CN108700777A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element - Google Patents
Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element Download PDFInfo
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- CN108700777A CN108700777A CN201680082511.XA CN201680082511A CN108700777A CN 108700777 A CN108700777 A CN 108700777A CN 201680082511 A CN201680082511 A CN 201680082511A CN 108700777 A CN108700777 A CN 108700777A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Abstract
It provides:Aligning agent for liquid crystal for the liquid crystal orientation film for obtaining to mitigate the liquid crystal aligning unevenness generated in ODF modes etc..A kind of aligning agent for liquid crystal, it is characterized in that, containing selected from least one of the polyamic acid obtained from making diamine component be reacted with tetracarboxylic dianhydride's ingredient and the group for forming the polyimides that the polyamic acid imidizate obtains polymer, the diamine component contains:Diamines with crown ether structures and aromatic ring;With the diamines of the side chain with the pre-tilt angle for embodying liquid crystal.
Description
Technical field
The present invention relates to the aligning agent for liquid crystal used when making liquid crystal orientation film, liquid crystal orientation film and use its liquid crystal
Indicate element.
Background technology
Currently, indicating element as liquid crystal, there is following liquid crystal watch to show element:It is formed with the 2 of liquid crystal orientation film on the electrode
Between electrode base board, the long axis of the nematic liquid crystal with positive dielectric anisotropy it is continuous from a substrate to another substrate
Reversed 90 °, so-called twisted-nematic (TN) type liquid crystal indicate element;On unilateral substrate with comb teeth-shaped be formed with electrode and
Electric field is set transversely to generate to drive liquid crystal, plane switching (IPS) type liquid crystal expression element relative to real estate.In addition,
Different from these ground, it also developed following vertical (VA) type liquid crystal and indicate element:Its make with negative dielectric anisotropy to
Row liquid crystalline phase is for real estate along vertical orientation.These liquid crystal indicate that the liquid crystal orientation film used in element has mainly used polyamides
The liquid crystal orientation film of imines system develops the polyimides system alignment films of various structures (referring for example to patent document 1).
(cell gap) between 2 substrates for being formed with liquid crystal orientation film is needed to fill in the making of liquid crystal expression element
The process of liquid crystal.So far, it is usually following vacuum injection mode in liquid crystal filling:Using the pressure difference of atmospheric pressure and vacuum, 2
Filling liquid crystal between substrate.However, in the case of which, liquid crystal injecting port is only arranged at the unilateral side of substrate, therefore, in order to
The filling liquid crystal between cell gap is 3~5 μm of substrate, needs longer time, accordingly, it is difficult to which carrying out liquid crystal indicates element
Manufacturing process simplification.Especially liquid crystal TV, large-scale monitor manufacture in such case become larger problem.
Therefore, in order to solve the problems in above-mentioned vacuum injection mode, liquid crystal drop add mode (ODF modes) is developed.It should
Mode is such as under type:Liquid crystal is added dropwise on the substrate for be formed with liquid crystal orientation film, after being bonded in a vacuum with another substrate,
Sealing material UV is set to cure, to filling liquid crystal.
On the other hand, it as liquid crystal indicates the in-depth of the High precision of element, gradually needs to inhibit to indicate uneven.Liquid crystal drop
In add mode, the manufacture of the influence of water, impurity is adsorbed in the mitigations such as vacuum degree when by reducing the dripping quantity of liquid crystal, improving fitting
The optimization of process and be resolved.However, as liquid crystal indicates the enlargement of element manufacturing line, manufacturing process so far
It can not inhibit to indicate uneven in optimization, seek that uneven liquid crystal orientation film can be orientated than mitigating in the past.
Existing technical literature
Patent document
Patent document 1:The flat 11-249148 bulletins of Japanese Laid-Open
Invention content
Problems to be solved by the invention
In ODF modes, alignment films are applied due to being directly added dropwise liquid crystal in alignment films, accordingly, there exist the liquid crystal drop added-time
Add physical stress, needs the dropwise addition point for needing to increase liquid crystal in panel whole region filling liquid crystal.Therefore, it is added dropwise in liquid crystal
Portion, the drop of liquid crystal and the part of adjacent drop contact generate orientation unevenness that trace, lattice unevenness etc is added dropwise, so-called,
In the case of being formed liquid crystal expression element, there is a problem of the uneven expression unevenness of generating source auto-orientation.Think the orientation
Unevenness generates as follows:The absorption water of liquid crystal aligning film surface attachment on being formed in substrate, impurity is due in ODF processes
The liquid crystal being added dropwise is swept, to make the amount of absorption water, impurity in the part that the drop of liquid crystal dropwise addition portion, liquid crystal is in contact with each other
Difference, to generate.
The present invention makes in view of the foregoing, the problem to be solved by the present invention is to provide:Formation can mitigate
The aligning agent for liquid crystal of the liquid crystal orientation film of the liquid crystal aligning unevenness generated in ODF modes provides in turn:Mitigate and is originated from ODF modes
The liquid crystal that the liquid crystal aligning of middle generation is uneven, expression is uneven indicates element.
The solution to the problem
Present inventor has performed further investigations, as a result so far complete the present invention for reaching the above subject.
That is, the present invention has purport below.
1. a kind of aligning agent for liquid crystal, which is characterized in that containing selected from by making diamine component be reacted with tetracarboxylic dianhydride's ingredient
Obtained from polyamic acid and the polyimides of the acid imide compound as polyamic acid composition at least one of group it is poly-
Object is closed, the diamine component contains:Diamines containing crown ether structures and aromatic ring;With the pre-tilt angle with embodiment liquid crystal
The diamines of side chain.
2. a kind of liquid crystal orientation film is obtained by aligning agent for liquid crystal described above.
3. a kind of liquid crystal indicates element, has liquid crystal orientation film described above.
The effect of invention
Aligning agent for liquid crystal according to the present invention can obtain:Liquid crystal can be mitigated and be filled in liquid in such a way that (ODF) is added dropwise in liquid crystal
The liquid crystal of brilliant unit indicates the liquid crystal orientation film of the liquid crystal aligning unevenness generated in element etc..In turn, it can obtain:Mitigation is originated from
The liquid crystal of the uneven expression unevenness of liquid crystal aligning generated in ODF modes etc. indicates element.
It is still unknown about the liquid crystal aligning unevenness that occurs in why in such a way that the aligning agent for liquid crystal of the present invention mitigates ODF etc.
Really, but think:The crown ether used in the raw material of the aligning agent for liquid crystal of the present invention has big cricoid alkyl ether structure, therefore, with
Structure (reference International Publication the bulletin WO2011-010619, WO2012- with carboxyl, the heterocycle structure of alkalinity used in the past
014898) it compares, hydrophobicity is high, is not easily susceptible to the influence of absorption water, impurity, as a result, being not likely to produce liquid crystal aligning unevenness.
Specific implementation mode
< contains the diamines > of crown ether structures and aromatic ring
The above-mentioned diamines (hereinafter also referred to as specific diamines 1) containing crown ether structures and aromatic ring is as long as have crown ether knot
Structure and aromatic ring structure just do not limit its structure.However, the exceedingly structure with large volume or the big ring of molecular weight
In the case of, there is the possibility for upsetting liquid crystal aligning, therefore, molecular weight preferably 250~1500, particularly more preferable 250~
1000。
Herein, aromatic rings can may be any one of heterocycle for carbocyclic ring, be to eliminate 1 in the case of carbocyclic ring
Residue obtained from the hydrogen atom of carbocyclic aromatic compounds, in addition, in the case of heterocycle, such as nitrogen atom heteroaromatic
Refer to residue obtained from the hydrogen atom for the heterocyclic aromatic compound for eliminating 1 nitrogen atom in the case of compounds of group.
As the concrete example of above-mentioned carbocyclic aromatic compounds, can enumerate cyclopentadiene, benzene, Azulene, naphthalene, anthracene, phenanthrene, pyrene,
Aphthacene, BaP, pentacene, that non-alkene, indenes, fluorenes, biphenyl alkene etc..
In addition, as above-mentioned heterocycle, i.e., the concrete example of the heterocyclic aromatic compound of nitrogen atom, can enumerate pyrroles,
Pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, imidazoles, pyrazoles, oxazole, isoxazole, oxadiazoles, thiazole, isothiazole, thiadiazoles
It is triazole, tetrazolium, indoles, indazole, benzimidazole, benzoxazole, benzoisoxazole, benzothiazole, benzisothiazole, quinoline, different
Quinoline, cinnolines, phthalazines, quinazoline, quinoxaline, naphthyridines, pteridine, purine, cumarin, isocoumarin, carbazole, acridine, phenanthroline,
Thienopyridine, furopyridine, indolizine, quinolizine, carboline etc..In addition, positions N-H in pyrroles, pyrazoles, imidazoles etc. can be with
The alkylations such as keep intact or be methylated.
On the carbon atom of composition ring in the heterocyclic aromatic compound of above-mentioned carbocyclic aromatic compounds or nitrogen atom
Or the hydrogen atom on nitrogen-atoms is optionally substituted.Type, the quantity of substituent group are not particularly limited, methyl, ethyl, alkoxy,
Substituent group, carboxyl, nitro, the cyano etc. of methoxyl group, ethyoxyl, amino, the smaller electron of dimethylamino equimolecular quantity
What the smaller electron-withdrawing substituent group of molecular weight made electronics gives and receives activation, therefore it is preferred that.Carbocyclic aromatic compounds or
The position of substituent group in heterocyclic aromatic compound is not particularly limited, and in the case of nitrogen heterocyclic ring aromatic compound, takes
The position of Dai Ji preferably with the non-conterminous position of nitrogen-atoms.
On the other hand, from liquid crystal aligning, resistance to brushing and the sights such as easiness of synthesis when forming liquid crystal orientation film
Point sets out, carbocyclic aromatic compounds or nitrogen atom preferably unsubstituted or with the smaller substituent group substitution such as methyl, ethyl
Heterocyclic aromatic compound.
In the present invention, as the preference of specific diamines 1, diamines shown in following formula (1) can be enumerated.
In formula (1), X1,X2Each independently represent singly-bound or-(OCH2CH2)n-.Herein, n indicates 1~6 integer, preferably
1~4 integer.R1Indicate any one of 2 structures below.It should be noted that 2 R1It can be the same or different.
Above-mentioned expression R1Formula in, R2And R4Each independently represent the alkylidene of singly-bound or carbon number 1~5, R3Indicate single
The alkylidene or carbonyl of key, carbon number 1~5, X indicate aromatic rings.
As aromatic rings, preferably benzene, pyridine, pyridazine, pyrimidine, pyrazine, triazine pyrroles, oxazole, oxadiazoles, thiazole, thiophene two
Azoles, imidazoles, pyrazoles or triazole.Wherein, preferred benzene.
As the preferred concrete example of specific diamines 1, DA-1~DA-10 below can be enumerated.Wherein, preferably DA-2,
DA-3, DA-6 or DA-7.
Specific diamines 1 relative to the diamine component (1mol) used in the synthesis of polyamic acid, preferably 10~80mol%,
More preferable 10~70mol%, particularly preferred 20~50mol%.
< has the diamines > of the side chain for the pre-tilt angle for embodying liquid crystal
As the diamines (hereinafter also referred to as specific diamines 2) of the side chain with the pre-tilt angle for embodying liquid crystal, can enumerate:
With chain alkyl, perfluoroalkyl, aromatic cyclic groups, aliphatic cyclic group or the substituent group or class that are combined with them
The diamines of sterol skeleton base etc., they can be indicated with the following general formula.
X1To be selected from-O- ,-CH2O-,-COO-,-(CH2)a(integer that a is 1~10) ,-NH- ,-N (CH3)-,-
CONH-,-NHCO-,-OCO-,-CON(CH3)-,-N(CH3) CO- or the divalent in singly-bound organic group.X2For be selected from singly-bound,
Or-(CH2)bThe organic group of divalent in (integer that b is 1~10).X3To be selected from singly-bound ,-(CH2)c(c be 1~10 it is whole
Number) ,-O- ,-NH- ,-N (CH3)-,-CONH-,-NHCO-,-CH2O-,-COO-,-OCO-,-CON(CH3)-or-N (CH3)CO-
In divalent organic group.X4It indicates the cyclic group of the divalent in phenyl ring, cyclohexyl ring or heterocycle or there is steroids
The organic group of the divalent of the carbon number 12~25 of skeleton, arbitrary hydrogen atom on aforementioned cyclic group optionally by selected from carbon number 1~
3 alkyl, the alkoxy of carbon number 1~3, the fluoroalkoxy containing fluoroalkyl or carbon number 1~3 of carbon number 1~3, in fluorine atom
Group is replaced.
X5Indicate the cyclic group of the divalent in cyclohexyl ring, phenyl ring or heterocycle, it is arbitrary on these cyclic groups
Hydrogen atom optionally by the alkoxy of alkyl, carbon number 1~3 selected from carbon number 1~3, carbon number 1~3 contain fluoroalkyl or carbon number 1~3
Fluoroalkoxy, the group in fluorine atom replaced.The integer that n is 0~4.
X6For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18, carbon number 1~18
Fluoroalkoxy or hydrogen atom, the integer that m is 1~4.
For X1, wherein singly-bound ,-(CH2) a- (a be 1~10 integer) ,-O- ,-CONH- ,-CH2When O- or-COO-,
It is readily synthesized side-chain structure, therefore it is preferred that.More preferable singly-bound ,-(CH2)a(integer that a is 1~10) ,-O- ,-CONH- ,-CH2O-,
Or-COO-.Further preferred singly-bound ,-(CH2)a(integer that a is 1~10) ,-O- ,-CH2O- or-COO-.
For X2, wherein preferred singly-bound or-(CH2)b(integer that b is 1~10).
For X3, wherein singly-bound ,-(CH2)c(integer that c is 1~10) ,-O- ,-CH2O- ,-COO- or-OCO- hold
Easily synthesized, therefore it is preferred that.More preferable singly-bound ,-(CH2)c(integer that c is 1~10) ,-O- ,-CH2O- ,-COO- or-
OCO-。
For X4, wherein preferred phenyl ring, cyclohexyl ring, i.e., phenylene, cyclohexylidene or the carbon with steroid skeleton
The organic group of number 12~25.
For X5, wherein preferred phenyl ring or cyclohexyl ring.
For X6, wherein the alkyl of preferred carbon number 1~18, the alcoxyl containing fluoroalkyl, carbon number 1~18 of carbon number 1~10
The fluoroalkoxy of base or carbon number 1~10.The alkyl of more preferable carbon number 1~12 or the alkoxy of carbon number 1~12.It is further excellent
Select the alkyl of carbon number 1~9 or the alkoxy of carbon number 1~9.
The integer of n preferably 0~2.The integer of m preferably 1~2.
Shi [1]In X1,X2,X3,X4,X5,X6, n it is preferred combination can enumerate:With International Publication bulletin WO2011/
Identical group of (1-1)~(1-629) described in 1~table of table 42 of page 11 of 132752 (2011.10.27 is disclosed)~page 32
It closes.
Hereinafter, the concrete example of the diamine compound of the side chain with the pre-tilt angle for embodying liquid crystal is enumerated, but the present invention is unlimited
Due to these.
Above-mentioned Shi [1a-1], Shi [1a-2]In, R1Expression-O- ,-OCH2-,-CH2O-,-COOCH2-,-CH2OCO-, R2For
1 or more and 22 alkyl below of carbon number, contains fluoroalkyl or fluoroalkoxy at alkoxy).
Above-mentioned Shi [1a-3]~Shi [1a-5]In, R3Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH2-,-
CH2OCO-,-CH2O-,-OCH2Or-CH2, R4For carbon number 1 or more and 22 alkyl below, alkoxy, containing fluoroalkyl or contain
Fluoroalkyloxy).
Above-mentioned Shi [1a-6], Shi [1a-7]In, R5Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH2-,-
CH2OCO-,-CH2O-,-OCH2-,-CH2,-O- or-NH-, R6For fluorine-based, cyano, fluoroform alkyl, nitro, azo group, first
Acyl group, acetyl group, acetoxyl group or hydroxyl).
Above-mentioned Shi [1a-8], Shi [1a-9]In, R7For 3 or more and 12 alkyl below of carbon number, Isosorbide-5-Nitrae-cyclohexylene it is suitable
Formula-trans-isomerism is respectively transisomer.
Above-mentioned Shi [1a-10], Shi [1a-11]In, R8For 3 or more and 12 alkyl below of carbon number, Isosorbide-5-Nitrae-cyclohexylene
Sys-trans isomerism is respectively transisomer.
Above-mentioned Shi [1a-12]In, A4For the alkyl of the carbon number 3~20 optionally replaced by fluorine atom, A3For the Asias 1,4- hexamethylene
Base or Isosorbide-5-Nitrae-phenylene, A2(the atom key and A of " * " wherein, are marked for oxygen atom or-COO-*3Bonding), A1For oxygen atom,
Or-COO-* (wherein, marks the atom key and (CH of " * "2)a2) bonding).In addition, a1For 0 or 1 integer, a2For 2~10 it is whole
Number, a3For 0 or 1 integer.
What is used in the aligning agent for liquid crystal of the present invention has the diamines of the side chain for the pre-tilt angle for embodying liquid crystal relative to aforementioned
Whole diamine components (1mol), preferably 10~80mol%, more preferable 20~80mol%, particularly preferred 20~70mol%.
Other diamines of < >
In the case of obtaining the aligning agent for liquid crystal of the present invention, other diamines in addition to specific diamines 1,2 can be used.Make
For other above-mentioned diamines, ester ring type diamines, aromatic diamine, hetero ring type diamines, aliphatic diamine, aromatic series-fat can be enumerated
Fat race diamines etc..The concrete example of above-mentioned diamines described below.
As the example of ester ring type diamines, Isosorbide-5-Nitrae-diaminocyclohexane, 1,3- diaminocyclohexanes, 4,4 '-can be enumerated
Diamino-dicyclohexyl methane, 4,4 '-diamino -3,3 '-dimethyl dicyclohexyl amine, isophorone diamine etc..
As the example of aromatic diamine, can enumerate:O-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 2,4- diamino first
Benzene, 2,5- diaminotoluenes, 3,5- diaminotoluenes, 3,5- diamino-Ns, N- diallyl anilines, 2,4- diamino-Ns, N-
Diallyl aniline, 1,4- diamino -2- methoxybenzenes, 2,5- diamino-paraxylene, 1,3- diamino -4- chlorobenzenes, 3,5-
Diaminobenzoic acid, 1,4- diamino -2,5- dichloro-benzenes, 4,4 '-diaminostilbenes, 2- diphenylethanes, 4,4 '-diamino -2,
2 '-dimethyl bibenzyls, 4,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diamino-diphenyl first
Alkane, 4,4 '-diamino -3,3 '-dimethyl diphenylmethane, 2,2 '-diamino-stilbene, 4,4 '-diamino-stilbene, 4,4 '-diamino
Diphenyl ether, 3,4 '-diaminodiphenyl ethers, 4,4 '-diamino diphenyl sulfides, 4,4 '-diamino diphenyl sulfones, 3,3 '-diaminos
Bis- (3- amino-benzene oxygens) benzene of base diphenyl sulfone, 4,4 '-diaminobenzophenones, 1,3-, bis- (4- amino-benzene oxygens) benzene of 1,3-,
Bis- (4- amino-benzene oxygens) benzene of 1,4-, bis- (4- amino-benzene oxygens) benzoic acid of 3,5-, 4,4 '-bis- (4- amino-benzene oxygens) bibenzyls,
The bis- [ of 2,2-;(4- amino-benzene oxygens) Jia Ji ]The bis- [ of propane, 2,2-;4- (4- amino-benzene oxygens) Ben Ji ]The bis- [ of hexafluoropropane, 2,2-;4-
(4- amino-benzene oxygens) Ben Ji ]Propane, Shuan [4- (3- amino-benzene oxygens) Ben Ji ]Sulfone, Shuan [4- (4- amino-benzene oxygens) Ben Ji ]
Bis- (4- aminobenzyls) ureas of sulfone, 1,3-, bis- (4- aminophenethyls) ureas of 1,3-, bis- (4- aminophenyls) hexamethylenes of 1,1-, α, α '-
Bis- (4- aminophenyls) fluorenes of bis- (4- aminophenyls) -1,4- diisopropyl benzenes, 9,9-, bis- (3- aminophenyls) hexafluoros third of 2,2-
Bis- (4- aminophenyls) hexafluoropropane of alkane, 2,2-, 4,4 '-diamino-diphenylamines, 2,4- diamino-diphenylamines, 1,8- diamino
Naphthalene, 1,5- diaminonaphthalenes, 1,5- diamino-anthraquinones, 1,3- diamino pyrene, 1,6- diamino pyrene, 1,8- diamino pyrene, 2,7- bis-
Bis- (4- aminophenyls) tetramethyl disiloxanes of aminofluorene, 1,3-, benzidine, 2,2 '-dimethylbenzidines, bis- (the 4- ammonia of 1,2-
Base phenyl) ethane, bis- (4- aminophenyls) propane of 1,3-, bis- (4- aminophenyls) butane of 1,4-, 1,5- bis- (4- aminophenyls)
Bis- (4- aminophenyls) hexanes of pentane, 1,6-, bis- (4- aminophenyls) heptane of 1,7-, bis- (4- aminophenyls) octanes of 1,8-, 1,
Bis- (4- aminophenyls) nonanes of 9-, bis- (4- aminophenyls) decane of 1,10-, bis- (4- amino-benzene oxygens) propane of 1,3-, 1,4- are bis-
Bis- (4- amino-benzene oxygens) pentanes of (4- amino-benzene oxygens) butane, 1,5-, bis- (4- amino-benzene oxygens) hexanes of 1,6-, 1,7- are bis-
Bis- (4- amino-benzene oxygens) octanes of (4- amino-benzene oxygens) heptane, 1,8-, bis- (4- amino-benzene oxygens) nonanes of 1,9-, 1,10- are bis-
(4- amino-benzene oxygens) decane, 1,3- malonic acid two (4- aminophenyls) ester, 1,4- succinic acid two (4- aminophenyls) ester, 1,5-
Glutaric acid two (4- aminophenyls) ester, 1,6- adipic acids two (4- aminophenyls) ester, 1,7- pimelic acid two (4- aminophenyls) ester,
1,8- suberic acids two (4- aminophenyls) ester, 1,9- azelaic acids two (4- aminophenyls) ester, (the 4- aminobenzenes of 1,10- decanedioic acid two
Base) ester, bis- (4- (4- amino-benzene oxygens) phenoxy group) propane of 1,3-, bis- (4- (4- amino-benzene oxygens) phenoxy group) butane of 1,4-,
Bis- (4- (4- amino-benzene oxygens) phenoxy group) pentanes of 1,5-, bis- (4- (4- amino-benzene oxygens) phenoxy group) hexanes of 1,6-, 1,7- are bis-
Bis- (4- (4- amino-benzene oxygens) phenoxy group) octanes of (4- (4- amino-benzene oxygens) phenoxy group) heptane, 1,8-, the bis- (4- (4- of 1,9-
Amino-benzene oxygen) phenoxy group) nonane, bis- (4- (4- amino-benzene oxygens) phenoxy group) decane of 1,10- etc..
As the example of hetero ring type diamines, 2,6-diaminopyridine, 2,4- diamino-pyridines, 2,4- diaminos can be enumerated
Base -1,3,5- triazines, 2,7 diaminodibenz of uran, 3,6- diaminocarbazoles, 2,4- diamino -6- isopropyls -1,3,5-
Bis- (4- aminophenyls) -1,3,4- oxadiazoles of triazine, 2,5- etc..
As the example of aliphatic diamine, 1,2-Diaminoethane, 1,3- diaminopropanes, Isosorbide-5-Nitrae-diamino can be enumerated
Butane, 1,5- 1,5-DAPs, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diamino nonyls
Alkane, 1,10- diamino decanes, 1,3- diamino -2,2- dimethylpropanes, 1,6- diamino -2,5- dimethylhexanes, 1,7- bis-
Amino -2,5- dimethyl heptanes, 1,7- diamino -4,4- dimethyl heptanes, 1,7- diamino -3- methyl heptanes, 1,9- diaminos
Bis- (3- amino propoxyl group) ethane of base -5- methyl heptanes, 1,12- diamino dodecanes, 1,18- diamino octadecane, 1,2- etc..
As the example of aromatic-aliphatic diamines, Shi [ can be enumerated;3]Shown in diamines.
H2N-Ar'-R5-NH-R6[3]
Shi [3]In, Ar ' is phenylene or naphthylene, R5For the alkylidene of carbon number 1~5, preferably 1~3, R6For hydrogen atom or
The alkyl of carbon number 1~5, preferably hydrogen atom or methyl.
As Shi [3]Shown in diamines concrete example, 3- amino-benzylamines, 4- amino-benzylamines, 3- amino-N- first can be enumerated
Base benzylamine, 4- Amino-N-methyls benzylamine, 3- amino phenyl ethylamine, 4- amino phenyl ethylamine, 3- Amino-N-methyls phenyl ethylamine, 4- ammonia
Base-N- Methylphenethylamines, 3- (3- aminopropyls) aniline, 4- (3- aminopropyls) aniline, 3- (3- dimethylaminopropyls) aniline,
4- (3- dimethylaminopropyls) aniline, 3- (4- aminobutyls) aniline, 4- (4- aminobutyls) aniline, 3- (4- methylamino fourths
Base) aniline, 4- (4- methylaminos butyl) aniline, 3- (5- Aminopentyls) aniline, 4- (5- Aminopentyls) aniline, 3- (5- first
Base Aminopentyl) aniline, 4- (5- methylamino-pentyls) aniline, 2- (6- amino naphthalene) methylamine, 3- (6- amino naphthalene) methylamine,
2- (6- amino naphthalene) ethamine, 3- (6- amino naphthalene) ethamine etc..
< tetracarboxylic dianhydride's ingredients >
In the present invention, the tetracarboxylic dianhydride's ingredient reacted with above-mentioned diamine component is not particularly limited, furthermore it is possible to be 1
Tetracarboxylic dianhydride of more than two kinds is applied in combination in kind.
As the tetracarboxylic dianhydride reacted with aforementioned diamine component, from the voltage retention that can further increase liquid crystal cells
Aspect etc. set out, it is preferable to use the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure.
As the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, 1,2,3,4- cyclobutane tetracarboxylic acids can be enumerated
Acid dianhydride, 1,2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid two
Acid anhydride, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 2,3,4,5-
Tetrahydrofuran tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylics dianhydride, 3,4- dicarboxyl -1- cyclohexyl ambers acid dianhydride, 3,
4- dicarboxyl -1,2,3,4- tetrahydrochysene -1- naphthalene succinics dianhydride, (4- (2,5- dioxotetrahydro furans -3- bases) -1,2,3,4- four
Hydrogen naphthalene -1,2- dicarboxylic anhydrides), it is 1,2,3,4- butane tetracarboxylics acid dianhydride, bicyclic;3,3,0]Octane -2,4,6,8- tetracarboxylic dianhydrides,
3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydrides, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, cis- -3,7- dibutyl ring octyl-
1,5- diene -1,2,5,6- tetracarboxylic dianhydrides, San Huan [4.2.1.02,5]Nonane -3,4,7,8- tetrabasic carboxylic acids -3,4:7,8- dianhydrides,
Six Huan [6.6.0.12,7.03,6.19,14.010,13]Hexadecane -4,5,11,12- tetrabasic carboxylic acids -4,5:11,12- dianhydrides etc..Its
In, 1,2,3,4- cyclobutane tetracarboxylic dianhydride can obtain the excellent alignment films of liquid crystal aligning, therefore particularly preferably.
In turn, if aromatic tetracarboxylic acid's dianhydride is applied in combination, liquid crystal aligning improves, and can accelerate liquid crystal cells
Charge accumulation disengaging.As aromatic tetracarboxylic acid's dianhydride, pyromellitic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic acids can be enumerated
Acid dianhydride, 2,2 ', 3,3 '-biphenyltetracarboxylic dianhydrides, 2,3,3 ', 4- biphenyltetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone four
Carboxylic acid dianhydride, 2,3,3 ', 4- benzophenone tetracarboxylic dianhydrides, bis- (3,4- dicarboxyphenyis) ether dianhydrides, bis- (3,4- dicarboxyl benzene
Base) sulfone dianhydride, 1,2,5,6- naphthalene tetracarboxylic acids dianhydride, 2,3,6,7- naphthalene tetracarboxylic acids dianhydride, 4,4 '-(hexafluoroisopropyli,ene base) two adjacent benzene
Dicarboxylic acid anhydride etc..Wherein particularly preferred pyromellitic acid dianhydride.
It is each from orientation, voltage retention, the charge accumulation etc. of the dissolubility of gained polyamic acid or polyimides, liquid crystal
Balanced aspect of characteristic is set out, the tetracarboxylic dianhydride preferably with ester ring type structure or aliphatic structure and aromatic series tetracarboxylic acid
Acid dianhydride is applied in combination, in addition, the former/usage rate of the latter with molar ratio computing, preferably 90/10~50/50, more preferably
80/20~60/40.
The manufacture > of < polyamic acids and polyimides
The polyamic acid used in the present invention can utilize well known polymerization.Generally make tetracarboxylic dianhydride's ingredient with
The method that diamine component reacts in organic solvent.Tetracarboxylic dianhydride and diamines react from be easier in organic solvent into
It goes and is advantageous in terms of not generating by-product.
The organic solvent used at this time is not particularly limited as long as so that the polyamic acid of generation is dissolved.It is exemplified below its tool
Body example.
For:N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl -2- pyrroles
Alkanone, 1,3- dimethyl -2- imidazolidinones, N- methyl caprolactams, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone,
Hexamethyl sulfoxide, gamma-butyrolacton, isopropanol, methoxy amylalcohol, dipentene, ethylpentyl ketone, methyl nonyl ketone, first and second
The molten fibre of ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl
Agent acetic acid esters, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol list
The tertiary butyl ether of butyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-, dipropylene glycol monomethyl ether, diethyl two
Alcohol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropyl
Glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol list second
Acid esters list propyl ether, 3- methyl -3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanols, diisopropyl
Ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two oneself
Ether, dioxane, n-hexane, pentane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, lactic acid
Methyl esters, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, acetone
Acetoacetic ester, 3- methoxy methyl propionates, 3- ethoxy-propionic acids Methylethyl, 3- methoxypropionates, 3- ethoxy-propionic acids, 3-
Methoxypropionic acid, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyls -2- penta
Ketone etc..They can be used alone, and can also mix and use.In turn, even if not make the solvent of polyamic acid dissolving, in life
At polyamic acid be not precipitated in the range of, can also be blended in above-mentioned solvent and use.In addition, the moisture in organic solvent
The reason of interfering polymerisation, and then becoming the polyamic acid hydrolysis for making generation, therefore, it is preferable to use be dehydrated as possible for organic solvent
Dry organic solvent.
As the method for making tetracarboxylic dianhydride be reacted in organic solvent with diamines, following method can be enumerated:It will be organic
Dispersion or the solution stirring dissolved with diamines, directly add tetracarboxylic dianhydride, or it is made to be dispersed or dissolved in solvent
Solvent and the method added;On the contrary, adding two in dispersion or the solution dissolved with tetracarboxylic dianhydride in organic solvent
The method of amine;Alternately add the method etc. of tetracarboxylic dianhydride and diamines, these any means.In addition, tetracarboxylic dianhydride or
It in the case that diamines is made of multiple compounds, can react, can also react successively respectively in the state of being pre-mixed, into
And can also low-molecular weight obtained by the reaction respectively be subjected to hybrid reaction and form high molecular weight body.
The temperature when synthesis of above-mentioned polyamic acid can select -20 DEG C~150 DEG C of arbitrary temp, and preferably -5 DEG C~100
DEG C range.In addition, reaction can carry out under arbitrary concentration, when concentration is too low, it is difficult to the polymer of high molecular weight is obtained,
When excessive concentration, the viscosity of reaction solution becomes excessively high, and uniform stirring becomes difficult, it is therefore preferable that 1~50 mass %, more preferable 5
~30 mass %.Reaction is initially carried out with high concentration, later, can add organic solvent.
In the synthetic reaction of polyamic acid, the ratio between the molal quantity of the molal quantity of diamine component relative to tetracarboxylic dianhydride is preferably
0.8~1.2.In the same manner as common polycondensation reaction, closer to 1.0, the molecular weight of the polyamic acid of generation becomes the molar ratio
It is bigger.
The polyimides used in the present invention is polyimides obtained from making foregoing polyamides acid dehydration closed-loop, as with
It is useful in obtaining the polymer of liquid crystal orientation film.
In the polyimides used in the present invention, the dehydration closed-loop rate (acid imide rate) of amide acidic group may not be 100%,
It can arbitrarily be adjusted according to purposes, purpose.
As the method for making polyamic acid imidizate, can enumerate:By the direct-fired hot acyl of the solution of polyamic acid
Imidization;The catalysis imidizate of catalyst is added in the solution of polyamic acid.
Temperature when polyamic acid being made to carry out hot-imide in the solution is 100~400 DEG C, preferably 120~250 DEG C,
It is preferred that side removes the water generated by imidization reaction to the method for progress outside system.
The catalysis imidizate of polyamic acid can carry out as follows:In the solution of polyamic acid add basic catalyst and
Acid anhydrides, by the stirring at -20 DEG C~250 DEG C, preferably 0~180 DEG C, to carry out.The amount of basic catalyst is amide acidic group
0.5~30 mole times, preferably 2~20 moles times, the amount of acid anhydrides is 1~50 mole times, preferably 3~30 moles of amide acidic group
Times.
As basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated, wherein pyridine has
Have suitable for make reaction carry out alkalinity, therefore it is preferred that.As acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride can be enumerated
Deng, wherein when using acetic anhydride, purifying after reaction becomes easy, therefore it is preferred that.Imidizate based on catalysis imidizate
Rate can be controlled by adjusting catalytic amount, reaction temperature and reaction time.
The acid imide rate of polyimides used in the aligning agent for liquid crystal of the present invention is not particularly limited, from can obtain
Set out in terms of the liquid crystal orientation film of higher voltage retention, acid imide rate preferably 40~90%, it is more preferable 50~90%,
Particularly preferred 60~90%.
It, can be in poor solvent in the case that the reaction solution of polyamic acid or polyimides recycles component of polymer
Input reaction solution simultaneously makes its precipitation.As the poor solvent used in precipitation, it is molten that methanol, acetone, hexane, butyl can be enumerated
Fine agent, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene, water etc..It is put into poor solvent and it is made to precipitate
Polymer filtration and after recycling, air drying or heated and dried under normal pressure either decompression.In addition, precipitation is made to return
The polymer of receipts is re-dissolved in organic solvent, carries out reprecipitation recycling, when which is repeated 2~10 times, it is possible to reduce polymerization
Impurity in object.For example, if using 3 kinds of alcohols, ketone, hydrocarbon etc. or more poor solvent as poor solvent at this time, then it is pure
The efficiency of change further improves, therefore it is preferred that.
When the molecular weight of the polyamic acid and polyimides that are used in the present invention considers to apply film strength and film formation
In the case of operability, the uniformity of film, with GPC (gel permeation chromatography (Gel Permeation
Chromatography Weight-average molecular gauge that)) method measures, be preferably set to 5000~1000000 respectively, it is more preferable 10000~
150000。
< aligning agent for liquid crystal >
The aligning agent for liquid crystal of the present invention is the coating fluid for making liquid crystal orientation film, and principal component is by being used to form resin
The resin component of overlay film and for dissolve the resin component organic solvent constitute.In the present invention, aforementioned resin ingredient be comprising
The resin component of polyamic acid and/or polyimides.At this point, the content of resin component is 1~20 mass %, preferably 2~10 matter
Measure %.
In the present invention, aforementioned resin ingredient can all be reacted using specific diamines 1,2 as with tetracarboxylic dianhydride
The polymer (hereinafter also referred to as particular polymers) of diamine component, alternatively, it is also possible to containing without using specific diamines 1,2 its
His polymer.The content of particular polymers in resin component preferably 0.5~15 mass %, preferably 1~10 mass %.
Organic solvent for dissolving resin ingredient is not particularly limited.As concrete example, N, N '-dimethyl can be enumerated
Formamide, N, N '-dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl caprolactams, 2-Pyrrolidone, N- ethyl pyrroles
Pyrrolidone, n-vinyl pyrrolidone, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-Ding Nei
Ester, 1,3- dimethyl -2- imidazolidinones, dipentene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, first
Base nezukone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanones etc..
These solvents can mix two or more and use.
When polyimides being made to be dissolved in organic solvent, in order to promote the dissolving of polyimides, it can be heated.Heating
When the temperature is excessively high, the molecular weight of polyimides reduces sometimes, therefore, preferably 30~100 DEG C of temperature.The solution of specific polyimides
Concentration be not particularly limited, due to being easy uniformly to mix with certain amines, it is dense as the specific polyimides in solution
Degree, preferably 1~20 mass %, more preferable 3~15 mass %, particularly preferred 3~10 mass %.
The aligning agent for liquid crystal of the present invention can contain ingredient than that described above.As its example, it can contain and be useful for carrying
The solvent of film thickness uniformity, surface smoothness when high coating of liquid crystalline alignment agent, compound;For improving liquid crystal orientation film and base
The compound etc. of the adaptation of plate.
The concrete example of solvent (poor solvent) as uniformity, surface smoothness for improving film thickness, can enumerate
Following solvent.
For example,:Isopropanol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve,
Methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, second two
Alcohol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol list
The tertiary butyl ether of methyl ether, propylene glycol-, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethyl
Glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol list second
Acid esters list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyls acetic acid esters, three
Propylene glycol monomethyl ether, 3- methyl -3- methoxybutanols, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyric acid fourth
Ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, n-hexane, pentane, normal octane, diethyl ether, lactic acid first
Ester, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, pyruvic acid
Ethyl ester, 3- methoxy methyl propionates, 3- ethoxy-propionic acids Methylethyl, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- first
Oxygroup propionic acid, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, 1- methoxy-2-propanols, 1- ethyoxyl -2- propyl alcohol, 1-
Butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl ethers -
2- acetic acid esters, propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-cs oxygroup) propyl alcohol, methyl lactate, breast
Acetoacetic ester, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc. have the solvent etc. of low surface tension.
Among them, more preferable butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethyl lactate.
These poor solvents can use a kind, can also use a variety of mixing.The case where using above-mentioned solvent
Under, preferably 5~80 mass % of solvent entirety contained in aligning agent for liquid crystal, more preferably 20~60 mass %.
As for improving the uniformity of film thickness, the compound of surface smoothness, fluorine system surfactant can be enumerated, had
Machine silicon-based surfactant, nonionic surfactants etc..
More specifically, for example, EFTOP EF301, EF303, EF352 (Products plants of formula meetings of Tochem
Society's trade name), Megafac F171, F173, R-30 (big Japanese ink Co., Ltd. trade name), Fluorad FC430,
FC431 (Sumitomo 3M Ltd., system), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103,
SC104, SC105, SC106 (Asahi Glass Co., Ltd's trade name) etc..The use ratio of these surfactants is relative to liquid crystal
100 mass parts of the resin component contained in alignment agent, preferably 0.01~2 mass parts, more preferable 0.01~1 mass parts.
The concrete example of compound as the adaptation for improving liquid crystal orientation film and substrate can be enumerated as follows
The compound containing functional silanes, the compound containing epoxy group.
For example,:3- TSL 8330s, 3-aminopropyltriethoxysilane, 2- aminopropyls
Trimethoxy silane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- TSL 8330s, N-
(2- amino-ethyls) -3- aminopropylmethyldimethoxysilanes, 3- ureido-propyl trimethoxy silanes, three second of 3- ureido-propyls
Oxysilane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyl -3- aminopropyl triethoxies
Silane, N- triethoxysilylpropyltetrasulfides diethylenetriamine, N- trimethoxy-silylpropyls diethylenetriamine,
Three azepine decane of 10- trimethoxysilyls -1,4,7-, three azepine decane of 10- triethoxysilyls -1,4,7-, 9-
Trimethoxysilyl -3,6- diaza nonyls acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyl acetic acid
Ester, N- benzyl -3- TSL 8330s, N- benzyls -3-aminopropyltriethoxysilane, N- phenyl -3- amino
Bis- (oxygen the ethylidene) -3- aminopropyl front threes of propyl trimethoxy silicane, N- phenyl -3-aminopropyltriethoxysilane, N-
Bis- (oxygen the ethylidene) -3-aminopropyltriethoxysilane of oxysilane, N-, ethylene glycol diglycidylether, polyethylene glycol two
Glycidol ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, new penta
Hexanediol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycols two contract
Water glycerin ether, tetra- glycidol -2,4- hexylene glycols of 1,3,5,6-, N, N, N ', N ',-four glycidols-m-xylene diamine, 1,3-
Bis- (N, N- 2-glycidyl amino methyl) hexamethylenes, N, N, N ', N ',-four glycidyl group -4,4 '-diamino-diphenyl first
Alkane etc..
In the case of using these compounds closely sealed with substrate, relative to the resin component contained in aligning agent for liquid crystal
100 mass parts, preferably 0.1~30 mass parts, more preferable 1~20 mass parts.When less than 0.1 mass parts, adaptation can not be expected
The effect of raising, when being more than 30 mass parts, the orientation of liquid crystal is deteriorated sometimes.
In the aligning agent for liquid crystal of the present invention, apart from the above, dielectric constant, conduction so that liquid crystal orientation film can be added
Property etc. dielectric for the purpose of electrical property changes, conductive materials and then the hardness of film, densification when forming liquid crystal orientation film to improve
Cross-linked compound for the purpose of degree.
The concentration of solid constituent in the aligning agent for liquid crystal of the present invention can be fitted according to the film thickness of Object LC alignment films
The reasons why preferably changing, for the flawless film of formation and the film thickness appropriate as liquid crystal orientation film can be obtained, preferably 1~
20 mass %, more preferable 2~10 mass %.
< liquid crystal orientation film liquid crystal indicates element >
After the aligning agent for liquid crystal of the present invention is coated on substrate and is burnt into, orientation position is carried out with brushing processing, light irradiation etc.
Reason, or without orientation process in vertical orientation purposes etc., so as to be used as liquid crystal orientation film.At this point, conduct
The substrate used is not particularly limited as long as the high substrate of the transparency, can use glass substrate, acrylic acid substrate, gather
Plastic bases such as carbonic ester substrate etc..In addition, from the perspective of the chemical industry skill that conforms to the principle of simplicity, it is preferable to use be formed with for liquid crystal drive
The substrate of ITO electrode etc..In addition, the liquid crystal of reflection-type indicates in element, if only becoming unilateral substrate, can also use
The opaque substance such as Silicon Wafer, electrode at this time can also use the material of the reflected lights such as aluminium.
The coating method of aligning agent for liquid crystal is not particularly limited, it is industrial it is general be, with silk-screen printing, hectographic printing,
The method of the progress such as flexible printing, ink-jet.As other coating methods, have:Dipping, roller coating, slot coated, spin coating etc., can be with
Them are used according to purpose.
Firing after aligning agent for liquid crystal is coated on substrate can by heating meanss such as hot plates, 50~200 DEG C, it is excellent
Selecting makes evaporation of the solvent at 80~150 DEG C, form film.When the thickness of film after firing is blocked up, disappearing for element is indicated in liquid crystal
Become unfavorable in terms of power consumption power, when excessively thin, liquid crystal indicates that the reliability of element reduces sometimes, it is therefore preferable that 5~300nm, more
It is preferred that 10~100nm.In the case of making liquid crystal horizontal alignment, tilted alignment, to the film brushing or polarized UV after firing
Line irradiation etc. is handled.
The liquid crystal of the present invention indicates that element obtains as follows:By the above method, obtained using the aligning agent for liquid crystal of the present invention
After substrate with liquid crystal orientation film, liquid crystal cells are made with well known method, to form element.
If enumerating an example of liquid crystal cells making, can enumerate:Prepare 1 pair of substrate for being formed with liquid crystal orientation film,
Spacer is spread on the liquid crystal orientation film of a substrate, in such a way that liquid crystal alignment film surface becomes inside, is bonded another base
Liquid crystal is depressurized the method injected and sealed by plate;Or, after liquid crystal is added dropwise in the liquid crystal alignment film surface for be scattered with spacer, make
Substrate sticking and the method etc. being sealed.It is preferably 1~30 μm of the thickness of spacer at this time, 2~10 μm more preferable.
The liquid crystal made using the aligning agent for liquid crystal of invention indicates that element becomes the liquid crystal for mitigating and being originated from and being generated in ODF modes
It is orientated the liquid crystal uneven, expression is uneven and indicates element.
Embodiment
It enumerates embodiment below further to illustrate the present invention, but the present invention is not limited to these embodiments.With
The lower abbreviation used and assay method are as described below.
(acid dianhydride)
BODA:Shuan Huan [3,3,0]Octane -2,4,6,8- tetracarboxylic dianhydrides.
CBDA:1,2,3,4- cyclobutane tetracarboxylic dianhydrides.
(diamines)
< additives >
3AMP:3- pyridyl-methanamines.
< solvents >
NMP:N-methyl-2-pyrrolidone.
BCS:Butyl cellosolve.
> is determined in the measurement of < polyimide molecules
The molecule measuring fixed condition of polyimides is as described below.
Device:Senshu Kagaku Co. Ltd. system room temperature gel permeation chromatography (GPC) device (SSC-7200),
Column:Shodex corporations column (KD-803, KD-805),
Column temperature:50℃,
Eluent:N, N '-dimethyl formamide is (as additive, lithium bromide-hydrate (LiBrH2O) it is 30mmol/
L (liter), phosphoric acid anhydrous crystalline (orthophosphoric acid) are 30mmol/L, tetrahydrofuran (THF) is 10ml/L)
Flow velocity:1.0ml/ minutes,
Standard curve making standard sample:(molecular weight is about for TOSOH Co., Ltd TSK standards polyethylene oxide
9000000,150000,100000,30000) and Polymer Laboratories Ltd. polyethylene glycol (molecular weight is about
12000,4000,1000)。
The measurement > of < acid imide rates
Polyimide powder 20mg is put into NMR sample cells (wasteland's science Co. Ltd. system, NMR sample cell specifications φ
5) deuterated dimethyl sulfoxide (DMSO-d6,0.05%TMS melange) 1.0ml, is added, applies ultrasonic wave and makes it completely dissolved.
The solution is measured to the proton NMR of 500MHz using JEOL DATUM corporation NMR analyzers (JNW-ECA500).Imidizate
Rate determines the proton from not changed structure before and after imidizate as reference proton, is accumulated using the peak of the proton
The proton peak integrated value for the NH bases from amic acid that score value and 9.5ppm~10.0ppm nearby occur, is found out using following formula.
It should be noted that in following formula, x is the peak integral of proton on the basis of the proton peak integrated value of the NH bases from amic acid, y
1 that value, α are reference proton number in the case of polyamic acid (acid imide rate is 0%) relative to the NH bases of amic acid
The ratio of a proton.
Acid imide rate (%)=(1- α x/y) × 100
The making > of < liquid crystal aligning unevenness evaluation liquid crystal cells
It is the ITO that 300 μm of 100 μ m and line/space are respectively 5 μm that aligning agent for liquid crystal, which is spun on, and is formed with Pixel Dimensions
The ito surface of the ITO electrode substrate of electrode pattern, after 80 DEG C of press drying 90 seconds, in 200 DEG C of heated air circulation type baking oven
Be burnt within 20 minutes, forms the liquid crystal orientation film of film thickness 100nm.
And then aligning agent for liquid crystal is spun on to the ITO electrode substrate of the spacer (photospacer) of 3.3 μm of band
The ito surface of (not forming electrode pattern) carries out after 80 DEG C of press drying 90 seconds in 200 DEG C of heated air circulation type baking oven
It is burnt within 20 minutes, forms the liquid crystal orientation film of film thickness 100nm.
For above-mentioned 2 substrates, using dispenser device (Musashi Engineering Company systems, FAD630),
It is coated with sealant (solvent type light-cured type) on the liquid crystal orientation film of a substrate, and then PSA is added dropwise on liquid crystal orientation film
It is dripped with negative liquid crystal MLC-3023 (Merck corporations trade name) 6.Then, the substrate is made to be pasted in a vacuum with another substrate
It closes, sealing material is made to carry out UV solidifications, to filling liquid crystal.
Later, in the state of being applied with the D/C voltage of 15V, irradiation has passed through the UV of 325nm or less edge filters
15J/cm2, make liquid crystal aligning unevenness evaluation liquid crystal cells.
The evaluation > of < liquid crystal aligning unevenness
The liquid crystal cells made under these conditions are arranged to 2 polarizations configured in a manner of becoming orthogonal by polarizing axis
Between piece, backlight is lighted.Later, liquid crystal cells are applied with the AC voltages of 4Vpp.Observe the liquid crystal list after 3 minutes from applying
It is uneven to evaluate liquid crystal aligning by visual observation for member.At this point, the case where dropwise addition trace for having no liquid crystal (being orientated uneven), is determined as
The case where dropwise addition trace of " good ", visible liquid crystal, is determined as " bad ".
The making > of < voltage retention evaluation liquid crystal cells
It is 300 μm of 100 μ m and line/space is respectively 5 μm that aligning agent for liquid crystal, which is spun on, and is formed with Pixel Dimensions
ITO electrode pattern, ITO electrode substrate ito surface dries after 80 DEG C of press drying 90 seconds in 200 DEG C of heated air circulation types
It carries out being burnt into for 20 minutes in case, forms the liquid crystal orientation film of film thickness 100nm.
In addition, aligning agent for liquid crystal to be spun on to the ito surface for not forming electrode pattern, after 80 DEG C of press drying 90 seconds,
It carries out being burnt into for 20 minutes in 200 DEG C of heated air circulation type baking oven, forms the liquid crystal orientation film of film thickness 100nm.
For above-mentioned 2 substrates, after spreading 4 μm of pearl spacer on the liquid crystal orientation film of a substrate, from the upper side
Printing and sealing agent (epoxy resin of solvent type heat-curing type).Then, the formation of another substrate is made to have liquid crystal orientation film side
To be inside make sealant cures after being pasted with aforesaid substrate in face, make dummy cell.
MLC-3023 is injected in the dummy cell by depressurizing injection method, makes liquid crystal cells.Measure the liquid crystal cells
Voltage retention (VHR).
Then, in the state that the liquid crystal cells are applied with the D/C voltage of 15V, later, in the D/C voltage for being applied with 15V
In the state of, irradiation has passed through the UV 15J/cm of 325nm or less edge filters2, make voltage retention evaluation liquid crystal list
Member.
The evaluation > of < voltage retentions
For above-mentioned voltage retention evaluation liquid crystal cells, apply the voltage 60 of 1V in 60 DEG C of heated-air circulation oven
The time of μ s measures the voltage after 1667msec later, finds out voltage can keep how much being used as voltage retention.Voltage retention
Measurement in use Toyo Technica Co Ltd VHR-1.
(embodiment 1)
By BODA (3.15g, 12.6mmol), DA-1 (4.00g, 10.5mmol), DA-2 (0.45g, 4.2mmol), DA-3
(2.46g, 6.30mmol) dissolving in NMP (40.2g), after being reacted 3 hours at 60 DEG C, addition CBDA (1.58g,
8.06mmol) with NMP (6.4g), is reacted 10 hours at 40 DEG C, obtain polyamic acid solution.
NMP is added in the polyamic acid solution (25.0g), after being diluted to 6.5 mass %, addition is urged as imidizate
The acetic anhydride (4.58g) and pyridine (3.55g) of agent, react 4 hours at 80 DEG C.The reaction solution is put into methanol
In (300g), gained sediment is filtered.The sediment is cleaned with methanol, is dried under reduced pressure at 100 DEG C, obtains polyimide powder
Last A.The acid imide rate of the polyimides is 73%, number-average molecular weight 16600, weight average molecular weight 73800.
NMP (29.0g) is added in gained polyimide powder A (3.0g), stirs 12 hours and makes it dissolve at 70 DEG C.
3AMP (1 mass %NMP solution) 3.0g, BCS (15.0g) is added in the solution, is stirred at room temperature 5 hours, to obtain
Aligning agent for liquid crystal A1.
(embodiment 2)
By BODA (2.55g, 10.2mmol), DA-1 (3.23g, 12.9mmol), DA-2 (0.37g, 3.4mmol), DA-4
(2.44g, 5.10mmol) dissolving in NMP (34.4g), after being reacted 3 hours at 60 DEG C, addition CBDA (1.28g,
6.53mmol) with NMP (5.2g), is reacted 10 hours at 40 DEG C, obtain polyamic acid solution.
NMP is added in the polyamic acid solution (25.0g), after being diluted to 6.5 mass %, addition is urged as imidizate
The acetic anhydride (4.37g) and pyridine (3.39g) of agent, react 4 hours at 80 DEG C.The reaction solution is put into methanol
In (300g), gained sediment is filtered.The sediment is cleaned with methanol, is dried under reduced pressure at 100 DEG C, obtains polyimide powder
Last B.The acid imide rate of the polyimides is 73%, number-average molecular weight 13700, weight average molecular weight 48600.
NMP (29.0g) is added in gained polyimide powder B (3.0g), stirs 12 hours and makes it dissolve at 70 DEG C.
3AMP (1 mass %NMP solution) 3.0g, BCS (15.0g) is added in the solution, is stirred at room temperature 5 hours, to obtain
Aligning agent for liquid crystal B1.
(comparative example 1)
By BODA (3.15g, 12.6mmol), DA-1 (4.00g, 10.5mmol), DA-2 (0.45g, 4.2mmol), DA-5
(0.96g, 6.3mmol) dissolving in NMP (34.2g), after being reacted 3 hours at 60 DEG C, addition CBDA (1.61g,
8.21mmol) with NMP (6.4g), is reacted 10 hours at 40 DEG C, obtain polyamic acid solution.
NMP is added in the polyamic acid solution (25.0g), after being diluted to 6.5 mass %, addition is urged as imidizate
The acetic anhydride (5.25g) and pyridine (4.07g) of agent, react 4 hours at 80 DEG C.The reaction solution is put into methanol
In (300g), gained sediment is filtered.The sediment is cleaned with methanol, is dried under reduced pressure at 100 DEG C, obtains polyimide powder
Last C.The acid imide rate of the polyimides is 72%, number-average molecular weight 12800, weight average molecular weight 38400.
NMP (29.0g) is added in gained polyimide powder C (3.0g), stirs 12 hours and makes it dissolve at 70 DEG C.
3AMP (1 mass %NMP solution) 3.0g, BCS (15.0g) is added in the solution, is stirred at room temperature 5 hours, to obtain
Aligning agent for liquid crystal C1.
(comparative example 2)
By BODA (15.01g, 59.99mmol), DA-1 (19.03g, 50.00mmol), DA-2 (2.16g, 20.0mmol),
DA-6 (7.27g, 30.0mmol) dissolvings in NMP (173.9g), after being reacted 3 hours at 60 DEG C, addition CBDA (7.75g,
39.5mmol) with NMP (30.4g), is reacted 10 hours at 40 DEG C, obtain polyamic acid solution.
NMP is added in the polyamic acid solution (25.0g), after being diluted to 6.5 mass %, addition is urged as imidizate
The acetic anhydride (4.97g) and pyridine (3.86g) of agent, react 4 hours at 80 DEG C.The reaction solution is put into methanol
In (300g), gained sediment is filtered.The sediment is cleaned with methanol, is dried under reduced pressure at 100 DEG C, obtains polyimide powder
Last D.The acid imide rate of the polyimides is 72%, number-average molecular weight 14000, weight average molecular weight 46300.
NMP (29.0g) is added in gained polyimide powder D (3.0g), stirs 12 hours and makes it dissolve at 70 DEG C.
3AMP (1 mass %NMP solution) 3.0g, BCS (15.0g) is added in the solution, is stirred at room temperature 5 hours, to obtain
Aligning agent for liquid crystal D1.
Using each aligning agent for liquid crystal obtained in above-described embodiment 1,2 and Comparative Examples 1 and 2, it is uneven to make above-mentioned liquid crystal aligning
Evaluation liquid crystal cells and voltage retention evaluation liquid crystal cells carry out above-mentioned liquid crystal aligning unevenness and voltage retention respectively
Evaluation.It will be each evaluation result is shown in table 1 and table 2.
[Table 1]
| Aligning agent for liquid crystal | Liquid crystal aligning is uneven | |
| Embodiment 1 | A1 | Well |
| Embodiment 2 | B1 | Well |
| Comparative example 1 | C1 | It is bad |
| Comparative example 2 | D1 | It is bad |
[Table 2]
By the result of above-mentioned Tables 1 and 2 it is found that the liquid crystal orientation film obtained by the aligning agent for liquid crystal of embodiment with compared with
The liquid crystal orientation film that the aligning agent for liquid crystal of example obtains is compared, and mitigates the liquid crystal aligning unevenness generated in liquid crystal cells, in addition, voltage
Conservation rate is high.
Industrial availability
The liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention can mitigate the expression from liquid crystal aligning unevenness not
, therefore, in wide scopes such as High precisions, liquid crystal TV, large size or small-sized expression monitor, smart mobile phone, tablet computer
Expression element in be useful.
It should be noted that by the specification of Japanese patent application filed in 25 days December in 2015 2015-254920,
Claims, drawings and abstract full content quote so far, the disclosure as description of the invention is incorporated to.
Claims (12)
1. a kind of aligning agent for liquid crystal, which is characterized in that containing selected from being obtained by making diamine component be reacted with tetracarboxylic dianhydride's ingredient
At least one of the group of the polyamic acid arrived and the polyimides of the acid imide compound as polyamic acid composition polymer,
The diamine component contains:Diamines with crown ether structures and aromatic ring;With the side chain with the pre-tilt angle for embodying liquid crystal
Diamines.
2. aligning agent for liquid crystal according to claim 1, wherein under the diamines with crown ether structures and aromatic ring is
The Shi [ stated;1]Shown in diamines,
X1,X2Each independently represent singly-bound or-(OCH2CH2)n, the integer of n expressions 1~4, R1It indicates in structure below
Any one,
R2And R4Each independently represent the alkylidene of singly-bound or carbon number 1~5, R3Indicate the alkylidene or carbonyl of singly-bound, carbon number 1~5
Base, X indicate aromatic rings.
3. aligning agent for liquid crystal according to claim 2, wherein the expression R1Formula in X be phenyl ring.
4. aligning agent for liquid crystal described in any one of claim 1 to 3 comprising be relative to the diamine component
The diamines containing the crown ether structures and aromatic ring of 10~80 moles of %.
5. aligning agent for liquid crystal according to any one of claims 1 to 4, wherein described that there is the pre-tilt angle for embodying liquid crystal
Side chain diamines be Xia Shushi [1a]Shown in diamines,
X1To be selected from-O- ,-CH2O-,-COO-,-(CH2)a-,-NH-,-N(CH3)-,-CONH-,-NHCO-,-OCO-,-CON
(CH3)-,-N(CH3) CO- or the divalent in singly-bound organic group, wherein the integer that a is 1~10, X2For be selected from singly-bound or-
(CH2)bIn divalent organic group, wherein b be 1~10 integer, X3To be selected from singly-bound ,-(CH2)c-,-O-,-NH-,-N
(CH3)-,-CONH-,-NHCO-,-CH2O-,-COO-,-OCO-,-CON(CH3)-or-N (CH3) divalent in CO- organic group
Group, wherein the integer that c is 1~10, X4It indicates the cyclic group of the divalent in phenyl ring, cyclohexyl ring or heterocycle or has
The organic group of the divalent of the carbon number 12~25 of steroid skeleton, arbitrary hydrogen atom on the cyclic group optionally by selected from
The alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, the fluoroalkoxy containing fluoroalkyl or carbon number 1~3 of carbon number 1~3, fluorine
Group in atom is replaced, X5Indicate the cyclic group of the divalent in cyclohexyl ring, phenyl ring or heterocycle, these cyclic groups
Arbitrary hydrogen atom in group optionally contains fluothane by the alkoxy of alkyl, carbon number 1~3 selected from carbon number 1~3, carbon number 1~3
Group in the fluoroalkoxy of base or carbon number 1~3, fluorine atom is replaced, the integer that n is 0~4, X6For carbon number 1~18
Alkyl, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18, the fluoroalkoxy of carbon number 1~18 or hydrogen atom, m 1
~4 integer.
6. aligning agent for liquid crystal according to any one of claims 1 to 5, wherein tetracarboxylic dianhydride's ingredient contains:Tool
There is the tetracarboxylic dianhydride of ester ring type structure or aliphatic structure;With aromatic tetracarboxylic acid's dianhydride.
7. aligning agent for liquid crystal according to any one of claims 1 to 5, wherein described that there is the pre-tilt angle for embodying liquid crystal
Side chain diamines relative to the diamine component be 10~80 moles of %.
8. the aligning agent for liquid crystal described according to claim 6 or 7, wherein there is ester ring type structure or aliphatic structure with described
Tetracarboxylic dianhydride and aromatic tetracarboxylic acid's dianhydride containing molar ratio be 90/10~50/50 mode contain.
9. according to aligning agent for liquid crystal according to any one of claims 1 to 6, wherein the polyamides contained in the polymer is sub-
The acid imide rate of amine is 40~90%.
10. a kind of liquid crystal orientation film is obtained by aligning agent for liquid crystal according to any one of claims 1 to 9.
11. a kind of liquid crystal indicates element, has liquid crystal orientation film according to any one of claims 10.
12. liquid crystal according to claim 11 indicates element, wherein liquid crystal is filled in liquid in such a way that (ODF) is added dropwise in liquid crystal
Brilliant unit.
Applications Claiming Priority (3)
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| JP2015254920 | 2015-12-25 | ||
| JP2015-254920 | 2015-12-25 | ||
| PCT/JP2016/088539 WO2017111117A1 (en) | 2015-12-25 | 2016-12-22 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
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| JP (1) | JP7027890B2 (en) |
| KR (1) | KR20180098328A (en) |
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| WO (1) | WO2017111117A1 (en) |
Cited By (6)
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|---|---|---|---|---|
| CN110643374A (en) * | 2019-09-27 | 2020-01-03 | 江苏三月光电科技有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN111263913A (en) * | 2017-10-25 | 2020-06-09 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN111763518A (en) * | 2020-06-12 | 2020-10-13 | 江苏三月科技股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element thereof |
| CN112877079A (en) * | 2020-12-03 | 2021-06-01 | 深圳清荷科技有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN116478396A (en) * | 2022-01-14 | 2023-07-25 | 天津工业大学 | Preparation method of dibenzo-14-crown-4 polyamide for extracting lithium from salt lake |
| CN117510845A (en) * | 2023-11-08 | 2024-02-06 | 波米科技有限公司 | Liquid crystal aligning agent with high pretilt angle and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019189632A1 (en) * | 2018-03-30 | 2019-10-03 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| CN112250864B (en) * | 2020-10-26 | 2023-04-07 | Tcl华星光电技术有限公司 | Alignment layer material, preparation method of alignment layer material and liquid crystal display |
| CN114958393B (en) * | 2022-06-16 | 2023-09-05 | 长沙道尔顿电子材料有限公司 | Polyamic acid liquid crystal orientation agent with nitrogen-containing aromatic ring structure, liquid crystal orientation film and preparation method thereof |
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| JP4171851B2 (en) | 1997-12-02 | 2008-10-29 | 日産化学工業株式会社 | Liquid crystal alignment treatment agent |
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- 2016-12-22 JP JP2017558303A patent/JP7027890B2/en active Active
- 2016-12-22 CN CN201680082511.XA patent/CN108700777A/en active Pending
- 2016-12-22 WO PCT/JP2016/088539 patent/WO2017111117A1/en active Application Filing
- 2016-12-22 KR KR1020187021109A patent/KR20180098328A/en not_active Application Discontinuation
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| CN102754020A (en) * | 2009-12-14 | 2012-10-24 | 日产化学工业株式会社 | Liquid crystal aligning agent and liquid crystal display element using same |
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| CN111263913A (en) * | 2017-10-25 | 2020-06-09 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
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| CN112877079A (en) * | 2020-12-03 | 2021-06-01 | 深圳清荷科技有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN116478396A (en) * | 2022-01-14 | 2023-07-25 | 天津工业大学 | Preparation method of dibenzo-14-crown-4 polyamide for extracting lithium from salt lake |
| CN116478396B (en) * | 2022-01-14 | 2024-05-07 | 天津工业大学 | Preparation method of dibenzo-14-crown-4 polyamide for extracting lithium from salt lake |
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Also Published As
| Publication number | Publication date |
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| TWI793067B (en) | 2023-02-21 |
| TW201736440A (en) | 2017-10-16 |
| WO2017111117A1 (en) | 2017-06-29 |
| KR20180098328A (en) | 2018-09-03 |
| JP7027890B2 (en) | 2022-03-02 |
| JPWO2017111117A1 (en) | 2018-10-11 |
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