and is scaled 20J/cm with 365nm2Ultraviolet, obtain the liquid crystal cells (SC-PVA unit) that the differently-oriented directivity of liquid crystal is controlled.The temperature in irradiation unit during to liquid crystal cells irradiation ultraviolet radiation is 50 DEG C.
Measure before the ultraviolet radiation of this liquid crystal cells and the response speed of liquid crystal after ultraviolet radiation.Response speed measures the T90 → T10 from absorbance 90% to absorbance 10%.
Compared with the liquid crystal cells before ultraviolet radiation, the response speed of the SC-PVA unit obtained in any embodiment liquid crystal cells after uv irradiation all accelerates, and the differently-oriented directivity therefore confirming liquid crystal is controlled.It addition, confirm by utilizing micropolariscope (ECLIPSEE600WPOL) (NIKON's system) to carry out observing: the arbitrarily liquid crystal orientation all equably of liquid crystal cells.
<embodiment 1>
S1 (8.17g), K1 (0.18g), NEP (3.92g) and PB (19.6g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (1) (10.0g) utilizing the synthetic method of synthesis example 1 to obtain, stir 8 hours with 25 DEG C, thus obtaining compositions (1).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (1) also serves as aligning agent for liquid crystal (1) and is used for evaluating.
Use resulting composition (1) and aligning agent for liquid crystal (1), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 2>
S1 (16.8g) and BCS (16.4g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (2) (10.5g) utilizing the synthetic method of synthesis example 2 to obtain, stir 4 hours with 25 DEG C, thus obtaining compositions (2).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (2) also serves as aligning agent for liquid crystal (2) and is used for evaluating.
Use resulting composition (2) and aligning agent for liquid crystal (2), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 3>
In the polyimide powder (3) (1.60g) utilizing the synthetic method of synthesis example 3 to obtain, add S1 (13.8g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (11.3g), stirring 3 hours with 40 DEG C, thus obtaining compositions (3).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (3) also serves as aligning agent for liquid crystal (3) and is used for evaluating.
Use resulting composition (3) and aligning agent for liquid crystal (3), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 4>
In the polyimide powder (4) (1.70g) utilizing the synthetic method of synthesis example 4 to obtain, add S1 (14.1g) and NEP (9.37g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (9.37g) and PB (14.1g), stirring 3 hours with 40 DEG C, thus obtaining compositions (4).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (4) is used for evaluating as aligning agent for liquid crystal (4).
Use resulting composition (4) and aligning agent for liquid crystal (4), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (normal cells) of voltage retention (VHR) " and " evaluation of the ink-jet application of aligning agent for liquid crystal ".
<embodiment 5>
S1 (14.0g) and BCS (17.7g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (5) (10.0g) utilizing the synthetic method of synthesis example 5 to obtain, stir 4 hours with 25 DEG C, thus obtaining compositions (5).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (5) also serves as aligning agent for liquid crystal (5) and is used for evaluating.
Use resulting composition (5) and aligning agent for liquid crystal (5), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 6>
In the polyimide powder (6) (1.70g) utilizing the synthetic method of synthesis example 6 to obtain, add S1 (14.7g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (12.0g), stirring 3 hours with 40 DEG C, thus obtaining compositions (6).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (6) also serves as aligning agent for liquid crystal (6) and is used for evaluating.
Use resulting composition (6) and aligning agent for liquid crystal (6), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (normal cells) of voltage retention (VHR) ", " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning " and " making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning ".
<embodiment 7>
In the polyimide powder (6) (1.65g) utilizing the synthetic method of synthesis example 6 to obtain, add S1 (9.10g) and NEP (13.7g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (22.8g), stirring 3 hours with 40 DEG C, thus obtaining compositions (7).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (7) is used for evaluating as aligning agent for liquid crystal (7).
Use resulting composition (7) and aligning agent for liquid crystal (7), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (normal cells) of voltage retention (VHR) " and " evaluation of the ink-jet application of aligning agent for liquid crystal ".
<embodiment 8>
In the polyimide powder (7) (1.60g) utilizing the synthetic method of synthesis example 7 to obtain, add S1 (6.27g) and NEP (7.52g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (2.51g) and PB (8.77g), stirring 3 hours with 40 DEG C, thus obtaining compositions (8).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (8) also serves as aligning agent for liquid crystal (8) and is used for evaluating.
Use resulting composition (8) and aligning agent for liquid crystal (8), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 9>
In the polyimide powder (8) (1.60g) utilizing the synthetic method of synthesis example 8 to obtain, add S1 (7.52g) and NMP (5.01g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (10.0g) and DME (2.51g), stirring 5 hours with 40 DEG C, thus obtaining compositions (9).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (9) also serves as aligning agent for liquid crystal (9) and is used for evaluating.
Use resulting composition (9) and aligning agent for liquid crystal (9), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (normal cells) of voltage retention (VHR) ", " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning " and " making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning ".
<embodiment 10>
In the polyimide powder (9) (1.65g) utilizing the synthetic method of synthesis example 9 to obtain, add S1 (10.3g) and NEP (7.76g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (6.46g) and EC (1.29g), stirring 3 hours with 40 DEG C, thus obtaining compositions (10).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (10) also serves as aligning agent for liquid crystal (10) and is used for evaluating.
Use resulting composition (10) and aligning agent for liquid crystal (10), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 11>
In the polyimide powder (10) (1.60g) utilizing the synthetic method of synthesis example 10 to obtain, add S1 (3.76g) and NEP (10.0g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (11.3g), stirring 3 hours with 40 DEG C, thus obtaining compositions (11).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (11) also serves as aligning agent for liquid crystal (11) and is used for evaluating.
Use resulting composition (11) and aligning agent for liquid crystal (11), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 12>
In the polyimide powder (11) (1.70g) utilizing the synthetic method of synthesis example 11 to obtain, add S1 (5.33g) and γ-BL (13.3g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (7.99g), stirring 3 hours with 40 DEG C, thus obtaining compositions (12).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (12) also serves as aligning agent for liquid crystal (12) and is used for evaluating.
Use resulting composition (12) and aligning agent for liquid crystal (12), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 13>
In the polyimide powder (12) (1.65g) utilizing the synthetic method of synthesis example 12 to obtain, add S1 (7.76g) and NMP (5.17g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (5.17g) and PB (7.76g), stirring 3 hours with 40 DEG C, thus obtaining compositions (13).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (13) also serves as aligning agent for liquid crystal (13) and is used for evaluating.
Use resulting composition (13) and aligning agent for liquid crystal (13), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 14>
In the polyimide powder (13) (1.60g) utilizing the synthetic method of synthesis example 13 to obtain, add S1 (5.01g) and NEP (7.52g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (12.5g), stirring 3 hours with 40 DEG C, thus obtaining compositions (14).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (14) also serves as aligning agent for liquid crystal (14) and is used for evaluating.
Use resulting composition (14) and aligning agent for liquid crystal (14), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (normal cells) of voltage retention (VHR) ", " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning " and " making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning ".
<embodiment 15>
In the polyimide powder (13) (1.70g) utilizing the synthetic method of synthesis example 13 to obtain, add S1 (4.69g) and γ-BL (18.8g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (9.37g) and PB (14.1g), stirring 3 hours with 40 DEG C, thus obtaining compositions (15).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (15) is used for evaluating as aligning agent for liquid crystal (15).
Use resulting composition (15) and aligning agent for liquid crystal (15), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (normal cells) of voltage retention (VHR) " and " evaluation of the ink-jet application of aligning agent for liquid crystal ".
<embodiment 16>
In the polyimide powder (14) (1.60g) utilizing the synthetic method of synthesis example 14 to obtain, add S1 (12.5g) and NEP (2.51g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding K1 (0.08g) and BCS (10.0g), stirring 5 hours with 40 DEG C, thus obtaining compositions (16).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (16) also serves as aligning agent for liquid crystal (16) and is used for evaluating.
Use resulting composition (16) and aligning agent for liquid crystal (16), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 17>
In the polyimide powder (15) (1.60g) utilizing the synthetic method of synthesis example 15 to obtain, add S1 (15.0g) and γ-BL (2.51g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding K1 (0.08g), BCS (2.51g) and PB (5.01g), stirring 5 hours with 40 DEG C, thus obtaining compositions (17).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (17) also serves as aligning agent for liquid crystal (17) and is used for evaluating.
Use resulting composition (17) and aligning agent for liquid crystal (17), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 18>
In the polyimide powder (16) (1.70g) utilizing the synthetic method of synthesis example 16 to obtain, add S1 (2.66g) and NEP (10.7g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (5.33g) and PB (7.99g), stirring 3 hours with 40 DEG C, thus obtaining compositions (18).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (18) also serves as aligning agent for liquid crystal (18) and is used for evaluating.
Use resulting composition (18) and aligning agent for liquid crystal (18), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 19>
In the polyimide powder (17) (1.60g) utilizing the synthetic method of synthesis example 17 to obtain, add S1 (8.77g) and NMP (5.01g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (8.77g) and EC (2.51g), stirring 3 hours with 40 DEG C, thus obtaining compositions (19).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (19) also serves as aligning agent for liquid crystal (19) and is used for evaluating.
Use resulting composition (19) and aligning agent for liquid crystal (19), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<embodiment 20>
In the polyimide powder (18) (1.60g) utilizing the synthetic method of synthesis example 18 to obtain, add S1 (10.0g) and NEP (3.76g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (3.76g) and PB (7.52g), stirring 3 hours with 40 DEG C, thus obtaining compositions (20).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (20) also serves as aligning agent for liquid crystal (20) and is used for evaluating.
Use resulting composition (20) and aligning agent for liquid crystal (20), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<comparative example 1>
NMP (16.0g) and BCS (15.7g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (19) (10.0g) utilizing the synthetic method of synthesis example 19 to obtain, stir 4 hours with 25 DEG C, thus obtaining compositions (21).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (21) also serves as aligning agent for liquid crystal (21) and is used for evaluating.
Use resulting composition (21) and aligning agent for liquid crystal (21), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<comparative example 2>
In the polyimide powder (3) (1.70g) utilizing the synthetic method of synthesis example 3 to obtain, add NMP (14.7g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (12.0g), stirring 3 hours with 40 DEG C, thus obtaining compositions (22).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (22) also serves as aligning agent for liquid crystal (22) and is used for evaluating.
Use resulting composition (22) and aligning agent for liquid crystal (22), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<comparative example 3>
NMP (14.7g) and BCS (18.5g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (20) (10.5g) utilizing the synthetic method of synthesis example 20 to obtain, stir 4 hours with 25 DEG C, thus obtaining compositions (23).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (23) also serves as aligning agent for liquid crystal (23) and is used for evaluating.
Use resulting composition (23) and aligning agent for liquid crystal (23), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
<comparative example 4>
In the polyimide powder (6) (1.65g) utilizing the synthetic method of synthesis example 6 to obtain, add NMP (14.2g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (11.6g), stirring 3 hours with 40 DEG C, thus obtaining compositions (24).Do not observe that said composition produces muddiness, precipitate etc. abnormal, confirm as uniform solution.It should be noted that said composition (24) also serves as aligning agent for liquid crystal (24) and is used for evaluating.
Use resulting composition (24) and aligning agent for liquid crystal (24), carry out " evaluation (evaluation of pin hole) of the printing of compositions and aligning agent for liquid crystal ", " evaluation (evaluation of film end) of the printing of compositions and aligning agent for liquid crystal " and " evaluation (normal cells) of voltage retention (VHR) ".
[table 3]
* 1: represent the import volume (mass parts) of the specific solvent relative to whole solvent 100 mass parts.
* 2: represent the import volume (mass parts) of other solvent relative to whole solvent 100 mass parts.
* 3: represent the ratio (quality %) shared by whole polymer in compositions and aligning agent for liquid crystal.
[table 4]
* 1: represent the import volume (mass parts) of the specific solvent relative to whole solvent 100 mass parts.
* 2: represent the import volume (mass parts) of other solvent relative to whole solvent 100 mass parts.
* 3: represent the ratio (quality %) shared by whole polymer in compositions and aligning agent for liquid crystal.
[table 5]
* 1: represent the import volume (mass parts) of the specific solvent relative to whole solvent 100 mass parts.
* 2: represent the import volume (mass parts) of other solvent relative to whole solvent 100 mass parts.
* 3: represent the ratio (quality %) shared by whole polymer in compositions and aligning agent for liquid crystal.
[table 6]
[table 7]
[table 8]
[table 9]
[table 10]
[table 11]
From the above results: compared with the polyimide film obtained by the compositions of comparative example, the polyimide film obtained by the compositions of the embodiment of the present invention demonstrates the uniform coating that pin hole does not occur, and then, high and its end the protuberance of the end rectilinearity of polyimide film diminishes.Specifically, the contrast being the use of (A) composition of the present invention and the compositions of specific solvent and do not use the contrast with the contrast of comparative example 2, embodiment 5 and comparative example 3 of the contrast of compositions of specific solvent, i.e. embodiment 2 and the contrast of comparative example 1, embodiment 3 and embodiment 6 and comparative example 4.These comparative examples, compared with corresponding embodiment, present the result that the pin hole quantity on polyimide film is many and then the film of the film end of polyimide film is also poor.It addition, the compositions of these embodiments is also used for as aligning agent for liquid crystal evaluating, therefore, the result employing the embodiment of these compositionss also regards as the result of aligning agent for liquid crystal.
Additionally, compared with the liquid crystal orientation film obtained by the aligning agent for liquid crystal of comparative example, even if the liquid crystal orientation film obtained by the aligning agent for liquid crystal employing the present composition can obtain burning till with low temperature when making liquid crystal orientation film, liquid crystal represents the result that the voltage retention (also referred to as VHR) of element is also excellent.Specifically, the contrast being the use of (A) composition of the present invention and the aligning agent for liquid crystal of specific solvent and do not use the contrast with the contrast of comparative example 2, embodiment 5 and comparative example 3 of the contrast of aligning agent for liquid crystal of specific solvent, i.e. embodiment 2 and the contrast of comparative example 1, embodiment 3 and embodiment 6 and comparative example 4.These comparative examples compared with corresponding embodiment, the value step-down of VHR.Especially, not only just having made the VHR value after liquid crystal cells low, the VHR value after the keeping of high temperature groove is also low, namely presents the obvious result of reduction of the VHR accompanied with high temperature.
Industrial applicability
The compositions of the present invention is when forming polyimide film, it is possible to obtain the polyimide film that can suppress to produce the film also excellence of pin hole, its end with shrinking.Now, it also is able to make polyimide film even if carrying out burning till with low temperature.
It addition, when the compositions of the present invention is used for aligning agent for liquid crystal, it is possible to the liquid crystal orientation film that the pin hole that obtains suppressing producing with shrinking, the film of its end are also excellent.And then, even if burning till with low temperature when making liquid crystal orientation film, the liquid crystal orientation film that liquid crystal represents that the electrical characteristics of element, especially voltage retention (also referred to as VHR) are excellent also can be formed.Thus, the liquid crystal with the liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention represents the excellent in reliability of element, can being suitably employed in the LCD TV of big picture and high-resolution, middle-size and small-size auto-navigation system, smart mobile phone etc., the vertical alignment-type liquid crystal for TN element, STN element, TFT liquid crystal cell, especially VA pattern, PSA pattern and SC-PVA pattern etc. represents that element is useful.

Claims (26)

1. a compositions, it contains:
(A) composition: the solvent shown in following formula [A]；And
(B) composition: at least one polymer in polyimide precursor and polyimides,
In formula [A], X1And X2Represent the alkyl of carbon number 1～3, X independently of one another3And X4Represent the alkyl of carbon number 1～3 independently of one another.
2. compositions according to claim 1, wherein, the solvent of described (A) composition is the solvent shown in following formula [A-1],
3. the compositions according to claim 1 or claim 2, wherein, described (B) composition be the diamine compound of at least one structure having in structure shown in following formula [1-1] and formula [1-2] is obtained for the part of raw material, at least one polymer in polyimide precursor and polyimides
In formula [1-1], Y1Represent selected from singly-bound ,-(CH2)a-、-O-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) at least one binding groups in CO-,-COO-and-OCO-, wherein, a is the integer of 1～15；Y2Represent singly-bound or-(CH2)b-, wherein, b is the integer of 1～15；Y3Represent selected from singly-bound ,-(CH2)c-、-O-、-CH2At least one binding groups in O-,-COO-and-OCO-, wherein, c is the integer of 1～15；Y4The divalent organic group of the bivalent cyclic group representing at least one ring in phenyl ring, cyclohexane ring and heterocycle or the carbon number 17～51 with steroid skeleton, any hydrogen atom on described cyclic group is optionally by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, the replacing containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom of carbon number 1～3；Y5Representing the bivalent cyclic group of at least one ring in phenyl ring, cyclohexane ring and heterocycle, any hydrogen atom on these cyclic groups is optionally by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, the replacing containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom of carbon number 1～3；N represents the integer of 0～4；Y6Represent selected from the alkyl of carbon number 1～22, the thiazolinyl of carbon number 2～22, carbon number 1～22 containing at least one in fluoroalkyl, the alkoxyl of carbon number 1～22 and the fluoroalkoxy of carbon number 1～22,
-Y7-Y8[1-2]
In formula [1-2], Y7Represent selected from singly-bound ,-O-,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) at least one binding groups in CO-,-COO-and-OCO-；Y8Represent the alkyl of carbon number 8～22 or carbon number 6～18 containing fluoroalkyl.
4. compositions according to claim 3, wherein, having the diamine compound of structure shown in described formula [1-1] and formula [1-2] is the diamine compound shown in following formula [1a],
In formula [1a], Y represents at least one structure in structure shown in described formula [1-1] and formula [1-2], and m represents the integer of 1～4.
5. the compositions according to any one of claim 1～claim 4, wherein, the polymer of described (B) composition be the diamine compound of at least one substituent group having in carboxyl (COOH yl) and hydroxyl (OH yl) is obtained for the part of raw material, at least one polymer in polyimide precursor and polyimides.
6. compositions according to claim 5, wherein, the diamine compound with described carboxyl and hydroxyl is the diamine compound shown in following formula [2a],
In formula [2a], A represents the substituent group of at least one structure in following formula [2-1] and formula [2-2], and m represents the integer of 1～4,
-(CH2)a-COOH[2-1]-(CH2)b-OH[2-2]
In formula [2-1], a represents the integer of 0～4；In formula [2-2], b represents the integer of 0～4.
7. the compositions according to any one of claim 1～claim 6, wherein, the polymer of described (B) composition be the diamine compound shown in following formula [3a] is obtained for the part of raw material, at least one polymer in polyimide precursor and polyimides
In formula [3a], B1Represent selected from-O-,-NH-,-N (CH3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)-and-N (CH3) at least one binding groups in CO-；B2Represent at least one in singly-bound, the divalent group of aliphatic hydrocarbon of carbon number 1～20, the divalent group of non-aromatic ring type hydrocarbon and the divalent group of aromatic hydrocarbon；B3Represent selected from singly-bound ,-O-,-NH-,-N (CH3)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-、-N(CH3) CO-and-O (CH2)m-at least one binding groups, wherein, m is the integer of 1～5；B4Represent nitrogen heterocycle；N represents the integer of 1～4.
8. compositions according to claim 7, wherein, is the B in described formula [3a]1Represent-CONH-, B2Represent the alkylidene of carbon number 1～5, B3Represent singly-bound, B4Represent the diamine compound that imidazole radicals or pyridine radicals, n represent 1.
9. the compositions according to any one of claim 1～claim 8, wherein, the polymer of described (B) composition be the tetrabasic carboxylic acid composition shown in following formula [4] is obtained for the part of raw material, at least one polymer in polyimide precursor and polyimides
In formula [4], Z represents the group of at least one structure in following formula [4a]～formula [4k],
In formula [4a], Z1～Z4Represent hydrogen atom, methyl, chlorine atom or phenyl independently of one another；In formula [4g], Z5And Z6Represent hydrogen atom or methyl independently of one another.
10. the compositions according to any one of claim 1～claim 9, wherein, the polymer of described (B) composition is at least one polymer in polyamic acid Arrcostab and polyimides.
11. according to the compositions according to any one of claim 1～claim 10, wherein, as (C) composition, containing at least one solvent in METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone and gamma-butyrolacton.
12. according to the compositions according to any one of claim 1～claim 11, wherein, as (D) composition, containing selected from 1-hexanol, Hexalin, 1,2-ethylene glycol, 1, at least one solvent in solvent shown in 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dimethyl ether and following formula [D-1]～formula [D-3]
In formula [D-1], D1Represent the alkyl of carbon number 1～3；In formula [D-2], D2Represent the alkyl of carbon number 1～3；In formula [D-3], D3Represent the alkyl of carbon number 1～4.
13. according to the compositions according to any one of claim 1～claim 12, wherein, compositions comprises at least one cross-linked compound being selected from cross-linked compound: there is the cross-linked compound of epoxy radicals, NCO, oxetanylmethoxy or cyclocarbonate radical；There is the cross-linked compound of at least one substituent group in the group selecting free hydroxyl, hydroxy alkyl and low-grade alkoxy alkyl composition；And, there is the cross-linked compound of polymerism unsaturated bond.
14. according to the compositions according to any one of claim 1～claim 13, wherein, described (A) composition is 5～70 mass % that the solvent comprised in compositions is overall.
15. according to the compositions according to any one of claim 11～claim 14, wherein, described (C) composition is 40～80 mass % that the solvent comprised in compositions is overall.
16. according to the compositions according to any one of claim 12～claim 15, wherein, described (D) composition is 1～50 mass % that the solvent comprised in compositions is overall.
17. according to the compositions according to any one of claim 1～claim 16, wherein, described (B) composition is 0.1 mass %～30 mass % in the composition.
18. a polyimide film, it is that the compositions according to any one of claim 1～claim 17 obtains.
19. an aligning agent for liquid crystal, it is that the compositions according to any one of claim 1～claim 17 obtains.
20. a liquid crystal orientation film, it is to use aligning agent for liquid crystal described in claim 19 to obtain.
21. a liquid crystal orientation film, it is to use the aligning agent for liquid crystal described in claim 19 to be obtained by ink-jet method.
22. liquid crystal represents an element, it has the liquid crystal orientation film described in claim 20 or claim 21.
23. according to the liquid crystal orientation film described in claim 20 or claim 21, it is characterized in that, it is used to have liquid crystal layer between a pair substrate possessing electrode and the liquid crystal that manufactures via following operation represents element: configure liquid-crystal composition between aforementioned a pair substrate, described liquid-crystal composition comprises at least one utilizing active energy beam and hanker and carries out the polymerizable compound being polymerized, while make described polymerizable compound be polymerized to applying voltage limit between described electrode.
24. a liquid crystal represents element, it is characterised in that it has the liquid crystal orientation film described in claim 23.
25. according to the liquid crystal orientation film described in claim 20 or claim 21, it is characterized in that, it is used to have liquid crystal layer between a pair substrate possessing electrode and the liquid crystal that manufactures via following operation represents element: configure liquid crystal orientation film between aforementioned a pair substrate, described liquid crystal orientation film comprises at least one utilizing active energy beam and hanker and carries out the polymerizable group being polymerized, while make described polymerizable group be polymerized to applying voltage limit between described electrode.
26. a liquid crystal represents element, it is characterised in that it has the liquid crystal orientation film described in claim 25.
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CN110291455B (en) * 2017-02-28 2022-03-22 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film and method for producing the same, liquid crystal element and polymer
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CN110945416B (en) * 2017-07-27 2022-08-26 日产化学株式会社 Resin composition, resin film, and liquid crystal display element

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