CN107003567A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element - Google Patents

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element Download PDF

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CN107003567A
CN107003567A CN201580061923.0A CN201580061923A CN107003567A CN 107003567 A CN107003567 A CN 107003567A CN 201580061923 A CN201580061923 A CN 201580061923A CN 107003567 A CN107003567 A CN 107003567A
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liquid crystal
ring
carbon number
group
aligning agent
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CN107003567B (en
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桥本淳
若林晓子
三木德俊
保坂和義
中家直树
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • 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

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  • Polymers & Plastics (AREA)
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  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

A kind of aligning agent for liquid crystal, it contains following (A) compositions and (B) composition.(A) composition：Heteropoly acid.(B) composition：Polymer.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element
Technical field
Handled the present invention relates to the aligning agent for liquid crystal used in the manufacture that liquid crystal represents element, by the liquid crystal aligning Liquid crystal orientation film and used the liquid crystal of the liquid crystal orientation film to represent element that agent is obtained.
Background technology
Liquid crystal represent element it is current as realize volume it is thin/the expression equipment of light weight and be widely used.Generally, the liquid Crystalline substance represents that element uses liquid crystal orientation film to determine the state of orientation of liquid crystal.
As liquid crystal represents the high-definition of element, represent that the contrast reduction of element, reduction ghost show from liquid crystal is suppressed As from the viewpoint of, it is desirable to which the voltage retention of the liquid crystal orientation film wherein used is also high.In this regard, using containing polyamide Aligning agent for liquid crystal on the basis of acid, its imide amination polymer etc. also containing the following compounds of very small amount, the chemical combination Thing, which is selected from intramolecular and contains compound and intramolecular that the compound of 1 carboxylic acid group, intramolecular contain 1 acid anhydride, to be contained There is the compound of 1 tertiary amino (referring for example to patent document 1).
In addition, as liquid crystal represents the high-definition of element, it is desirable to suppress contrast reduction and length that liquid crystal represents element Phase uses associated expression bad.In this regard, for the liquid crystal orientation film for having used polyimides, being used as raising liquid crystal aligning Property, be difficult to represent that picture periphery produces the bad method of representing in liquid crystal, it is proposed that using being added with alkoxy silane chemical combination Liquid crystal orientation film obtained from the aligning agent for liquid crystal of thing (referring for example to patent document 2 or patent document 3).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 8-76128 publications
Patent document 2：Japanese Unexamined Patent Application 61-171762 publications
Patent document 3：Japanese Unexamined Patent Publication 11-119226 publications
The content of the invention
Problems to be solved by the invention
As liquid crystal in recent years represents the high performance of element, in big picture and the liquid crystal TV set of high-resolution, vehicle-mounted Purposes represents element in the purposes such as auto-navigation system, instrument board panel using liquid crystal.In these purposes, in order to obtain height Brightness, sometimes using the big backlight of thermal discharge.Therefore, highly reliable further is required to liquid crystal orientation film from other viewpoints Property, there is high stability to the light from backlight.Especially, represent that the voltage of one of the electrical characteristics of element is kept as liquid crystal When rate is reduced because of the light irradiation from backlight, easily occur to represent that one of bad after image of the expression of element is bad as liquid crystal (also referred to as line after image), it is impossible to obtain the high liquid crystal of reliability and represent element.Therefore, for liquid crystal orientation film, Ask initial stage characteristic it is good on the basis of, even if also require for example for a long time be exposed to light irradiation after, voltage retention be not easy to reduction.
In addition, in the mobile purposes such as smart mobile phone, portable phone, compared with the past, its use environment gradually becomes tight It is severe.That is, in addition in the environment of room temperature so far and low humidity, also used sometimes under hot and humid.This In use, there are following problems under the conditions of hot and humid：The water capacity easily from liquid crystal represent the sealant of element and liquid crystal orientation film it Between be mixed into, represent that the adjacent edges of element easily occur to represent uneven in liquid crystal.It is therefore desirable under the conditions of hot and humid This expression does not occur bad yet.
Therefore, it is an object of the present invention to provide having the liquid crystal orientation film of above-mentioned characteristic concurrently.That is, the purpose of the present invention exists In there is provided can also suppress the liquid crystal orientation film that voltage retention is reduced after light irradiation even in for a long time.In addition, purpose It is to produce the liquid crystal for representing uneven there is provided the adjacent edges that will not also represent element in liquid crystal under the conditions of hot and humid Alignment films.
Represent element in addition, purpose is also resided in there is provided the liquid crystal with above-mentioned liquid crystal orientation film, above-mentioned liquid crystal can be provided The composition used in the aligning agent for liquid crystal of alignment films and the aligning agent for liquid crystal.
The solution used to solve the problem
Present inventor has performed further investigation, as a result find：The liquid crystal of compound and polymer comprising specific structure takes For realizing above-mentioned purpose it is extremely effective to inorganic agent, so as to complete the present invention.
That is, the present invention has following purports.
(1) a kind of aligning agent for liquid crystal, it contains following (A) compositions and (B) composition.
(A) composition：Heteropoly acid.
(B) composition：Polymer.
(2) aligning agent for liquid crystal according to above-mentioned (1), wherein, foregoing heteropoly acid is selected from by phosphomolybdic acid, silicon molybdenum It is at least one kind of in the group that acid, phosphotungstic acid, silico-tungstic acid and phosphotungstomolybdic acid are constituted.
(3) aligning agent for liquid crystal according to above-mentioned (1) or above-mentioned (2), wherein, aforementioned polymer has nitrogenous virtue Fragrant race's heterocycle.
(4) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (3), wherein, aforementioned polymer is Selected from before acrylic polymer, methacrylic polymer, novolac resin, polycarboxylated styrene, polyimides It is at least one kind of in the group that body, polyimides, polyamide, polyester, cellulose and polysiloxanes are constituted.
(5) aligning agent for liquid crystal according to above-mentioned (4), wherein, aforementioned polymer is by diamine component and four Polyimide precursor that the reaction of carboxylic acid composition is obtained or polyamides obtained from the polyimide precursor is carried out into imidizate Imines.
(6) aligning agent for liquid crystal according to above-mentioned (5), wherein, foregoing diamine component, which is included, has following formula [2] The diamine compound of shown structure.
-W1-W2-W3-W4 [2]
(W1Represent to be selected from by-O- ,-NH- ,-N (CH3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)- With-N (CH3) CO- composition group at least one kind of binding groups.W2Represent to be selected from by the singly-bound, alkylidene of carbon number 1~20, non- It is at least one kind of in the group of aromatic ring and aromatic ring composition.W3Represent to be selected from by singly-bound ,-O- ,-NH- ,-N (CH3)-、- CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-、-N(CH3) CO- and-O (CH2)m- (m represents 1~5 integer) constitutes Group in it is at least one kind of.W4Represent nitrogenous heteroaromatic.)
(7) aligning agent for liquid crystal according to above-mentioned (6), wherein, foregoing diamine component includes following formula [2a] institute The diamine compound shown.
(W represents the structure shown in previously described formula [2].M1 represents 1~4 integer.)
(8) aligning agent for liquid crystal according to any one of above-mentioned (5)~above-mentioned (7), wherein, foregoing diamine component Include the diamine compound with structure shown in following formula [3-1] or formula [3-2].
(Y1Represent to be selected from by singly-bound ,-(CH2)a- (a is 1~15 integer) ,-O- ,-CH2O-、-CONH-、-NHCO-、- CON(CH3)-、-N(CH3) CO- ,-COO- and-OCO- composition group at least one kind of binding groups.Y2Represent singly-bound or- (CH2)b- (b is 1~15 integer).Y3Represent to be selected from by singly-bound ,-(CH2)c- (c is 1~15 integer) ,-O- ,-CH2O-、- It is at least one kind of in the group that COO- and-OCO- is constituted.Y4Represent in the group being made up of phenyl ring, cyclohexane ring and heterocycle extremely On the divalent organic group of few a kind of divalent cyclic group or the carbon number 17~51 with steroid skeleton, aforementioned cyclic group Any hydrogen atom optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 containing fluoroalkyl, carbon number 1~3 Fluoroalkoxy or fluorine atom substitution.Y5Represent at least one kind of ring-type in the group being made up of phenyl ring, cyclohexane ring and heterocycle Any hydrogen atom on group, these cyclic groups is optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 Containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom substitution.N represents 0~4 integer.Y6Represent to be selected from by carbon number 1 ~18 alkyl, the alkenyl of carbon number 2~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 and carbon number 1~18 It is at least one kind of in the group of fluoroalkoxy composition.)
-Y7-Y8 [3-2]
(Y7Represent to be selected from by singly-bound ,-O- ,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3)CO-、-COO- At least one kind of binding groups in the group constituted with-OCO-.Y8Represent carbon number 8~18 alkyl or carbon number 6~18 contain fluothane Base.)
(9) aligning agent for liquid crystal according to above-mentioned (8), wherein, foregoing diamine compound following formula [3a] table Show.
(Y represents previously described formula [3-1] or the structure shown in formula [3-2].N1 represents 1~4 integer.)
(10) aligning agent for liquid crystal according to any one of above-mentioned (5)~above-mentioned (9), wherein, foregoing tetrabasic carboxylic acid Composition includes the tetracarboxylic dianhydride shown in following formula [4].
(Z represents to be selected from as at least one kind of structure in the group of the structure composition shown in following formula [4a]~formula [4k].)
(Z1~Z4At least 1 in the group being made up of hydrogen atom, methyl, chlorine atom and phenyl ring is represented independently of one another Kind.Z5And Z6Hydrogen atom or methyl are represented independently of one another.)
(11) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (10), wherein, foregoing liquid crystal takes Contain to inorganic agent in the group being made up of METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones and gamma-butyrolacton At least one kind of solvent.
(12) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (11), wherein, foregoing liquid crystal takes Contain to inorganic agent selected from by 1- hexanols, cyclohexanol, 1,2- ethylene glycol, 1,2- propane diols, propylene glycol monobutyl ether, ethylene glycol only son At least one kind of solvent in the group of solvent composition shown in ether, dimethyl ether and following formulas [D1]~formula [D3].
(D1Represent the alkyl of carbon number 1~3.D2Represent the alkyl of carbon number 1~3.D3Represent the alkyl of carbon number 1~4.)
(13) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (12), wherein, foregoing liquid crystal takes Contain to inorganic agent：With the base in the group being made up of epoxy radicals, NCO, oxetanylmethoxy and cyclocarbonate radical The cross-linked compound of group；With the base in the group for selecting the alkoxyalkyl of free hydroxyl, hydroxy alkyl and carbon number 1~3 to constitute The cross-linked compound of group；Or the cross-linked compound with the unsaturated binding groups of polymerism.
(14) a kind of liquid crystal orientation film, it is as the aligning agent for liquid crystal any one of above-mentioned (1)~above-mentioned (13) Obtain.
(15) a kind of liquid crystal orientation film, it is to be coated with by ink-jet method any one of above-mentioned (1)~above-mentioned (13) Obtained from aligning agent for liquid crystal.
(16) a kind of liquid crystal represents element, and it has the liquid crystal orientation film described in above-mentioned (14) or above-mentioned (15).
(17) liquid crystal orientation film according to above-mentioned (14) or above-mentioned (15), it is characterised in that it is used for possessing electricity The liquid crystal with liquid crystal layer represents element between a pair of substrates of pole, and the liquid crystal represents that element is manufactured via following process 's：Configuration includes the polymerism polymerizeing by least one of active energy beam and heat between foregoing a pair of substrates The liquid-crystal composition of compound, while to applying voltage between former electrodes while polymerizeing aforementioned polymeric compound.
(18) a kind of liquid crystal represents element, it is characterised in that it has the liquid crystal orientation film described in above-mentioned (17).
(19) liquid crystal orientation film according to above-mentioned (14) or above-mentioned (15), it is characterised in that it is used for possessing electricity The liquid crystal with liquid crystal layer represents element between a pair of substrates of pole, and the liquid crystal represents that element is manufactured via following process 's：Configuration includes the polymerism base polymerizeing by least one of active energy beam and heat between foregoing a pair of substrates The liquid crystal orientation film of group, while to applying voltage between former electrodes while polymerizeing aforementioned polymeric group.
(20) a kind of liquid crystal represents element, it is characterised in that it has the liquid crystal orientation film described in above-mentioned (19).
The effect of invention
Even if the aligning agent for liquid crystal comprising specific compound and polymer of the present invention can obtain being exposed to for a long time Also the liquid crystal orientation film of voltage retention reduction can be suppressed after light irradiation.Also, it can be formed under the conditions of hot and humid Also it will not represent that uneven liquid crystal orientation film occurs to represent for the adjacent edges of element in liquid crystal.
Represent that the mechanism of element is still not clear by the way that why the present invention can obtain the liquid crystal with above-mentioned excellent specific property, can Substantially it is presumed as follows.
Handled the present invention relates to the aligning agent for liquid crystal containing following (A) compositions and (B) composition, using the liquid crystal aligning The liquid crystal orientation film that agent is obtained and the liquid crystal with the liquid crystal orientation film represent element.
(A) composition：Heteropoly acid (also referred to as specific compound).
(B) composition：Polymer.
As the effect of specific compound, it can consider as follows.The principal element reduced as voltage retention, has When liquid crystal in there are a large amount of ionic impurity compositions.To this it is believed that representing that element is exposed to light irradiation for a long time in liquid crystal And in the case of occurring liquid crystal decomposition, specific compound can adsorb the ionic impurity composition now produced, so as to suppress voltage The reduction of conservation rate.Furthermore, it is possible to think：When having used the polymer with nitrogenous heteroaromatic, the heterocycle can enter one Step improves its effect.
In addition, polymer uses the polyimide precursor or general that the reaction by diamine component and tetrabasic carboxylic acid composition obtains The polyimide precursor carries out polyimides obtained from imidizate, and diamine component now is used with previously described formula [3-1] Or the diamine compound of structure shown in formula [3-2], vertical-type (VA is made：Vertical Alignment) pattern, PSA The liquid crystal of (Polymer Sustained Alignment) pattern and SC-PVA patterns represents the aligning agent for liquid crystal of element When, especially the structure shown in formula [3-1] shows upright and outspoken structure, therefore, has used the liquid crystal orientation film with the structure Liquid crystal represent that element is just stable to ultraviolet etc., the hair of ionic impurity for reducing voltage retention can be suppressed It is raw.
So, the liquid crystal for possessing the liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention represents the reliable of element Property is excellent, can be suitably employed in big picture and the liquid crystal TV set of high-resolution etc..Especially, it is right when making liquid crystal represents element The liquid crystal obtained from using the PSA patterns of irradiation high energy UV, SC-PVA patterns is useful for representing element.
Embodiment
<Specific compound>
Specific compound in the present invention is heteropoly acid.
Heteropoly acid typically refers to：With with shown in the Keggin-type shown in following formula [1-1] or formula [1-2] Dawson type chemical constitutions are represented, hetero atom is located at the structure of molecular center, and by being used as vanadium (V), molybdenum (Mo), tungsten (W) etc. Oxyacid isopolyacid and not same element oxyacid through polyacid obtained from condensation.It is used as such not same element Oxyacid, can mainly include silicon (Si), phosphorus (P), the oxyacid of arsenic (As).
As the concrete example of heteropoly compound, phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silico-tungstic acid or phosphorus tungsten can be included Acid etc., in the present invention, it is preferred to use them.In addition, they may be used singly or in combination of two or more.Should Illustrate, the present invention in heteropoly compound can be obtained in the form of commercially available product, in addition it is also possible to by known method come Synthesis.
In the quantitative analyses such as elementary analysis, structure of the heteropoly acid according to formula, no matter the quantity of element be it is many or It is few, as long as it is the acquisition in the form of commercially available product or the material suitably synthesized according to known synthetic method, it is possible to Use in the present invention.
I.e. for example, in general, phosphotungstic acid is the structure shown in following formula [1a], phosphomolybdic acid is the knot shown in formula [1b] Structure.
H3(PW12O40)·nH2O [1a] H3(PMo12O40)·nH2O [1b]
They in quantitative analysis, no matter P (phosphorus), O (oxygen) in these formulas or W (tungsten) or Mo (molybdenum) quantity be it is many or It is few, as long as it is the acquisition in the form of commercially available product or the material suitably synthesized according to known synthetic method, so that it may To use in the present invention.Now, the phosphorus tungsten of the quality of heteropoly acid specified in the present invention not in synthetic and/or commercially available product The pure quality (phosphotungstic acid content) of acid, and refer to：In the form that can be obtained in the form of commercially available product and in known synthesis side Under the form that can be separated in method, the gross mass in the state of hydrate water or other impurity etc. is included.
<Polymer>
The polymer of the present invention is preferably selected from by acrylic polymer, methacrylic polymer, novolaks The group that resin, polycarboxylated styrene, polyimide precursor, polyimides, polyamide, polyester, cellulose and polysiloxanes are constituted In at least one kind of polymer.More preferably polyimide precursor, polyimides or polysiloxanes.Particularly preferably polyimides Precursor or polyimides (also referred to collectively as specific polyimides based polymer).
In addition, as described above, in order to further improve effect of the invention, these polymer preferably comprise nitrogenous aromatic series Heterocycle.
Nitrogenous heteroaromatic is the heterocycle containing structure shown in following formula [a], formula [b] or formula [c].
(Wa represents the alkyl of carbon number 1~5.)
More specifically, can include pyrrole ring, imidazole ring, oxazole rings, 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), benzimidazole ring (Benzoimidazole Ring), cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenthazine Huan, oxadiazole rings and acridine ring etc.. Wherein, preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzene And imidazole ring or benzimidazole ring.From the viewpoint of it can suppress the long-term voltage retention reduction being exposed to after light irradiation, More preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring.Particularly preferably imidazole ring or pyridine ring.
<Specific polyimides based polymer>
When the polymer of the present invention uses specific polyimides based polymer, they are preferably to make diamine component and tetrabasic carboxylic acid Polyimide precursor or polyimides obtained from composition reacts.
Polyimide precursor has the structure shown in following formula [A].
(R1Represent 4 valency organic groups.R2Represent divalent organic group.A1And A2Hydrogen atom or carbon number 1 are represented independently of one another ~8 alkyl.A3And A4Hydrogen atom, the alkyl or acetyl group of carbon number 1~5 are represented independently of one another.NA represents positive integer.
As foregoing diamine component, diamines of the intramolecular with 2 primary amino radicals or secondary amino group can be included.It is used as tetrabasic carboxylic acid Composition, can include tetracarboxylic compound, tetracarboxylic dianhydride, the acetyl halide compound of tetrabasic carboxylic acid two, tetracarboxylic acid acid dialkyl ester compound Or the acetyl halide compound of tetracarboxylic acid acid dialkyl ester two.
From can be by being compared using the diamines shown in the tetracarboxylic dianhydride shown in following formula [B] and following formula [C] as raw material More easily obtain this reason to set out, specific polyimides based polymer is preferably to include repeat unit shown in following formula [D] Structural formula polyamic acid or make the polyamic acid carry out imidizate polyimides.Wherein, in the present invention, It is preferably that polyimide precursor is subjected to acid imide from the viewpoint of the physical stability and chemical stability of liquid crystal orientation film The polyimides changed.
(R1And R2It is identical with the implication defined in formula [A].)
(R1、R2It is identical with the implication defined in formula [A] with nA.)
In addition it is also possible to using common synthetic method, introducing-type [A] institute into formula obtained above [D] polymer The A shown1And A2Carbon number 1~8 alkyl and formula [A] shown in A3And A4Carbon number 1~5 alkyl or acetyl group.
As the diamine component in the present invention, known composition can be used.
Wherein, as described above, in order to further improve effect of the invention, preferably using and being tied with following formula [2] Suo Shi The diamine compound of structure (also referred to as specific structure (1)).
-W1-W2-W3-W4 [2]
In formula [2], W1、W2、W3And W4As defined above, wherein, be respectively preferably following radicals.
W1Preferably-O- ,-NH- ,-CONH- ,-NHCO- ,-CH2O-、-OCO-、-CON(CH3)-or-N (CH3)CO-.From Synthesize from the viewpoint of easness, be more preferably-O- ,-NH- ,-CONH- ,-NHCO- ,-CH2O- ,-OCO- or-CON (CH3)-。 Particularly preferably-O- ,-CONH- or-CH2O-。
W2Represent in the group being made up of singly-bound, the alkylidene of carbon number 1~20, non-aromatic ring and aromatic ring extremely It is few a kind.
The alkylidene of carbon number 1~20 can be straight-chain, it is possibility to have side chain.Further, it is also possible to have unsaturated bond.Its In, from the viewpoint of synthesis easness, the preferably alkylidene of carbon number 1~10.
As the concrete example of non-aromatic ring, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, ring can be included Heptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, the ring tetradecane Ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three rings 20 Alkane ring, three ring docosane rings, norbornane ring, decahydro naphthalene nucleus, ENB ring and adamantane ring etc..Wherein, preferably ring Propane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, ENB ring or adamantane ring.
As the concrete example of aromatic ring, can include phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, Phenanthrene ring and Fei Na alkene rings etc..Wherein, preferably phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring or anthracene nucleus.
It is used as W2, preferably singly-bound, the alkylidene of carbon number 1~10, cyclopropane ring, cyclobutane ring, pentamethylene ring, hexamethylene Ring, cycloheptane ring, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring or anthracene nucleus.Wherein, it is easy from synthesis The viewpoint of degree and from the viewpoint of can suppressing the long-term voltage retention reduction being exposed to after light irradiation, preferably singly-bound, Alkylidene, cyclohexane ring or the phenyl ring of carbon number 1~5.
W3Preferably singly-bound ,-O- ,-COO- ,-OCO- or-O (CH2)m- (m represents 1~5 integer).From synthesis easness From the viewpoint of, more preferably singly-bound ,-O- ,-OCO- or-O (CH2)m- (m represents 1~5 integer).
W4Nitrogenous heteroaromatic is represented, is represented in the same manner as foregoing containing knot shown in previously described formula [a], formula [b] or formula [c] The heterocycle of structure.Specifically, as described above, it is preferred to for pyrrole ring therein, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, rattle away Piperazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring or benzimidazole ring.From can suppress to be exposed to after light irradiation for a long time Voltage retention reduction from the viewpoint of, more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring.It is especially excellent Elect imidazole ring or pyridine ring as.
In addition, the W in formula [2]3It is preferred that with W4In the substituent adjacent with formula [c] not with formula [a], formula [b] that includes carry out Bonding.
W in formula [2]1、W2、W3With W4Preferred compositions as shown in table 1 below~table 31.
[table 1]
W1 W2 W3 W4
a-1 -O- Singly-bound Singly-bound Pyrrole ring
a-2 -NH- Singly-bound Singly-bound Pyrrole ring
a-3 -CONH- Singly-bound Singly-bound Pyrrole ring
a-4 -NHCO- Singly-bound Singly-bound Pyrrole ring
a-5 -CH2O- Singly-bound Singly-bound Pyrrole ring
a-6 -OCO- Singly-bound Singly-bound Pyrrole ring
a-7 -CON(CH3)- Singly-bound Singly-bound Pyrrole ring
a-8 -O- Singly-bound Singly-bound Imidazole ring
a-9 -NH- Singly-bound Singly-bound Imidazole ring
a-10 -CONH- Singly-bound Singly-bound Imidazole ring
a-11 -NHCO- Singly-bound Singly-bound Imidazole ring
a-12 -CH2O- Singly-bound Singly-bound Imidazole ring
a-13 -OCO- Singly-bound Singly-bound Imidazole ring
a-14 -CON(CH3)- Singly-bound Singly-bound Imidazole ring
a-15 -O- Singly-bound Singly-bound Pyrazole ring
[table 2]
W1 W2 W3 W4
a-16 -NH- Singly-bound Singly-bound Pyrazole ring
a-17 -CONH- Singly-bound Singly-bound Pyrazole ring
a-18 -NHCO- Singly-bound Singly-bound Pyrazole ring
a-19 -CH2O- Singly-bound Singly-bound Pyrazole ring
a-20 -OCO- Singly-bound Singly-bound Pyrazole ring
a-21 -CON(CH3)- Singly-bound Singly-bound Pyrazole ring
a-22 -O- Singly-bound Singly-bound Pyridine ring
a-23 -NH- Singly-bound Singly-bound Pyridine ring
a-24 -CONH- Singly-bound Singly-bound Pyridine ring
a-25 -NHCO- Singly-bound Singly-bound Pyridine ring
a-26 -CH2O- Singly-bound Singly-bound Pyridine ring
a-27 -OCO- Singly-bound Singly-bound Pyridine ring
a-28 -CON(CH3)- Singly-bound Singly-bound Pyridine ring
a-29 -O- Singly-bound Singly-bound Pyrimidine ring
a-30 -NH- Singly-bound Singly-bound Pyrimidine ring
[table 3]
W1 W2 W3 W4
a-31 -CONH- Singly-bound Singly-bound Pyrimidine ring
a-32 -NHCO- Singly-bound Singly-bound Pyrimidine ring
a-33 -CH2O- Singly-bound Singly-bound Pyrimidine ring
a-34 -OCO- Singly-bound Singly-bound Pyrimidine ring
a-35 -CON(CH3)- Singly-bound Singly-bound Pyrimidine ring
a-36 -O- The alkylidene of carbon number 1~5 Singly-bound Pyrrole ring
a-37 -NH- The alkylidene of carbon number 1~5 Singly-bound Pyrrole ring
a-38 -CONH- The alkylidene of carbon number 1~5 Singly-bound Pyrrole ring
a-39 -NHCO- The alkylidene of carbon number 1~5 Singly-bound Pyrrole ring
a-40 -CH2O- The alkylidene of carbon number 1~5 Singly-bound Pyrrole ring
a-41 -OCO- The alkylidene of carbon number 1~5 Singly-bound Pyrrole ring
a-42 -CON(CH3)- The alkylidene of carbon number 1~5 Singly-bound Pyrrole ring
a-43 -O- The alkylidene of carbon number 1~5 Singly-bound Imidazole ring
a-44 -NH- The alkylidene of carbon number 1~5 Singly-bound Imidazole ring
a-45 -CONH- The alkylidene of carbon number 1~5 Singly-bound Imidazole ring
[table 4]
W1 W2 W3 W4
a-46 -NHCO- The alkylidene of carbon number 1~5 Singly-bound Imidazole ring
a-47 -CH2O- The alkylidene of carbon number 1~5 Singly-bound Imidazole ring
a-48 -OCO- The alkylidene of carbon number 1~5 Singly-bound Imidazole ring
a-49 -CON(CH3)- The alkylidene of carbon number 1~5 Singly-bound Imidazole ring
a-50 -O- The alkylidene of carbon number 1~5 Singly-bound Pyrazole ring
a-51 -NH- The alkylidene of carbon number 1~5 Singly-bound Pyrazole ring
a-52 -CONH- The alkylidene of carbon number 1~5 Singly-bound Pyrazole ring
a-53 -NHCO- The alkylidene of carbon number 1~5 Singly-bound Pyrazole ring
a-54 -CH2O- The alkylidene of carbon number 1~5 Singly-bound Pyrazole ring
a-55 -OCO- The alkylidene of carbon number 1~5 Singly-bound Pyrazole ring
a-56 -CON(CH3)- The alkylidene of carbon number 1~5 Singly-bound Pyrazole ring
a-57 -O- The alkylidene of carbon number 1~5 Singly-bound Pyridine ring
a-58 -NH- The alkylidene of carbon number 1~5 Singly-bound Pyridine ring
a-59 -CONH- The alkylidene of carbon number 1~5 Singly-bound Pyridine ring
a-60 -NHCO- The alkylidene of carbon number 1~5 Singly-bound Pyridine ring
[table 5]
W1 W2 W3 W4
a-61 -CH2O- The alkylidene of carbon number 1~5 Singly-bound Pyridine ring
a-62 -OCO- The alkylidene of carbon number 1~5 Singly-bound Pyridine ring
a-63 -CON(CH3)- The alkylidene of carbon number 1~5 Singly-bound Pyridine ring
a-64 -O- The alkylidene of carbon number 1~5 Singly-bound Pyrimidine ring
a-65 -NH- The alkylidene of carbon number 1~5 Singly-bound Pyrimidine ring
a-66 -CONH- The alkylidene of carbon number 1~5 Singly-bound Pyrimidine ring
a-67 -NHCO- The alkylidene of carbon number 1~5 Singly-bound Pyrimidine ring
a-68 -CH2O- The alkylidene of carbon number 1~5 Singly-bound Pyrimidine ring
a-69 -OCO- The alkylidene of carbon number 1~5 Singly-bound Pyrimidine ring
a-70 -CON(CH3)- The alkylidene of carbon number 1~5 Singly-bound Pyrimidine ring
a-71 -O- Cyclohexane ring Singly-bound Pyrrole ring
a-72 -NH- Cyclohexane ring Singly-bound Pyrrole ring
a-73 -CONH- Cyclohexane ring Singly-bound Pyrrole ring
a-74 -NHCO- Cyclohexane ring Singly-bound Pyrrole ring
a-75 -CH2O- Cyclohexane ring Singly-bound Pyrrole ring
[table 6]
W1 W2 W3 W4
a-76 -OCO- Cyclohexane ring Singly-bound Pyrrole ring
a-77 -CON(CH3)- Cyclohexane ring Singly-bound Pyrrole ring
a-78 -O- Cyclohexane ring Singly-bound Imidazole ring
a-79 -NH- Cyclohexane ring Singly-bound Imidazole ring
a-80 -CONH- Cyclohexane ring Singly-bound Imidazole ring
a-81 -NHCO- Cyclohexane ring Singly-bound Imidazole ring
a-82 -CH2O- Cyclohexane ring Singly-bound Imidazole ring
a-83 -OCO- Cyclohexane ring Singly-bound Imidazole ring
a-84 -CON(CH3)- Cyclohexane ring Singly-bound Imidazole ring
a-85 -O- Cyclohexane ring Singly-bound Pyrazole ring
a-86 -NH- Cyclohexane ring Singly-bound Pyrazole ring
a-87 -CONH- Cyclohexane ring Singly-bound Pyrazole ring
a-88 -NHCO- Cyclohexane ring Singly-bound Pyrazole ring
a-89 -CH2O- Cyclohexane ring Singly-bound Pyrazole ring
a-90 -OCO- Cyclohexane ring Singly-bound Pyrazole ring
[table 7]
W1 W2 W3 W4
a-91 -CON(CH3)- Cyclohexane ring Singly-bound Pyrazole ring
a-92 -O- Cyclohexane ring Singly-bound Pyridine ring
a-93 -NH- Cyclohexane ring Singly-bound Pyridine ring
a-94 -CONH- Cyclohexane ring Singly-bound Pyridine ring
a-95 -NHCO- Cyclohexane ring Singly-bound Pyridine ring
a-96 -CH2O- Cyclohexane ring Singly-bound Pyridine ring
a-97 -OCO- Cyclohexane ring Singly-bound Pyridine ring
a-98 -CON(CH3)- Cyclohexane ring Singly-bound Pyridine ring
a-99 -O- Cyclohexane ring Singly-bound Pyrimidine ring
a-100 -NH- Cyclohexane ring Singly-bound Pyrimidine ring
a-101 -CONH- Cyclohexane ring Singly-bound Pyrimidine ring
a-102 -NHCO- Cyclohexane ring Singly-bound Pyrimidine ring
a-103 -CH2O- Cyclohexane ring Singly-bound Pyrimidine ring
a-104 -OCO- Cyclohexane ring Singly-bound Pyrimidine ring
a-105 -CON(CH3)- Cyclohexane ring Singly-bound Pyrimidine ring
[table 8]
W1 W2 W3 W4
a-106 -O- Phenyl ring Singly-bound Pyrrole ring
a-107 -NH- Phenyl ring Singly-bound Pyrrole ring
a-108 -CONH- Phenyl ring Singly-bound Pyrrole ring
a-109 -NHCO- Phenyl ring Singly-bound Pyrrole ring
a-110 -CH2O- Phenyl ring Singly-bound Pyrrole ring
a-111 -OCO- Phenyl ring Singly-bound Pyrrole ring
a-112 -CON(CH3)- Phenyl ring Singly-bound Pyrrole ring
a-113 -O- Phenyl ring Singly-bound Imidazole ring
a-114 -NH- Phenyl ring Singly-bound Imidazole ring
a-115 -CONH- Phenyl ring Singly-bound Imidazole ring
a-116 -NHCO- Phenyl ring Singly-bound Imidazole ring
a-117 -CH2O- Phenyl ring Singly-bound Imidazole ring
a-118 -OCO- Phenyl ring Singly-bound Imidazole ring
a-119 -CON(CH3)- Phenyl ring Singly-bound Imidazole ring
a-120 -O- Phenyl ring Singly-bound Pyrazole ring
[table 9]
W1 W2 W3 W4
a-121 -NH- Phenyl ring Singly-bound Pyrazole ring
a-122 -CONH- Phenyl ring Singly-bound Pyrazole ring
a-123 -NHCO- Phenyl ring Singly-bound Pyrazole ring
a-124 -CH2O- Phenyl ring Singly-bound Pyrazole ring
a-125 -OCO- Phenyl ring Singly-bound Pyrazole ring
a-126 -CON(CH3)- Phenyl ring Singly-bound Pyrazole ring
a-127 -O- Phenyl ring Singly-bound Pyridine ring
a-128 -NH- Phenyl ring Singly-bound Pyridine ring
a-129 -CONH- Phenyl ring Singly-bound Pyridine ring
a-130 -NHCO- Phenyl ring Singly-bound Pyridine ring
a-131 -CH2O- Phenyl ring Singly-bound Pyridine ring
a-132 -OCO- Phenyl ring Singly-bound Pyridine ring
a-133 -CON(CH3)- Phenyl ring Singly-bound Pyridine ring
a-134 -O- Phenyl ring Singly-bound Pyrimidine ring
a-135 -NH- Phenyl ring Singly-bound Pyrimidine ring
[table 10]
W1 W2 W3 W4
a-136 -CONH- Phenyl ring Singly-bound Pyrimidine ring
a-137 -NHCO- Phenyl ring Singly-bound Pyrimidine ring
a-138 -CH2O- Phenyl ring Singly-bound Pyrimidine ring
a-139 -OCO- Phenyl ring Singly-bound Pyrimidine ring
a-140 -CON(CH3)- Phenyl ring Singly-bound Pyrimidine ring
a-141 -O- The alkylidene of carbon number 1~5 -O- Pyrrole ring
a-142 -NH- The alkylidene of carbon number 1~5 -O- Pyrrole ring
a-143 -CONH- The alkylidene of carbon number 1~5 -O- Pyrrole ring
a-144 -NHCO- The alkylidene of carbon number 1~5 -O- Pyrrole ring
a-145 -CH2O- The alkylidene of carbon number 1~5 -O- Pyrrole ring
a-146 -OCO- The alkylidene of carbon number 1~5 -O- Pyrrole ring
a-147 -CON(CH3)- The alkylidene of carbon number 1~5 -O- Pyrrole ring
a-148 -O- The alkylidene of carbon number 1~5 -O- Imidazole ring
a-149 -NH- The alkylidene of carbon number 1~5 -O- Imidazole ring
a-150 -CONH- The alkylidene of carbon number 1~5 -O- Imidazole ring
[table 11]
W1 W2 W3 W4
a-151 -NHCO- The alkylidene of carbon number 1~5 -O- Imidazole ring
a-152 -CH2O- The alkylidene of carbon number 1~5 -O- Imidazole ring
a-153 -OCO- The alkylidene of carbon number 1~5 -O- Imidazole ring
a-154 -CON(CH3)- The alkylidene of carbon number 1~5 -O- Imidazole ring
a-155 -O- The alkylidene of carbon number 1~5 -O- Pyrazole ring
a-156 -NH- The alkylidene of carbon number 1~5 -O- Pyrazole ring
a-157 -CONH- The alkylidene of carbon number 1~5 -O- Pyrazole ring
a-158 -NHCO- The alkylidene of carbon number 1~5 -O- Pyrazole ring
a-159 -CH2O- The alkylidene of carbon number 1~5 -O- Pyrazole ring
a-160 -OCO- The alkylidene of carbon number 1~5 -O- Pyrazole ring
a-161 -CON(CH3)- The alkylidene of carbon number 1~5 -O- Pyrazole ring
a-162 -O- The alkylidene of carbon number 1~5 -O- Pyridine ring
a-163 -NH- The alkylidene of carbon number 1~5 -O- Pyridine ring
a-164 -CONH- The alkylidene of carbon number 1~5 -O- Pyridine ring
a-165 -NHCO- The alkylidene of carbon number 1~5 -O- Pyridine ring
[table 12]
W1 W2 W3 W4
a-166 -CH2O- The alkylidene of carbon number 1~5 -O- Pyridine ring
a-167 -OCO- The alkylidene of carbon number 1~5 -O- Pyridine ring
a-168 -CON(CH3)- The alkylidene of carbon number 1~5 -O- Pyridine ring
a-169 -O- The alkylidene of carbon number 1~5 -O- Pyrimidine ring
a-170 -NH- The alkylidene of carbon number 1~5 -O- Pyrimidine ring
a-171 -CONH- The alkylidene of carbon number 1~5 -O- Pyrimidine ring
a-172 -NHCO- The alkylidene of carbon number 1~5 -O- Pyrimidine ring
a-173 -CH2O- The alkylidene of carbon number 1~5 -O- Pyrimidine ring
a-174 -OCO- The alkylidene of carbon number 1~5 -O- Pyrimidine ring
a-175 -CON(CH3)- The alkylidene of carbon number 1~5 -O- Pyrimidine ring
a-176 -O- The alkylidene of carbon number 1~5 -OCO- Pyrrole ring
a-177 -NH- The alkylidene of carbon number 1~5 -OCO- Pyrrole ring
a-178 -CONH- The alkylidene of carbon number 1~5 -OCO- Pyrrole ring
a-179 -NHCO- The alkylidene of carbon number 1~5 -OCO- Pyrrole ring
a-180 -CH2O- The alkylidene of carbon number 1~5 -OCO- Pyrrole ring
[table 13]
W1 W2 W3 W4
a-181 -OCO- The alkylidene of carbon number 1~5 -OCO- Pyrrole ring
a-182 -CON(CH3)- The alkylidene of carbon number 1~5 -OCO- Pyrrole ring
a-183 -O- The alkylidene of carbon number 1~5 -OCO- Imidazole ring
a-184 -NH- The alkylidene of carbon number 1~5 -OCO- Imidazole ring
a-185 -CONH- The alkylidene of carbon number 1~5 -OCO- Imidazole ring
a-186 -NHCO- The alkylidene of carbon number 1~5 -OCO- Imidazole ring
a-187 -CH2O- The alkylidene of carbon number 1~5 -OCO- Imidazole ring
a-188 -OCO- The alkylidene of carbon number 1~5 -OCO- Imidazole ring
a-189 -CON(CH3)- The alkylidene of carbon number 1~5 -OCO- Imidazole ring
a-190 -O- The alkylidene of carbon number 1~5 -OCO- Pyrazole ring
a-191 -NH- The alkylidene of carbon number 1~5 -OCO- Pyrazole ring
a-192 -CONH- The alkylidene of carbon number 1~5 -OCO- Pyrazole ring
a-193 -NHCO- The alkylidene of carbon number 1~5 -OCO- Pyrazole ring
a-194 -CH2O- The alkylidene of carbon number 1~5 -OCO- Pyrazole ring
a-195 -OCO- The alkylidene of carbon number 1~5 -OCO- Pyrazole ring
[table 14]
W1 W2 W3 W4
a-196 -CON(CH3)- The alkylidene of carbon number 1~5 -OCO- Pyrazole ring
a-197 -O- The alkylidene of carbon number 1~5 -OCO- Pyridine ring
a-198 -NH- The alkylidene of carbon number 1~5 -OCO- Pyridine ring
a-199 -CONH- The alkylidene of carbon number 1~5 -OCO- Pyridine ring
a-200 -NHCO- The alkylidene of carbon number 1~5 -OCO- Pyridine ring
a-201 -CH2O- The alkylidene of carbon number 1~5 -OCO- Pyridine ring
a-202 -OCO- The alkylidene of carbon number 1~5 -OCO- Pyridine ring
a-203 -CON(CH3)- The alkylidene of carbon number 1~5 -OCO- Pyridine ring
a-204 -O- The alkylidene of carbon number 1~5 -OCO- Pyrimidine ring
a-205 -NH- The alkylidene of carbon number 1~5 -OCO- Pyrimidine ring
a-206 -CONH- The alkylidene of carbon number 1~5 -OCO- Pyrimidine ring
a-207 -NHCO- The alkylidene of carbon number 1~5 -OCO- Pyrimidine ring
a-208 -CH2O- The alkylidene of carbon number 1~5 -OCO- Pyrimidine ring
a-209 -OCO- The alkylidene of carbon number 1~5 -OCO- Pyrimidine ring
a-210 -CON(CH3)- The alkylidene of carbon number 1~5 -OCO- Pyrimidine ring
[table 15]
W1 W2 W3 W4
a-211 -O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-212 -NH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-213 -CONH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-214 -NHCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-215 -CH2O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-216 -OCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-217 -CON(CH3)- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-218 -O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-219 -NH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-220 -CONH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-221 -NHCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-222 -CH2O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-223 -OCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-224 -CON(CH3)- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-225 -O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrazole ring
[table 16]
W1 W2 W3 W4
a-226 -NH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-227 -CONH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-228 -NHCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-229 -CH2O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-230 -OCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-231 -CON(CH3)- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-232 -O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-233 -NH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-234 -CONH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-235 -NHCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-236 -CH2O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-237 -OCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-238 -CON(CH3)- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-239 -O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-240 -NH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
[table 17]
W1 W2 W3 W4
a-241 -CONH- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-242 -NHCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-243 -CH2O- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-244 -OCO- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-245 -CON(CH3)- The alkylidene of carbon number 1~5 - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-246 -O- Cyclohexane ring -O- Pyrrole ring
a-247 -NH- Cyclohexane ring -O- Pyrrole ring
a-248 -CONH- Cyclohexane ring -O- Pyrrole ring
a-249 -NHCO- Cyclohexane ring -O- Pyrrole ring
a-250 -CH2O- Cyclohexane ring -O- Pyrrole ring
a-251 -OCO- Cyclohexane ring -O- Pyrrole ring
a-252 -CON(CH3)- Cyclohexane ring -O- Pyrrole ring
a-253 -O- Cyclohexane ring -O- Imidazole ring
a-254 -NH- Cyclohexane ring -O- Imidazole ring
a-255 -CONH- Cyclohexane ring -O- Imidazole ring
[table 18]
W1 W2 W3 W4
a-256 -NHCO- Cyclohexane ring -O- Imidazole ring
a-257 -CH2O- Cyclohexane ring -O- Imidazole ring
a-258 -OCO- Cyclohexane ring -O- Imidazole ring
a-259 -CON(CH3)- Cyclohexane ring -O- Imidazole ring
a-260 -O- Cyclohexane ring -O- Pyrazole ring
a-261 -NH- Cyclohexane ring -O- Pyrazole ring
a-262 -CONH- Cyclohexane ring -O- Pyrazole ring
a-263 -NHCO- Cyclohexane ring -O- Pyrazole ring
a-264 -CH2O- Cyclohexane ring -O- Pyrazole ring
a-265 -OCO- Cyclohexane ring -O- Pyrazole ring
a-266 -CON(CH3)- Cyclohexane ring -O- Pyrazole ring
a-267 -O- Cyclohexane ring -O- Pyridine ring
a-268 -NH- Cyclohexane ring -O- Pyridine ring
a-269 -CONH- Cyclohexane ring -O- Pyridine ring
a-270 -NHCO- Cyclohexane ring -O- Pyridine ring
[table 19]
W1 W2 W3 W4
a-271 -CH2O- Cyclohexane ring -O- Pyridine ring
a-272 -OCO- Cyclohexane ring -O- Pyridine ring
a-273 -CON(CH3)- Cyclohexane ring -O- Pyridine ring
a-274 -O- Cyclohexane ring -O- Pyrimidine ring
a-275 -NH- Cyclohexane ring -O- Pyrimidine ring
a-276 -CONH- Cyclohexane ring -O- Pyrimidine ring
a-277 -NHCO- Cyclohexane ring -O- Pyrimidine ring
a-278 -CH2O- Cyclohexane ring -O- Pyrimidine ring
a-279 -OCO- Cyclohexane ring -O- Pyrimidine ring
a-280 -CON(CH3)- Cyclohexane ring -O- Pyrimidine ring
a-281 -O- Cyclohexane ring -OCO- Pyrrole ring
a-282 -NH- Cyclohexane ring -OCO- Pyrrole ring
a-283 -CONH- Cyclohexane ring -OCO- Pyrrole ring
a-284 -NHCO- Cyclohexane ring -OCO- Pyrrole ring
a-285 -CH2O- Cyclohexane ring -OCO- Pyrrole ring
[table 20]
W1 W2 W3 W4
a-286 -OCO- Cyclohexane ring -OCO- Pyrrole ring
a-287 -CON(CH3)- Cyclohexane ring -OCO- Pyrrole ring
a-288 -O- Cyclohexane ring -OCO- Imidazole ring
a-289 -NH- Cyclohexane ring -OCO- Imidazole ring
a-290 -CONH- Cyclohexane ring -OCO- Imidazole ring
a-291 -NHCO- Cyclohexane ring -OCO- Imidazole ring
a-292 -CH2O- Cyclohexane ring -OCO- Imidazole ring
a-293 -OCO- Cyclohexane ring -OCO- Imidazole ring
a-294 -CON(CH3)- Cyclohexane ring -OCO- Imidazole ring
a-295 -O- Cyclohexane ring -OCO- Pyrazole ring
a-296 -NH- Cyclohexane ring -OCO- Pyrazole ring
a-297 -CONH- Cyclohexane ring -OCO- Pyrazole ring
a-298 -NHCO- Cyclohexane ring -OCO- Pyrazole ring
a-299 -CH2O- Cyclohexane ring -OCO- Pyrazole ring
a-300 -OCO- Cyclohexane ring -OCO- Pyrazole ring
[table 21]
W1 W2 W3 W4
a-301 -CON(CH3)- Cyclohexane ring -OCO- Pyrazole ring
a-302 -O- Cyclohexane ring -OCO- Pyridine ring
a-303 -NH- Cyclohexane ring -OCO- Pyridine ring
a-304 -CONH- Cyclohexane ring -OCO- Pyridine ring
a-305 -NHCO- Cyclohexane ring -OCO- Pyridine ring
a-306 -CH2O- Cyclohexane ring -OCO- Pyridine ring
a-307 -OCO- Cyclohexane ring -OCO- Pyridine ring
a-308 -CON(CH3)- Cyclohexane ring -OCO- Pyridine ring
a-309 -O- Cyclohexane ring -OCO- Pyrimidine ring
a-310 -NH- Cyclohexane ring -OCO- Pyrimidine ring
a-311 -CONH- Cyclohexane ring -OCO- Pyrimidine ring
a-312 -NHCO- Cyclohexane ring -OCO- Pyrimidine ring
a-313 -CH2O- Cyclohexane ring -OCO- Pyrimidine ring
a-314 -OCO- Cyclohexane ring -OCO- Pyrimidine ring
a-315 -CON(CH3)- Cyclohexane ring -OCO- Pyrimidine ring
[table 22]
W1 W2 W3 W4
a-316 -O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-317 -NH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-318 -CONH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-319 -NHCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-320 -CH2O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-321 -OCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-322 -CON(CH3)- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-323 -O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-324 -NH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-325 -CONH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-326 -NHCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-327 -CH2O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-328 -OCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-329 -CON(CH3)- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-330 -O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
[table 23]
W1 W2 W3 W4
a-331 -NH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-332 -CONH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-333 -NHCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-334 -CH2O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-335 -OCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-336 -CON(CH3)- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-337 -O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-338 -NH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-339 -CONH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-340 -NHCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-341 -CH2O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-342 -OCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-343 -CON(CH3)- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-344 -O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-345 -NH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
[table 24]
W1 W2 W3 W4
a-346 -CONH- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-347 -NHCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-348 -CH2O- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-349 -OCO- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-350 -CON(CH3)- Cyclohexane ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-351 -O- Phenyl ring -O- Pyrrole ring
a-352 -NH- Phenyl ring -O- Pyrrole ring
a-353 -CONH- Phenyl ring -O- Pyrrole ring
a-354 -NHCO- Phenyl ring -O- Pyrrole ring
a-355 -CH2O- Phenyl ring -O- Pyrrole ring
a-356 -OCO- Phenyl ring -O- Pyrrole ring
a-357 -CON(CH3)- Phenyl ring -O- Pyrrole ring
a-358 -O- Phenyl ring -O- Imidazole ring
a-359 -NH- Phenyl ring -O- Imidazole ring
a-360 -CONH- Phenyl ring -O- Imidazole ring
[table 25]
W1 W2 W3 W4
a-361 -NHCO- Phenyl ring -O- Imidazole ring
a-362 -CH2O- Phenyl ring -O- Imidazole ring
a-363 -OCO- Phenyl ring -O- Imidazole ring
a-364 -CON(CH3)- Phenyl ring -O- Imidazole ring
a-365 -O- Phenyl ring -O- Pyrazole ring
a-366 -NH- Phenyl ring -O- Pyrazole ring
a-367 -CONH- Phenyl ring -O- Pyrazole ring
a-368 -NHCO- Phenyl ring -O- Pyrazole ring
a-369 -CH2O- Phenyl ring -O- Pyrazole ring
a-370 -OCO- Phenyl ring -O- Pyrazole ring
a-371 -CON(CH3)- Phenyl ring -O- Pyrazole ring
a-372 -O- Phenyl ring -O- Pyridine ring
a-373 -NH- Phenyl ring -O- Pyridine ring
a-374 -CONH- Phenyl ring -O- Pyridine ring
a-375 -NHCO- Phenyl ring -O- Pyridine ring
[table 26]
W1 W2 W3 W4
a-376 -CH2O- Phenyl ring -O- Pyridine ring
a-377 -OCO- Phenyl ring -O- Pyridine ring
a-378 -CON(CH3)- Phenyl ring -O- Pyridine ring
a-379 -O- Phenyl ring -O- Pyrimidine ring
a-380 -NH- Phenyl ring -O- Pyrimidine ring
a-381 -CONH- Phenyl ring -O- Pyrimidine ring
a-382 -NHCO- Phenyl ring -O- Pyrimidine ring
a-383 -CH2O- Phenyl ring -O- Pyrimidine ring
a-384 -OCO- Phenyl ring -O- Pyrimidine ring
a-385 -CON(CH3)- Phenyl ring -O- Pyrimidine ring
a-386 -O- Phenyl ring -OCO- Pyrrole ring
a-387 -NH- Phenyl ring -OCO- Pyrrole ring
a-388 -CONH- Phenyl ring -OCO- Pyrrole ring
a-389 -NHCO- Phenyl ring -OCO- Pyrrole ring
a-390 -CH2O- Phenyl ring -OCO- Pyrrole ring
[table 27]
W1 W2 W3 W4
a-391 -OCO- Phenyl ring -OCO- Pyrrole ring
a-392 -CON(CH3)- Phenyl ring -OCO- Pyrrole ring
a-393 -O- Phenyl ring -OCO- Imidazole ring
a-394 -NH- Phenyl ring -OCO- Imidazole ring
a-395 -CONH- Phenyl ring -OCO- Imidazole ring
a-396 -NHCO- Phenyl ring -OCO- Imidazole ring
a-397 -CH2O- Phenyl ring -OCO- Imidazole ring
a-398 -OCO- Phenyl ring -OCO- Imidazole ring
a-399 -CON(CH3)- Phenyl ring -OCO- Imidazole ring
a-400 -O- Phenyl ring -OCO- Pyrazole ring
a-401 -NH- Phenyl ring -OCO- Pyrazole ring
a-402 -CONH- Phenyl ring -OCO- Pyrazole ring
a-403 -NHCO- Phenyl ring -OCO- Pyrazole ring
a-404 -CH2O- Phenyl ring -OCO- Pyrazole ring
a-405 -OCO- Phenyl ring -OCO- Pyrazole ring
[table 28]
W1 W2 W3 W4
a-406 -CON(CH3)- Phenyl ring -OCO- Pyrazole ring
a-407 -O- Phenyl ring -OCO- Pyridine ring
a-408 -NH- Phenyl ring -OCO- Pyridine ring
a-409 -CONH- Phenyl ring -OCO- Pyridine ring
a-410 -NHCO- Phenyl ring -OCO- Pyridine ring
a-411 -CH2O- Phenyl ring -OCO- Pyridine ring
a-412 -OCO- Phenyl ring -OCO- Pyridine ring
a-413 -CON(CH3)- Phenyl ring -OCO- Pyridine ring
a-414 -O- Phenyl ring -OCO- Pyrimidine ring
a-415 -NH- Phenyl ring -OCO- Pyrimidine ring
a-416 -CONH- Phenyl ring -OCO- Pyrimidine ring
a-417 -NHCO- Phenyl ring -OCO- Pyrimidine ring
a-418 -CH2O- Phenyl ring -OCO- Pyrimidine ring
a-419 -OCO- Phenyl ring -OCO- Pyrimidine ring
a-420 -CON(CH3)- Phenyl ring -OCO- Pyrimidine ring
[table 29]
W1 W2 W3 W4
a-421 -O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-422 -NH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-423 -CONH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-424 -NHCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-425 -CH2O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-426 -OCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-427 -CON(CH3)- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrrole ring
a-428 -O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-429 -NH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-430 -CONH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-431 -NHCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-432 -CH2O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-433 -OCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-434 -CON(CH3)- Phenyl ring - O (CH2) m- (m is 1~5 integer) Imidazole ring
a-435 -O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
[table 30]
W1 W2 W3 W4
a-436 -NH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-437 -CONH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-438 -NHCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-439 -CH2O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-440 -OCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-441 -CON(CH3)- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrazole ring
a-442 -O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-443 -NH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-444 -CONH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-445 -NHCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-446 -CH2O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-447 -OCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-448 -CON(CH3)- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyridine ring
a-449 -O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-450 -NH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
[table 31]
W1 W2 W3 W4
a-451 -CONH- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-452 -NHCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-453 -CH2O- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-454 -OCO- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
a-455 -CON(CH3)- Phenyl ring - O (CH2) m- (m is 1~5 integer) Pyrimidine ring
Wherein, be preferably (a-43)~(a-49), (a-57)~(a-63), (a-218)~(a-224), (a-232)~ (a-238), (a-323)~(a-329), (a-337)~(a-343), (a-428)~(a-434) or (a-442)~(a-448) Combination.From the viewpoint of it can suppress the long-term voltage retention reduction being exposed to after light irradiation, more preferably (a-44), (a-45), (a-58) or (a-59) combination.
As the diamine compound with specific structure (1), preferably use shown in following formula [2a] diamine compound ( Referred to as specific diamine compound (1)).
In formula [2a], W represents the structure shown in previously described formula [2].
In addition, the W in formula [2]1、W2、W3And W4Details and preferred compositions such as previously described formula [2] shown in.
From the viewpoint of synthesis easness, m1 is preferably 1.
From the viewpoint of it can suppress the long-term voltage retention reduction being exposed to after light irradiation, specific diamine compound (1) use ratio is preferably integrally 1~60 mole of % relative to diamine component.More preferably 1~50 mole %, particularly preferably For 5~50 moles of %.
In addition, specific diamine compound (1) can according to the dissolubility of specific polyimides based polymer in a solvent, be made Liquid crystal aligning or liquid crystal during liquid crystal orientation film represent the characteristics such as the electrical characteristics of element and using a kind or are used in mixed way 2 More than kind.
The liquid crystal that the aligning agent for liquid crystal of the present invention is used for VA patterns, PSA patterns or SC-PVA patterns is represented into element When, diamine component preferably uses the diamines with structure shown in following formula [3-1] or formula [3-2] (also referred to as specific structure (2)) Compound.
In formula [3-1], Y1、Y2、Y3、Y4、Y5、Y6It is shown as defined above with n, wherein, it is respectively preferably following radicals.
From the viewpoint of raw material availability, synthesis easness, Y1Preferably singly-bound ,-(CH2)a- (a for 1~15 it is whole Number) ,-O- ,-CH2O- or-COO-.More preferably singly-bound ,-(CH2)a- (a is 1~10 integer) ,-O- ,-CH2O- or-COO-.
Y2Preferably singly-bound or-(CH2)b- (b is 1~10 integer).
From the viewpoint of synthesis easness, Y3Preferably singly-bound ,-(CH2)c- (c be 1~15 integer) ,-O- ,- CH2O- or-COO-.More preferably singly-bound ,-(CH2)c- (c is 1~10 integer) ,-O- ,-CH2O- or-COO-.
From the viewpoint of synthesis easness, Y4Preferably phenyl ring, cyclohexane ring or the carbon number with steroid skeleton 17~51 organic group.
Y5Preferably phenyl ring or cyclohexane ring.
Y6Preferably the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, carbon number 1~10 contain fluoroalkyl, carbon number 1~18 Alkoxy or carbon number 1~10 fluoroalkoxy.The more preferably alkenyl or carbon number of the alkyl of carbon number 1~12, carbon number 2~18 1~12 alkoxy.The particularly preferably alkoxy of the alkyl of carbon number 1~9, the alkenyl of carbon number 2~12 or carbon number 1~9.
From the viewpoint of raw material availability, synthesis easness, n is preferably 0~3, more preferably 0~2.
Y1、Y2、Y3、Y4、Y5、Y6It can be included and International Publication publication WO2011/132751 with n preferred compositions (2-1)~(2-629) identicals combination described in 6~table of table 47 of page 13 of (2011.10.27 is disclosed)~page 34.Should Illustrate, in each table of International Publication publication, the Y in the present invention1~Y6Y1~Y6 is represented as, but Y1~Y6 can be regarded as Y1~ Y6.It is of the invention that there is steroid skeleton in addition, in (2-605)~(2-629) described in each table of International Publication publication The organic group of carbon number 17~51 is illustrated as having the organic group of the carbon number 12~25 of steroid skeleton, but with steroids The organic group of the carbon number 12~25 of skeleton can be regarded as the organic group of the carbon number 17~51 with steroid skeleton.
Wherein, be preferably (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268)~ (2-315), (2-364)~(2-387), (2-436)~(2-483) or (2-603)~(2-615) combination.It is particularly preferred It is combined as (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2-606), (2- 607)~(2-609), (2-611), (2-612) or (2-624).
-Y7-Y8 [3-2]
In formula [3-2], Y7And Y8It is shown as defined above, wherein, it is respectively preferably following radicals.
Y7Preferably singly-bound ,-O- ,-CH2O-、-CONH-、-CON(CH3)-or-COO-.More preferably singly-bound ,-O- ,- CONH- or-COO-.
Y8The preferably alkyl of carbon number 8~18.
In the present invention, from the viewpoint of high and stable liquid crystal vertical-tropism is resulted in, specific structure (2) is preferably Use the structure shown in formula [3-1].
As the diamine compound with specific structure (2), preferably use shown in following formula [3a] diamine compound ( Referred to as specific diamine compound (2)).
In formula [3a], Y represents previously described formula [3-1] or the structure shown in formula [3-2].
In addition, the Y in formula [3-1]1、Y2、Y3、Y4、Y5、Y6With n details and preferred compositions such as previously described formula [3-1], formula [3- 2] Y in7And Y8Details and preferred compositions such as previously described formula [3-2].
From the viewpoint of synthesis easness, n1 is preferably 1.
As the specific diamine compound (2) with specific structure shown in formula [3-1], specifically, it can include for example Diamine compound shown in following formula [3a-1]~formula [3a-31].
(R1Represent to be selected from by-O- ,-OCH respectively2-、-CH2O-、-COOCH2- and-CH2At least 1 in the group of OCO- compositions Plant binding groups.R2The straight-chain or branched-chain alkyl, the straight-chain or branched of carbon number 1~18 of carbon number 1~18 are represented respectively Alkoxy, the straight-chain of carbon number 1~18 or branched straight-chain or branched containing fluoroalkyl or carbon number 1~18 contain fluothane Epoxide.)
(R3Represent to be selected from by-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH respectively2-、-CH2OCO-、-CH2O-、- OCH2- and-CH2At least one kind of binding groups in the group of-composition.R4The straight-chain or branched alkane of carbon number 1~18 are represented respectively Base, the straight-chain of carbon number 1~18 or branched alkoxy, the straight-chain of carbon number 1~18 or branched contain fluoroalkyl or carbon number 1~18 straight-chain or branched fluoroalkoxy.)
(R5Represent to be selected from by-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH respectively2-、-CH2OCO-、-CH2O-、- OCH2-、-CH2- ,-O- and-NH- composition group at least one kind of binding groups.R6Represent to be selected from by fluorine-based, cyano group, three respectively It is at least one kind of in the group that fluoromethane base, nitro, azo group, formoxyl, acetyl group, acetoxyl group and hydroxyl are constituted.)
(R7The straight-chain or branched-chain alkyl of carbon number 3~12 are represented respectively, and the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylene is anti- Formula isomers.)
(R8The straight-chain or branched-chain alkyl of carbon number 3~12 are represented respectively, and the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylene is anti- Formula isomers.)
(A4The straight-chain or branched-chain alkyl for the carbon number 3~18 that expression is optionally replaced by fluorine atoms.A3Represent that 1,4- rings are sub- Hexyl or 1,4- phenylenes.A2Represent that oxygen atom or-COO-* (wherein, mark the key and A of " * "3Bonding).A1Represent oxygen atom Or-COO-* (wherein, marks the key and (CH of " * "2)a2Bonding).In addition, a1The integer of expression 0 or 1.a2Represent 2~10 it is whole Number.a3The integer of expression 0 or 1.)
In above-mentioned formula [3a-1]~[3a-31], diamine compound preferably is formula [3a-1]~formula [3a-6], formula [3a-9] ~formula [3a-13] or formula [3a-22]~formula [3a-31].
As the specific diamine compound (2) with specific structure (2) shown in previously described formula [3-2], specifically, it can enumerate Go out the diamine compound for example shown in following formula [3a-32]~[3a-35].
(A1The alkyl of carbon number 8~18 is represented respectively or containing fluoroalkyl.)
Especially in the case where representing element for the liquid crystal of VA patterns, PSA patterns or SC-PVA patterns, specific diamines The use ratio of compound (2) is preferably integrally 10~70 moles of % relative to diamine component.More preferably 20~70 moles %, Particularly preferably 20~60 moles %.
In addition, specific diamine compound (2) can according to the dissolubility of specific polyimides based polymer in a solvent, be made Liquid crystal aligning or liquid crystal during liquid crystal orientation film represent the characteristics such as the electrical characteristics of element using a kind or are used in mixed way 2 kinds More than.
In the diamine component of the present invention, the intermediate scheme, i.e. TN (Twisted of element can be represented according to liquid crystal Nematic) pattern, IPS (In-plane Switching) pattern, VA patterns, PSA patterns and SC-PVA patterns, appropriate selection And use foregoing specific diamine compound (1) and specific diamine compound (2).In addition, these specific diamine compounds also may be used To use two or more, you can with using a variety of.
As the diamine component for making specific polyimides based polymer, following diamine compounds can also be used (also referred to as other diamine compounds).
Specifically, can include such as 2,4- dimethyl-m-phenylenediamines, 2,6- diaminotoluenes, m-phenylene diamine (MPD), to benzene Between diamines, 2,4- diaminophenols, 3,5- diaminophenols, 3,5- diaminourea benzylalcohol, 2,4- diaminourea benzylalcohol, 4,6- diaminourea Benzenediol, 2,4- diaminobenzoic acids, 2,5- diaminobenzoic acids, 3,5- diaminobenzoic acids, 4,4 '-benzidine, 3, 3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy -4,4 '-diamino Base biphenyl, 3,3 '-dicarboxyl -4,4 '-benzidine, the fluoro- 4,4 '-biphenyl of 3,3 '-ジ, '-two of 3,3 '-trifluoromethyl -4,4 Aminobphenyl, 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 '-diaminourea two Phenylmethane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 3,4 '-diamino Yl diphenyl ether, 2,2 '-diaminodiphenyl ether, 2,3 '-diaminodiphenyl ether, 4,4 '-sulfonyldianiline, 3,3 '-sulfonyl two Aniline, double (4- aminophenyls) silane, double (3- aminophenyls) silane, dimethyl-bis- (4- aminophenyls) silane, dimethyl- Double (3- aminophenyls) 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 '-diaminourea hexichol Base) amine, N- methyl (2,2 '-diamino-diphenyl) amine, N- methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminourea hexichol Ketone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 1,4- diaminonaphthalenes, 2,2 '-diaminourea hexichol first Ketone, 2,3 '-diaminobenzophenone, 1,5- diaminonaphthalenes, 1,6- diaminonaphthalenes, 1,7- diaminonaphthalenes, 1,8- diaminonaphthalenes, 2, 5- diaminonaphthalenes, 2,6- diaminonaphthalenes, 2,7- diaminonaphthalenes, 2,8- diaminonaphthalenes, 1,2- double (4- aminophenyls) ethane, 1,2- Double (4- aminophenyls) propane of double (3- aminophenyls) ethane, 1,3-, double (3- aminophenyls) propane of 1,3-, double (4 amino of 1,4- Phenyl) butane, double (3- aminophenyls) butane of 1,4-, double (3,5- diethyl -4- aminophenyls) methane, double (the 4- amino of 1,4- Phenoxy group) benzene, double (4- amino-benzene oxygens) benzene of 1,3-, double (4- aminophenyls) benzene of 1,4-, 1,3- double (4- aminophenyls) benzene, 1, Double (4- aminobenzyls) benzene of 4-, 1,3- double (4- amino-benzene oxygens) benzene, 4,4 '-[1,4- phenylenes dimethylene] diphenylamines, 4, 4 '-[1,3- phenylenes dimethylene] diphenylamines, 3,4 '-[1,4- phenylenes dimethylene] diphenylamines, 3,4 '-[1,3- Asias benzene Base dimethylene] diphenylamines, 3,3 '-[1,4- phenylenes dimethylene] diphenylamines, 3,3 '-[1,3- phenylenes dimethylene] two Aniline, 1,4- phenylenes double [(4- aminophenyls) ketones], 1,4- phenylenes double [(3- aminophenyls) ketone], 1,3- phenylenes Double [(4- aminophenyls) ketones], 1,3- phenylenes double [(3- aminophenyls) ketones], the double (PABAs of 1,4- phenylenes Ester), 1,4- phenylenes double (3- Aminobenzoates), 1,3- phenylenes double (PABA esters), the double (3- of 1,3- phenylenes Aminobenzoate), double (4- aminophenyls) terephthalates, double (3- aminophenyls) terephthalates, double (4- amino Phenyl) isophthalic acid ester, double (3- aminophenyls) isophthalic acid esters, N, N '-(1,4- phenylenes) double (4- aminobenzoyls Amine), N, N '-(1,3- phenylenes) double (4- aminobenzamides), N, N '-(1,4- phenylenes) double (3-ABs), N, N '-(1,3- phenylenes) double (3-ABs), N, N '-bis- (4- aminophenyls) terephthalamide, N, N '-bis- Between (3- aminophenyls) terephthalamide, N, N '-bis- (4- aminophenyls) phenyl-diformyl press, N, N '-bis- (3- aminophenyls) Between phenyl-diformyl press, double (4- aminophenyls) anthracenes of 9,10-, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfones, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] propane, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] HFC-236fas, 2,2 '-bis- (4- amino Phenyl) HFC-236fa, 2,2 '-bis- (3- aminophenyls) HFC-236fas, 2,2 '-bis- (3- amino -4- aminomethyl phenyls) HFC-236fas, 2,2 '-bis- (4- aminophenyls) propane, 2,2 '-bis- (3- aminophenyls) propane, 2,2 '-bis- (3- amino -4- aminomethyl phenyls) third Double (4- amino-benzene oxygens) propane of alkane, 1,3-, double (3- amino-benzene oxygens) propane of 1,3-, double (4- amino-benzene oxygens) fourths of 1,4- Double (3- amino-benzene oxygens) butane of alkane, 1,4-, double (4- amino-benzene oxygens) pentanes of 1,5-, double (the 3- amino-benzene oxygens) penta of 1,5- Double (4- amino-benzene oxygens) hexanes of alkane, 1,6-, double (3- amino-benzene oxygens) hexanes of 1,6-, 1,7- pairs of (4- amino-benzene oxygens) heptan Double (3- amino-benzene oxygens) heptane of alkane, 1,7-, double (4- amino-benzene oxygens) octanes of 1,8-, 1,8- double (3- amino-benzene oxygens) are pungent Double (4- amino-benzene oxygens) nonanes of alkane, 1,9-, double (3- amino-benzene oxygens) nonanes of 1,9-, 1,10- double (4- amino-benzene oxygens) last of the ten Heavenly stems Double (3- amino-benzene oxygens) decane of alkane, 1,10-, double (4- amino-benzene oxygens) hendecanes of 1,11-, double (the 3- aminobenzene oxygen of 1,11- Base) hendecane, double (4- amino-benzene oxygens) dodecanes of 1,12-, 1,12- double (3- amino-benzene oxygens) dodecane, double (4- amino rings Hexyl) methane, double (4- amino -3- methylcyclohexyls) methane, 1,3- diaminopropanes, 1,4- diaminobutanes, 1,5- diaminos Base pentane, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diamino nonanes, 1,10- diaminos Base decane, 1,11- diamino undecanes or 1,12- diamino dodecanes etc..
In addition, as other diamine compounds, two amine compounds shown in following formula [D1]~formula [DA15] can also be used Thing.
(p represents 1~10 integer.)
(L1Represent the alkyl of hydrogen atom or carbon number 1~5.N represents 1~5 integer.)
Other diamine compounds can according to the dissolubility of specific polyimides based polymer in a solvent, liquid crystal aligning is made Liquid crystal aligning or liquid crystal during film represent the characteristics such as the electrical characteristics of element and using a kind or are mixed with two or more.
Tetrabasic carboxylic acid shown in following formula [4] is preferably used for making the tetrabasic carboxylic acid composition of specific polyimides based polymer Dianhydride (also referred to as specific tetrabasic carboxylic acid composition).
In formula [4], Z represents to be selected from as at least one kind of knot in the group of the structure composition shown in previously described formula [4a]~formula [4k] Structure.
From the viewpoint of polymerisation reactivity easness when synthesizing easness, manufacture polymer, the Z in formula [4] is preferred For the structure shown in formula [4a], formula [4c], formula [4d], formula [4e], formula [4f], formula [4g] or formula [4k].More preferably formula [4a], Structure shown in formula [4e], formula [4f], formula [4g] or formula [4k].Particularly preferably formula [4e], formula [4f], formula [4g] or formula [4k] Shown structure.
The use ratio of specific tetrabasic carboxylic acid composition is preferably 1 mole of more than % relative to whole tetrabasic carboxylic acid compositions.More preferably For 5 moles of more than %.Particularly preferably 10 moles more than %, from the voltage retention that can suppress for a long time after light irradiation From the viewpoint of reduction, most preferably 10~90 moles %.
In addition, using during the tetrabasic carboxylic acid composition of structure, passing through shown in previously described formula [4e], formula [4f], formula [4g] or formula [4k] Its consumption is set to 20 moles of overall more than % of tetrabasic carboxylic acid composition, intended effect can be obtained.Preferably 30 moles % with On.And then, tetrabasic carboxylic acid composition can be entirely the tetrabasic carboxylic acid composition of formula [4e], formula [4f], formula [4g] or structure shown in formula [4k].
As the tetrabasic carboxylic acid composition in the present invention, in the range of effect of the present invention is not damaged, it can use except specific Other tetrabasic carboxylic acid compositions outside tetrabasic carboxylic acid composition.
Specifically, such as pyromellitic acid, 2 can be included, 3,6,7- naphthalene tetracarboxylic acids, 1,2,5,6- naphthalene tetracarboxylic acids, Isosorbide-5-Nitrae, 5,8- naphthalene tetracarboxylic acids, 2,3,6,7- anthracenes tetrabasic carboxylic acid, 1,2,5,6- anthracenes tetrabasic carboxylic acid, 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acid, 2,3,3 ', 4 '-xenyl tetrabasic carboxylic acid, double (3,4- dicarboxyphenyis) ethers, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, double (3,4- dicarboxyl benzene Base) sulfone, double (3,4- dicarboxyphenyis) methane, 2,2- double (3,4- dicarboxyphenyis) propane, 1,1,1,3,3,3- hexafluoros -2,2- Double (3,4- dicarboxyphenyis) propane, double (3,4- dicarboxyphenyis) dimethylsilanes, double (3,4- dicarboxyphenyis) diphenyl Double (3,4- dicarboxyphenyis) pyridines of silane, 2,3,4,5- pyridines tetrabasic carboxylic acid, 2,6-, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid, 3,4,9,10- perylene tetracarboxylic acids or 1,3- diphenyl -1,2,3,4- cyclobutane tetrabasic carboxylic acids etc..
Specific tetrabasic carboxylic acid composition and other tetrabasic carboxylic acid compositions can be according to specific polyimides based polymers in a solvent Dissolubility, liquid crystal aligning when liquid crystal orientation film is made or liquid crystal represent the characteristics such as the electrical characteristics of element and use a kind or Person is mixed with two or more.
Method for making specific polyimides based polymer is not particularly limited.It is typically to make diamine component and tetracarboxylic acid Sour composition reacts and obtained.It is selected from what is be made up of the derivative of tetracarboxylic dianhydride and its tetrabasic carboxylic acid in general, can enumerate and send as an envoy to At least one kind of tetrabasic carboxylic acid composition in group reacts with the diamine component comprising one or more diamine compounds, so as to be gathered The method of amic acid.Specifically, it can make with the following method：Make tetracarboxylic dianhydride and primary diamines compound or secondary diamine chemical combination Thing polycondensation and obtain the method for polyamic acid, tetrabasic carboxylic acid and primary diamines compound or secondary diamine compounds is occurred dehydrating polycondensation anti- Answer and obtain the method for polyamic acid or the carboxylic acid halides of tetrabasic carboxylic acid two is reacted with primary diamines compound or secondary diamine compounds And the method for obtaining polyamic acid.
In order to obtain polyamic acid Arrcostab, it can make with the following method：Make to have carried out carboxylic acid group dialkyl group esterification Tetrabasic carboxylic acid and primary diamines compound or the method for secondary diamine compounds polycondensation, make tetracarboxylic acid that dialkyl group esterification has been carried out to carboxylic acid group Method or be converted into the carboxyl of polyamic acid that sour two carboxylic acid halides react with primary diamines compound or secondary diamine compounds The method of ester.
In order to obtain polyimides, foregoing polyamides acid or polyamic acid Arrcostab closed loop can be used and polyamides is made The method of imines.
The reaction of diamine component and tetrabasic carboxylic acid composition generally makes diamine component and tetrabasic carboxylic acid composition carry out in organic solvent. As the organic solvent now used, as long as the solvent of the generated polyimide precursor of dissolving, is just not particularly limited.With Under include the concrete example of organic solvent used in reaction, but be not limited to these examples.
Such as METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, gamma-butyrolacton, N, N- dimethyl can be included Formamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) or 1,3- dimethyl-imidazol alkanones etc..In addition, in polyimide precursor Solvent solubility it is high in the case of, can use MEK, cyclohexanone, cyclopentanone, 4- hydroxy-4-methyl-2-pentanones or under State the solvent shown in formula [D-1]~formula [D-3].
(D1Represent the alkyl of carbon number 1~3.D2Represent the alkyl of carbon number 1~3.D3Represent the alkyl of carbon number 1~4.)
They can be used alone, and can also be used in mixed way.And then, even the solvent of insoluble polyimide precursor, It can also mix to above-mentioned solvent to use in the range of the polyimide precursor generated will not be separated out.In addition, organic molten Moisture in agent can hinder polymerisation and then turn into make the reason for generated polyimide precursor is hydrolyzed, therefore organic molten Agent is used after preferably dehydrating.
When diamine component and the tetrabasic carboxylic acid composition is reacted in organic solvent, following method can be included：Stirring makes diamines Composition is dispersed or dissolved in the solution of organic solvent, and tetrabasic carboxylic acid composition is directly added or is dispersed or dissolved in organic molten The method added after agent；Conversely, to make tetrabasic carboxylic acid composition be dispersed or dissolved in the solution of organic solvent add diamines into The method divided；Alternately method of addition diamine component and tetrabasic carboxylic acid composition etc., can use any means in these.This Outside, it can be reacted respectively using a variety of diamine components and tetrabasic carboxylic acid composition and when reacting it in the state of being pre-mixed, It can react successively respectively, and then, the low-molecular weight reacted respectively can also be carried out to hybrid reaction poly- so as to be made Compound.Polymerization temperature now can select -20 DEG C~150 DEG C of arbitrary temp, be preferably -5 DEG C~100 DEG C of scope.This Outside, reaction can be carried out under any concentration, but concentration it is too low when, it is difficult to obtain the polymer of HMW, during excessive concentration, The viscosity of reaction solution becomes too high and is difficult to uniform stirring.It is therefore preferable that being 1~50 mass %, more preferably 5~30 matter Measure %.The initial stage of polymerisation can also be carried out in higher concentrations, add organic solvent again thereafter.
In the polymerisation of polyimide precursor, the ratio between the total mole number of diamine component and the total mole number of tetrabasic carboxylic acid composition Preferably 0.8~1.2.In the same manner as common polymerisation, the mol ratio is before 1.0, then the polyimides generated The molecular weight of body becomes bigger.
Polyimides is to make polyimides obtained from foregoing polyimide precursor closed loop, the closed loop rate of acid amides acidic group ( Referred to as acid imide rate) it is not necessarily required to as 100%, can be according to purposes, purpose come any adjustment.Wherein, it is of the invention specific Polyimides based polymer is preferably polyimides obtained from polyimide precursor is carried out into imidizate.Acid imide now Rate is preferably 40~90%.More preferably 50~90%.
As the method for making polyimide precursor carry out imidizate, it can include：The solution of polyimide precursor is straight Connect the hot-imide of heating or the catalysis imidizate of catalyst is added into the solution of polyimide precursor.Make polyamides Temperature when imines precursor carries out hot-imide in the solution is 100 DEG C~400 DEG C, is preferably 120 DEG C~250 DEG C, preferably , while the water generated by imidization reaction is expelled to outside system while the method carried out.
The catalysis imidizate of polyimide precursor can be by adding base catalysis in the solution to polyimide precursor Agent and acid anhydrides, -20~250 DEG C, be preferably stirred and to implement at 0~180 DEG C.The amount of base catalyst is acid amides acidic group 0.5~30 mole times, be preferably 2~20 moles times, the amount of acid anhydrides is 1~50 mole times of acid amides acidic group, is preferably 3~30 Mole times.As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine or trioctylamine etc. can be included.Wherein, pyridine has There is the alkalescence suitable for promoting reaction, so it is preferred that.As acid anhydrides, acetic anhydride, trimellitic anhydride or pyromellitic dianhydride can be included Deng.When wherein, using acetic anhydride, reaction terminate after it is refined become easy, so it is preferred that.Acyl based on catalysis imidizate is sub- Amination rate can be controlled by adjusting catalytic amount, reaction temperature and reaction time.
The generated polyimide precursor of recovery or polyamides are sub- from the reaction solution of polyimide precursor or polyimides During amine, reaction solution, which is put into, precipitates it into solvent.As the solvent for precipitation, can include methanol, ethanol, Isopropanol, acetone, hexane, butyl cellosolve, heptane, MEK, methyl iso-butyl ketone (MIBK), toluene, benzene or water etc..Put into solvent And the polymer for making its precipitation can carry out air drying or heat drying under normal or reduced pressure after being recovered by filtration.In addition, When the operation that reprecipitation recovery is carried out making the polymer that precipitation is reclaimed be dissolved in organic solvent again is repeated 2~10 times, energy Enough reduce the impurity in polymer.As solvent now, it can include such as alcohols, ketone or hydrocarbon, using from these it During more than 3 kinds solvents of middle selection, purification efficiency is further improved, so it is preferred that.
Molecular weight on polyimides based polymer, it is contemplated that liquid crystal aligning film strength therefrom, formation liquid When workability during brilliant alignment films and film, to utilize GPC (gel permeation chromatography, Gel Permeation Chromatography) the Weight-average molecular gauge that method is determined, preferably 5,000~1,000,000.Wherein, preferably 10,000 ~150,000.
Specific polyimides based polymer in the present invention from even if long-term after light irradiation as described above, also can Suppress from the viewpoint of voltage retention reduction, be preferably by obtained from foregoing polyimide precursor progress catalysis imidizate Polyimides.Acid imide rate now is preferably foregoing scope.
<Aligning agent for liquid crystal>
The aligning agent for liquid crystal of the present invention is the coating solution for being used to be formed liquid crystal orientation film (also referred to as resin coating), Preferably comprise specific compound, polymer and solvent.
Shown in the use ratio of specific compound in aligning agent for liquid crystal is preferably as follows.That is, relative to all polymerizations The mass parts of the mass parts of thing 100, preferably 1 mass parts~30.The mass parts of more preferably 1 mass parts~20, particularly preferably 3 mass Part~15 mass parts.
Component of polymer in aligning agent for liquid crystal preferably uses specific polyimides based polymer, can also be mixed with In addition other polymer.Now, the content of other polymer in addition polymerize relative to specific polyimides system The mass parts of thing 100 are preferably the mass parts of 0.5 mass parts~15.The mass parts of more preferably 1 mass parts~10.In addition as Other polymer, can include aforesaid propylene acids polymers, methacrylic polymer, novolac resin, poly- hydroxyl Styrene, polyamide, polyester, cellulose or polysiloxanes etc..
On the solvent in aligning agent for liquid crystal, go out from uniform liquid crystal orientation film this viewpoint is formed by coating Solvent in hair, aligning agent for liquid crystal is preferably 70~99.9 mass %.The content can be according to the mesh of liquid crystal orientation film Mark thickness is suitably changed.
As long as the solvent (also referred to as good solvent) that the solvent used in aligning agent for liquid crystal can dissolve polymer does not just have It is particularly limited to.The concrete example using good solvent during specific polyimides based polymer is exemplified below out, but is not limited to this A little examples.
Such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N- second can be included Base -2-Pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolacton, 1,3- dimethyl-imidazols alkanone, MEK, cyclohexanone, cyclopentanone or 4- hydroxy-4-methyl-2-pentanones etc..
Wherein, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones or gamma-butyrolacton are preferably used.
And then, when the dissolubility of specific polyimides based polymer in a solvent is high, preferably use previously described formula [D-1]~formula Solvent shown in [D-3].
The use ratio of good solvent in aligning agent for liquid crystal is preferably that the solvent included in aligning agent for liquid crystal is whole 10~100 mass % of body.More preferably 20~90 mass %, particularly preferably 30~80 mass %.
In the range of effect of the present invention is not damaged, aligning agent for liquid crystal, which can be used, is coated with liquid crystal aligning processing The solvent (also referred to as poor solvent) that the film of liquid crystal orientation film during agent, surface smoothness are improved.It is exemplified below out bad The concrete example of solvent, but it is not limited to these examples.
Such as ethanol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohols, 2- amylalcohols, 3- can be included Amylalcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanols, 2- methyl-1-pentenes alcohol, 2- Methyl -2- amylalcohols, 2- ethyls-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanols, sec-n-octyl alcohol, 2- ethyl -1- hexanols, ring Hexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 2,3- butanediols, 1,5- pentanediols, 2- methyl -2,4-PD, 2- second Base -1,3- hexylene glycols, dipropyl ether, butyl oxide, two hexyl ether, dioxanes, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol two Butyl ether, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ether, diethylene glycol two Butyl ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, 3- ethoxybutyls acetic acid esters, 1- methyl amyls acetic acid esters, 2- ethyl-butyls acetic acid esters, 2- ethylhexyl acetates, ethylene glycol acetate, ethylene acetate, propylene carbonate, carbon Sour ethyl, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl ether, ethylene glycol monohexylether, 2- (oneself Base epoxide) ethanol, furfuryl alcohol, diethylene glycol, propane diols, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propyl alcohol, propane diols list first Ether acetic acid ester, DPG, dipropylene glycol monomethyl ether, DPE, dimethyl ether, tripropylene glycol list first Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol acetate, second Glycol diacetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, 2- (2- ethoxy ethoxies) ethyl Acetic acid esters, diethylene glycol acetic acid esters, triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, methyl lactate, lactic acid second Ester, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, glutaric acid methyl esters, pentanedioic acid diethyl ester, 3- methoxies Base methyl propionate, 3- ethoxy-propionic acids Methylethyl, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- Methoxy propyl propyl propionate, 3- methoxy propyls acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, lactic acid Solvent shown in isopentyl ester or previously described formula [D-1]~formula [D-3] etc..
Wherein, 1- hexanols, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, ethylene glycol are preferably used Solvent shown in monobutyl ether, dimethyl ether or previously described formula [D-1]~formula [D-3].
The use ratio of these poor solvents is preferably 1~70 overall matter of the solvent included in aligning agent for liquid crystal Measure %.More preferably 1~60 mass %, particularly preferably 5~60 mass %.
The aligning agent for liquid crystal of the present invention is preferably imported：With selected from by epoxy radicals, NCO, oxetanylmethoxy The cross-linked compound of group in the group constituted with cyclocarbonate radical；With selecting free hydroxyl, hydroxy alkyl and carbon number 1~3 Alkoxyalkyl composition group in group cross-linked compound；Or the crosslinking with the unsaturated binding groups of polymerism Property compound (also referred to collectively as specific cross-linked compound).Now, these groups need have more than 2 in compound.
As the cross-linked compound with epoxy radicals or NCO, such as bisphenol acetone glycidol can be included Ether, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl group isocyanuric acid ester, four shrink sweet Oil base aminobphenyl, four glycidyl group m-xylene diamine, four glycidyl group -1,3- double (amino-ethyl) hexamethylene, four benzene Base glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl ether, 1,3- pairs (1- (2, 3- glycidoxies) -1- trifluoromethyl -2,2,2- trifluoromethyls) benzene, 4,4- double (2,3- glycidoxies) octafluorobiphenyl, three Glycidyl para-aminophenol, four glycidyl group m-xylene diamine, 2- (4- (2,3- glycidoxies) phenyl) -2- (4- (1,1- double (4- (2,3- glycidoxies) phenyl) ethyls) phenyl) propane or the double (4- (1- (4- (oxygen of 2,3- epoxies third of 1,3- Base) phenyl) -1- (4- (1- (4- (2,3- glycidoxies) phenyl) -1- Methylethyls) phenyl) ethyl) phenoxy group) -2- propyl alcohol Deng.
As the cross-linked compound with oxetanylmethoxy, for oxa- ring fourth shown at least two following formula [4A] The cross-linked compound of base.
Specifically, page 58~the 59 of International Publication publication WO2011/132751 (2011.10.27 is disclosed) can be included The cross-linked compound shown in formula [4a]~formula [4k] described in page.
As the cross-linked compound with cyclocarbonate radical, for cyclic carbonate ester shown at least two following formula [5A] The cross-linked compound of base.
Specifically, page 76~page 82 of International Publication publication WO2012/014898 (2012.2.2 is disclosed) can be included Described in formula [5-1]~formula [5-42] shown in cross-linked compound.
As the cross-linked compound with least one kind of group in the group for selecting free hydroxyl and alkoxy to constitute, it can arrange Enumerate amino resins, such as melmac, carbamide resin, guanamine resin, the glycoluril-formaidehyde for example with hydroxyl or alkoxy Resin, succinamide-formaldehyde resin or ethylene urea-formaldehyde resins etc..Specifically, the hydrogen atom of amino can be used by hydroxyl first Base or alkoxy methyl or melamine derivative, benzoguanamine derivative or the glycoluril of both substitution.The trimerization Cyanamide derivative or benzoguanamine derivative can also exist in the form of dimer or tripolymer.Their preferably every 1 triazines Ring has average more than 3 and less than 6 methylol or alkoxy methyl.
As this melamine derivative or benzoguanamine derivative, every 1 triazine of such as commercially available product can be included Ring substitution has the MX-750 of average 3.7 methoxies, the substitution of every 1 triazine ring to have the MW- of average 5.8 methoxies 30 (being above Sanwa Chemical Co., Ltd's system)；CYMEL 300,301,303,350,370,771,325,327,703,712 etc. Methoxymethylated melamine；The methoxymethylated butoxymethyls such as CYMEL 235,236,238,212,253,254 Melamine；The butoxymethyl melamines such as CYMEL 506,508；CYMEL 1141 etc carboxylic methoxy methyl Base isobutoxymethyl melamine；CYMEL 1123 etc methoxymethylated ethoxyl methyl benzoguanamine； CYMEL 1123-10 etc methoxymethylated butoxymethyl benzoguanamine；CYMEL 1128 etc butoxy first Base benzoguanamine；CYMEL 1125-80 etc carboxylic methoxymethylated ethoxyl methyl benzoguanamine (more than For three well サ イ ア Na ミ De company systems).In addition, as the example of glycoluril, CYMEL 1170 etc butoxy first can be included Base glycoluril, CYMEL 1172 etc methylolation glycoluril etc., Powder link 1174 etc methoxyl group methylolation Glycoluril etc..
As the benzene with hydroxyl or alkoxy or benzene phenoloid, such as 1,3,5- tri- (methoxy methyls can be included Base) benzene, 1,2,4- tri- (i-propoxymethyl) benzene, double (sec-butoxymethyl) benzene of 1,4- or 2,6- bishydroxymethyls be to the tert-butyl group Phenol etc..More specifically, page 62~the 66 of International Publication publication WO2011/132751 (2011.10.27 is disclosed) can be included The cross-linked compound shown in formula [6-1]~formula [6-48] described in page.
As the cross-linked compound with polymerism unsaturated bond, such as trimethylolpropane tris (methyl) can be included Acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyl groups There are 3 in epoxide ethyoxyl trimethylolpropane or poly- (methyl) the acrylate equimolecular of glycerine polyglycidyl ether to gather The cross-linked compound of conjunction property unsaturated group；Ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, poly- third 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-HD two (methyl) propylene Acid esters, glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) Acrylate, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) There are 2 polymerism unsaturated groups in acrylate or (methyl) acrylate of 3-hydroxypivalic acid neopentyl glycol two equimolecular Cross-linked compound of group etc..
The content of specific cross-linked compound in aligning agent for liquid crystal is relative to whole mass parts of component of polymer 100 Preferably 1~50 mass parts.Target effect is shown in order to promote cross-linking reaction, more preferably 1~30 mass parts, it is especially excellent Elect 1~10 mass parts as.
In the range of effect of the present invention is not damaged, aligning agent for liquid crystal, which can be used, is coated with liquid crystal aligning processing The compound that film thickness uniformity, the surface smoothness of liquid crystal orientation film during agent are improved.And then, liquid crystal aligning can also be used Compound that the adaptation of film and substrate is improved etc..
As the compound for improving the film thickness uniformity of liquid crystal orientation film, surface smoothness, fluorine system surface can be included Activating agent, silicone based surfactants or nonionic surfactants etc..Specifically, such as Eftop can be included EF301, EF303, EF352 (being above Tohkem products Corporation systems)；Megafac F171、F173、R-30 (being above big Japanese ink Co. Ltd. system)；Fluorad FC430, FC431 (are above Sumitomo 3M Limited System)；AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (are above Asahi Glass Co., Ltd's system) etc..The use ratio of these surfactants is relative to the whole contained in aligning agent for liquid crystal The mass parts of component of polymer 100 are preferably 0.01~2 mass parts.More preferably 0.01~1 mass parts.
As the concrete example of compound that the adaptation of liquid crystal orientation film and substrate improves is made, silicon containing functionality can be included The compound of alkane, the compound containing epoxy radicals.Such as 3- TSL 8330s, the second of 3- aminopropyls three can be included TMOS, 2- TSL 8330s, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- amino Propyl trimethoxy silicane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, 3- urea propyl trimethoxy silicon Alkane, 3- ureas propyl-triethoxysilicane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyl -3- ammonia Base propyl-triethoxysilicane, N- triethoxysilylpropyltetrasulfides diethylenetriamine, N- trimethoxy-silylpropyls Diethylenetriamine, the azepine decane of 10- trimethoxysilyls -1,4,7- three, 10- triethoxysilyls -1,4,7- Three azepine decane, 9- trimethoxysilyl -3,6- diaza nonyls acetic acid esters, 9- triethoxysilyls -3,6- two Azepine nonyl acetic acid esters, N- benzyl -3- TSL 8330s, N- benzyls-APTES, N- Double (epoxide the ethylidene) -3- of phenyl -3- TSL 8330s, N- phenyl-APTES, N- TSL 8330, N- double (epoxide ethylidene)-APTES, ethylene glycol diglycidyls Ether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol two contract Water glycerin ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- bis- Bromine neopentylglycol diglycidyl ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycols, N, N, N ', N ',-four glycidols Double (N, the N- diglycidyl amino methyl) hexamethylenes of base m-xylene diamine, 1,3- or N, N, N ', N ' ,-four glycidols Base -4,4 '-diaminodiphenyl-methane etc..
The use ratio of the compound closely sealed with these substrates polymerize relative to the whole contained in aligning agent for liquid crystal The mass parts of thing composition 100 are preferably 0.1~30 mass parts.More preferably 1~20 mass parts.During less than 0.1 mass parts, it is impossible to the phase The effect of adaptation to be improved, during more than 30 mass parts, the storage stability of aligning agent for liquid crystal is deteriorated sometimes.
In aligning agent for liquid crystal, outside the compound in addition to addition is above-mentioned, as long as not damaging effect of the present invention In the range of, dielectric substance, the conductive material for electrical characteristics such as the dielectric constant, the electric conductivity that change liquid crystal orientation film can also be added Matter.
<Liquid crystal orientation film/liquid crystal represents element>
The aligning agent for liquid crystal of the present invention is handled, light irradiation etc. is entered after being applied on substrate and burning till using brushing Row orientation process, so as to as liquid crystal orientation film.In addition, in the case where the liquid crystal of VA patterns represents element etc., Liquid crystal orientation film can be used as without orientation process.As the substrate now used, as long as the high substrate of the transparency is just It is not particularly limited, in addition to glass substrate, plastic bases such as acrylic substrate, polycarbonate substrate etc. can also be used. From the viewpoint of the chemical industry skill that conforms to the principle of simplicity, ITO (tin indium oxide, Indium Tin being formed with for driving liquid crystal are preferably used Oxide) the substrate of electrode etc..In addition, the liquid crystal of reflection-type is represented in element, if being only unilateral substrate, it can also use The opaque substrate such as silicon wafer, as electrode now, can also use the material of the meeting reflected light such as aluminium.
The coating method of aligning agent for liquid crystal is not particularly limited, and industrial is usually to utilize silk-screen printing, intaglio process The method of the progress such as brush, hectographic printing, ink-jet method.As other coating methods, have dip coating, rolling method, slot coated method, Spin-coating method, spray-on process etc., can use them according to purpose.
After aligning agent for liquid crystal is coated on substrate, hot plate, thermal cycle type baking oven, IR (infrared ray) type baking oven are utilized Deng heater meanses, according to the solvent used in aligning agent for liquid crystal, with 30~300 DEG C, preferably made with 30~250 DEG C of temperature Solvent evaporates, so as to which liquid crystal orientation film is made.When the thickness of liquid crystal orientation film after burning till is blocked up, element is represented in liquid crystal Power consumption in terms of be unfavorable, when thickness is excessively thin, liquid crystal represents that the reliability of element is reduced sometimes, so preferably 5~ 300nm, more preferably 10~100nm.Liquid crystal such as TN patterns, IPS patterns makes liquid crystal enter line tilt representing element When orientation, horizontal alignment, the liquid crystal orientation film after being irradiated etc. using brushing or polarized UV rays to burning till is handled.
Liquid crystal on the present invention represents element, and band liquid is obtained by the aligning agent for liquid crystal of the present invention using the above method After the substrate of brilliant alignment films, liquid crystal cells are made using known method, so that liquid crystal, which is made, represents element.
As the preparation method of liquid crystal cells, following method can be exemplified：Preparation is formed with a pair of bases of liquid crystal orientation film Plate, sept is spread on the liquid crystal orientation film of single substrate, and another is pasted in the way of liquid crystal orientation film is facing to inner side Substrate, sealedly decompression injection liquid crystal and method；Or, to the liquid crystal aligning film surface for spread sept on be added dropwise liquid crystal after, Adhesive substrate simultaneously carries out sealed method (also referred to as ODF：One Drop Filling methods) etc..
The aligning agent for liquid crystal of the present invention is also preferably used between a pair of substrates for possessing electrode with liquid crystal layer Liquid crystal represents element, and the liquid crystal represents that element is manufactured via following process：Configuration is included by living between a pair of substrates Property at least one of energy-ray and heat and polymerize polymerizable compound liquid-crystal composition, while between electrode apply Voltage, while at least one of irradiation and heating for passing through active energy beam and polymerize polymerizable compound.Herein, make For active energy beam, ultraviolet is suitably for.As ultraviolet, wavelength is 300~400nm, is preferably 310~360nm.Pass through When heating is polymerize, heating-up temperature is 40~120 DEG C, is preferably 60~80 DEG C.In addition it is also possible to simultaneously apply ultraviolet and Heating.
Above-mentioned liquid crystal represents element and controlled using the mode of PSA patterns the pre-dumping of liquid crystal molecule.In PSA patterns, in advance First a small amount of photopolymerizable compound is mixed into liquid crystal material, photopolymerization monomer is for example mixed into, after assembling liquid crystal cells, Liquid crystal layer is applied in the state of assigned voltage, to photopolymerizable compound irradiation ultraviolet radiation etc., utilize generated polymer Control the pre-dumping of liquid crystal molecule.The state of orientation of liquid crystal molecule during generation polymer even can also be remembered after voltage is removed Recall, therefore by electric field for controlling to be formed in liquid crystal layer etc., the pre-dumping of liquid crystal molecule can be adjusted.In addition, in PSA patterns, Brushing processing is not needed, therefore is suitable for being difficult to the formation of vertical alignment-type liquid crystal layer that pre-dumping is controlled by brushing processing. That is, in liquid crystal of the invention represents element, the base with liquid crystal orientation film is obtained by aligning agent for liquid crystal using the above method After plate, liquid crystal cells are made, polymerize polymerizable compound using at least one of ultraviolet irradiation and heating, so as to Enough control the orientation of liquid crystal molecule.
It is if including one of the liquid crystal cells for making PSA patterns, such as follows.That is, above-mentioned preparation method is passed through To make liquid crystal cells.Mixed into liquid crystal now because of the polymerizable compound that heat, ultraviolet irradiate and polymerize.It is used as polymerization Property compound, intramolecular can be included with polymerism unsaturated groups such as more than 1 acrylate-based, methacrylic acid ester groups Compound.Now, polymerizable compound is preferably 0.01~10 mass parts, more preferably relative to the mass parts of liquid crystal composition 100 For 0.1~5 mass parts.If polymerizable compound is less than 0.01 mass parts, polymerizable compound will not polymerize and uncontrollable The orientation of liquid crystal, if polymerizable compound is more than 10 mass parts, unreacted polymerizable compound becomes many and liquid crystal represents member The after image characteristic reduction of part.Make after liquid crystal cells, while applying alternating voltage or DC voltage to liquid crystal cells, while irradiation Heat, ultraviolet and polymerizable compound is polymerize.Orientation thus, it is possible to control liquid crystal molecule.
And then, aligning agent for liquid crystal of the invention can be additionally used in having liquid crystal layer between a pair of substrates for possessing electrode And the liquid crystal manufactured via following processes represents element, i.e. SC-PVA patterns：Configuration is comprising logical between foregoing a pair of substrates The liquid crystal orientation film for the polymerizable group crossed at least one of active energy beam and heat and polymerize, and to applying between electrode Voltage.Herein, as active energy beam, it is suitably for ultraviolet.As ultraviolet, wavelength is 300~400nm, is more preferably 310~360nm.When being polymerize by heating, heating-up temperature is 40~120 DEG C, more preferably 60~80 DEG C.In addition, also may be used To apply ultraviolet and heating simultaneously.
Taken to obtain the liquid crystal for including the polymerizable group polymerizeing by least one of active energy beam and heat To film, it can include：The method that compound comprising the polymerizable group is added in aligning agent for liquid crystal；Using comprising The method of the component of polymer of polymerizable group.
It is if including one of the liquid crystal cells for making SC-PVA patterns, such as follows.That is, above-mentioned making side is utilized Legal system makees liquid crystal cells.Thereafter, alternating voltage or DC voltage are applied to liquid crystal cells by one side, while irradiating hot, ultraviolet Line, so as to control the orientation of liquid crystal molecule.
Operate as above, by using the aligning agent for liquid crystal of the present invention, using the teaching of the invention it is possible to provide be exposed to even in for a long time Also voltage retention reduction can be suppressed after light irradiation and also element will not be represented in liquid crystal under the conditions of hot and humid Uneven liquid crystal orientation film occurs to represent for adjacent edges.Therefore, the liquid crystal watch made using the aligning agent for liquid crystal of the present invention Showing the reliability of element becomes excellent, can be suitably employed in large-scale liquid crystal TV set, middle-size and small-size auto-navigation system, intelligence Mobile phone etc..Especially, aligning agent for liquid crystal of the invention is for having used the liquid of VA patterns, PSA patterns and SC-PVA patterns Crystalline substance is useful for representing the liquid crystal orientation film of element.
Embodiment
Embodiment is exemplified below out, the present invention is further illustrated, but be not limited to them.
The abbreviation used in synthesis example, embodiment and comparative example is as follows.
(specific compound)
S1：Phosphotungstic acid (Japan New Metals Co., Ltd.'s system)
S2：Phosphomolybdic acid (12 molybdenums (IV) phosphoric acid n hydrates) (Kanto Kagaku K. K.'s system)
(specific diamine compound (1))
A1：Diamine compound shown in following formula [A1]
A2：Diamine compound shown in following formula [A2]
(specific diamine compound (2))
B1：1,3- diaminourea -4- (4- (trans- 4- n-heptyls cyclohexyl) phenoxy group) benzene
B2：1,3- diaminourea -5- (4- (trans- 4- n-heptyls cyclohexyl) phenoxymethyl) benzene
B3：1,3- diaminourea -4- { 4- (trans- 4- (trans- 4- pentyl cyclohexyls) cyclohexyl) phenoxy group } benzene
B4：Diamine compound shown in following formula [B4]
B5：1,3- diaminourea -4- octadecane epoxide benzene
(other diamine compounds)
C1：P-phenylenediamine
C2：M-phenylene diamine (MPD)
C3：Diamine compound shown in following formula [C3]
C4：4,4 '-diamino-diphenyl amine
C5：3,5- diaminobenzoic acids
(specific tetracarboxylic dianhydride)
D1：1,2,3,4- cyclobutane tetracarboxylic dianhydrides
D2：Bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydrides
D3：Tetracarboxylic dianhydride shown in following formula [D3]
D4：Tetracarboxylic dianhydride shown in following formula [D4]
D5：Tetracarboxylic dianhydride shown in following formula [D5]
(cross-linked compound)
M1：Cross-linked compound shown in following formula [M1]
(solvent)
NMP：METHYLPYRROLIDONE
NEP：N- ethyl-2-pyrrolidones
γ-BL：Gamma-butyrolacton
BCS：Ethylene glycol monobutyl ether
PB：Propylene glycol monobutyl ether
DME：Dimethyl ether
" molecular weight determination of polyimides based polymer "
Using normal temperature gel permeation chromatography (GPC) device (GPC-101, Showa Denko K. K's system), post (KD-803, KD-805, Shodex company system), it is following to operate to be measured.
Column temperature：50℃
Eluent：N, N '-dimethyl formamide (is used as additive, lithium bromide monohydrate (LiBrH2O) it is 30mmol/L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) are that 30mmol/L, tetrahydrofuran (THF) are 10ml/L)
Flow velocity：1.0ml/ minute
Standard curve making standard sample：TSK standard PEO (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) (Polymer Laboratories Ltd. systems).
" measure of the acid imide rate of polyimides based polymer "
Polyimide powder 20mg is put into NMR (nuclear magnetic resonance) sample cell (NMR sample cells specification, (the wasteland sections of φ 5 Learn Co. Ltd. system)), addition deuterated dimethyl sulfoxide (DMSO-d6,0.05 mass %TMS (tetramethylsilane) melange) (0.53ml), applying ultrasonic wave is completely dissolved it.With NMR analyzers (JNW-ECA500, JEOL DATUM company systems) to this Solution determines 500MHz proton NMR.Acid imide rate is by the proton from the structure not changed before and after imidizate Determined as reference proton, the acid amides occurred using the peak accumulated value of the proton and from 9.5ppm~10.0ppm vicinity The proton peak accumulated value of the NH bases of acid, is obtained using following formula.
Acid imide rate (%)=(1- α x/y) × 100
(x is the peak accumulated value of proton on the basis of the proton peak accumulated value of the NH bases from amic acid, y, and α is in polyamide Number ratio of the reference proton relative to 1 NH matrix of amic acid in the case of acid (acid imide rate is 0%).)
" synthesis of polyimides based polymer "
<Synthesis example 1>
By D4 (9.65g, 32.1mmol), B5 (1.36g, 3.61mmol) and C1 (3.52g, 32.6mmol) in NMP Mixed in (30.5g), after being reacted 6 hours with 40 DEG C, addition D1 (0.70g, 3.57mmol) and NMP (15.2g), with 40 DEG C of reactions 6 hours, so as to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.
NMP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (3.90g) and pyridine (2.40g), are reacted 4 hours with 70 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (1).The acid imide rate of the polyimides is 85%, and number-average molecular weight is 19,800, weight average molecular weight For 51,800.
<Synthesis example 2>
By D2 (5.95g, 23.8mmol), B3 (4.47g, 10.3mmol), C1 (1.49g, 13.8mmol) and C3 (2.10g, 10.3mmol) mixed in NEP (32.0g), after being reacted 5 hours with 80 DEG C, addition D1 (2.00g, 10.2mmol) and NEP (16.0g), is reacted 6 hours with 40 DEG C, so as to obtain the polyamic acid solution (2) that resin solid content concentration is 25 mass %. The number-average molecular weight of the polyamic acid is that 20,200, weight average molecular weight is 68,300.
<Synthesis example 3>
It is diluted to by the middle addition NEP of polyamic acid solution (2) (30.0g) that synthesis example 2 is obtained after 6 mass %, As imidization catalyst addition acetic anhydride (4.50g) and pyridine (3.30g), reacted 4 hours with 80 DEG C.By the reaction solution Input is into methanol (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, it is dry to carry out decompression with 100 DEG C It is dry, so as to obtain polyimide powder (3).The acid imide rate of the polyimides is 80%, and number-average molecular weight is 18,300, again Average molecular weight is 46,800.
<Synthesis example 4>
By D2 (2.98g, 11.9mmol), A1 (1.25g, 5.16mmol), B3 (2.23g, 5.15mmol) and C1 (0.74g, 6.84mmol) mixed in NEP (16.4g), after being reacted 5 hours with 80 DEG C, addition D1 (1.00g, 5.10mmol) and NEP (8.21g), is reacted 6 hours with 40 DEG C, so as to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.
NEP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (4.50g) and pyridine (3.30g), are reacted 4 hours with 80 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (4).The acid imide rate of the polyimides is 81%, and number-average molecular weight is 17,800, weight average molecular weight For 44,900.
<Synthesis example 5>
By D2 (2.17g, 8.67mmol), A1 (1.28g, 5.28mmol), B1 (2.67g, 7.02mmol) and C1 (0.57g, 5.27mmol) mixed in NMP (16.8g), after being reacted 5 hours with 80 DEG C, addition D1 (1.70g, 8.67mmol) and NMP (8.39g), is reacted 6 hours with 40 DEG C, so as to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.
NMP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (3.80g) and pyridine (2.40g), are reacted 2 hours with 60 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (5).The acid imide rate of the polyimides is 56%, and number-average molecular weight is 17,000, weight average molecular weight For 43,200.
<Synthesis example 6>
By D2 (2.17g, 8.67mmol), A1 (1.28g, 5.28mmol), B5 (2.65g, 7.04mmol) and C1 (0.57g, 5.27mmol) mixed in NMP (16.7g), after being reacted 5 hours with 80 DEG C, addition D1 (1.70g, 8.67mmol) and NMP (8.36g), is reacted 6 hours with 40 DEG C, so as to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.
NMP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (3.80g) and pyridine (2.40g), are reacted 2 hours with 60 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (6).The acid imide rate of the polyimides is 55%, and number-average molecular weight is 16,300, weight average molecular weight For 41,100.
<Synthesis example 7>
By D2 (1.31g, 5.24mmol), A1 (0.86g, 3.55mmol), B2 (2.80g, 7.10mmol), C1 (0.57g, 5.27mmol) mixed with C4 (0.35g, 1.76mmol) in NMP (16.6g), after being reacted 5 hours with 80 DEG C, add D1 (2.40g, 12.2mmol) and NMP (8.29g), is reacted 6 hours with 40 DEG C, so as to obtain resin solid content concentration for 25 matter Measure % polyamic acid solution.
NMP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (3.80g) and pyridine (2.40g), are reacted 2.5 hours with 60 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (7).The acid imide rate of the polyimides is 60%, and number-average molecular weight is 17,500, weight average molecular weight For 43,800.
<Synthesis example 8>
By D2 (2.04g, 8.15mmol), A2 (1.07g, 4.13mmol), B2 (2.94g, 7.45mmol), C1 (0.36g, 3.33mmol) mixed with C5 (0.25g, 1.64mmol) in NEP (16.5g), after being reacted 5 hours with 80 DEG C, add D1 (1.60g, 8.16mmol) and NEP (8.26g), is reacted 6 hours with 40 DEG C, so as to obtain resin solid content concentration for 25 matter Measure % polyamic acid solution.
NMP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (4.50g) and pyridine (3.30g), are reacted 3 hours with 80 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (8).The acid imide rate of the polyimides is 72%, and number-average molecular weight is 16,800, weight average molecular weight For 41,900.
<Synthesis example 9>
By D2 (2.30g, 9.19mmol), A1 (0.90g, 3.71mmol), B4 (2.29g, 4.65mmol) and C2 (1.11g, 10.3mmol) mixed in NMP (16.8g), after being reacted 5 hours with 80 DEG C, addition D1 (1.80g, 9.18mmol) and NMP (8.39g), is reacted 6 hours with 40 DEG C, so as to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.
NMP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (3.80g) and pyridine (2.40g), are reacted 2 hours with 60 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (9).The acid imide rate of the polyimides is 52%, and number-average molecular weight is 15,300, weight average molecular weight For 39,700.
<Synthesis example 10>
By D3 (7.10g, 31.7mmol), A1 (3.11g, 12.8mmol), B2 (5.06g, 12.8mmol) and C1 (0.69g, 6.38mmol) mix, reacted 8 hours with 40 DEG C in NMP (47.9g), so as to obtain resin solid content concentration for 25 matter Measure % polyamic acid solution.
NMP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (4.50g) and pyridine (3.30g), are reacted 3 hours with 80 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (10).The acid imide rate of the polyimides is 73%, and number-average molecular weight is 18,600, weight average molecular weight For 48,400.
<Synthesis example 11>
By D4 (3.22g, 10.7mmol), A1 (0.38g, 1.57mmol), B1 (2.95g, 7.75mmol), C2 (0.34g, 3.14mmol) mixed with C4 (0.62g, 3.11mmol) in NMP (16.8g), after being reacted 5 hours with 80 DEG C, add D1 (0.90g, 4.59mmol) and NMP (8.39g), is reacted 6 hours with 40 DEG C, so as to obtain resin solid content concentration for 25 matter Measure % polyamic acid solution.
NEP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (4.50g) and pyridine (3.30g), are reacted 4 hours with 80 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (11).The acid imide rate of the polyimides is 85%, and number-average molecular weight is 16,200, weight average molecular weight For 41,500.
<Synthesis example 12>
By D4 (3.67g, 12.2mmol), A2 (1.00g, 3.86mmol), B3 (2.35g, 5.43mmol), C1 (0.50g, 4.62mmol) mixed with C3 (0.32g, 1.57mmol) in NMP (16.9g), after being reacted 5 hours with 80 DEG C, add D1 (0.60g, 3.06mmol) and NMP (8.44g), is reacted 6 hours with 40 DEG C, so as to obtain resin solid content concentration for 25 matter Measure % polyamic acid solution.
NEP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (4.50g) and pyridine (3.30g), are reacted 3 hours with 80 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (12).The acid imide rate of the polyimides is 72%, and number-average molecular weight is 17,500, weight average molecular weight For 43,100.
<Synthesis example 13>
By D2 (2.48g, 9.91mmol), A1 (1.62g, 6.69mmol), B2 (2.64g, 6.69mmol) and C1 (0.36g, 3.33mmol) mixed in NMP (17.0g), after being reacted 5 hours with 80 DEG C, addition D5 (1.40g, 6.60mmol) and NMP (8.50g), is reacted 6 hours with 40 DEG C, so as to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.
NEP is added into gained polyamic acid solution (30.0g) and is diluted to after 6 mass %, is catalyzed as imidizate Agent addition acetic anhydride (4.50g) and pyridine (3.30g), are reacted 3.5 hours with 80 DEG C.The reaction solution is put into methanol In (460ml), the sediment obtained by leaching.The sediment is cleaned with methanol, is dried under reduced pressure with 100 DEG C, so that To polyimide powder (13).The acid imide rate of the polyimides is 74%, and number-average molecular weight is 16,200, weight average molecular weight For 41,500.
The polyimides based polymer obtained by synthesis example is shown in table 32 and table 33.
[table 32]
*1：Polyamic acid.
[table 33]
" manufacture of aligning agent for liquid crystal "
Aftermentioned embodiment and comparative example record the Production Example of aligning agent for liquid crystal.In addition, the aligning agent for liquid crystal is also The making and its evaluation of element are represented for liquid crystal.Each aligning agent for liquid crystal obtained in embodiment and comparative example is shown in table 34~table 36.
" evaluation of the ink-jet application of aligning agent for liquid crystal "
Using the aligning agent for liquid crystal obtained in aftermentioned embodiment 7 and embodiment 11, the evaluation of ink-jet application is carried out. Specifically, these aligning agent for liquid crystal are subjected to pressure filtration with aperture for 1 μm of molecular filter, spreading area for 70 × 70mm, injector spacing are that 0.423mm, sweep span are that 0.5mm, coating speed are under conditions of 40mm/ seconds, to be coated on and use pure water (vertical 100mm × horizontal 100mm, thickness are the substrate of subsidiary ITO (tin indium oxide) electrode cleaned with IPA (isopropanol) On ito surface 0.7mm).Now, ink-jet application machine has used HIS-200 (Hitachi Plant Technologies, Ltd. System).In addition, from be applied to it is predrying untill time be 60 seconds, it is predrying on hot plate with 70 DEG C under conditions of 5 minutes Carry out.
The evaluation of coating is visually observed by the coated surface of the substrate to subsidiary liquid crystal orientation film obtained above Come carry out.Specifically, coated surface is visually observed under sodium vapor lamp, confirms the presence or absence of pin hole.As a result, by any real Apply the liquid crystal orientation film that example obtains and do not observe pin hole on coated surface, obtain the excellent liquid crystal orientation film of film.
" evaluation (normal cells) of the uneven characteristic of expression of the adjacent edges of liquid crystal cells "
The aligning agent for liquid crystal obtained in aftermentioned embodiment and comparative example is pressurizeed with aperture for 1 μm of molecular filter Filtering, and be spin-coated on the substrate of subsidiary ITO electrode clean with pure water and IPA (indulging 40mm × horizontal 30mm, thickness is On ito surface 0.7mm), heated 5 minutes with 100 DEG C on hot plate, baking oven is cleaned with 230 DEG C of heating with thermal cycle type Processing 30 minutes, so as to obtain the ito substrate for the liquid crystal orientation film that subsidiary thickness is 100nm.It should illustrate, for embodiment 7 With the aligning agent for liquid crystal of embodiment 11, with above-mentioned " evaluation of the ink-jet application of aligning agent for liquid crystal " identical bar Substrate is made under part, and (substrate has used the substrate of the subsidiary ITO electrode cleaned with pure water and IPA same as described above (vertical 40mm × horizontal 30mm, thickness are 0.7mm)), thereafter, clean baking oven with thermal cycle type and heated 30 minutes with 230 DEG C, from And the ito substrate for the liquid crystal orientation film that subsidiary thickness is 100nm is made.
Then, for the coated surface of the substrate, using the brushing device that roller diameter is 120mm, using rayon cloth, in roller Rotating speed is that 1000rpm, roller pace are that 50mm/sec, intrusion are to carry out brushing processing under conditions of 0.1mm.
Thereafter, prepare the substrate after 2 brushing processing, make coated surface medially to clamp 6 μm of sept and combination, use Dummy cell is made around sealant bonding.Liquid crystal is injected by depressurizing in the injection normal direction dummy cell, inlet is sealed and obtains To liquid crystal cells.It should illustrate, in embodiment 1 and comparative example 1, liquid crystal uses MLC-3018U (MERCK JAPAN company systems), In addition in embodiment and comparative example, liquid crystal has used MLC-6608 (MERCK JAPAN company systems).
Liquid crystal cells obtained by use, have carried out the evaluation of the uneven characteristic of expression of the adjacent edges of liquid crystal cells.It is specific and Speech, using polarizer and backlight, observation by visual observation carries out the evaluation of the liquid crystal aligning near sealant.As a result, passing through All liquid crystal cells that embodiment and comparative example are obtained show uniform liquid crystal aligning.
Thereafter, liquid crystal cells are taken care of 96 hours in the hot and humid groove that temperature is 80 DEG C, humidity is 90%, with it is upper State the evaluation for carrying out the liquid crystal aligning near sealant under the same conditions.On evaluating, after being taken care of in hot and humid groove, It was observed that the situation of liquid crystal aligning sexual disorder is regarded as, the evaluation is excellent (not to be expressed as good in 37~table of table 39 near sealant It is good).The expression uneven characteristic of the adjacent edges of liquid crystal cells after being taken care of in hot and humid groove is shown in 37~table of table 39 As a result.
" evaluation (normal cells) of voltage retention "
Using with foregoing " evaluations (normal cells) of the uneven characteristic of expression of the adjacent edges of liquid crystal cells " identical Under the conditions of the liquid crystal cells that make, carry out the evaluation of voltage retention.Specifically, to passing through above-mentioned side at a temperature of 80 DEG C The liquid crystal cells that method is obtained apply 60 μ s 1V voltages, determine the voltage after 50ms, and voltage can be remained into which kind of degree is made Calculated for voltage retention (also referred to as VHR).It should illustrate, device (VHR-1) (TOYO is determined using voltage retention Corporation systems), at Voltage (voltage)：± 1V, Pulse Width (pulse width)：60μs、Flame Period (frame period)：It is measured under 50ms setting.
And then, the liquid crystal cells of the measure for finishing just to make the voltage retention after above-mentioned liquid crystal cells make With desktop UV solidification equipments (HCT3B28HEX-1) (SENTLIGHT company systems), irradiation is scaled 50J/cm with 365nm2's Ultraviolet, carries out the measure of voltage retention under conditions of same as described above.
In the evaluation, the height of the voltage retention value after liquid crystal cells has just been made, and then, with just making after liquid crystal cells Voltage retention value (also referred to as initial stage) compare, the reduction of the value (also referred to as after ultraviolet irradiation) after ultraviolet irradiation is smaller Situation to be regarded as the evaluation excellent.Each VHR value is shown in 37~table of table 39.
<Embodiment 1>
Addition NMP (7.83g), γ-BL into the polyimide powder (1) (2.50g) obtained by synthesis example 1 (23.5g), so that 70 DEG C are stirred 24 hours and dissolve it.S1 (0.25g) and BCS (7.83g) is added into the solution, with 25 DEG C Stirring 6 hours, so as to obtain aligning agent for liquid crystal (1).Do not observe that muddy, precipitation etc. is different in the aligning agent for liquid crystal Often, uniform solution is confirmed as.
<Embodiment 2>
To the polyamic acid solution (2) that the resin solid content concentration obtained by synthesis example 2 is 25.0 mass % Addition S1 (0.125g), NEP (14.0g) and PB (17.6g) in (10.0g), are stirred 6 hours with 25 DEG C, are taken so as to obtain liquid crystal To inorganic agent (2).Do not observe that muddy, precipitation etc. is abnormal, confirms as uniform solution in the aligning agent for liquid crystal.
<Embodiment 3>
The addition NEP (23.5g) into the polyimide powder (3) (2.50g) obtained by synthesis example 3, with 70 DEG C of stirrings 24 hours and dissolve it.S1 (0.25g), BCS (3.92g) and PB (11.8g) are added into the solution, it is small with 25 DEG C of stirrings 6 When, so as to obtain aligning agent for liquid crystal (3).Do not observe that muddy, precipitation etc. is abnormal, confirms as in the aligning agent for liquid crystal Uniform solution.
It should illustrate, on " evaluations (normal cells) of the uneven characteristic of expression of the adjacent edges of liquid crystal cells ", as Experiment is emphasized together with being tested with aforesaid standards, has also carried out protecting in the hot and humid groove that temperature is 80 DEG C, humidity is 90% Evaluation during pipe 144 hours (other conditions are identical with aforementioned condition).As a result, in liquid crystal cells, being played in self-sealing substance The disorder of liquid crystal aligning is observed untill 0.5cm width regions.
<Embodiment 4>
The addition NEP (23.5g) into the polyimide powder (4) (2.50g) obtained by synthesis example 4, with 70 DEG C of stirrings 24 hours and dissolve it.S1 (0.25g), BCS (3.92g) and PB (11.8g) are added into the solution, it is small with 25 DEG C of stirrings 6 When, so as to obtain aligning agent for liquid crystal (4).Do not observe that muddy, precipitation etc. is abnormal, confirms as in the aligning agent for liquid crystal Uniform solution.
It should illustrate, on " evaluations (normal cells) of the uneven characteristic of expression of the adjacent edges of liquid crystal cells ", as Experiment is emphasized together with being tested with aforesaid standards, has also carried out protecting in the hot and humid groove that temperature is 80 DEG C, humidity is 90% Evaluation during pipe 144 hours (other conditions are identical with aforementioned condition).As a result, in liquid crystal cells, not seen near sealant Observe the disorder of liquid crystal aligning.
<Embodiment 5>
The addition NEP (23.5g) into the polyimide powder (5) (2.50g) obtained by synthesis example 5, with 70 DEG C of stirrings 24 hours and dissolve it.S1 (0.175g) and PB (15.7g) is added into the solution, is stirred 6 hours with 25 DEG C, so as to obtain Aligning agent for liquid crystal (5).Do not observe that muddy, precipitation etc. is abnormal, confirms as uniform solution in the aligning agent for liquid crystal.
It should illustrate, on " evaluations (normal cells) of the uneven characteristic of expression of the adjacent edges of liquid crystal cells ", as Experiment is emphasized together with being tested with aforesaid standards, has also carried out protecting in the hot and humid groove that temperature is 80 DEG C, humidity is 90% Evaluation during pipe 168 hours (other conditions are identical with aforementioned condition).As a result, in liquid crystal cells, not seen near sealant Observe the disorder of liquid crystal aligning.
<Embodiment 6>
The addition NEP (23.5g) into the polyimide powder (6) (2.50g) obtained by synthesis example 6, with 70 DEG C of stirrings 24 hours and dissolve it.S1 (0.175g) and PB (15.7g) is added into the solution, is stirred 6 hours with 25 DEG C, so as to obtain Aligning agent for liquid crystal (6).Do not observe that muddy, precipitation etc. is abnormal, confirms as uniform solution in the aligning agent for liquid crystal.
It should illustrate, on " evaluations (normal cells) of the uneven characteristic of expression of the adjacent edges of liquid crystal cells ", as Experiment is emphasized together with being tested with aforesaid standards, has also carried out protecting in the hot and humid groove that temperature is 80 DEG C, humidity is 90% Evaluation during pipe 168 hours (other conditions are identical with aforementioned condition).As a result, in liquid crystal cells, being observed near sealant To the disorder of liquid crystal aligning.
<Embodiment 7>
The addition NEP (20.7g) into the polyimide powder (7) (1.50g) obtained by synthesis example 7, with 70 DEG C of stirrings 24 hours and dissolve it.S2 (0.105g), PB (16.5g) and DME (4.14g) are added into the solution, it is small with 25 DEG C of stirrings 6 When, so as to obtain aligning agent for liquid crystal (7).Do not observe that muddy, precipitation etc. is abnormal, confirms as in the aligning agent for liquid crystal Uniform solution.
<Embodiment 8>
The addition NMP (23.5g) into the polyimide powder (8) (2.50g) obtained by synthesis example 8, with 70 DEG C of stirrings 24 hours and dissolve it.S1 (0.075g), M1 (0.125g), BCS (7.83g) and PB (7.83g) are added into the solution, with 25 DEG C are stirred 6 hours, so as to obtain aligning agent for liquid crystal (8).Muddy, precipitation etc. is not observed in the aligning agent for liquid crystal It is abnormal, confirm as uniform solution.
<Embodiment 9>
The addition NEP (25.5g) into the polyimide powder (9) (2.50g) obtained by synthesis example 9, with 70 DEG C of stirrings 24 hours and dissolve it.S1 (0.30g), BCS (5.88g) and PB (7.83g) are added into the solution, it is small with 25 DEG C of stirrings 6 When, so as to obtain aligning agent for liquid crystal (9).Do not observe that muddy, precipitation etc. is abnormal, confirms as in the aligning agent for liquid crystal Uniform solution.
<Embodiment 10>
Into the polyimide powder (10) (2.50g) obtained by synthesis example 10, addition NEP (23.5g), is stirred with 70 DEG C Mix 24 hours and dissolve it.S2 (0.125g) and PB (15.7g) is added into the solution, is stirred 6 hours with 25 DEG C, so that To aligning agent for liquid crystal (10).Do not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, confirm as uniform molten Liquid.
<Embodiment 11>
The addition NEP (16.5g) and γ-BL into the polyimide powder (11) (1.50g) obtained by synthesis example 11 (4.14g), so that 70 DEG C are stirred 24 hours and dissolve it.S1 (0.105g), BCS (8.27g) and PB are added into the solution (12.4g), is stirred 6 hours with 25 DEG C, so as to obtain aligning agent for liquid crystal (11).Do not observed in the aligning agent for liquid crystal Muddy, precipitation etc. is abnormal, confirms as uniform solution.
<Embodiment 12>
Into the polyimide powder (12) (2.50g) obtained by synthesis example 12, addition NMP (19.6g), is stirred with 70 DEG C Mix 24 hours and dissolve it.S1 (0.25g), M1 (0.175g), BCS (15.7g) and DME (3.92g) are added into the solution, Stirred 6 hours with 25 DEG C, so as to obtain aligning agent for liquid crystal (12).Muddy, analysis is not observed in the aligning agent for liquid crystal Go out etc. abnormal, confirm as uniform solution.
<Embodiment 13>
Into the polyimide powder (13) (2.50g) obtained by synthesis example 13, addition NEP (23.5g), is stirred with 70 DEG C Mix 24 hours and dissolve it.S2 (0.175g), BCS (7.83g) and PB (7.83g) are added into the solution, with 25 DEG C of stirrings 6 Hour, so as to obtain aligning agent for liquid crystal (13).Do not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, really Think uniform solution.
<Comparative example 1>
Addition NMP (7.83g), γ-BL into the polyimide powder (1) (2.50g) obtained by synthesis example 1 (23.5g), so that 70 DEG C are stirred 24 hours and dissolve it.BCS (7.83g) is added into the solution, is stirred 6 hours with 25 DEG C, So as to obtain aligning agent for liquid crystal (14).Do not observe that muddy, precipitation etc. is abnormal, confirms as in the aligning agent for liquid crystal Even solution.
<Comparative example 2>
The addition NEP (23.5g) into the polyimide powder (3) (2.50g) obtained by synthesis example 3, with 70 DEG C of stirrings 24 hours and dissolve it.BCS (3.92g) and PB (11.8g) is added into the solution, is stirred 6 hours with 25 DEG C, so as to obtain Aligning agent for liquid crystal (15).Do not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, confirm as uniform molten Liquid.
[table 34]
Aligning agent for liquid crystal Polyimides based polymer Specific compound (ratio) * 1 Solid component concentration * 2
Embodiment 1 Aligning agent for liquid crystal (1) Polyimide powder (1) S1(10) 6.0
Embodiment 2 Aligning agent for liquid crystal (2) Polyamic acid solution (2) S1(5) 6.0
Embodiment 3 Aligning agent for liquid crystal (3) Polyimide powder (3) S1(10) 6.0
Embodiment 4 Aligning agent for liquid crystal (4) Polyimide powder (4) S1(10) 6.0
Embodiment 5 Aligning agent for liquid crystal (5) Polyimide powder (5) S1(7) 6.0
Embodiment 6 Aligning agent for liquid crystal (6) Polyimide powder (6) S1(7) 6.0
Embodiment 7 Aligning agent for liquid crystal (7) Polyimide powder (7) S2(7) 3.5
Embodiment 8 Aligning agent for liquid crystal (8) Polyimide powder (8) S1(3) 6.0
Embodiment 9 Aligning agent for liquid crystal (9) Polyimide powder (9) S1(12) 6.0
Embodiment 10 Aligning agent for liquid crystal (10) Polyimide powder (10) S2(5) 6.0
[table 35]
Aligning agent for liquid crystal Polyimides based polymer Specific compound (ratio) * 1 Solid component concentration * 2
Embodiment 11 Aligning agent for liquid crystal (11) Polyimide powder (11) S1(7) 3.5
Embodiment 12 Aligning agent for liquid crystal (12) Polyimide powder (12) S1(10) 6.0
Embodiment 13 Aligning agent for liquid crystal (13) Polyimide powder (13) S2(7) 6.0
[table 36]
Aligning agent for liquid crystal Polyimides based polymer Specific compound (ratio) * 1 Solid component concentration * 2
Comparative example 1 Aligning agent for liquid crystal (14) Polyimide powder (1) - 6.0
Comparative example 2 Aligning agent for liquid crystal (15) Polyimide powder (3) - 6.0
*1：Represent import volume (mass parts) of the specific compound relative to the mass parts of polyimides based polymer 100.
*2：Represent the ratio shared by the polyimides based polymer in aligning agent for liquid crystal.
[table 37]
[table 38]
[table 39]
*1：In liquid crystal cells, the disorder of liquid crystal aligning is observed near sealant.
*2：In liquid crystal cells, the disorder of liquid crystal aligning is observed untill self-sealing substance plays 0.5cm width regions (compared with * 1, it was observed that the width of liquid crystal aligning sexual disorder is larger).
From the above results：Compared with the aligning agent for liquid crystal of comparative example, at the liquid crystal aligning of the embodiment of the present invention Reason agent carries out ultraviolet irradiation even if to liquid crystal cells can also suppress the reduction of voltage retention.Even if in addition, by liquid crystal list First long-term keeping does not also observe the disorder of liquid crystal aligning in hot and humid groove near sealant.That is, liquid of the invention Brilliant aligning agent can be formed can also suppress voltage retention reduction and high in high temperature even in long-term be exposed to after light irradiation Liquid crystal can be suppressed under the conditions of wet and represent that the adjacent edges of element produce the liquid crystal orientation film for representing uneven.
It is specific to understand：At liquid crystal aligning for having used specific compound of the present invention and specific polyimides based polymer For the embodiment of reason agent and the comparative example without using the aligning agent for liquid crystal of specific compound, the liquid crystal aligning of comparative example The above-mentioned characteristic of inorganic agent is poor.More specifically, it is contrast and embodiment 3 and comparative example 3 of the embodiment 1 with comparative example 1 Contrast.
In addition, having used the aligning agent for liquid crystal of the specific diamine compound (1) with specific structure (1) of the present invention Compared with the aligning agent for liquid crystal of the specific diamine compound (1) is not used, in experiment is emphasized, even if liquid crystal cells are long Phase keeping does not also observe the disorder of liquid crystal aligning in hot and humid groove near sealant.More particularly, for strong The contrast under the same terms in testing is debugged, is the contrast of embodiment 3 and embodiment 4.
In addition, among the specific structure (2) of the present invention, having two of specific structure shown in previously described formula [3-2] with having used The aligning agent for liquid crystal of amines is compared, and has used specific two amine compounds with specific structure shown in previously described formula [3-1] Thing (2) though aligning agent for liquid crystal emphasize experiment in by liquid crystal cells for a long time take care of in hot and humid groove, sealing Also the disorder of liquid crystal aligning is not observed near agent.More particularly, for the contrast under the same terms emphasized in experiment, It is the contrast of embodiment 5 and embodiment 6.
Industrial applicability
The aligning agent for liquid crystal of the present invention can be provided can also suppress voltage after light irradiation is exposed to for a long time Conservation rate reduces and can improve the cementability of sealant and liquid crystal orientation film, suppress the liquid that occurs under the conditions of hot and humid Crystalline substance represents the uneven liquid crystal orientation film of the expression of the adjacent edges of element.And it is possible to provide with above-mentioned liquid crystal orientation film Liquid crystal 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 aligning agent for liquid crystal of the present invention represents the reliability of element Become excellent, be applicable to big picture and the liquid crystal TV set of high-resolution etc., for TN elements, STN elements, TFT liquid crystal cells, The liquid crystal of especially vertical orientating type represents that element is useful.
And then, by the present invention the obtained liquid crystal orientation film of aligning agent for liquid crystal make when liquid crystal represents element for Need the liquid crystal of irradiation ultraviolet radiation represent element for be also useful.That is, represent that element is particularly useful for following liquid crystal , a kind of liquid crystal represents element, and it is that have liquid crystal layer between a pair of substrates for possessing electrode and made via following processes The liquid crystal made represents element：Configuration is included by least one of active energy beam and heat between foregoing a pair of substrates The liquid-crystal composition of the polymerizable compound of polymerization, while to applying voltage between former electrodes while making aforementioned polymeric chemical combination Thing is polymerize；Especially a kind of liquid crystal represents element, and it is that have liquid crystal layer and warp between a pair of substrates for possessing electrode The liquid crystal manufactured by following processes represents element：Configuration, which is included, between foregoing a pair of substrates passes through active energy beam and heat At least one of and polymerize aforementioned polymeric group liquid crystal orientation film, while between former electrodes apply voltage on one side It polymerize polymerizable group.

Claims (20)

1. a kind of aligning agent for liquid crystal, it contains following (A) compositions and (B) composition,
(A) composition：Heteropoly acid；
(B) composition：Polymer.
2. aligning agent for liquid crystal according to claim 1, wherein, the heteropoly acid be selected from by phosphomolybdic acid, silicomolybdic acid, It is at least one kind of in the group of phosphotungstic acid, silico-tungstic acid and phosphotungstomolybdic acid composition.
3. aligning agent for liquid crystal according to claim 1 or 2, wherein, the polymer has nitrogenous heteroaromatic.
4. according to aligning agent for liquid crystal according to any one of claims 1 to 3, wherein, the polymer is selected from by third Alkene acids polymers, methacrylic polymer, novolac resin, polycarboxylated styrene, polyimide precursor, polyamides are sub- It is at least one kind of in the group that amine, polyamide, polyester, cellulose and polysiloxanes are constituted.
5. aligning agent for liquid crystal according to claim 4, wherein, the polymer is by diamine component and tetrabasic carboxylic acid Polyimide precursor that the reaction of composition is obtained or polyimides obtained from the polyimide precursor is carried out into imidizate.
6. aligning agent for liquid crystal according to claim 5, wherein, the diamine component, which is included, has following formula [2] institute Show the diamine compound of structure,
-W1-W2-W3-W4 [2]
W1Represent to be selected from by-O- ,-NH- ,-N (CH3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)-and-N (CH3) CO- composition group at least one kind of binding groups；W2Represent to be selected from by the singly-bound, alkylidene of carbon number 1~20, non-aromatic It is at least one kind of in the group of race's ring and aromatic ring composition；W3Represent to be selected from by singly-bound ,-O- ,-NH- ,-N (CH3)-、-CONH-、- NHCO-、-COO-、-OCO-、-CON(CH3)-、-N(CH3) CO- and-O (CH2)mIt is at least one kind of in the group of-composition, wherein, m tables Show 1~5 integer；W4Represent nitrogenous heteroaromatic.
7. aligning agent for liquid crystal according to claim 6, wherein, the diamine component is comprising shown in following formula [2a] Diamine compound,
W represents the structure shown in previously described formula [2]；M1 represents 1~4 integer.
8. the aligning agent for liquid crystal according to any one of claim 5~7, wherein, the diamine component, which is included, to be had The diamine compound of structure shown in following formula [3-1] or formula [3-2],
Y1Represent to be selected from by singly-bound ,-(CH2)a-、-O-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3)CO-、- At least one kind of binding groups in the group that COO- and-OCO- is constituted, wherein, a is 1~15 integer；Y2Represent singly-bound or- (CH2)b-, wherein, b is 1~15 integer；Y3Represent to be selected from by singly-bound ,-(CH2)c-、-O-、-CH2O- ,-COO- and-OCO- groups Into group in it is at least one kind of, wherein, c be 1~15 integer；Y4Represent selected from the group being made up of phenyl ring, cyclohexane ring and heterocycle In at least one kind of divalent cyclic group or carbon number 17~51 with steroid skeleton divalent organic group, the cyclic group Any hydrogen atom in group optionally contains fluoroalkyl, carbon number by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 1~3 fluoroalkoxy or fluorine atom substitution；Y5Represent at least 1 in the group being made up of phenyl ring, cyclohexane ring and heterocycle Any hydrogen atom on cyclic group, these cyclic groups is planted optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon Number 1~3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom substitution；N represents 0~4 integer；Y6Expression is selected from By the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, carbon number 1~18 the alkoxy and carbon number containing fluoroalkyl, carbon number 1~18 It is at least one kind of in the group of 1~18 fluoroalkoxy composition,
-Y7-Y8 [3-2]
Y7Represent to be selected from by-O- ,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO- ,-COO- and-OCO- composition Group at least one kind of binding groups；Y8Represent carbon number 8~18 alkyl or carbon number 6~18 contain fluoroalkyl.
9. aligning agent for liquid crystal according to claim 8, wherein, the diamine compound is represented with following formula [3a],
Y represents previously described formula [3-1] or the structure shown in formula [3-2]；N1 represents 1~4 integer.
10. the aligning agent for liquid crystal according to any one of claim 5~9, wherein, the tetrabasic carboxylic acid composition is included down The tetracarboxylic dianhydride shown in formula [4] is stated,
Z represent be selected from as at least one kind of structure in the group of the structure composition shown in following formula [4a]~formula [4k],
Z1~Z4Represent at least one kind of in the group being made up of hydrogen atom, methyl, chlorine atom and phenyl ring independently of one another；Z5With Z6Hydrogen atom or methyl are represented independently of one another.
11. according to aligning agent for liquid crystal according to any one of claims 1 to 10, wherein, the aligning agent for liquid crystal Containing at least one kind of molten in the group being made up of METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones and gamma-butyrolacton Agent.
12. the aligning agent for liquid crystal according to any one of claim 1~11, wherein, the aligning agent for liquid crystal Containing selected from by 1- hexanols, cyclohexanol, 1,2- ethylene glycol, 1,2- propane diols, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropyl At least one kind of solvent in the group of solvent composition shown in glycol dimethyl ether and following formula [D1]~formula [D3],
D1Represent the alkyl of carbon number 1~3；D2Represent the alkyl of carbon number 1~3；D3Represent the alkyl of carbon number 1~4.
13. the aligning agent for liquid crystal according to any one of claim 1~12, wherein, the aligning agent for liquid crystal Contain following cross-linked compounds：With selected from being made up of epoxy radicals, NCO, oxetanylmethoxy and cyclocarbonate radical The cross-linked compound of group in group；Constituted with the alkoxyalkyl for selecting free hydroxyl, hydroxy alkyl and carbon number 1~3 The cross-linked compound of group in group；Or the cross-linked compound with the unsaturated binding groups of polymerism.
14. a kind of liquid crystal orientation film, it is obtained as the aligning agent for liquid crystal any one of claim 1~13.
15. a kind of liquid crystal orientation film, it is coated with by ink-jet method at the liquid crystal aligning any one of claim 1~13 Obtained from reason agent.
16. a kind of liquid crystal represents element, it has the liquid crystal orientation film described in claims 14 or 15.
17. the liquid crystal orientation film according to claims 14 or 15, it is characterised in that it is used for possessing a pair of bases of electrode The liquid crystal with liquid crystal layer represents element between plate, and the liquid crystal represents that element is manufactured via following process：Described Configuration includes the liquid for the polymerizable compound polymerizeing by least one of active energy beam and heat between a pair of substrates Crystal composite, while to applying voltage between the electrode while polymerizeing the polymerizable compound.
18. a kind of liquid crystal represents element, it is characterised in that it has the liquid crystal orientation film described in claim 17.
19. the liquid crystal orientation film according to claims 14 or 15, it is characterised in that it is used for possessing a pair of bases of electrode The liquid crystal with liquid crystal layer represents element between plate, and the liquid crystal represents that element is manufactured via following process：Described Configuration includes the liquid crystal for the polymerizable group polymerizeing by least one of active energy beam and heat between a pair of substrates Alignment films, while to applying voltage between the electrode while polymerizeing the polymerizable group.
20. a kind of liquid crystal represents element, it is characterised in that it has the liquid crystal orientation film described in claim 19.
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