CN105765453A - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Liquid crystal aligning agent and liquid crystal display element using same Download PDF

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CN105765453A
CN105765453A CN201480064518.XA CN201480064518A CN105765453A CN 105765453 A CN105765453 A CN 105765453A CN 201480064518 A CN201480064518 A CN 201480064518A CN 105765453 A CN105765453 A CN 105765453A
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liquid crystal
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aligning agent
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CN105765453B (en
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铁谷尚士
樱井宏之
保坂和義
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

A liquid crystal aligning agent which contains the component (A) and the component (B) described below. Component (A): a polymer containing at least one material selected from among polyimides and polyimide precursors having a structure having a nitrogen atom Component (B): a polymer containing at least one material selected from among polyimides and polyimide precursors having a urea structure or a thiourea structure In this connection, the polymer of the component (A) and/or the polymer of the component (B) contains a specific side chain structure.

Description

Aligning agent for liquid crystal and the liquid crystal employing it represent element
Technical field
The present invention relates to and represent the aligning agent for liquid crystal used in the manufacture of element, this aligning agent for liquid crystal liquid crystal orientation film obtained at liquid crystal and employ the liquid crystal of this liquid crystal orientation film and represent element.
Background technology
Liquid crystal represent element as realize volume thin/the expression equipment of light weight and now widely available.Generally, this liquid crystal represents that element uses liquid crystal orientation film to determine the state of orientation of liquid crystal.
As to one of characteristic that liquid crystal orientation film requires, have and liquid crystal molecule is remained arbitrary value relative to the orientation inclination angle of real estate, namely controls the tilt angle of liquid crystal.The big I of this tilt angle known changes by selecting the structure constituting the polyimides of liquid crystal orientation film.Control among the technology of tilt angle by the structure of polyimides, the method of the part that the diamidogen with side chain is used as polyimides raw material can control tilt angle according to the usage ratio of this diamidogen, therefore being easier to obtain target tilt angle, the means as increase tilt angle are useful (referring for example to patent documentations 1).Additionally, for like this for increasing the diamine component of liquid crystal pretilt angle, also carry out the structural research for improving tilt angle stability, process dependency, as side-chain structure used herein, it is proposed that comprise the structure (referring for example to patent documentation 2) of the ring structure such as phenyl, cyclohexyl.
Additionally, along with liquid crystal represents the high-definition of element, from the view point of liquid crystal represents that the suppression of contrast reduction of element, persistence of vision reduce, for the liquid crystal orientation film wherein used, the characteristic that the accumulated charge electric charge that is few or that accumulate because of DC voltage when voltage retention height, applying DC voltage quickly relaxes becomes important gradually.
In the liquid crystal orientation film of polyimides system, the liquid crystal orientation film that time till disappearing as the after image that produces because of DC voltage is short, it is known that: employ polyamic acid, containing the basis of the polyamic acid of imide on possibly together with the liquid crystal orientation film (referring for example to patent documentation 3) of aligning agent for liquid crystal of tertiary amine of ad hoc structure；Employing the liquid crystal orientation film of the aligning agent for liquid crystal containing soluble polyimide, the specific diamidogen with pyridine skeleton etc. is used for raw material (referring for example to patent documentation 4) etc. by described soluble polyimide.Additionally, after image that is high as voltage retention and that produce because of DC voltage disappear till time short liquid crystal orientation film, it is known that employ on the basis of polyamic acid, its imide amination polymer etc. the liquid crystal orientation film of aligning agent for liquid crystal possibly together with the following compound of minute quantity, described compound is selected from: molecule is contained within the compound of 1 carboxylic acid group, molecule is contained within the compound of 1 acid anhydride and molecule is contained within the compound (referring for example to patent documentation 5) of 1 tertiary amino.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2-282726 publication
Patent documentation 2: Japanese Unexamined Patent Publication 9-278724 publication
Patent documentation 3: Japanese Unexamined Patent Publication 9-316200 publication
Patent documentation 4: Japanese Unexamined Patent Publication 10-104633 publication
Patent documentation 5: Japanese Unexamined Patent Publication 8-76128 publication
Summary of the invention
The problem that invention to solve
Liquid crystal orientation film is additionally operable to the control carrying out liquid crystalline phase for the angle of substrate, i.e. liquid crystal pretilt angle.Especially, in VA (VerticalAlignment) pattern, PSA (PolymerSustainedAlignment) pattern etc., need to make liquid crystal vertical-tropism, therefore, liquid crystal orientation film requires to make the ability (also referred to as vertical orientated property, high tilt angle) of liquid crystal vertical-tropism.And then, for liquid crystal orientation film, it is not only high vertical orientated property, its stability is also become important.Especially, use to obtain high brightness the liquid crystal of the backlight that caloric value is big, light irradiation dose is many to represent element such as auto-navigation system, large-scale tv, sometimes use under the environment being exposed to high temperature and light irradiation for a long time or place.Under this critical conditions, when vertical orientated property reduces, produce to obtain the characterization at initial stage or represent the unequal problem of generation.
And then, it is voltage retention about one of liquid crystal electrical characteristics representing element, also requires the high stability under above-mentioned etc critical conditions.That is, voltage retention is because the light being derived from backlight irradiates when reducing, it is easy to occur liquid crystal to represent one of the bad i.e. after image bad (also referred to as line after image) of the expression of element, it is impossible to the liquid crystal obtaining reliability high represents element.Therefore, for liquid crystal orientation film, requiring on the good basis of initial stage characteristic, for instance, even if after also requiring that being exposed to light for a long time irradiates, voltage retention is also difficult to reduce.And then, for the bad i.e. face after image of another kind of after image, also require that the light by being derived from backlight irradiates, the liquid crystal orientation film quickly relaxed of the residual charge accumulated because of DC voltage.
Thus, it is an object of the invention to, it is provided that have the aligning agent for liquid crystal of above-mentioned characteristic concurrently.That is, it is an object of the invention to, it is provided that even if also being able to show the liquid crystal orientation film of stable tilt angle after being exposed to high temperature and light irradiation for a long time.Further, its object is to, it is provided that even if being exposed to the reduction also being able to suppression voltage retention after light irradiates and the liquid crystal orientation film quickly relaxed of the residual charge accumulated because of DC voltage for a long time.
And, it is provided that the liquid crystal with above-mentioned liquid crystal orientation film represents element, can provide the aligning agent for liquid crystal of above-mentioned liquid crystal orientation film.
And then, it is an object of the invention to, it is provided that the liquid crystal possessing the liquid crystal orientation film being consistent with above-mentioned requirements represents element.
For solving the scheme of problem
Present inventor has performed further investigation, found that: the aligning agent for liquid crystal with 2 kinds of polymer with ad hoc structure 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 aligning agent for liquid crystal, it contains following (A) composition and (B) composition:
(A) composition: containing at least any of polymer in polyimide precursor and polyimides, described polyimide precursor and polyimides have the structure with nitrogen-atoms.
(B) composition: containing at least any of polymer in polyimide precursor and polyimides, described polyimide precursor and polyimides have the structure shown in following formula [2].
It should be noted that in the polymer of (A) composition and (B) composition at least any one contains the structure shown in following formula [3].
(in formula [2], Y1And Y7Represent singly-bound independently of one another, selected from the alkylidene of carbon number 1～10 ,-O-,-N (R1)-(R1Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CON (R2)-(R2Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-N (R3)CO-(R3Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CH2At least one organic group in O-,-COO-and-OCO-；Y2And Y6Represent the alkylidene of carbon number 1～10 independently of one another；Y3And Y5Represent the alkylidene of hydrogen atom or carbon number 1～10 independently of one another；Y4Represent oxygen atom or sulphur atom).
(in formula [3], B1Represent singly-bound ,-(CH2)a-(a is the integer of 1～15) ,-O-,-CH2O-,-COO-or-OCO-；B2Represent singly-bound or-(CH2)b-(b is the integer of 1～15)；B3Represent singly-bound ,-(CH2)c-(c is the integer of 1～15) ,-O-,-CH2O-,-COO-or-OCO-；B4Representing the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle or have the divalent organic group of carbon number 17～51 of 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；B5Representing the divalent cyclic group in phenyl ring, cyclohexane ring or 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；B6Represent the fluoroalkoxy containing fluoroalkyl, the alkoxyl of carbon number 1～18 or carbon number 1～18 of the alkyl of carbon number 1～18, carbon number 1～18).
(2) aligning agent for liquid crystal according to above-mentioned (1), wherein, the structure with nitrogen-atoms in aforementioned (B) composition is at least one structure in structure shown in following formula [1a]～formula [1c].
(in formula [1a], X1Represent phenyl ring or nitrogenous heteroaromatic, X2Represent hydrogen atom or the disubstituted amido replaced by the aliphatic group of carbon number 1～12；In formula [1b], X3And X7Represent independently of one another and there are 6～15 carbon atoms and there is the aromatic group of 1～2 phenyl ring, X4And X6Represent the alkylidene of hydrogen atom or carbon number 1～5, X independently of one another5Representing alkylidene or the xenyl of carbon number 2～5, m represents the integer of 0 or 1；In formula [1c], X8And X10Represent at least one structure in structure shown in following formula [1c-a] and formula [1c-b], X independently of one another9Represent alkylidene or the phenyl ring of carbon number 1～5).
(3) aligning agent for liquid crystal according to above-mentioned (1) or above-mentioned (2), wherein, the polymer of aforementioned (A) composition is the polymer obtained for the part of raw material by the diamine compound shown in following formula [1-1].
(in formula [1-1], XARepresent the organic group of at least one structure having in structure shown in previously described formula [1a]～formula [1c]；A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another).
(4) aligning agent for liquid crystal according to above-mentioned (3), it is by the aforementioned diamine compound polymer that to be the diamine compound shown in following formula [1a-1]～formula [1c-1] obtain for the part of raw material.
(in formula [1a-1], X1Represent phenyl ring or nitrogenous heteroaromatic, X2Represent hydrogen atom or the disubstituted amido replaced by the aliphatic group of carbon number 1～12；In formula [1b-1], X3And X7Represent independently of one another and there are 6～15 carbon atoms and there is the aromatic group of 1～2 phenyl ring, X4And X6Represent the alkylidene of hydrogen atom or carbon number 1～5, X independently of one another5Representing alkylidene or the xenyl of carbon number 2～5, m represents the integer of 0 or 1；In formula [1c-1], X8And X10Represent at least one structure in structure shown in previously described formula [1c-a] and formula [1c-b], X independently of one another9Represent alkylidene or the phenyl ring of carbon number 1～5；In formula [1a-1]～formula [1c-1], A1～A6Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another).
(5) aligning agent for liquid crystal according to above-mentioned (4), wherein, aforementioned diamine compound is at least one diamine compound in the diamine compound shown in following formula [1-1a]～formula [1-4a].
(in formula [1-3a], R1Represent the alkylidene of hydrogen atom or carbon number 1～5；In formula [1-4a], n represents the integer of 1～10；In formula [1-1a]～formula [1-4a], A1～A8Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another).
(6) aligning agent for liquid crystal according to any one of above-mentioned (1)～above-mentioned (5), wherein, the polymer of aforementioned (B) composition is the polymer obtained for the part of raw material by the diamine compound shown in following formula [2-1].
(in formula [2-1], YARepresent that there is the organic group of structure shown in previously described formula [2]；A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another).
(7) aligning agent for liquid crystal according to above-mentioned (6), it is by the aforementioned diamine compound polymer that to be the diamine compound shown in following formula [2a] obtain for the part of raw material.
(in formula [2a], Y1And Y7Represent singly-bound independently of one another, selected from the alkylidene of carbon number 1～10 ,-O-,-N (R1)-(R1Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CON (R2)-(R2Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-N (R3)CO-(R3Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CH2At least one organic group in O-,-COO-and-OCO-；Y2And Y6Represent the alkylidene of carbon number 1～10 independently of one another；Y3And Y5Represent the alkylidene of hydrogen atom or carbon number 1～10 independently of one another；Y4Represent oxygen atom or sulphur atom；A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another).
(8) aligning agent for liquid crystal according to above-mentioned (7), wherein, aforementioned diamine compound is at least one diamine compound in the diamine compound shown in following formula [2-1a]～formula [2-3a].
(in formula [2-1a]～formula [2-3a], A1～A6Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another).
(9) aligning agent for liquid crystal according to any one of above-mentioned (1)～above-mentioned (8), wherein, at least any one the polymer in aforementioned (A) composition and (B) composition is by the part for raw material of the diamine compound shown in following formula [3a].
(in formula [3a], B represents previously described formula [3]；A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another；M represents the integer of 1～4).
(10) aligning agent for liquid crystal according to any one of above-mentioned (1)～above-mentioned (9), wherein, the polymer of aforementioned (A) composition and the polymer of (B) composition are at least one polymer in the polyimide precursor obtained selected from the tetrabasic carboxylic acid composition shown in use following formula [4] and polyimides.
(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 ring, optionally identical or different each other；In formula [4g], Z5And Z6Represent hydrogen atom or methyl, optionally identical or different each other).
(11) aligning agent for liquid crystal according to above-mentioned (10), wherein, aforementioned tetrabasic carboxylic acid composition is the tetrabasic carboxylic acid composition being at least one structure in structure shown in previously described formula [4a] and formula [4e]～formula [4g] of the Z in previously described formula [4].
(12) aligning agent for liquid crystal according to any one of above-mentioned (4)～above-mentioned (11), wherein, in the polymer of aforementioned (A) composition, the diamine compound shown in previously described formula [1a-1]～formula [1c-1] is 5 moles of %～95 mole % in 100 moles of % of whole diamine component.
(13) aligning agent for liquid crystal according to any one of above-mentioned (7)～above-mentioned (12), wherein, in the polymer of aforementioned (B) composition, the diamine compound shown in previously described formula [2a] is 5 moles of %～95 mole % in 100 moles of % of whole diamine component.
(14) aligning agent for liquid crystal according to any one of above-mentioned (1)～above-mentioned (13), wherein, the polymer phase of aforementioned (B) composition is 0.5 mass parts～950 mass parts for polymer 100 mass parts of aforementioned (A) composition.
(15) aligning agent for liquid crystal according to any one of above-mentioned (1)～above-mentioned (14), wherein, as the solvent of aligning agent for liquid crystal, containing at least one solvent in METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone and gamma-butyrolacton.
(16) aligning agent for liquid crystal according to any one of above-mentioned (1)～above-mentioned (15), wherein, solvent as aligning agent for liquid crystal, containing selected from 1-hexanol, Hexalin, 1, at least one solvent in 2-ethylene glycol, 1,2-PD, glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether.
(17) aligning agent for liquid crystal according to any one of above-mentioned (1)～above-mentioned (16), wherein, aligning agent for liquid crystal comprises at least one cross-linked compound being selected from cross-linked compound: there is the cross-linked compound of epoxy radicals, NCO, oxetanyl or cyclocarbonate radical；There is the cross-linked compound of at least one substituent group in the group selecting free hydroxyl, hydroxy alkyl or low-grade alkoxy alkyl composition；And, there is the cross-linked compound of polymerism unsaturated bond.
(18) a kind of liquid crystal orientation film, it is that the aligning agent for liquid crystal according to any one of above-mentioned (1)～above-mentioned (17) obtains.
(19) a kind of liquid crystal orientation film, it is to use the aligning agent for liquid crystal according to any one of above-mentioned (1)～above-mentioned (17) to be obtained by ink-jet method.
(20) a kind of liquid crystal represents element, and it has the liquid crystal orientation film described in above-mentioned (18) or above-mentioned (19).
(21) liquid crystal orientation film according to above-mentioned (18) or above-mentioned (19), 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 the polymerizable compound being polymerized because of active energy beam and at least one hankered, while make aforementioned polymeric compound polymerization to applying voltage limit between former electrodes.
(22) a kind of liquid crystal represents element, it is characterised in that have the liquid crystal orientation film described in above-mentioned (21).
(23) liquid crystal orientation film according to above-mentioned (18) or above-mentioned (19), 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 the polymerizable group being polymerized because of active energy beam and at least one hankered, while make aforementioned polymeric radical polymerisation to applying voltage limit between former electrodes.
(24) a kind of liquid crystal represents element, it is characterised in that have the liquid crystal orientation film described in above-mentioned (23).
The effect of invention
Even if the aligning agent for liquid crystal comprising 2 kinds of polymer of the present invention can obtain also can showing the liquid crystal orientation film of stable tilt angle after being exposed to high temperature and light irradiation for a long time, described polymer is chosen from least one in the polyimide precursor with ad hoc structure or polyimides.Further, even if being formed and being exposed to the reduction that also can suppress voltage retention after light irradiates for a long time and liquid crystal orientation film that the residual charge accumulated because of DC voltage quickly relaxes.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 etc. of big picture and high-resolution.
Detailed description of the invention
It is described in detail below for the present invention.
The present invention is the aligning agent for liquid crystal containing following (A) composition and (B) composition, use 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 kind of aligning agent for liquid crystal, it contains following (A) composition and (B) composition.
(A) composition: containing at least any of polymer (also referred to as particular polymers (A)) in polyimide precursor and polyimides, described polyimide precursor and polyimides have the structure with nitrogen-atoms.
(B) composition: containing at least any of polymer (also referred to as particular polymers (B)) in polyimide precursor and polyimides, described polyimide precursor and polyimides have the structure (also referred to as ad hoc structure (2)) shown in following formula [2].
It should be noted that in the polymer of (A) composition and (B) composition at least any one contains the structure (also referred to as particular side chain structure) shown in following formula [3].
(in formula [2], Y1And Y7Represent singly-bound independently of one another, selected from the alkylidene of carbon number 1～10 ,-O-,-N (R1)-(R1Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CON (R2)-(R2Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-N (R3)CO-(R3Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CH2At least one organic group in O-,-COO-and-OCO-；Y2And Y6Represent the alkylidene of carbon number 1～10 independently of one another；Y3And Y5Represent the alkylidene of hydrogen atom or carbon number 1～10 independently of one another；Y4Represent oxygen atom or sulphur atom).
(in formula [3], B1Represent singly-bound ,-(CH2)a-(a is the integer of 1～15) ,-O-,-CH2O-,-COO-or-OCO-；B2Represent singly-bound or-(CH2)b-(b is the integer of 1～15)；B3Represent singly-bound ,-(CH2)c-(c is the integer of 1～15) ,-O-,-CH2O-,-COO-or-OCO-；B4Representing the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle or have the divalent organic group of carbon number 17～51 of 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；B5Representing the divalent cyclic group in phenyl ring, cyclohexane ring or 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；B6Represent the fluoroalkoxy containing fluoroalkyl, the alkoxyl of carbon number 1～18 or carbon number 1～18 of the alkyl of carbon number 1～18, carbon number 1～18).
For the liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention, about why can solve the problem that the problem of the present invention is still not clear, it may be considered that approximately as.
That is, at least any one the particular side chain structure shown in contained previously described formula [3] in the particular polymers (A) of the present invention and particular polymers (B) has phenyl ring, cyclohexyl ring or heterocycle or has the divalent organic group of carbon number 17～51 of steroid skeleton at side chain position.Compared with the side-chain structure of the prior art making liquid crystal vertical-tropism and chain alkyl, the side-chain structure of these rings and organic group shows upright and outspoken structure.Thus, compared with the product of the side-chain structure of conventional chain alkyl, the aligning agent for liquid crystal with particular side chain structure of the present invention liquid crystal orientation film obtained can obtain high and stable liquid crystal vertical-tropism.
It addition, compared with the side-chain structure of conventional chain alkyl, the particular side chain structure of the present invention is just stable for ultraviolet etc..Therefore, even if the particular side chain structure of the present invention is exposed to light for a long time and irradiates, it is also possible to suppress voltage retention to reduce and suppress to accumulate because of DC voltage the analyte of the side chain moiety of residual charge.
And then, it is believed that: by the nitrogen-atoms in the previously described formula [2] in the interaction with the carboxyl (COOH yl) in the nitrogen-atoms in the structure of nitrogen-atoms and particular polymers (B) comprised in the particular polymers (A) of the present invention and particular polymers (B) and the interaction of the carboxyl in particular polymers (A), the movement of electric charge can be there is between which.Accompanying with this, the residual charge accumulated can effectively in the molecule of polymer or intermolecular movement.Namely it is believed that: the removal of the residual charge caused by DC voltage can be promoted.
And it is possible to think: the structure with nitrogen-atoms in the particular polymers (A) of the present invention can catch the main cause making voltage retention reduce and ionic impurity composition.That is, liquid crystal represents that element can catch the ionic impurity produced because being exposed to light irradiation for a long time, accompanies with this, it is possible to suppress the reduction of voltage retention.
From the view point of above, even if the aligning agent for liquid crystal of the polymer comprising 2 kinds of at least one in the polyimide precursor with ad hoc structure or polyimides of the present invention can obtain also can showing the liquid crystal orientation film of stable tilt angle after being exposed to high temperature and light irradiation for a long time.Further, even if being formed and being exposed to the reduction that also can suppress voltage retention after light irradiates for a long time and liquid crystal orientation film that the residual charge accumulated because of DC voltage quickly relaxes.
<structure with nitrogen-atoms>
The particular polymers (A) of the present invention is that described polyimide precursor and polyimides have the structure with nitrogen-atoms containing at least any of polymer in polyimide precursor and polyimides.
As the concrete structure of the structure with nitrogen-atoms, the structure shown in following formula [1a]～formula [1c] can be listed.
In formula [1a], X1Represent phenyl ring or nitrogenous heteroaromatic.
In formula [1a], X2Represent hydrogen atom or the disubstituted amido replaced by the aliphatic group of carbon number 1～12.
It should be noted that in formula [1a], X2During for hydrogen atom, X1Represent nitrogenous heteroaromatic；X2For replaced by the aliphatic group of carbon number 1～12 disubstituted amido time, X1Represent phenyl ring.
In formula [1b], X3And X7Represent independently of one another and there are 6～15 carbon atoms and there is the aromatic group of 1～2 phenyl ring.
In formula [1b], X4And X6Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
In formula [1b], X5Represent alkylidene or the xenyl of carbon number 2～5.
In formula [1b], m represents the integer of 0 or 1.
In formula [1c], X8And X10Represent at least one structure in structure shown in following formula [1c-a] and formula [1c-b] independently of one another.
In formula [1c], X9Represent alkylidene or the phenyl ring of carbon number 1～5.
<ad hoc structure (2)>
The particular polymers (B) of the present invention is that described polyimide precursor and polyimides have the ad hoc structure shown in following formula [2] containing at least any of polymer in polyimide precursor and polyimides.
In formula [2], Y1And Y7Represent singly-bound independently of one another, selected from the alkylidene of carbon number 1～10 ,-O-,-S-,-N (R1)-(R1Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CON (R2)-(R2Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-N (R3)CO-(R3Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CH2At least one organic group in O-,-COO-and-OCO-.Wherein, it is preferred to singly-bound ,-O-,-S-,-OCO-or-COO-.From the view point of the film hardness of liquid crystal aligning and liquid crystal orientation film, more preferably singly-bound ,-O-or-S-.
In formula [2], Y2And Y6Represent the alkylidene of carbon number 1～10 independently of one another.Wherein, it is preferred to the alkylidene of carbon number 1～3, its structure can be any one in straight or branched.Specifically, from the view point of the film hardness of liquid crystal aligning and liquid crystal orientation film, it is preferred to possess and rotate freely position and sterically hindered little structure and methylene (-CH2-), ethylidene (-CH2CH2-), propylidene (-(CH2)3-) or isopropyl (-C (CH2)2-)。
In formula [2], Y3And Y5Represent the alkyl of hydrogen atom or carbon number 1～10 independently of one another.Wherein, it is preferred to the alkyl of hydrogen atom or carbon number 1～3.It is particularly preferably hydrogen atom.
In formula [2], Y4Represent oxygen atom or sulphur atom.Wherein, from the view point of the film hardness of liquid crystal orientation film, it is preferred to oxygen atom.
<particular side chain structure>
At least any one particular side chain structure shown in contained previously described formula [3] in the particular polymers (A) of the present invention and particular polymers (B) is the structure shown in following formula [3].
In formula [3], B1Represent singly-bound ,-(CH2)a-(a is the integer of 1～15) ,-O-,-CH2O-,-COO-or-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 [3], B2Represent 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 [3], B3Represent singly-bound ,-(CH2)c-(c is the integer of 1～15) ,-O-,-CH2O-,-COO-or-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 [3], B4For the divalent cyclic group in phenyl ring, cyclohexane ring or 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, B4The 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 phenyl ring, cyclohexane ring or there is the organic group of carbon number 17～51 of steroid skeleton.
In formula [3], B5Representing the divalent cyclic group in phenyl ring, cyclohexane ring or 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 [3], 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 [3], B6Represent the fluoroalkoxy containing fluoroalkyl, the alkoxyl of carbon number 1～18 or carbon number 1～18 of the alkyl of carbon number 1～18, carbon number 1～18.Wherein, it is preferred to the alkyl of carbon number 1～18, 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 alkyl of carbon number 1～12 or the alkoxyl of 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 B in formula [3]1～B6With 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 WO2011/132751 (2011.10.27 is open).It should be noted that in each table of International Publication publication, the B in the present invention1～B6It is considered Y1～Y6, but Y1～Y6 can be regarded as B1～B6.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 of the present invention is considered 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.
<particular polymers (A)/particular polymers (B)>
Particular polymers (A) and the particular polymers (B) of the present invention 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 refers to the structure shown in following formula [A].
(in formula [A], R1It is 4 valency organic groups, R2For divalent organic group, A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5, A independently of one another3And A4Representing hydrogen atom, the alkylidene 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 dihalide, tetrabasic carboxylic acid dialkyl compound or tetrabasic carboxylic acid dialkyl dihalide can be listed.
In order to obtain the A in formula [A]1And A2Polyamic acid for hydrogen atom, it is possible to by making the diamine compound in previous molecular with 2 primary amino radicals or secondary amino group react with tetracarboxylic compound or tetracarboxylic anhydride and obtain.
In order to obtain the A in formula [A]1And A2Polyamic acid Arrcostab for the alkylidene of carbon number 1～5, it is possible to by making aforementioned diamine compound react with tetrabasic carboxylic acid dihalide, tetrabasic carboxylic acid dialkyl compound or tetrabasic carboxylic acid dialkyl dihalide and obtain.Alternatively, it is also possible to the A shown in lead-in [A] in the polyamic acid utilizing preceding method to obtain1And A2The alkylidene of carbon number 1～5.
The particular polymers (A) of the present invention is the polymer with the structure with nitrogen-atoms.Wherein, it is preferred to the structure shown in previously described formula [1a]～formula [1c].
Method structure with nitrogen-atoms being directed in particular polymers (A) is not particularly limited, it is preferable that will have the part for raw material of the diamine compound of structure shown in previously described formula [1a]～formula [1c].
Specifically, it is preferred to use the diamine compound (also referred to as specific diamine compound (1)) shown in following formula [1-1].
In formula [1-1], XARepresent the organic group of the carbon number 5～50 of at least one structure having in structure shown in previously described formula [1a]～formula [1c].
In formula [1-1], A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
More specifically, it is preferred to use the diamine compound shown in following formula [1a-1]～formula [1c-1].
In formula [1a-1], X1Represent phenyl ring or nitrogenous heteroaromatic.
In formula [1a-1], X2Represent hydrogen atom or the disubstituted amido replaced by the aliphatic group of carbon number 1～12.
It should be noted that in formula [1a-1], X2During for hydrogen atom, X1Represent nitrogenous heteroaromatic；X2For replaced by the aliphatic group of carbon number 1～12 disubstituted amido time, X1Represent phenyl ring.
In formula [1b-1], X3And X7Represent independently of one another and there are 6～15 carbon atoms and there is the aromatic group of 1～2 phenyl ring.
In formula [1b-1], X4And X6Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
In formula [1b-1], X5Represent alkylidene or the xenyl of carbon number 2～5.
In formula [1b-1], m represents the integer of 0 or 1.
In formula [1c-1], X8And X10Represent at least one structure in structure shown in following formula [1c-a] and formula [1c-b] independently of one another.
In formula [1c-1], X9Represent alkylidene or the phenyl ring of carbon number 1～5.
As the concrete diamine compound of the specific diamine compound (1) of the present invention, the diamine compound shown in following formula [1-1a]～formula [1-4a] can be listed.
In formula [1-3a], R1Represent the alkylidene of hydrogen atom or carbon number 1～5.
In formula [1-4a], n represents the integer of 1～10.
In formula [1-1a]～formula [1-4a], A1～A8Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
Wherein, it is preferred to use previously described formula [1-3a] or the diamine compound shown in formula [1-4a].
Specific diamine compound (1) in the particular polymers (A) of the present invention is preferably 1 mole of %～95 mole % in 100 moles of % of whole diamine component.Wherein, it is preferred to 5 moles of %～95 mole %.It is more preferably 20 moles of %～80 mole %.
The specific diamine compound (1) of the present invention can also according to the particular polymers (A) of present invention dissolubility in a solvent, 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 (B) of the present invention is the polymer with ad hoc structure (2).
The method that the ad hoc structure (2) of the present invention is directed in particular polymers (B) is not particularly limited, it is preferable that will have the diamine compound of ad hoc structure (2) for diamine component.Particularly preferably use and there is the diamine compound of structure shown in previously described formula [2].
Specifically, it is preferred to use the diamine compound (also referred to as specific diamine compound (2)) shown in following formula [2-1].
In formula [2-1], YARepresent that there is the organic group of structure shown in previously described formula [2].
In formula [2-1], A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
More specifically, it is preferred to use the diamine compound shown in following formula [2a].
In formula [2a], Y1And Y7Represent singly-bound independently of one another, selected from the alkylidene of carbon number 1～10 ,-O-,-S-,-N (R1)-(R1Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CON (R2)-(R2Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-N (R3)CO-(R3Represent the alkylidene of hydrogen atom or carbon number 1～3) ,-CH2At least one organic group in O-,-COO-and-OCO-.Wherein, it is preferred to singly-bound ,-O-,-S-,-OCO-or-COO-.From the view point of liquid crystal aligning and film hardness, more preferably soft as far as possible and sterically hindered little structure and singly-bound ,-O-or-S-.
In formula [2a], Y2And Y6Represent the alkylidene of carbon number 1～10 independently of one another.Wherein, it is preferred to the alkylidene of carbon number 1～3, its structure can be any one in straight or branched.Specifically, from the view point of the film hardness of liquid crystal aligning and liquid crystal orientation film, it is preferred to possess and rotate freely position and sterically hindered little structure and methylene (-CH2-), ethylidene (-CH2CH2-), propylidene (-(CH2)3-) or isopropyl (-C (CH2)2-)。
In formula [2a], Y3And Y5Represent the alkyl of hydrogen atom or carbon number 1～10 independently of one another.Wherein, it is preferred to the alkyl of hydrogen atom or carbon number 1～3.It is particularly preferably hydrogen atom.
In formula [2a], Y4Represent oxygen atom or sulphur atom.Wherein, from the view point of the film hardness of liquid crystal orientation film, it is preferred to oxygen atom.
Y in formula [2a]1、Y2、Y3、Y4、Y5、Y6And Y7Preferred compositions as described in Table 1.
[table 1]
Y1 Y2 Y3 Y4 Y5 Y6 Y7
2-1a Singly-bound -CH2- Hydrogen atom Oxygen atom Hydrogen atom -CH2- Singly-bound
2-2a -O- -CH2- Hydrogen atom Oxygen atom Hydrogen atom -CH2- -O-
2-3a -S- -CH2- Hydrogen atom Oxygen atom Hydrogen atom -CH2- -S-
2-4a Singly-bound -CH2CH2- Hydrogen atom Oxygen atom Hydrogen atom -CH2CH2- Singly-bound
2-5a -O- -CH2CH2- Hydrogen atom Oxygen atom Hydrogen atom -CH2CH2- -O-
2-6a -S- -CH2CH2- Hydrogen atom Oxygen atom Hydrogen atom -CH2CH2- -S-
2-7a Singly-bound -(CH2)3- Hydrogen atom Oxygen atom Hydrogen atom -(CH2)3- Singly-bound
2-8a -O- -(CH2)3- Hydrogen atom Oxygen atom Hydrogen atom -(CH2)3- -O-
2-9a -S- -(CH2)3- Hydrogen atom Oxygen atom Hydrogen atom -(CH2)3- -S-
2-10a Singly-bound -(CH3)2- Hydrogen atom Oxygen atom Hydrogen atom -(CH3)2- Singly-bound
2-11a -O- -(CH3)2- Hydrogen atom Oxygen atom Hydrogen atom -(CH3)2- -O-
2-12a -S- -(CH3)2- Hydrogen atom Oxygen atom Hydrogen atom -(CH3)2- -S-
Wherein, it is preferred to the combination shown in formula [2-1a], formula [2-2a], formula [2-4a], formula [2-5a], formula [2-7a] and formula [2-8a].
In formula [2a], A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
As the concrete diamine compound of the specific diamine compound (2) of the present invention, the diamine compound shown in following formula [2-1a]～formula [2-3a] can be listed.
(in formula [2-1a]～formula [2-3a], A1～A6Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another).
Specific diamine compound (2) in the particular polymers (B) of the present invention is preferably 1 mole of %～95 mole % in 100 moles of % of whole diamine component.Wherein, it is preferred to 5 moles of %～95 mole %.It is more preferably 20 moles of %～80 mole %.
The specific diamine compound (2) of the present invention can according to the particular polymers (B) of present invention dissolubility in a solvent, 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 (A) of the present invention and particular polymers (B) at least any one contains particular side chain structure.
The method particular side chain structure of the present invention being directed in particular polymers (A) or particular polymers (B) is not particularly limited, 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 [3a].
In formula [3a], B represents previously described formula [3].It should be noted that the B in formula [3]1～B6As implied above with the preferred compositions of n.
In formula [3a], A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.Wherein, it is preferred to the alkylidene of hydrogen atom or carbon number 1 or 2.
In formula [3a], m represents the integer of 1～4.Wherein, it is preferred to 1.
It is the diamine compound of secondary amino group that the particular side chain diamine compound of the present invention specifically can list the such as diamine compound shown in following formula [3a-1]～formula [3a-31] and these amino.
(in formula [3a-1]～formula [3a-3], R1、R3And R5Represent-O-,-OCH independently of one another2-、-CH2O-、-COOCH2-or-CH2OCO-；In formula [3a-1]～formula [3a-3], R2、R4And R6Represent the straight-chain of carbon number 1～22 or branched alkylidene, the straight-chain of carbon number 1～22 or branched alkoxyl, the straight-chain of carbon number 1～22 or branched fluorine-containing alkylidene or fluoroalkoxy independently of one another).
(in formula [3a-4]～formula [3a-6], R1、R3And R5Represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH independently of one another2-、-CH2OCO-、-CH2O-、-OCH2-or-CH2-；In formula [3a-4]～formula [3a-6], R2、R4And R6Represent the straight-chain of carbon number 1～22 or branched alkylidene, the straight-chain of carbon number 1～22 or branched alkoxyl, the straight-chain of carbon number 1～22 or branched fluorine-containing alkylidene or fluoroalkoxy independently of one another).
(formula [3a-7] and in formula [3a-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, fluoroform alkyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl independently of one another).
(formula [3a-9] and in formula [3a-10], R1And R2Represent straight-chain or branched alkylidene, the cis-trans isomerization of the Isosorbide-5-Nitrae-cyclohexylene respectively transisomer of carbon number 3～12 independently of one another).
(formula [3a-11] and in formula [3a-12], R1And R2Represent straight-chain or branched alkylidene, 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 Isosorbide-5-Nitrae-cyclohexylene or Isosorbide-5-Nitrae-phenylene, A2For oxygen atom or-COO-* (wherein, subsidiary " * " key and A3It is bonded), A1For oxygen atom or-COO-* (wherein, subsidiary " * " key and (CH2) a2) be bonded).It addition, a1It is the integer of 0 or 1, a2It is the integer of 2～10, a3It is the integer of 0 or 1).
In above-mentioned formula [3a-1]～[3a-31], it is particularly preferred to the diamine compound of structure is formula [3a-1]～formula [3a-6], formula [3a-9]～formula [3a-13] or formula [3a-22]～formula [3a-31].
It is at least any of that the particular side chain diamine compound of the present invention may be used in particular polymers (A) and particular polymers (B), it is also possible to for two kinds of particular polymers.Wherein, it is preferable that for particular polymers (A).
Particular side chain diamine compound in the particular polymers (A) of the present invention and/or particular polymers (B) 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 particular side chain diamine compound of the present invention also dependent on the particular polymers (A) of the present invention and particular polymers (B) dissolubility in a solvent, 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.
Diamine component as the particular polymers (A) of the present invention and particular polymers (B), in the scope not damaging effect of the present invention, it is possible to use other diamine compound (also referred to as other diamine compound) beyond specific diamine compound (1), specific diamine compound (2) and particular side chain diamine compound.
nullSpecifically，2 can be listed,4-dimethyl-m-phenylenediamine、2,6-diaminotoluene、M-diaminobenzene.、P-phenylenediamine、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 '-biphenyl、3,3 '-trifluoromethyl-4,4 '-benzidine、3,4 '-benzidine、3,3 '-benzidine、2,2 '-benzidine、2,3 '-benzidine、4,4 '-diaminodiphenyl-methane、3,3 '-diaminodiphenyl-methane、3,4 '-diaminodiphenyl-methane、2,2 '-diaminodiphenyl-methane、2,3 '-diaminodiphenyl-methane、4,4 '-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、1,12-(3-amino-benzene oxygen) dodecane、Double; two (4-aminocyclohexyl) methane、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、1,11-diamino undecane or 1,12-diamino dodecane、And these amino are the diamine compound of secondary amino group.
And then, diamine compound can also use the diamine compound with carboxyl (COOH yl), hydroxyl (OH yl).
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 using the diamine compound shown in following formula [3b-1]～formula [3b-4] and these amino is the diamine compound of secondary amino group.
(in formula [3b-1], A1Represent singly-bound ,-CH2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3)-or-N (CH3) CO-, m1And m2Represent the integer of 0～4 and m independently of one another1+m2Represent the integer of 1～4；In formula [3b-2], m3And m4Represent the integer of 1～5 independently of one another；In formula [3b-3], A2Represent the straight chain of carbon number 1～5 or the alkylidene of branch, m5Represent the integer of 1～5；In formula [3b-4], A3And A4Represent singly-bound ,-CH independently of one another2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3)-or-N (CH3) CO-, m6Represent the integer of 1～4).
And, it is possible to use diamine compound has the nitrogenous heterocyclic diamine compound shown in following formula [3c] and these amino are the diamine compound of secondary amino group.
In formula [3c], D1Represent-O-,-NH-,-N (CH3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)-or-N (CH3)CO-.Wherein ,-O-,-NH-,-CONH-,-NHCO-,-CH2O-、-OCO-、-CON(CH3)-or-N (CH3) CO-is readily synthesized diamine compound, so preferably.It is more preferably-O-,-NH-,-CONH-,-NHCO-,-CH2O-,-OCO-or-CON (CH3)-.It is particularly preferably-O-,-CONH-or-CH2O-。
In formula [3c], D2Represent singly-bound, the aliphatic alkyl of carbon number 1～20, non-aromatic ring type alkyl or aromatic hydrocarbyl.
The aliphatic alkyl of carbon number 1～20 can be straight-chain, it is also possible to for branched.Furthermore it is possible to have unsaturated bond.Wherein, it is preferred to the alkylidene of carbon number 1～10.
As the concrete example of non-aromatic alkyl, 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 D in formula [3c]2, for singly-bound, the alkylidene of carbon number 1～10, cyclopropane ring, Tetramethylene. ring, Pentamethylene. ring, cyclohexane ring, cycloheptane ring, norborene ring, diamantane (obsolete) ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring or anthracene nucleus.Wherein, it is preferred to singly-bound, the alkylidene of carbon number 1～5, cyclohexane ring or phenyl ring.
In formula [3c], D3Represent singly-bound ,-O-,-NH-,-N (CH3)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-or-N (CH3)CO-、-O(CH2)m-(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 [3c], D4For nitrogenous heteroaromatic, for containing the heteroaromatic of at least 1 structure in following formula [a], formula [b] and formula [c].
(in formula [c], Z represents the alkylidene 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, benzimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, diazole ring or acridine ring etc. can be listed can list.Wherein, it is preferred to pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring or benzimidazole ring.It is more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring.
It addition, the D in formula [3c]3Preferably it is bonded to D4Not adjacent with formula [a], formula [b] and formula [c] substituent group comprised.
In formula [3c], n is the integer of 1～4, from its reactive viewpoint with tetrabasic carboxylic acid composition, it is preferred to 1 or 2.
D in formula [3c]1～D4Particularly preferably combination with n is D1Represent-CONH-, D2Represent the alkyl of carbon number 1～5, D3Represent singly-bound, D4Represent the diamine compound that imidazole ring or pyridine ring, n represent 1.
Two amino (-NH in formula [3c]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.
And then, as other diamine compound, it is possible to use the diamine compound shown in following formula [3d-1]～formula [3d-13] and these amino are the diamine compound of secondary amino group.
(in formula [3d-1]～formula [3d-4], A1～A4Represent the alkylidene of carbon number 1～22 or fluorine-containing alkylidene independently of one another).
(in formula [3d-5], A1And A3Represent-COO-,-OCO-,-CONH-,-NHCO-,-CH independently of one another2-,-O-,-CO-or-NH-, A2Represent the straight-chain of carbon number 1～22 or the straight-chain of branched alkylidene or carbon number 1～22 or branched fluorine-containing alkylidene；In formula [3d-6], A4And A6Represent-COO-,-OCO-,-CONH-,-NHCO-,-CH independently of one another2-,-O-,-CO-or-NH-, A5Represent the straight-chain of carbon number 1～22 or the straight-chain of branched alkylidene or carbon number 1～22 or branched fluorine-containing alkylidene).
(in formula [3d-7], A1And A3Represent-COO-,-OCO-,-CONH-,-NHCO-,-CH independently of one another2-,-O-,-CO-or-NH-, A2Represent the straight-chain of carbon number 1～22 or the straight-chain of branched alkylidene or carbon number 1～22 or branched fluorine-containing alkylidene；In formula [3d-8], A4And A6Represent-COO-,-OCO-,-CONH-,-NHCO-,-CH independently of one another2-,-O-,-CO-or-NH-, A5Represent the straight-chain of carbon number 1～22 or the straight-chain of branched alkylidene or carbon number 1～22 or branched fluorine-containing alkylidene).
(in formula [3d-9], A1And A3Represent-COO-,-OCO-,-CONH-,-NHCO-,-CH2-,-O-,-CO-or-NH-, A independently of one another2Represent the straight-chain of carbon number 1～22 or the straight-chain of branched alkylidene or carbon number 1～22 or branched fluorine-containing alkylidene；In formula [3d-10], A4And A6Represent-COO-,-OCO-,-CONH-,-NHCO-,-CH independently of one another2-,-O-,-CO-or-NH-, A5Represent the straight-chain of carbon number 1～22 or the straight-chain of branched alkylidene or carbon number 1～22 or branched fluorine-containing alkylidene).
(in formula [3d-11], p represents the integer of 1～10).
Other diamine compound of the present invention can also according to the particular polymers (A) of the present invention and particular polymers (B) dissolubility in a solvent, 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 particular polymers (A) and particular polymers (B) the 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 dihalide, tetrabasic carboxylic acid dialkyl compound or tetrabasic carboxylic acid dialkyl dihalide (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 ring, optionally identical or different each other.
In formula [4g], Z5And Z6Represent hydrogen atom or methyl, optionally identical or different each other.
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 formula [4a], formula [4e] or formula [4f].
Specific tetrabasic carboxylic acid composition in the particular polymers (A) of the present invention and particular polymers (B) 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 (A) of the present invention and particular polymers (B) dissolubility in a solvent, 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 (A) of the present invention and the polyimides based polymer of particular polymers (B), 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 dihalide, tetrabasic carboxylic acid dialkyl compound or tetrabasic carboxylic acid dialkyl dihalide 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 can also according to the particular polymers (A) of the present invention and particular polymers (B) dissolubility in a solvent, 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 (A)/particular polymers (B)>
In the present invention, it is used for making particular polymers (A) and particular polymers (B) the i.e. method of these polyimides based polymers is not particularly limited.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 dihalide 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 dihalide 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.
The reaction of diamine component and tetrabasic carboxylic acid composition is usually diamine component and carries out in a solvent with tetrabasic carboxylic acid composition.As the solvent now used, 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 alkylidene of carbon number 1～3；In formula [D-2], D2Represent the alkylidene of carbon number 1～3；In formula [D-3], D3Represent the alkylidene 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, 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 respectively and make it react, 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 %.Initial reaction stage carries out with high concentration, can 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 not necessarily needs to be 100%, it is possible to arbitrarily adjust 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 the method 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 being suitable to advance reaction, so preferably.As anhydride, acetic anhydride, trihemellitic acid acid anhydride or PMA etc. can be listed, wherein, when using acetic anhydride, reaction terminate after refining 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.
<aligning agent for liquid crystal>
The aligning agent for liquid crystal of the present invention is the coating solution for forming liquid crystal orientation film (also referred to as resin coating), is containing particular polymers (A), particular polymers (B) and solvent and for forming the coating solution of liquid crystal orientation film.
The particular polymers (A) 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.
The particular polymers (B) 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 or polyamic acid Arrcostab.It is more preferably polyamic acid.
Ratio about the particular polymers (A) in the aligning agent for liquid crystal of the present invention Yu particular polymers (B), relative to particular polymers (A) 100 mass parts, particular polymers (B) is preferably 0.5 mass parts～950 mass parts.Wherein, it is preferred to 10 mass parts～900 mass parts, more preferably 10 mass parts～400 mass parts.
Whole component of polymer in the aligning agent for liquid crystal of the present invention can be all particular polymers (A) and the particular polymers (B) of the present invention, it is also possible to is mixed with other polymer in addition.As polymer in addition, the polyimides based polymer of the structure with tertiary N atom without the present invention can be listed and not there is the polyimides based polymer of ad hoc structure (2).And then, also can list cellulose-based polymer, acrylic polymer, methacrylic polymer, polystyrene, polyamide or polysiloxanes etc..Now, the content of other polymer in addition is 0.5 mass parts～30 mass parts relative to particular polymers 100 mass parts particular polymers (A) and the particular polymers (B) of the present invention added up to.Wherein, it is preferred to 1 mass parts～20 mass parts.
It addition, the solvent in the aligning agent for liquid crystal of the present invention is preferably 70 mass %～99.9 mass %.This content suitably can change according to the target film thickness of the coating process of aligning agent for liquid crystal, liquid crystal orientation film.
As long as the solvent (also referred to as good solvent) that the solvent used in the aligning agent for liquid crystal of the present invention dissolves particular polymers (A) and particular polymers (B) is just not particularly limited.The following concrete example listing good solvent, but it is not limited to these examples.
Such as, N can be listed, dinethylformamide, N,N-dimethylacetamide, 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, gamma-butyrolacton.
And then, during particular polymers (A) and particular polymers (B) dissolubility height in a solvent, it is preferred to use the solvent shown in previously described formula [D-1]～formula [D-3].
Good solvent in the aligning agent for liquid crystal of the present invention is preferably the 20 mass %～99 mass % that the solvent comprised in aligning agent for liquid crystal is overall.Wherein, it is preferred to 20 mass %～90 mass %.It is more preferably 30 mass %～80 mass %.
In the aligning agent for liquid crystal of the present invention, in the scope not damaging effect of the present invention, it is possible to use the solvent (also referred to as poor solvent) that the film of liquid crystal orientation film when making coating of liquid crystalline aligning agent, surface smoothness improve.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、Dibutyl ethers、Hexyl ether、Dioxane、Ethylene glycol dimethyl ether、Ethylene glycol bisthioglycolate ethylether、Ethylene glycol bisthioglycolate butyl ether、1,2-butoxy ethane、Diethylene glycol dimethyl ether、Diethylene glycol diethyl ether、Diethylene glycol methyl ethyl ether、Diethylene glycol dibutyl 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 ether、Ethylene glycol mono hexyl ether、2-(hexyloxy) ethanol、Furfuryl alcohol、Diethylene glycol、Propylene glycol、Glycol monobutyl ether、1-(Butoxyethoxy) propanol、Propylene glycol monomethyl ether、Dipropylene glycol、DPGME、Dihydroxypropane single-ethyl ether、Dipropylene glycol dimethyl ether、Tripropylene glycol monomethyl ether、Ethylene glycol monomethyl ether acetic acid ester、Ethylene glycol monomethyl ether acetate、Ethylene glycol monobutyl ether acetas、Ethylene glycol acetate、Ethylene acetate、TC acetas、Diethylene glycol monobutyl ether acetas、2-(2-ethoxy ethoxy) ethylhexoate、Diethylene glycol acetas、Triethylene glycol、Triethylene glycol monomethyl ether、Triethylene glycol monoethyl ether、Methyl lactate、Ethyl lactate、Methyl acetate、Ethyl acetate、N-butyl acetate、Acetic acid propylene glycol monoethyl、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、Solvent etc. shown in isoamyl lactate or previously described formula [D-1]～formula [D-3].
Wherein, it is preferred to use 1-hexanol, Hexalin, 1，2-ethandiol, 1,2-PD, glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether.
These poor solvents are preferably the 1 mass %～80 mass % that the solvent comprised in aligning agent for liquid crystal is overall.Wherein, it is preferred to 10 mass %～80 mass %.It is more preferably 20 mass %～70 mass %.
The aligning agent for liquid crystal of the present invention preferably imports following cross-linked compound: there is the cross-linked compound of epoxy radicals, NCO, oxetanyl 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 oxetanyl is the cross-linked compound with the oxetanyl shown at least 2 following formula [4A].
Specifically, 58 pages of International Publication publication WO2011/132751 (2011.10.27 the is open)～59 pages disclosed cross-linked compound shown in formula [4a]～formula [4k] 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, 76 pages of International Publication publication WO2012/014898 (2012.2.2 the is open)～82 pages disclosed cross-linked compound shown in formula [5-1]～formula [5-42] 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 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 of CYMEL1125-80 etc (being three well サ イ ア Na ミ De company systems above).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 benzene phenoloid with hydroxyl or alkoxyl, include, for example out 1,3,5-tri-(methoxy) benzene, 1,2,4-tri-(i-propoxymethyl) benzene, Isosorbide-5-Nitrae-bis-(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 WO2011/132751 (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, 2-phenoxy group-2-hydroxypropyl (methyl) acrylate, 2-(methyl) acryloxy-2-hydroxypropyl phthalate, 3-chlorine-2-hydroxyl propyl group (methyl) acrylate, 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 aligning agent for liquid crystal of the present invention can be a kind, it is also possible to combine two or more.
The content of the cross-linked compound in the aligning agent for liquid crystal of the present invention 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 aligning agent for liquid crystal of the present invention, in the scope not damaging effect of the present invention, it is possible to use the compound that the film thickness uniformity of liquid crystal orientation film when making coating of liquid crystalline aligning agent, surface smoothness improve.
As the compound making the film thickness uniformity of liquid crystal orientation film, 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 aligning agent for liquid crystal, is more preferably 0.01 mass parts～1 mass parts.
And then, in the aligning agent for liquid crystal of the present invention, as promoting the electric charge in liquid crystal orientation film 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 WO2011/132751 (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 aligning agent for liquid crystal, it is preferable 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 above-mentioned particular polymers (A) and the solvent of particular polymers (B), just it is not particularly limited.
In the aligning agent for liquid crystal of the present invention, except above-mentioned poor solvent, cross-linked compound, make compound that resin coating or the film thickness uniformity of liquid crystal orientation film, surface smoothness improve and promote de-electric charge compound except, as long as in the scope not damaging effect of the present invention, then can also add for changing the dielectric substance of electrical characteristics, the conductive materials such as the dielectric constant of liquid crystal orientation film, electric conductivity.
<liquid crystal orientation film/liquid crystal represents element>
After the aligning agent for liquid crystal of the present invention can be coated on substrate and burn till, brushing process, light irradiation etc. is utilized to carry out orientation process such that it is able to as liquid crystal orientation film.It addition, when vertical orientated purposes etc., do not carry out orientation process and can also act 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.From the view point of Simplified flowsheet, it is preferred to use be formed with the substrate of ITO electrode etc. for driving liquid crystal.It addition, when the liquid crystal making reflection-type represents element, 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 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 10～100nm.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 said 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 a substrate spreads sept, being pasted on another substrate by the surface of 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 substrates 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 the polymerizable compound being polymerized because of active energy beam and at least one hankered, while to applying voltage limit between electrode 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 utilizing heating to be polymerized, heating-up temperature is 40～120 DEG C, is preferably 60～80 DEG C.Furthermore it is possible to carry out ultraviolet and heating simultaneously.
Above-mentioned liquid crystal represents that element passes through PSA (polymer stabilizing orientation, PolymerSustainedAlignment) mode and controls the tilt angle of liquid crystal molecule.In PSA mode, a small amount of photopolymerizable compound, such as photopolymerization monomer it is mixed in advance in liquid crystal material, after assembling liquid crystal cells, when liquid crystal layer is applied specific voltage, to photopolymerizable compound irradiation ultraviolet radiation etc., the polymer passing through to generate controls the tilt angle of liquid crystal molecule.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 tilt angle of liquid crystal molecule.It addition, without carrying out brushing process in PSA mode, therefore suitably form and be difficult to be processed the vertical alignment-type liquid crystal layer controlling tilt angle by brushing.
Namely, liquid crystal about the present invention represents element, said 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, by irradiation ultraviolet radiation 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: prepare to be formed with a pair substrate of liquid crystal orientation film, the liquid crystal orientation film of a 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 dripping liquid crystal on the liquid crystal aligning face be scattered with sept, adhesive substrate also carries out the method etc. sealed.
Liquid crystal is mixed with the polymerizable compound being polymerized because of heat, ultraviolet radiation.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.
After making liquid crystal cells, liquid crystal cells is applied the voltage of exchange or direct current, while heating, irradiation ultraviolet radiation, so that polymerizable compound polymerization.It is possible to control the orientation of liquid crystal molecule.
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, i.e. SC-PVA pattern: configure liquid crystal orientation film between aforementioned a pair substrate, described liquid crystal orientation film comprises the polymerizable group being polymerized because of active energy beam and at least one hankered, 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 the liquid crystal orientation film comprising the polymerizable group being polymerized because of active energy beam and at least one hankered, following method can be listed: the method being added in aligning agent for liquid crystal by the compound comprising this polymerizable group；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: prepare to be formed with a pair substrate of the liquid crystal orientation film of the present invention, the liquid crystal orientation film of a 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 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, while liquid crystal cells to be applied the voltage of exchange or direct current, limit heating, irradiation ultraviolet radiation such that it is able to control the orientation of liquid crystal molecule.
Operate as above, though the aligning agent for liquid crystal of the present invention can obtain being exposed to for a long time high temperature and light irradiate after also can show the liquid crystal orientation film of stable tilt angle.Further, even if being formed and being exposed to the reduction that also can suppress voltage retention after light irradiates for a long time and liquid crystal orientation film that the residual charge accumulated because of DC voltage quickly relaxes.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 "
Synthesis example, embodiment and comparative example use abbreviation as follows.
<for making the monomer of the polyimides based polymer of the present invention>
(specific diamine compound (1) of the present invention)
A1: the diamine compound shown in following formula [A1]
A2: the diamine compound shown in following formula [A2]
A3: the diamine compound shown in following formula [A3]
(specific diamine compound (2) of the present invention)
B1: the diamine compound shown in following formula [B1]
(the particular side chain diamine compound of the present invention)
C1:1,3-diaminourea-4-(4-(trans-4-n-heptyl cyclohexyl) phenoxy group) benzene
C2:1,3-diaminourea-4-(4-(trans-4-n-heptyl cyclohexyl) phenoxymethyl) benzene
C3:1,3-diaminourea-4-{4-(trans-4-(trans-4-n-pentyl cyclohexyl) cyclohexyl) phenoxy group } benzene
C4: the diamine compound shown in following formula [C4]
(other diamine compound)
D1: p-phenylenediamine
D2:3,5-diaminobenzoic acid
D3:1,3-diaminourea-4-octadecane oxygen base benzene
(the specific tetrabasic carboxylic acid composition of the present invention)
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]
<solvent used in the present invention>
NMP:N-N-methyl-2-2-pyrrolidone N
NEP:N-ethyl-2-pyrrolidone
γ-BL: gamma-butyrolacton
BCS: ethylene glycol monobutyl ether
PB: glycol monobutyl ether
EC: TC
DME: dipropylene glycol 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 crystal (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 900,000,150,000,100,000 and 30,000) (TOSOH Co., Ltd's system) and Polyethylene Glycol (molecular weight: about 12,000,4,000 and 1,000) (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)), add 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, and the proton peak integrating value of the peak integrating value using this proton and the NH base being derived from the amic acid occurred near 9.5ppm～10.0ppm utilizes following formula to obtain.
Acid imide rate (%)=(1-α x/y) × 100
In above-mentioned formula, x is the proton peak integrating value of the NH base being derived from amic acid, y be the peak integrating 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 (4.50g, 23.0mmol), A1 (1.85g, 9.30mmol), C1 (0.88g, 2.32mmol) and D1 (1.26g, 11.6mmol) in NMP (25.5g), 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 24,200, weight average molecular weight is 86,500.
<synthesis example 2>
Mixing E1 (4.10g, 20.9mmol), B1 (3.16g, 10.6mmol), D1 (0.46g, 4.24mmol) and D2 (0.97g, 6.35mmol) in NMP (26.1g), react 8 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 25,200, weight average molecular weight is 89,100.
<synthesis example 3>
Mixing E2 (3.96g, 15.8mmol), A1 (1.91g, 9.61mmol), C1 (6.09g, 16.0mmol) and D2 (0.97g, 6.41mmol) in NEP (32.1g), after reacting 5 hours with 80 DEG C, add E1 (3.10g, 15.8mmol) and NEP (16.0g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution (3) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 20,100, weight average molecular weight is 64,100.
<synthesis example 4>
After adding NEP in the polyamic acid solution (3) (30.0g) utilizing the synthetic method of synthesis example 3 to obtain and being diluted to 6 mass %, add acetic anhydride (3.45g) 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 (4) 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 18,500, weight average molecular weight is 49,300.
<synthesis example 5>
Mixing E2 (4.47g, 17.9mmol), B1 (3.24g, 10.9mmol), C1 (2.75g, 7.23mmol) and D2 (2.75g, 18.1mmol) in NEP (33.4g), after reacting 5 hours with 80 DEG C, add E1 (3.50g, 17.9mmol) and NEP (16.7g), 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 22,100, weight average molecular weight is 68,500.
<synthesis example 6>
After adding NEP 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 (3.40g) and pyridine (2.65g) 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 (6) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 58%, and number-average molecular weight is 19,800, weight average molecular weight is 52,900.
<synthesis example 7>
Mixing E2 (1.37g, 5.46mmol), A2 (1.18g, 5.53mmol), C2 (2.91g, 7.38mmol), D1 (0.20g, 1.84mmol) and D2 (0.56g, 3.69mmol) in NMP (17.4g), after reacting 5 hours with 80 DEG C, add E1 (2.50g, 12.8mmol) and NMP (8.72g), 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 (4.45g) and pyridine (3.30g) as imidization catalyst, react 3 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 17,100, weight average molecular weight is 47,800.
<synthesis example 8>
Mixing E2 (1.37g, 5.46mmol), B1 (1.38g, 4.61mmol), C2 (1.09g, 2.77mmol) and D2 (1.68g, 11.1mmol) in NMP (16.0g), after reacting 5 hours with 80 DEG C, add E1 (2.50g, 12.8mmol) and NMP (8.02g), 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 (3.35g) 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 (8) 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 18,800, weight average molecular weight is 49,800.
<synthesis example 9>
Mixing E3 (7.20g, 32.1mmol), A2 (2.78g, 13.0mmol), C2 (5.14g, 13.0mmol) and D2 (0.99g, 6.51mmol) in NEP (48.3g), react 8 hours with 40 DEG C, thus obtaining the polyamic acid solution (9) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 21,200, weight average molecular weight is 65,400.
<synthesis example 10>
After adding NEP in the polyamic acid solution (9) (30.0g) utilizing the synthetic method of synthesis example 9 to obtain and being diluted to 6 mass %, add acetic anhydride (3.40g) and pyridine (2.63g) 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 57%, and number-average molecular weight is 18,200, weight average molecular weight is 48,300.
<synthesis example 11>
Mixing E3 (3.85g, 17.2mmol), A3 (0.53g, 2.61mmol), C4 (2.14g, 4.35mmol) and D2 (1.59g, 10.4mmol) in NMP (24.3g), 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 (3.90g) and pyridine (2.65g) 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 (11) 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 17,500, weight average molecular weight is 47,900.
<synthesis example 12>
Mixing E4 (1.64g, 5.46mmol), B1 (1.65g, 5.53mmol), C1 (1.40g, 3.69mmol), D1 (0.20g, 1.84mmol) and D2 (1.12g, 7.38mmol) in NMP (17.0g), after reacting 6 hours with 80 DEG C, add E1 (2.50g, 12.8mmol) and NMP (8.52g), 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 (4.15g) and pyridine (2.95g) as imidization catalyst, react 3 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 (12) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 64%, and number-average molecular weight is 18,100, weight average molecular weight is 49,600.
<synthesis example 13>
Mixing E4 (2.87g, 9.56mmol), A3 (0.98g, 4.84mmol), C3 (2.44g, 5.65mmol), D1 (0.26g, 2.42mmol) and D2 (0.49g, 3.23mmol) in NEP (16.6g), after reacting 6 hours with 80 DEG C, add E1 (1.25g, 6.37mmol) and NEP (8.30g), 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 (4.55g) and pyridine (3.35g) as imidization catalyst, react 3 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 (13) 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 16,300, weight average molecular weight is 45,100.
<synthesis example 14>
Mixing E4 (3.57g, 11.9mmol), A1 (1.37g, 6.89mmol), C4 (1.70g, 3.44mmol) and D2 (1.05g, 6.89mmol) in NMP (17.4g), after reacting 6 hours with 80 DEG C, add E1 (1.00g, 5.10mmol) and NMP (8.69g), 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 (3.75g) and pyridine (2.35g) as imidization catalyst, react 3 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 (14) 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 17,800, weight average molecular weight is 48,900.
<synthesis example 15>
Mixing E2 (1.73g, 6.91mmol), A1 (0.70g, 3.50mmol), A2 (0.75g, 3.50mmol), C2 (2.76g, 7.00mmol) and D2 (0.53g, 3.50mmol) in NMP (17.3g), after reacting 6 hours with 80 DEG C, add E5 (2.20g, 10.4mmol) and NMP (8.67g), react 6 hours with 80 DEG C, thus obtaining the polyamic acid solution (15) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 20,100, weight average molecular weight is 62,600.
<synthesis example 16>
Mixing E2 (0.88g, 3.54mmol), B1 (1.60g, 5.37mmol), C1 (1.36g, 3.58mmol) and D2 (1.36g, 8.95mmol) in NMP (16.4g), after reacting 6 hours with 80 DEG C, add E5 (3.00g, 14.1mmol) and NMP (8.21g), react 6 hours with 80 DEG C, thus obtaining the polyamic acid solution (16) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 21,600, weight average molecular weight is 65,100.
<synthesis example 17>
After adding NMP in the polyamic acid solution (16) (30.0g) utilizing the synthetic method of synthesis example 16 to obtain and being diluted to 6 mass %, add acetic anhydride (4.50g) and pyridine (3.30g) as imidization catalyst, react 3 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 81%, and number-average molecular weight is 18,800, weight average molecular weight is 52,200.
<synthesis example 18>
Mixing E2 (1.73g, 6.91mmol), A3 (0.89g, 4.38mmol), C3 (2.65g, 6.13mmol) and D2 (1.07g, 7.00mmol) in NEP (17.1g), after reacting 6 hours with 80 DEG C, add E5 (2.20g, 10.4mmol) and NEP (8.54g), 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 (4.10g) and pyridine (3.05g) as imidization catalyst, react 2.5 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 (18) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 74%, and number-average molecular weight is 17,900, weight average molecular weight is 48,300.
<synthesis example 19>
Mixing E2 (0.80g, 3.18mmol), A1 (0.96g, 4.83mmol), C1 (3.37g, 8.86mmol) and D2 (0.37g, 2.42mmol) in NMP (16.4g), after reacting 6 hours with 80 DEG C, add E5 (2.70g, 12.7mmol) and NMP (8.20g), 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 (3.75g) 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 (19) 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 16,800, weight average molecular weight is 46,200.
<synthesis example 20>
Mixing E1 (5.00g, 25.5mmol), C1 (0.98g, 2.58mmol) and D1 (2.51g, 23.2mmol) in NMP (25.5g), react 8 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 25,800, weight average molecular weight is 88,900.
<synthesis example 21>
Mixing E1 (5.00g, 25.5mmol), D1 (1.96g, 18.1mmol) and D2 (1.18g, 7.75mmol) in NMP (24.4g), react 8 hours with 40 DEG C, thus obtaining the polyamic acid solution (21) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 27,100, weight average molecular weight is 90,100.
<synthesis example 22>
Mixing E2 (4.08g, 16.3mmol), C1 (6.29g, 16.5mmol), D1 (1.07g, 9.92mmol) and D2 (1.01g, 6.61mmol) in NEP (31.3g), after reacting 5 hours with 80 DEG C, add E1 (3.20g, 16.3mmol) and NEP (15.7g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution (22) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 22,500, weight average molecular weight is 66,900.
<synthesis example 23>
After adding NEP in the polyamic acid solution (22) (30.0g) utilizing the synthetic method of synthesis example 22 to obtain and being diluted to 6 mass %, add acetic anhydride (3.40g) 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 (23) 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 19,200, weight average molecular weight is 50,600.
<synthesis example 24>
Mixing E2 (4.72g, 18.9mmol), C1 (2.91g, 7.64mmol), D1 (1.24g, 11.5mmol) and D2 (2.91g, 19.1mmol) in NEP (31.0g), after reacting 5 hours with 80 DEG C, add E1 (3.70g, 18.9mmol) and NEP (15.5g), react 6 hours with 40 DEG C, thus obtaining the polyamic acid solution (24) that resin solid content concentration is 25 mass %.The number-average molecular weight of this polyamic acid is 23,000, weight average molecular weight is 68,800.
<synthesis example 25>
After adding NEP in the polyamic acid solution (24) (30.0g) utilizing the synthetic method of synthesis example 24 to obtain and being diluted to 6 mass %, add acetic anhydride (3.40g) and pyridine (2.65g) 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 (25) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 57%, and number-average molecular weight is 20,100, weight average molecular weight is 54,100.
<synthesis example 26>
Mixing E2 (2.04g, 8.16mmol), A1 (0.99g, 4.96mmol), D2 (0.50g, 3.31mmol) and D3 (3.11g, 8.26mmol) in NEP (16.5g), after reacting 5 hours with 80 DEG C, add E1 (1.60g, 8.16mmol) and NEP (8.25g), 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 (3.45g) and pyridine (2.65g) 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 (26) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 54%, and number-average molecular weight is 17,600, weight average molecular weight is 49,200.
<synthesis example 27>
Mixing E2 (2.23g, 8.92mmol), B1 (1.62g, 5.42mmol), D2 (1.38g, 9.04mmol) and D3 (1.36g, 3.62mmol) in NEP (16.7g), after reacting 5 hours with 80 DEG C, add E1 (1.75g, 8.92mmol) and NEP (8.34g), 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 (3.45g) and pyridine (2.65g) 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 (27) so that 100 DEG C carry out drying under reduced pressure.The acid imide rate of this polyimides is 57%, and number-average molecular weight is 18,600, weight average molecular weight is 51,500.
The polyimides based polymer of the present invention is shown in table 2～table 4.
[table 2]
* 1: polyamic acid.
[table 3]
* 1: polyamic acid.
[table 4]
* 1: polyamic acid.
" manufacture of the aligning agent for liquid crystal of the present invention "
In following embodiment 1～embodiment 19 and comparative example 1～comparative example 8, record the manufacture example of aligning agent for liquid crystal.It addition, this aligning agent for liquid crystal is additionally operable to be evaluated.
The aligning agent for liquid crystal of the present invention is shown in table 5～table 7.
Use the aligning agent for liquid crystal obtained in examples and comparative examples of the present invention, carry out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning ".
" evaluation of the ink-jet application of aligning agent for liquid crystal "
The aligning agent for liquid crystal (15) obtained in the aligning agent for liquid crystal (9) obtained in the aligning agent for liquid crystal (4) obtained in embodiments of the invention 4, embodiment 9 and embodiment 15 is carried out pressure filtration with the membrane filter that aperture is 1 μm, carries out the evaluation of ink-jet application.Ink-jet application machine uses HIS-200 (HitachiPlantTechnologies, Ltd. system).About coating, be deposited with on substrate at the ITO (tin indium oxide) through cleaning with pure water and IPA, to utilize nozzle pitch be 0.423mm, sweep spacing is 0.5mm, coating speed is the 40mm/ second, from coating time to predrying be 60 seconds, predrying carry out with the condition of 70 DEG C for 5 minutes on hot plate.
Confirm the film of the substrate of resulting tape liquid crystal orientation film.Specifically, undertaken by visualization film under sodium vapor lamp, confirm the presence or absence of pin hole.Its result, the liquid crystal orientation film obtained in any embodiment does not all observe pin hole on film, it is possible to obtain the liquid crystal orientation film that film is excellent.
" making of liquid crystal cells and the evaluation (normal cells) of tilt angle "
The membrane filter that aligning agent for liquid crystal aperture is 1 μm obtained in examples and comparative examples of the present invention is carried out pressure filtration, carries out the making (normal cells) of liquid crystal cells.This solution is spun on the ito surface of the substrate (indulging 40mm × horizontal 30mm, thickness 0.7mm) with ITO electrode of 40 × 30mm through cleaning with pure water and IPA, with 100 DEG C of heat treated 5 minutes on hot plate, utilize thermal cycle type cleaning baking oven with 230 DEG C of heat treated 30 minutes, thus obtaining the ito substrate with the polyimide liquid crystal direct action membrane that thickness is 100nm.It should be noted that, utilize the aligning agent for liquid crystal (15) obtained in the aligning agent for liquid crystal (9) obtained in the aligning agent for liquid crystal (4) obtained in embodiments of the invention 4, embodiment 9 and embodiment 15, identical with above-mentioned " evaluation of the ink-jet application of aligning agent for liquid crystal " when, make the substrate with liquid crystal orientation film, thereafter, baking oven is cleaned with 230 DEG C of heat treated 30 minutes, thus obtaining the ito substrate with the polyimide liquid crystal direct action membrane that thickness is 100nm by thermal cycle type.
Utilize the brushing device that roller diameter is 120mm, use artificial silk cloth, when roller rotating speed to be 1000rpm, roller pace be 50mm/ second, intrusion are 0.1mm, the coated surface of this ito substrate is carried out brushing process.
Prepare the ito substrate of 2 resulting tape liquid crystal orientation films, be combined towards the sept of inner side clamping 6 μm with the surface of liquid crystal orientation film, around make dummy cell with sealant is bonding.Inject by reducing pressure in this dummy cell of normal direction and inject nematic liquid crystal, inlet is sealed and obtains liquid crystal cells (normal cells).
It should be noted that, employing in the liquid crystal cells of the aligning agent for liquid crystal (21) obtained in the aligning agent for liquid crystal (1) and comparative example (1) obtained in embodiment 1, liquid crystal employs MLC-2003 (MERCKCORPORATION system).It addition, employ in the unit of the aligning agent for liquid crystal obtained in embodiment in addition and comparative example, liquid crystal employs MLC-6608 (MERCKCORPORATION system).
Then, the tilt angle carrying out this liquid crystal cells (normal cells) measures.Tilt angle so measures: carry out after the isotropism of liquid crystal processes (with 95 DEG C of heat treated 5 minutes), is heated processing (with 120 DEG C of heat treated 5 hours) to it, then liquid crystal cells is measured.
And then, after carrying out isotropism process for the liquid crystal cells made when same as described above, irradiate and be scaled 10J/cm with 365nm2Ultraviolet after, also liquid crystal cells is measured.It should be noted that tilt angle uses PAS-301 (ELSICON company system) to be at room temperature measured.And then, ultraviolet irradiation uses desktop UV solidification equipment (HCT3B28HEX-1) (セ Application ラ イ ト company system) to carry out.
About evaluation, the tilt angle after isotropism processes (after processing also referred to as Iso) relative to liquid crystal, after having carried out heat treated, (after high-temperature process) and after irradiation ultraviolet radiation, the change of tilt angle (after ultraviolet radiation) is little, then regard as good (table 8～table 10 illustrate Iso process after, the value of tilt angle after high-temperature process and after ultraviolet radiation).
Table 8～table 10 illustrates the result obtained in embodiment and comparative example.
" evaluation (normal cells) of voltage retention "
The liquid crystal cells (normal cells) made when being used in identical with above-mentioned " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", carries out the evaluation of voltage retention.Specifically, at the temperature of 80 DEG C, the liquid crystal cells (normal cells) utilizing said method to obtain is applied the 1V voltage of 60 μ s, measure the voltage after 50ms, can keep voltage to which kind of degree being calculated as voltage retention (also referred to as 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 terminating for the mensuration of the voltage retention after above-mentioned firm making liquid crystal cells, use desktop UV solidification equipment (HCT3B28HEX-1) (セ Application ラ イ ト company system), irradiate and be scaled 50J/cm with 365nm2Ultraviolet, when same as described above, carry out the mensuration of voltage retention.
About evaluation, just make the voltage retention value after liquid crystal cells high, and the voltage retention value after ultraviolet radiation is little relative to the reduction degree of the voltage retention value after just making liquid crystal cells, then regard as good (table 11～table 13 illustrates the VHR value just made after liquid crystal cells and after ultraviolet radiation).
Table 11～table 13 illustrates the result obtained in embodiment and comparative example.
" evaluation (normal cells) of the mitigation of residual charge "
The liquid crystal cells (normal cells) made when being used in identical with above-mentioned " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", carries out the evaluation of the mitigation of residual charge.Specifically, liquid crystal cells is applied the DC voltage 10V of 30 minutes so that it is after short-circuit 1 second, for the potential measurement of generation 1800 seconds in liquid crystal cells.Wherein, the residual charge value after using 50 seconds, it is denoted as the evaluation of the mitigation of residual charge.6254 types liquid crystal evaluation of physical property device (TOYOCorporation system) are employed it should be noted that measure.
And then, the liquid crystal cells after terminating for the mensuration of the residual charge after above-mentioned firm making liquid crystal cells, use desktop UV solidification equipment (HCT3B28HEX-1) (セ Application ラ イ ト company system), irradiate and be scaled 30J/cm with 365nm2Ultraviolet, when same as described above, carry out the mensuration of residual charge.
About evaluation, the residual charge value just made after liquid crystal cells and after ultraviolet radiation is little, then regard as good (table 11～table 13 illustrates the residual charge value just made after liquid crystal cells and after ultraviolet radiation).
Table 11～table 13 illustrates the result obtained in embodiment and comparative example.
" making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning "
The aligning agent for liquid crystal (16) obtained in the aligning agent for liquid crystal (8) obtained in the aligning agent for liquid crystal (6) obtained in the aligning agent for liquid crystal (5) obtained in the aligning agent for liquid crystal (3) obtained in embodiment 3, embodiment 5, embodiment 6, embodiment 8 and embodiment 16 is carried out pressure filtration with the membrane filter that aperture is 1 μm, carries out the making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning.This solution is spun on the ito surface of the substrate (indulging 40mm × horizontal 30mm, thickness 0.7mm) of the ITO electrode of the substrate through the ITO electrode with the center band 10 × 10mm of pure water and IPA and pattern spacing 20 μm (vertical 40mm × horizontal 30mm, thickness 0.7mm) and center band 10 × 40mm, with 100 DEG C of heat treated 5 minutes on hot plate, baking oven is cleaned with 230 DEG C of heat treated 30 minutes, thus thickness is the polyimide coating film of 100nm by thermal cycle type.
Substrate with this liquid crystal orientation film is combined facing to the sept of inner side clamping 6 μm with liquid crystal orientation film, around makes 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 obtain with the polymerizable compound (1) shown in following formula relative to nematic liquid crystal (MLC-6608) 100 mass % mode mixed polymerization compound (1) being 0.3 mass % in nematic liquid crystal (MLC-6608) (MERCKCORPORATION system), 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 liquid crystal aligning direction 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 of absorbance 90%～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.
<embodiment 1>
NMP (18.2g) and BCS (8.16g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (1) (5.00g) utilizing the synthetic method of synthesis example 1 to obtain and the polyamic acid solution that resin solid content concentration is 25 mass % (2) (3.33g) utilizing the synthetic method of synthesis example 2 to obtain, stir 6 hours with 25 DEG C, thus obtaining aligning agent for liquid crystal (1).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (1), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 2>
NEP (14.4g) and PB (14.1g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (3) (4.50g) utilizing the synthetic method of synthesis example 3 to obtain and the polyamic acid solution that resin solid content concentration is 25 mass % (5) (4.50g) utilizing the synthetic method of synthesis example 5 to obtain, stir 6 hours with 25 DEG C, thus obtaining aligning agent for liquid crystal (2).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (2), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 3>
In the polyimide powder (4) (1.15g) utilizing the synthetic method of synthesis example 4 to obtain and the polyimide powder (6) (1.15g) utilizing the synthetic method of synthesis example 6 to obtain, add NEP (21.6g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (14.4g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (3).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (3), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning ".
<embodiment 4>
In the polyimide powder (4) (0.65g) utilizing the synthetic method of synthesis example 4 to obtain and the polyimide powder (6) (0.43g) utilizing the synthetic method of synthesis example 6 to obtain, add NEP (14.9g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (5.97g), PB (8.96g) and K1 (0.032g), stirring 6 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (4).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (4), carry out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 5>
In the polyimide powder (7) (1.65g) utilizing the synthetic method of synthesis example 7 to obtain and the polyimide powder (8) (0.71g) utilizing the synthetic method of synthesis example 8 to obtain, add NMP (20.3g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (12.9g) and DME (3.69g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (5).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (5), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning ".
<embodiment 6>
NEP (14.0g), PB (10.3g) and EC (3.43g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (9) (3.50g) utilizing the synthetic method of synthesis example 9 to obtain and the polyamic acid solution that resin solid content concentration is 25 mass % (5) (5.25g) utilizing the synthetic method of synthesis example 5 to obtain, stir 6 hours with 25 DEG C, thus obtaining aligning agent for liquid crystal (6).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (6), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning ".
<embodiment 7>
In the polyimide powder (10) (1.75g) utilizing the synthetic method of synthesis example 10 to obtain, add NEP (15.0g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (11.0g) and DME (1.37g), stirring 4 hours with 40 DEG C, thus obtaining solution.
On the other hand, in the polyimide powder (6) (0.44g) utilizing the synthetic method of synthesis example 6 to obtain, add NEP (3.80g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (2.70g) and DME (0.34g), stirring 4 hours with 40 DEG C, thus obtaining solution.
By 2 kinds of solution mixing obtained above, adding K1 (0.153g) further, stirring 6 hours with 40 DEG C, thus obtaining liquid crystal to join aligning agent (7).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (7), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 8>
In the polyimide powder (11) (0.75g) utilizing the synthetic method of synthesis example 11 to obtain and the polyimide powder (8) (1.39g) utilizing the synthetic method of synthesis example 8 to obtain, add NMP (6.71g) and NEP (13.4g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (13.4g) and K1 (0.107g), stirring 6 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (8).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (8), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning ".
<embodiment 9>
In the polyimide powder (11) (0.55g) utilizing the synthetic method of synthesis example 11 to obtain and the polyimide powder (8) (0.83g) utilizing the synthetic method of synthesis example 8 to obtain, add NEP (15.2g) and γ-BL (3.79g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (15.2g) and DME (3.79g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (9).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (9), carry out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 10>
In the polyimide powder (4) (1.10g) utilizing the synthetic method of synthesis example 4 to obtain, add NMP (1.73g) and NEP (6.90g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (1.73g) and PB (6.90g), stirring 4 hours with 40 DEG C, thus obtaining solution.
On the other hand, in the polyimide powder (12) (1.10g) utilizing the synthetic method of synthesis example 12 to obtain, add NMP (1.73g) and NEP (6.90g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (1.73g) and PB (6.90g), stirring 4 hours with 40 DEG C, thus obtaining solution.
By 2 kinds of solution mixing obtained above, stir 6 hours with 25 DEG C, thus obtaining aligning agent for liquid crystal (10).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (10), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 11>
In the polyimide powder (13) (1.25g) utilizing the synthetic method of synthesis example 13 to obtain and the polyimide powder (8) (0.83g) utilizing the synthetic method of synthesis example 8 to obtain, add NEP (13.1g) and γ-BL (3.26g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (13.1g) and EC (3.26g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (11).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (11), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 12>
In the polyimide powder (10) (0.65g) utilizing the synthetic method of synthesis example 10 to obtain and the polyimide powder (8) (1.52g) utilizing the synthetic method of synthesis example 8 to obtain, add NMP (17.0g) and γ-BL (1.70g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (6.79g) and PB (8.49g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (12).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (12), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 13>
NMP (14.4g), BCS (3.53g), PB (10.6g) and K1 (0.225g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (15) (4.50g) utilizing the synthetic method of synthesis example 15 to obtain and the polyamic acid solution that resin solid content concentration is 25 mass % (16) (4.50g) utilizing the synthetic method of synthesis example 16 to obtain, stir 6 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (13).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (13), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 14>
In the polyimide powder (7) (0.90g) utilizing the synthetic method of synthesis example 7 to obtain and the polyimide powder (17) (1.35g) utilizing the synthetic method of synthesis example 17 to obtain, add NEP (15.9g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (5.29g) and PB (14.1g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (14).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (14), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 15>
In the polyimide powder (7) (0.55g) utilizing the synthetic method of synthesis example 7 to obtain and the polyimide powder (17) (0.83g) utilizing the synthetic method of synthesis example 17 to obtain, add NMP (3.79g) and NEP (15.2g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (19.0g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (15).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (15), carry out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 16>
In the polyimide powder (18) (1.25g) utilizing the synthetic method of synthesis example 18 to obtain, add NMP (8.82g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (2.94g) and PB (7.86g), stirring 4 hours with 40 DEG C, thus obtaining solution.
On the other hand, in the polyimide powder (17) (0.83g) utilizing the synthetic method of synthesis example 17 to obtain, add NMP (5.88g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (1.96g) and PB (5.24g), stirring 4 hours with 40 DEG C, thus obtaining solution.
By 2 kinds of solution mixing obtained above, stir 4 hours with 25 DEG C, thus obtaining aligning agent for liquid crystal (16).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (16), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning ".
<embodiment 17>
In the aligning agent for liquid crystal (16) (20.0g) utilizing the preparation method of embodiment 16 to obtain, adding K1 (0.06g), stirring 6 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (17).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (17), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 18>
In the polyimide powder (19) (0.45g) utilizing the synthetic method of synthesis example 19 to obtain and the polyimide powder (6) (1.80g) utilizing the synthetic method of synthesis example 6 to obtain, add NEP (21.2g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (3.53g) and PB (10.6g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (18).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (18), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<embodiment 19>
In the polyimide powder (19) (1.63g) utilizing the synthetic method of synthesis example 19 to obtain and the polyamic acid solution that resin solid content concentration is 25 mass % (5) (6.50g) utilizing the synthetic method of synthesis example 5 to obtain, add NEP (19.4g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding BCS (6.47g) and PB (6.47g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (19).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (19), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<comparative example 1>
NMP (18.0g) and BCS (8.08g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (20) (4.95g) utilizing the synthetic method of synthesis example 20 to obtain and the polyamic acid solution that resin solid content concentration is 25 mass % (21) (3.30g) utilizing the synthetic method of synthesis example 21 to obtain, stir 6 hours with 25 DEG C, thus obtaining aligning agent for liquid crystal (20).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (20), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<comparative example 2>
NEP (14.4g) and PB (14.1g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (3) (4.50g) utilizing the synthetic method of synthesis example 3 to obtain and the polyamic acid solution that resin solid content concentration is 25 mass % (24) (4.50g) utilizing the synthetic method of synthesis example 24 to obtain, stir 6 hours with 25 DEG C, thus obtaining aligning agent for liquid crystal (21).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (21), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<comparative example 3>
NEP (14.4g) and PB (14.1g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (22) (4.50g) utilizing the synthetic method of synthesis example 22 to obtain and the polyamic acid solution that resin solid content concentration is 25 mass % (5) (4.50g) utilizing the synthetic method of synthesis example 5 to obtain, stir 6 hours with 25 DEG C, thus obtaining aligning agent for liquid crystal (22).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (22), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<comparative example 4>
NEP (14.4g) and PB (14.1g) is added in the polyamic acid solution that resin solid content concentration is 25 mass % (22) (4.50g) utilizing the synthetic method of synthesis example 22 to obtain and the polyamic acid solution that resin solid content concentration is 25 mass % (24) (4.50g) utilizing the synthetic method of synthesis example 24 to obtain, stir 6 hours with 25 DEG C, thus obtaining aligning agent for liquid crystal (23).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (23), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<comparative example 5>
In the polyimide powder (4) (1.10g) utilizing the synthetic method of synthesis example 4 to obtain and the polyimide powder (25) (1.10g) utilizing the synthetic method of synthesis example 25 to obtain, add NEP (20.7g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (13.8g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (24).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (24), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<comparative example 6>
In the polyimide powder (23) (1.10g) utilizing the synthetic method of synthesis example 23 to obtain and the polyimide powder (6) (1.10g) utilizing the synthetic method of synthesis example 6 to obtain, add NEP (20.7g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (13.8g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (25).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (25), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<comparative example 7>
In the polyimide powder (23) (1.10g) utilizing the synthetic method of synthesis example 23 to obtain and the polyimide powder (25) (1.10g) utilizing the synthetic method of synthesis example 25 to obtain, add NEP (20.7g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (13.8g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (26).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (26), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
<comparative example 8>
In the polyimide powder (26) (1.10g) utilizing the synthetic method of synthesis example 26 to obtain and the polyimide powder (27) (1.10g) utilizing the synthetic method of synthesis example 27 to obtain, add NEP (20.7g), make it dissolve so that 70 DEG C are stirred 24 hours.In this solution, adding PB (13.8g), stirring 4 hours with 40 DEG C, thus obtaining aligning agent for liquid crystal (27).This aligning agent for liquid crystal not observed, muddiness, precipitation etc. are abnormal, confirms as uniform solution.
Use gained aligning agent for liquid crystal (27), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".
[table 5]
* 1: represent the particular polymers (A) import volume (mass parts) relative to whole polymer 100 mass parts.
* 2: represent the particular polymers (B) import volume (mass parts) relative to whole polymer 100 mass parts.
* 3: represent other polymer phase import volume (mass parts) for whole polymer 100 mass parts.
* 4: represent the cross-linked compound import volume (mass parts) relative to whole polymer 100 mass parts.
* 5: represent each solvent import volume (mass parts) relative to whole solvent 100 mass parts.
* 6: represent the ratio that whole polymer is shared in aligning agent for liquid crystal.
[table 6]
* 1: represent the particular polymers (A) import volume (mass parts) relative to whole polymer 100 mass parts.
* 2: represent the particular polymers (B) import volume (mass parts) relative to whole polymer 100 mass parts.
* 3: represent other polymer phase import volume (mass parts) for whole polymer 100 mass parts.
* 4: represent the cross-linked compound import volume (mass parts) relative to whole polymer 100 mass parts.
* 5: represent the import volume (mass parts) of each solvent whole solvent 100 mass parts.
* 6: represent the ratio that whole polymer is shared in aligning agent for liquid crystal.
[table 7]
* 1: represent the particular polymers (A) import volume (mass parts) relative to whole polymer 100 mass parts.
* 2: represent the particular polymers (B) import volume (mass parts) relative to whole polymer 100 mass parts.
* 3: represent other polymer phase import volume (mass parts) for whole polymer 100 mass parts.
* 4: represent the cross-linked compound import volume (mass parts) relative to whole polymer 100 mass parts.
* 5: represent each solvent import volume (mass parts) relative to whole solvent 100 mass parts.
* 6: represent the ratio that whole polymer is shared in aligning agent for liquid crystal.
[table 8]
[table 9]
[table 10]
[table 11]
[table 12]
[table 13]
From the above results: compared with the aligning agent for liquid crystal of comparative example, in the aligning agent for liquid crystal of embodiments of the invention, even if liquid crystal cells being carried out high-temperature process and ultraviolet radiation, display that stable tilt angle.And then it is presented below as result: even if carrying out ultraviolet radiation, also can suppress the reduction of voltage retention, and the residual charge accumulated because of DC voltage quickly relaxes.Namely, even if the aligning agent for liquid crystal of the present invention can form the liquid crystal orientation film also being able to show stable tilt angle after being exposed to high temperature and light irradiation for a long time, further, it is exposed to after light irradiates for a long time also to be able to suppress the liquid crystal orientation film that voltage retention reduces and the residual charge accumulated because of DC voltage quickly relaxes even if can be formed.
Specifically, employ the contrast of the embodiment of the particular polymers (A) of the present invention and the aligning agent for liquid crystal of particular polymers (B) and the embodiment of the aligning agent for liquid crystal only using one of which, i.e. the contrast of the contrast of embodiment 2 and comparative example 2 or comparative example 3 and embodiment 3 and comparative example 5 or comparative example 6.These only used the comparative example of particular polymers (A) or only used the comparative example of particular polymers (B) compared with corresponding embodiment, voltage retention especially relative to ultraviolet radiation is greatly reduced, and the value of residual charge also becomes big in addition.
Additionally, the comparative example of the embodiment employing the particular polymers (A) of the present invention and the aligning agent for liquid crystal of particular polymers (B) and the polymer employing the structure with tertiary N atom without the present invention and the aligning agent for liquid crystal of the polymer without ad hoc structure (2), i.e. the contrast of embodiment 1 and the contrast of comparative example 1, the contrast of embodiment 2 and comparative example 4 and embodiment 3 and comparative example 7.These comparative examples are compared with corresponding embodiment, and the voltage retention especially relative to ultraviolet radiation is greatly reduced, and the value of residual charge also becomes big in addition.
And, employ the embodiment of the particular polymers (A) of the present invention and the aligning agent for liquid crystal of particular polymers (B) and the contrast of the comparative example of the aligning agent for liquid crystal employing the polymer with conventional type side-chain structure, i.e. the contrast of embodiment 3 and comparative example 8.This comparative example is compared with corresponding embodiment, and the amplitude of variation carrying out the tilt angle after high-temperature process and ultraviolet radiation is relatively big, and is greatly reduced relative to the voltage retention of ultraviolet radiation, and the value of residual charge also becomes big in addition.Wherein, especially the reduction of voltage retention is obvious.
Industrial applicability
Even if the aligning agent for liquid crystal of the present invention can provide the liquid crystal orientation film that also can show stable tilt angle after being exposed to high temperature and light irradiation for a long time.Even if also can suppress, further, it is possible to provide to be exposed to for a long time after light irradiates, the liquid crystal orientation film that voltage retention reduces and the residual charge accumulated because of DC voltage quickly relaxes.And, it is possible to provide the liquid crystal with above-mentioned liquid crystal orientation film represents element, can provide the aligning agent for liquid crystal of above-mentioned liquid crystal orientation film.
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, the LCD TV etc. of big picture and high-resolution can be suitably employed in, for TN element, STN element, TFT liquid crystal cell, especially vertical orientating type liquid crystal represent that element is useful.
And then, the aligning agent for liquid crystal of the present invention for needing the liquid crystal of irradiation ultraviolet radiation when making liquid crystal and representing element, the liquid crystal orientation film obtained represents that element is also useful.Namely, following liquid crystal is represented that element is also useful: there is liquid crystal layer between a pair substrate possessing electrode and the liquid crystal that manufactures via following operation represents element, liquid-crystal composition is configured between aforementioned a pair substrate, described liquid-crystal composition comprises the polymerizable compound being polymerized because of active energy beam and at least one hankered, while make aforementioned polymeric compound polymerization to applying voltage limit between former electrodes；And, there is liquid crystal layer between a pair substrate possessing electrode and the liquid crystal that manufactures via following operation represents element, liquid crystal orientation film is configured between aforementioned a pair substrate, described liquid crystal orientation film comprises the polymerizable group being polymerized because of active energy beam and at least one hankered, while make aforementioned polymeric radical polymerisation to applying voltage limit between former electrodes.

Claims (24)

1. an aligning agent for liquid crystal, it contains following (A) composition and (B) composition:
(A) composition: containing at least any of polymer in polyimide precursor and polyimides, described polyimide precursor and polyimides have the structure with nitrogen-atoms,
(B) composition: containing at least any of polymer in polyimide precursor and polyimides, described polyimide precursor and polyimides have the structure shown in following formula [2],
Wherein, in the polymer of (A) composition and (B) composition at least any one contains the structure shown in following formula [3],
In formula [2], Y1And Y7Represent singly-bound independently of one another, selected from the alkylidene of carbon number 1～10 ,-O-,-N (R1)-、-CON(R2)-、-N(R3)CO-、-CH2At least one organic group in O-,-COO-and-OCO-, wherein, R1Represent the alkylidene of hydrogen atom or carbon number 1～3, R2Represent the alkylidene of hydrogen atom or carbon number 1～3, R3Represent the alkylidene of hydrogen atom or carbon number 1～3；Y2And Y6Represent the alkylidene of carbon number 1～10 independently of one another；Y3And Y5Represent the alkylidene of hydrogen atom or carbon number 1～10 independently of one another；Y4Represent oxygen atom or sulphur atom,
In formula [3], B1Represent singly-bound ,-(CH2)a-、-O-、-CH2O-,-COO-or-OCO-, wherein, a is the integer of 1～15；B2Represent singly-bound or-(CH2)b-, wherein, b is the integer of 1～15；B3Represent singly-bound ,-(CH2)c-、-O-、-CH2O-,-COO-or-OCO-, wherein, c is the integer of 1～15；B4Representing the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle or have the divalent organic group of carbon number 17～51 of 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；B5Representing the divalent cyclic group in phenyl ring, cyclohexane ring or 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；B6Represent the fluoroalkoxy containing fluoroalkyl, the alkoxyl of carbon number 1～18 or carbon number 1～18 of the alkyl of carbon number 1～18, carbon number 1～18.
2. aligning agent for liquid crystal according to claim 1, wherein, the structure with nitrogen-atoms in described (A) composition is at least one structure in structure shown in following formula [1a]～formula [1c],
In formula [1a], X1Represent phenyl ring or nitrogenous heteroaromatic, X2Represent hydrogen atom or the disubstituted amido replaced by the aliphatic group of carbon number 1～12；In formula [1b], X3And X7Represent independently of one another and there are 6～15 carbon atoms and there is the aromatic group of 1～2 phenyl ring, X4And X6Represent the alkylidene of hydrogen atom or carbon number 1～5, X independently of one another5Representing alkylidene or the xenyl of carbon number 2～5, m represents the integer of 0 or 1；In formula [1c], X8And X10Represent at least one structure in structure shown in following formula [1c-a] and formula [1c-b], X independently of one another9Represent alkylidene or the phenyl ring of carbon number 1～5,
3. the aligning agent for liquid crystal according to claim 1 or claim 2, wherein, the polymer of described (A) composition is the polymer obtained for the part of raw material by the diamine compound shown in following formula [1-1],
In formula [1-1], XARepresent the organic group of at least one structure having in structure shown in above-mentioned formula [1a]～formula [1c], A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
4. aligning agent for liquid crystal according to claim 3, it is by the described diamine compound polymer that to be the diamine compound shown in following formula [1a-1]～formula [1c-1] obtain for the part of raw material,
In formula [1a-1], X1Represent phenyl ring or nitrogenous heteroaromatic, X2Represent hydrogen atom or the disubstituted amido replaced by the aliphatic group of carbon number 1～12；In formula [1b-1], X3And X7Represent independently of one another and there are 6～15 carbon atoms and there is the aromatic group of 1～2 phenyl ring, X4And X6Represent the alkylidene of hydrogen atom or carbon number 1～5, X independently of one another5Representing alkylidene or the xenyl of carbon number 2～5, m represents the integer of 0 or 1；In formula [1c-1], X8And X10Represent at least one structure in structure shown in above-mentioned formula [1c-a] and formula [1c-b], X independently of one another9Represent alkylidene or the phenyl ring of carbon number 1～5；In formula [1a-1]～formula [1c-1], A1～A6Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
5. aligning agent for liquid crystal according to claim 4, wherein, described diamine compound is at least one diamine compound in the diamine compound shown in following formula [1-1a]～formula [1-4a],
In formula [1-3a], R1Represent the alkylidene of hydrogen atom or carbon number 1～5；In formula [1-4a], n represents the integer of 1～10；In formula [1-1a]～formula [1-4a], A1～A8Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
6. the aligning agent for liquid crystal according to any one of claim 1～claim 5, wherein, the polymer of described (B) composition is the polymer obtained for the part of raw material by the diamine compound shown in following formula [2-1],
In formula [2-1], YARepresent that there is the organic group of structure, A shown in previously described formula [2]1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
7. aligning agent for liquid crystal according to claim 6, it is by the described diamine compound polymer that to be the diamine compound shown in following formula [2a] obtain for the part of raw material,
In formula [2a], Y1And Y7Represent singly-bound independently of one another, selected from the alkylidene of carbon number 1～10 ,-O-,-N (R1)-、-CON(R2)-、-N(R3)CO-、-CH2At least one organic group in O-,-COO-and-OCO-, wherein, R1Represent the alkylidene of hydrogen atom or carbon number 1～3, R2Represent the alkylidene of hydrogen atom or carbon number 1～3, R3Represent the alkylidene of hydrogen atom or carbon number 1～3；Y2And Y6Represent the alkylidene of carbon number 1～10 independently of one another；Y3And Y5Represent the alkylidene of hydrogen atom or carbon number 1～10 independently of one another；Y4Represent oxygen atom or sulphur atom；A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
8. aligning agent for liquid crystal according to claim 7, wherein, described diamine compound is at least one diamine compound in the diamine compound shown in following formula [2-1a]～formula [2-3a],
In formula [2-1a]～formula [2-3a], A1～A6Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another.
9. the aligning agent for liquid crystal according to any one of claim 1～claim 8, wherein, at least any one polymer in described (A) composition and (B) composition is by the part for raw material of the diamine compound shown in following formula [3a]
In formula [3a], B represents above-mentioned formula [3]；A1And A2Represent the alkylidene of hydrogen atom or carbon number 1～5 independently of one another；M represents the integer of 1～4.
10. the aligning agent for liquid crystal according to any one of claim 1～claim 9, wherein, the polymer of described (A) composition and the polymer of (B) composition are at least one polymer in the polyimide precursor obtained selected from the tetrabasic carboxylic acid composition shown in use following formula [4] and polyimides
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 ring, optionally identical or different each other；In formula [4g], Z5And Z6Represent hydrogen atom or methyl, optionally identical or different each other.
11. aligning agent for liquid crystal according to claim 10, wherein, described tetrabasic carboxylic acid composition is the tetrabasic carboxylic acid composition being at least one structure in structure shown in described formula [4a] and formula [4e]～formula [4g] of the Z in described formula [4].
12. according to the aligning agent for liquid crystal according to any one of claim 4～claim 11, wherein, in the polymer of described (A) composition, the diamine compound shown in described formula [1a-1]～formula [1c-1] is 5 moles of %～95 mole % in 100 moles of % of whole diamine component.
13. according to the aligning agent for liquid crystal according to any one of claim 7～claim 12, wherein, in the polymer of described (B) composition, the diamine compound shown in described formula [2a] is 5 moles of %～95 mole % in 100 moles of % of whole diamine component.
14. according to the aligning agent for liquid crystal according to any one of claim 1～claim 13, wherein, the polymer phase of described (B) composition is 0.5 mass parts～950 mass parts for polymer 100 mass parts of described (A) composition.
15. according to the aligning agent for liquid crystal according to any one of claim 1～claim 14, wherein, as the solvent of aligning agent for liquid crystal, containing at least one solvent in METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone and gamma-butyrolacton.
16. according to the aligning agent for liquid crystal according to any one of claim 1～claim 15, wherein, solvent as aligning agent for liquid crystal, containing selected from 1-hexanol, Hexalin, 1, at least one solvent in 2-ethylene glycol, 1,2-PD, glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether.
17. according to the aligning agent for liquid crystal according to any one of claim 1～claim 16, wherein, aligning agent for liquid crystal comprises at least one cross-linked compound being selected from cross-linked compound: there is the cross-linked compound of epoxy radicals, NCO, oxetanyl or cyclocarbonate radical；There is the cross-linked compound of at least one substituent group in the group selecting free hydroxyl, hydroxy alkyl or low-grade alkoxy alkyl composition；And, there is the cross-linked compound of polymerism unsaturated bond.
18. a liquid crystal orientation film, it is that the aligning agent for liquid crystal according to any one of claim 1～claim 17 obtains.
19. a liquid crystal orientation film, it is to use the aligning agent for liquid crystal according to any one of claim 1～claim 17 to be obtained by ink-jet method.
20. liquid crystal represents an element, it has the liquid crystal orientation film described in claim 18 or claim 19.
21. according to the liquid crystal orientation film described in claim 18 or claim 19, 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 the pair of substrate, described liquid-crystal composition comprises the polymerizable compound being polymerized because of active energy beam and at least one hankered, while make described polymerizable compound be polymerized to applying voltage limit between described electrode.
22. a liquid crystal represents element, it is characterised in that have the liquid crystal orientation film described in claim 21.
23. according to the liquid crystal orientation film described in claim 18 or claim 19, 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 the pair of substrate, described liquid crystal orientation film comprises the polymerizable group being polymerized because of active energy beam and at least one hankered, while make described polymerizable group be polymerized to applying voltage limit between described electrode.
24. a liquid crystal represents element, it is characterised in that have the liquid crystal orientation film described in claim 23.
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