CN108604029A - Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it - Google Patents
Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it Download PDFInfo
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- CN108604029A CN108604029A CN201680080871.6A CN201680080871A CN108604029A CN 108604029 A CN108604029 A CN 108604029A CN 201680080871 A CN201680080871 A CN 201680080871A CN 108604029 A CN108604029 A CN 108604029A
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- YUNMGCVBJFSHGI-GICMACPYSA-N C[C@H](CCO)C(CCO)C(CCCCC(N(CCO)CCO)=O)=O Chemical compound C[C@H](CCO)C(CCO)C(CCCCC(N(CCO)CCO)=O)=O YUNMGCVBJFSHGI-GICMACPYSA-N 0.000 description 1
- VVJIVFKAROPUOS-UHFFFAOYSA-N NCC(CN)(CN)CN Chemical compound NCC(CN)(CN)CN VVJIVFKAROPUOS-UHFFFAOYSA-N 0.000 description 1
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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
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
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- 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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Abstract
There is provided obtain having good liquid crystal aligning, voltage retention, ageing resistance liquid crystal orientation film aligning agent for liquid crystal.A kind of aligning agent for liquid crystal, which is characterized in that it contains following ingredient (A) and ingredient (B), ingredient (A)：Copolymer with structural unit shown in structural unit shown in following formula (1) and following formula (2), (X1、X2It is independently 4 valence organic groups, Y1、Y2It is independently divalent organic group, R1It is the alkyl of carbon number 1~5, A1And A2It is the alkynyl of hydrogen atom or the alkyl of carbon number 1~10, the alkenyl of carbon number 2~10 or carbon number 2~10 optionally with substituent group each independently.)；Ingredient (B)：Compound with 2 or more cross-linking functional groups.
Description
Technical field
The present invention relates to the aligning agent for liquid crystal containing poly amic acid ester-polyamic acid copolymer, liquid crystal orientation film and make
Element is indicated with its liquid crystal.
Background technology
The liquid crystal used in LCD TV, liquid crystal display etc. indicates that element would commonly be used for the ordered state of control liquid crystal
Liquid crystal orientation film be set in element.Liquid crystal orientation film is the phase difference for indicating element in liquid crystal, having used polymerizable liquid crystal
In plate etc., it is used for the tropism control of liquid crystal molecule in the film of constant direction.Such as liquid crystal indicates that element has and forms liquid crystal layer
Liquid crystal molecule each surface for being formed on a pair of of substrate the structure that clips of liquid crystal orientation film.Then, liquid crystal indicates in element,
Liquid crystal molecule is orientated with pre-tilt angle by liquid crystal orientation film and in constant direction, by being set to substrate and liquid crystal aligning
Electrode between film applies voltage and carries out response.It is realized by the response of liquid crystal molecule as a result, liquid crystal indicates that element is utilized
Change in orientation carry out the expression of desirable image.
As liquid crystal orientation film, before main use will be with polyimides such as polyamic acids (polyamide acid) so far
Body, soluble polyimide solution make aligning agent for liquid crystal as main component be coated on glass substrate etc. and roast made of gather
The liquid crystal orientation film of imide series.
As liquid crystal indicates the multifunction of element, for liquid crystal orientation film, in addition to excellent liquid crystal aligning, surely
Except the performance of fixed pre-tilt angle is important, high voltage retention, when applying DC voltage few residual charge, and/or
The characteristics such as the quick mitigation for the residual charge accumulated due to DC voltage are also important, and indicate element towards liquid crystal in recent years
Power saving especially requires the material of high voltage retention.
For the liquid crystal orientation film of polyimides system, in response to above-mentioned requirements, it is proposed that various motions.Such as it carries
Go out using the also liquid crystal aligning of the tertiary amine containing specific structure other than polyamic acid, the polyamic acid containing imide
The technical solution (referring to patent document 1) of agent, technical solution (the reference patent text using the additive with isocyanate structural
2) etc. it offers.
On the other hand, it reports for using poly amic acid ester as the liquid crystal for the component of polymer for constituting aligning agent for liquid crystal
Alignment agent, heat treatment when will not be due to by its imidizate and generate molecular weight reduction, and used polyamic acid
Aligning agent for liquid crystal compare, the orientation stability voltage retention performance of liquid crystal is excellent (with reference to patent document 3).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 9-316200 bulletins
Patent document 2：WO2014/178406 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2003-26918 bulletins
Invention content
Problems to be solved by the invention
But if using the aligning agent for liquid crystal for having various crosslinking agents is added in polyamic acid, although obtaining voltage holding
The liquid crystal of excellent indicates element, it is possible that damage liquid crystal aligning.
In addition, as described above, compared with the aligning agent for liquid crystal for having used polyamic acid, the liquid crystal of poly amic acid ester has been used
Alignment agent obtains the excellent liquid crystal of voltage retention performance and indicates element, therefore estimated voltage is kept if crosslinking agent is added wherein
Characteristic further increases, but with anticipation on the contrary, cannot get this effect.
The object of the present invention is to provide obtain having both good liquid crystal aligning, voltage retention (Voltage
Holding Ratio：Hereinafter also referred to VHR) and ageing resistance liquid crystal orientation film aligning agent for liquid crystal.
The solution to the problem
The inventors of the present invention further investigate, as a result, it has been found that, by by the copolymer of poly amic acid ester and polyamic acid (with
Down be also referred to as PAE-PAA copolymers) and the crosslinking agent of specific structure be applied in combination, can solve the above problems, so as to complete
The present invention.
That is, the present invention is based on above-mentioned discovery, purport is following the description.
1. a kind of aligning agent for liquid crystal, which is characterized in that it contains following ingredient (A) and ingredient (B).
Ingredient (A)：Copolymer with structural unit shown in structural unit shown in following formula (1) and following formula (2).
In above-mentioned formula (1), formula (2), X1And X2It is 4 valence organic groups, Y each independently1And Y2It is divalent each independently
Organic group, R1It is the alkyl of carbon number 1~5, A1And A2It is each independently hydrogen atom or optionally there is the carbon number 1 of substituent group
The alkynyl of~10 alkyl, the alkenyl of carbon number 2~10 or carbon number 2~10.
Ingredient (B)：Compound with 2 or more cross-linking functional groups.
The effect of invention
Aligning agent for liquid crystal according to the present invention can form and have both good liquid crystal aligning, voltage retention and anti-ageing
The liquid crystal orientation film of the characteristics such as the property changed.Think itself main reason is that, by the liquid crystal aligning that is formed of aligning agent for liquid crystal of the present invention
In film, the fine bumps in its surface can be reduced.
Specific implementation mode
<Ingredient (A)：PAE-PAA copolymers>
The PAE-PAA copolymers used in the present invention are the polyimide precursor for obtaining polyimides, logical to have
Cross heating and can carry out it is following shown in imidization reaction position polymer.
(R is the alkyl of hydrogen atom or carbon number 1~5.)
PAE-PAA copolymers contained in the aligning agent for liquid crystal of the present invention have structural unit shown in following formula (1)
With structural unit shown in following formula (2).
In above-mentioned formula (1), R1It is the alkyl of carbon number 1~5, is examined from the viewpoint of the coating easy degree for glass substrate
Consider, preferably methyl or ethyl.
In above-mentioned formula (1) and (2), A1And A2Be each independently hydrogen atom or optionally with substituent group carbon number 1~
The alkynyl of 10 alkyl, the alkenyl of carbon number 2~10 or carbon number 2~10.As the concrete example of abovementioned alkyl, can enumerate methyl,
Ethyl, propyl, butyl, tertiary butyl, hexyl, octyl, decyl, cyclopenta, cyclohexyl, dicyclohexyl etc..As alkenyl, can enumerate
1 or more CH-CH structure replacing for going out to be present in alkyl is alkenyl made of C=C structures, specifically, second can be enumerated
Alkenyl, allyl, 1- acrylic, isopropenyl, 2- cyclobutenyls, 1,3- butadienyls, 2- pentenyls, 2- hexenyls, cyclopropylene
Base, cyclopentenyl, cyclohexenyl group etc..As alkynyl, it can enumerate and be present in 1 of alkyl or more CH2-CH2Structure replacing is C
Alkynyl made of ≡ C-structure, specifically, acetenyl, 1- propinyls, 2-propynyl etc. can be enumerated.
Above-mentioned alkyl, alkenyl and alkynyl can have substituent group and then can form ring structure by substituent group.It needs
Illustrate, forming ring structure by substituent group refers between substituent group or by substituent group is with a part of be bonded of female skeleton
Form ring structure.
Example as the substituent can enumerate halogen group, hydroxyl, sulfydryl, nitro, aryl, organic oxygroup, organic
Sulfenyl, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide groups, alkyl, alkenyl, alkynyl etc..
For the halogen group as substituent group, fluorine atom, chlorine atom, bromine atom, iodine atom can be enumerated.
For the aryl as substituent group, phenyl can be enumerated.Aforementioned others can be further substituted on the aryl
Substituent group.
For organic oxygroup as substituent group, structure shown in O-R can be shown.The R can be identical or different, can example
Alkyl above-mentioned, alkenyl, alkynyl, aryl etc. are shown.Substituent group above-mentioned can be further substituted on these R.As organic
The concrete example of oxygroup can enumerate methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy
Deng.
For organic sulfenyl as substituent group, structure shown in-S-R can be shown.As the R, can exemplify aforementioned
Alkyl, alkenyl, alkynyl, aryl etc..Substituent group above-mentioned can be further substituted on these R.Tool as organic sulfenyl
Body example can enumerate methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, sulfenyl in heptan, pungent sulfenyl etc..
For the Organosilyl as substituent group ,-Si- (R) can be shown3Shown in structure.The R can it is identical or
Difference can exemplify alkyl above-mentioned, alkenyl, alkynyl, aryl etc..Substituent group above-mentioned can be further substituted on these R.
As the concrete example of Organosilyl, trimethyl silyl, triethylsilyl, tripropylsilyl can be enumerated
Base, tributylsilyl, three amyl silicyls, three hexyl silicyls, amyl dimethyl silicyl, hexyl dimethyl
Silicyl etc..
For the acyl group as substituent group, structure shown in-C (O)-R can be shown.As the R, can exemplify above-mentioned
Alkyl, alkenyl, aryl etc..Substituent group above-mentioned can be further substituted on these R.As the concrete example of acyl group, can enumerate
Go out formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc..
For the ester group as substituent group, structure shown in-C (O) O-R or OC (O)-R can be shown.It, can example as the R
Alkyl above-mentioned, alkenyl, alkynyl, aryl etc. are shown.Substituent group above-mentioned can be further substituted on these R.
For the thioester substrate as substituent group, structure shown in-C (S) O-R or OC (S)-R can be shown.It, can as the R
Exemplify alkyl above-mentioned, alkenyl, alkynyl, aryl etc..Substituent group above-mentioned can be further substituted on these R.
For that as the phosphate-based of substituent group, can show-OP (O)-(OR)2Shown in structure.The R can it is identical or
Difference can exemplify alkyl above-mentioned, alkenyl, alkynyl, aryl etc..Substituent group above-mentioned can be further substituted on these R.
For the amide groups as substituent group ,-C (O) NH can be shown2、-C(O)NHR、-NHC(O)R、-C(O)N(R)2
Or structure shown in-NRC (O) R.The R can be identical or different, can exemplify alkyl above-mentioned, alkenyl, alkynyl, aryl etc..It can
To be further substituted with substituent group above-mentioned on these R.
For the aryl as substituent group, aryl identical with aryl above-mentioned can be enumerated.It can be enterprising in the aryl
One step replaces other substituent groups above-mentioned.
For the alkyl as substituent group, alkyl identical with alkyl above-mentioned can be enumerated.It can be enterprising in the alkyl
One step replaces other substituent groups above-mentioned.
For the alkenyl as substituent group, alkenyl identical with alkenyl above-mentioned can be enumerated.It can be enterprising in the alkenyl
One step replaces other substituent groups above-mentioned.
For the alkynyl as substituent group, alkynyl identical with alkynyl above-mentioned can be enumerated.It can be enterprising in the alkynyl
One step replaces other substituent groups above-mentioned.
As above-mentioned A1And A2, usually the reactivity of amino, liquid crystal aligning are likely to decrease if importing leavening structure,
Therefore the more preferably alkyl of hydrogen atom or the optional carbon number 1~5 with substituent group, particularly preferably hydrogen atom, methyl or second
Base.
In above-mentioned formula (1) and formula (2), if X1And X2Then its structure is not particularly limited for 4 valence organic groups, it can be with
Mix two or more.If showing X1And X2Concrete example can then enumerate X-1~X-47 as shown below.Wherein, obtaining from monomer
It obtains property and the viewpoints such as light illumination sensitivity and rub resistance intensity considers, preferably X1、X2And X-1, X-2, X-3, X-4,
X-5, X-6, X-8, X-16, X-19, X-21, X-25, X-26, X-27, X-28, X-32 or X-47.
In addition, in formula (1) and formula (2), Y1And Y2For divalent organic group, it is not particularly limited.Y1And Y2Can it is identical or
It is different.
If showing Y1And Y2Concrete example can then enumerate following Y-1~Y-99.Wherein, from the easiness in obtaining of monomer
From the viewpoint of, preferably Y-7, Y-8, Y-20, Y-21, Y-22, Y-28, Y-29, Y-30, Y-31, Y-41, Y-43, Y-64, Y-
65, Y-66, Y-68, Y-71, Y-72, Y-98 or Y-99, more preferably Y-22, Y-28, Y-30, Y-31, Y-72, Y-98, Y-99,
Y-100, Y-101, Y-102, Y-103 or Y-104.
In above-mentioned PAE-PAA copolymers, (containing) ratio of structural unit shown in formula (1) is relative to entire infrastructure list
Member, preferably 50~95 moles of %, more preferable 70~90 moles of %.In addition, in above-mentioned PAE-PAA copolymers, shown in formula (2)
(containing) ratio of structural unit is relative to entire infrastructure unit, preferably 5~50 moles of %, more preferable 10~30 moles of %.
<The manufacturing method of PAE-PAA copolymers>
The PAE-PAA copolymers of the present invention are manufactured by the following method.
In the presence of condensing agent, alkali and organic solvent, make to form X in structural unit shown in above-mentioned formula (1)1Four
Y is formed in carboxylic acid diesters and above-mentioned formula (1) and formula (2)1And Y2Diamines, at -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C,
After polycondensation reaction 30 minutes~24 hours, preferably 1~12 hour, diphenyl phosphate is added to neutralize alkali, is added above-mentioned
X is formed in structural unit shown in formula (2)2Tetrabasic carboxylic acid or its dianhydride, at a temperature of 0 DEG C~50 DEG C react 30 minutes~24
Hour, preferably 1~12 hour, thus manufacture above-mentioned PAE-PAA copolymers.
For the organic solvent used in above-mentioned reaction, consider from the dissolubility viewpoint of monomer and polymer, preferably N,
Dinethylformamide, n-methyl-2-pyrrolidone or gamma-butyrolacton, they using a kind or can mix two or more to make
With.For the concentration of polymer, from the viewpoint of the precipitation for being not likely to produce polymer and being easy to get high molecular weight body,
Preferably 1~30 mass %, more preferable 5~20 mass %.
Aforementioned condensation agent can use triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyls -3- (3- dimethylaminos
Base propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, O- (benzos
Triazol-1-yl)-N, N, N ', N '-tetramethyl tetrafluoro boric acids urea, O- (benzotriazole -1- bases)-N, N, N ', N '-tetramethyl hexafluoros
Urea phosphate, (thio -3- benzoxazolyls of 2,3- dihydros -2-) phosphonic acid diphenyl ester etc..The additive amount of condensing agent is relative to tetrabasic carboxylic acid
Diester is preferably 2~3 times moles.
Aforementioned bases can use the tertiary amines such as pyridine, triethylamine.For the additive amount of alkali, from the amount and appearance to easily remove
It is easy to get to from the viewpoint of high molecular weight body, is preferably 2~4 times moles relative to diamine component.
While reaction solution is sufficiently stirred, the PAE-PAA copolymers obtained as described above are injected into poor solvent,
It is possible thereby to which polymer is precipitated and is recycled.In addition, being precipitated for several times, after being washed with poor solvent, room temperature or heating are carried out
It is dry, it is hereby achieved that the powder of purified PAE-PAA copolymers.Poor solvent is not particularly limited, can be arranged
Enumerate water, methanol, ethyl alcohol, hexane, butyl cellosolve, acetone, toluene etc..
The weight average molecular weight of PAE-PAA copolymers is preferably 10000~305000, more preferable 10000~210000.Separately
Outside, number-average molecular weight is preferably 5000~152500, more preferable 10000~105000.
<Ingredient (B)：Compound containing 2 or more cross-linking functional groups>
Ingredient (B) contained in the aligning agent for liquid crystal of the present invention is the compound containing 2 or more cross-linking functional groups.
As cross-linking functional group, can enumerate select free hydroxyl, hydroxyalkylamides base, (methyl) it is acrylate-based,
At least one of the group of blocked isocyanate base, oxetanyl and epoxy group composition, but it is not limited to them.
Wherein, from the viewpoint of acquired and voltage retention improvement, preferably hydroxyl, blocked isocyanate
Base or epoxy group, more preferable hydroxyl or epoxy group.
It should be noted that for the compound of ingredient (B), there can be 2 or more identical crosslinkings in its structure
Property functional group can also have 2 or more different cross-linking functional groups of more than two kinds.
As the compound containing 2 or more hydroxyls, such as following formula (3) compound represented can be enumerated.
In above-mentioned formula (3), X3It is the n valence organic groups of the aliphatic alkyl containing carbon number 1~20 or aromatic hydrocarbyl.
These, it is preferred to the aliphatic alkyl of carbon number 1~20, preferably carbon number 1~10, more preferable carbon number 1~5.R2And R3It is respectively independent
Ground is the alkynes of hydrogen atom or the alkyl of carbon number 1~4, the alkenyl of carbon number 2~4 or carbon number 2~4 optionally with substituent group
Base, R2And R3At least one of with following formula (4) indicate, it is preferred that R2And R3In any one use following formula (4) table
Show.N be preferably 2~6 integer, particularly preferred 2.
In above-mentioned formula (4), R4~R7It is hydrogen atom, alkyl or the alkyl being optionally substituted by a hydroxyl group, preferably hydrogen each independently
Atom.
X3It is that aliphatic alkyl is preferred from the viewpoint of liquid crystal aligning and dissolubility as described above, more preferable carbon
Number 1~10.N indicates 2~6 integer, but from the viewpoint of dissolubility, n is preferably 2~4.
As the compound containing 2 or more hydroxyls, specifically, compound below can be exemplified.
As the compound containing 2 or more blocked isocyanate bases, following formula (5) compound represented can be exemplified.
In formula (5), Z is organic group shown in the alkyl, hydroxyl or following formula (6) of carbon number 1~3 each independently, in Z
It is at least one be organic group shown in following formula (6).
As the compound containing 2 or more blocked isocyanate bases, specifically, compound below can be exemplified.
As the compound containing 2 or more blocked isocyanate bases other than above-mentioned formula (7), belowization can be exemplified
Close object.
As the compound containing 2 or more epoxy groups, specifically, compound below can be exemplified.
As containing 2 or more (methyl) acrylate-based compound, specifically, chemical combination below can be exemplified
Object.
As the compound with 2 or more cross-linking functional groups, in addition, can also exemplify compound below.
The compound of ingredient (B) preferably comprises 1~30 weight relative to (A) ingredient in the aligning agent for liquid crystal of the present invention
Measure %, further preferably 3~15 weight %.
<Aligning agent for liquid crystal>
The aligning agent for liquid crystal of the present invention is above-mentioned PAE-PAA copolymers and the change containing 2 or more cross-linking functional groups
Close the form of solution made of object is dissolved in organic solvent.Can be institute in the case that each ingredient synthesizes in organic solvent
Obtained reaction solution itself, in addition reaction solution solvent appropriate can also be diluted.In addition, in powder form
In the case of each ingredient, organic solvent can be dissolved in and form solution.
The content (concentration) of the component of polymer containing PAE-PAA copolymers in the aligning agent for liquid crystal of the present invention can also
It is suitably changed according to the thickness setting for thinking polyimide film to be formed, but is formed from uniformly and does not have defective film
Viewpoint considers that, relative to organic solvent, the content of component of polymer is preferably 0.5 mass % or more, stablizes from the preservation of solution
From the viewpoint of property, preferably 15 mass % or less, more preferable 1~10 mass %.
At this point it is possible to the concentrate solution of pre-production polymer and when forming aligning agent for liquid crystal by above-mentioned concentrate solution into
Row dilution.The concentration of the concentrate solution of above-mentioned component of polymer is preferably 10~30 mass %, more preferable 10~15 mass %.Separately
Outside, it is heated when can also make solution the powder of component of polymer is dissolved in organic solvent.Heating temperature is preferred
For 20~150 DEG C, it is 20~80 DEG C particularly preferred.
The above-mentioned organic solvent contained in aligning agent for liquid crystal for the present invention, does not have if component of polymer uniform dissolution
It is particularly limited to.N,N-dimethylformamide, N, N- diethylformamides, N, N- bis- can be enumerated if enumerating its concrete example
Methylacetamide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidones, N- methyl caprolactams, 2-Pyrrolidone, N- second
Alkenyl -2-Pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl sulfone, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinones, 3- methoxyl group-N,
N- dimethylpropane amides etc..They using a kind or can mix two or more to use.Even in addition using only when not
The solvent of component of polymer uniform dissolution can also be mixed in above-mentioned organic if in the range of polymer will not be precipitated
Solvent.
The aligning agent for liquid crystal of the present invention can also contain useful other than the organic solvent for dissolving component of polymer
In the solvent for improving painting film uniformity when aligning agent for liquid crystal is applied to substrate.Above-mentioned solvent is less than usually using surface tension
The solvent of above-mentioned organic solvent.Ethyl cellosolve, butyl cellosolve, butyl cellosolve can be enumerated if enumerating its concrete example
Acetic acid esters, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1- methoxy-2-propanols, 1- ethoxies
Base -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, the third two
Alcohol -1- monomethyl ether -2- acetic acid esters, propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygen
Base) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc..These solvents can combine
Use two or more.
The film thickness that the aligning agent for liquid crystal of the present invention can also contain in addition to that mentioned above when being improved coating of liquid crystalline alignment agent is equal
The various additives such as even property, the compound of surface smoothness, silane coupling agent, crosslinking agent.
As uniformity, the compound of surface smoothness for improving film thickness, fluorine system surfactant, siloxanes can be enumerated
It is surfactant, nonionic surfactants etc..
More specifically, can enumerate such as EFTOP (Tochem Products Co., Ltd.s trade name, EF301,
EF303, EF352), Megaface (Dainippon Ink Co., Ltd. trade name, F171, F173, R-30, Fluorad
(Sumitomo 3M Limited trade names, FC430, FC431, Asahi Guard (Asahi Glass Co., Ltd's trade name,
AG710, Surflon (Asahi Glass Co., Ltd's trade name, S-382, SC101, SC102, SC103, SC104, SC105, SC106
Deng.
100 mass parts of the usage rate of these surfactants relative to the resin component contained in aligning agent for liquid crystal,
Preferably 0.01~2 mass parts, more preferable 0.01~1 mass parts.
Silane coupling agent is the adaptation in order to make the substrate of coating of liquid crystalline alignment agent, with its liquid crystal orientation film is formed in
Improve and add.Various silane coupling agents for example below can be enumerated as concrete example, but be not limited to them.
3-aminopropyltriethoxysilane, 3- (2- amino-ethyls) TSL 8330,3- (2- amino second
Base) aminopropylmethyldimethoxysilane, 3- TSL 8330s, 3- phenyl amino propyl trimethoxy silicon
Alkane, 3- triethoxysilyls-N- (1,3- dimethyl-butane) propyl amine, 3- aminopropyl diethoxymethylsilanes
Etc. amine systems；Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl three (2- methoxy ethoxies) silane, second
Enylmethyl dimethoxysilane, vinyltriacetoxy silane, vinyl silane triisopropoxide, allyl trimethoxy
Silane, to the ethylene base system such as styryltrimethoxysilane；3- glycidoxypropyltrime,hoxysilanes, the third oxygen of 3- epoxies
Base propyl-triethoxysilicane, 3- glycidoxypropyls diethoxy silane, 3- glycidoxypropyl diformazans
The epoxies such as oxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane；3- methacryloyloxypropyl methyls
Dimethoxysilane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloyloxypropyl methyl diethoxies
The metha crylics such as base silane, 3- methacryloxypropyls；3- acryloxypropyl trimethoxies
The acrylic acid series such as base silane；The urides systems such as 3- uride propyl-triethoxysilicanes；Bis- (3- (triethoxysilyl) propyl)
The thioethers systems such as disulfide, bis- (3- (triethoxysilyl) propyl) four thioethers；3- mercapto propyl methyl dimethoxy silanes,
The sulfydryls systems such as 3-mercaptopropyi trimethoxy silane, 3- Octanoylthio -1- propyl-triethoxysilicanes；3- isocyanates propyl
The isocyanates systems such as triethoxysilane, 3- isocyanate propyl trimethoxysilanes；The aldehyde such as triethoxysilyl butyraldehyde
System；Triethoxysilylpropyltetrasulfide methyl carbamate, (3- triethoxysilylpropyltetrasulfides)-tert-butylamino formic acid
The carbamate systems such as ester.
If the additive amount of silane coupling agent crosses at most unreacted reactant and is possible to cause harmful effect to liquid crystal aligning, if mistake
Cannot at least show the effect to adaptation, thus the solid constituent relative to polymer be preferably 0.01~5.0 weight %,
More preferable 0.1~1.0 weight %.
In the liquid crystal orientation film of the present invention, in order to which PAE-PAA copolymers or polyamide is effectively performed when roasting film
The imidizate of acid esters can add imidizate accelerating agent.
<Liquid crystal orientation film>
The liquid crystal orientation film of the present invention is that the aligning agent for liquid crystal of the present invention is coated on substrate and is roasted after drying as needed
Film obtained from burning.The substrate of aligning agent for liquid crystal as the coating present invention does not limit especially then if the high substrate of the transparency
It is fixed, such as other than glass substrate, the plastic bases such as acrylic acid substrate, polycarbonate substrate can also be used.Liquid crystal indicates
In the manufacture of element use the present invention aligning agent for liquid crystal in the case of, it is preferable to use being formed with the ITO (oxygen for driving liquid crystal
Change indium tin, Indium Tin Oxide) substrate of electrode etc. and form liquid crystal orientation film.In addition, the liquid crystal watch of manufacture reflection-type
In the case of showing element, the opaque substrates such as Silicon Wafer, electrode at this time can also be then used if only unilateral substrate
The material of the reflected lights such as aluminium can be used.
It is coated on the method on substrate as by the aligning agent for liquid crystal of the present invention, such as silk-screen printing, hectograph can be enumerated
Printing, flexible printing or ink-jet method.As other coating methods, there are infusion process, rolling method, slot coated method, spin-coating method or spray
Mist method etc. can use them as needed.
It is 1~10 point dry at 50~120 DEG C generally for the contained organic solvent of abundant removal for coated film
It clock and then is roasted 5 minutes~120 minutes at 150~300 DEG C.The thickness of film after roasting is not particularly limited, if
Excessively thin, liquid crystal indicates that the reliability of element is likely to decrease, therefore is 5~300nm, preferably 10~200nm.
As the method for carrying out orientation process for obtained liquid crystal orientation film, rubbing manipulation can be enumerated, at light orientation
Logos etc..
Existing rubbing device can be used by being formed in the friction treatment of the coated surface on substrate.As friction cloth at this time
Material, cotton, artificial silk, nylon etc. can be enumerated.As the condition of friction treatment, usually used rotary speed 300~
The conditions such as 2000rpm, 5~100mm/s of feed speed, 0.1~1.0mm of intrusion.Then, ultrasound is utilized using pure water, alcohol etc.
The residue that wave washing removal is generated due to friction.
As light orientation position logos, it can enumerate and the radiation of constant direction deviation is radiated at simultaneously for aforementioned film coated surface
The method for further being heated at a temperature of 150~250 DEG C as needed and assigning liquid crystal aligning ability.As spoke
Ray can use the ultraviolet light and luminous ray of the wavelength with 100~800nm.Wherein, it is however preferred to have 100~400nm
Wavelength ultraviolet light, particularly preferably with 200~400nm wavelength.It, can be in addition, in order to improve liquid crystal aligning
Apply illumination radiation line while ilm substrate heats at 50~250 DEG C.The exposure of aforementioned radiation line is preferably 1~10000mJ/
cm2, particularly preferred 100~5000mJ/cm2。
<Liquid crystal indicates element>
For the liquid crystal of the present invention indicates element, band liquid is obtained by the aligning agent for liquid crystal of the present invention using above-mentioned gimmick
After the substrate of brilliant alignment films, liquid crystal cells are made with well known method, liquid crystal is formed and indicates element.
Liquid crystal indicates that an example of the production method of element is as described below.Prepare 1 pair of base for being formed with liquid crystal orientation film first
Plate, by they with clip preferably 1~30 μm, more preferable 2~10 μm of spacer, frictional direction form 0 °~270 ° of random angle
The mode of degree is arranged, and surrounding is fixed with sealant.Then it liquid crystal and seals to being injected between substrate.Liquid crystal is enclosed
Method is not particularly limited, and can exemplify the vacuum method of injection liquid crystal after being depressurized in made liquid crystal cells, liquid crystal is added dropwise
The dripping method etc. being sealed later.
Embodiment
It is exemplified below out embodiment the present invention is specifically described, but the present invention is not limited to them to explain.With
The assay method of the abbreviation of the compound used afterwards and each characteristic is as described below.
<Monomer>
1,3DMCBDE-Cl：Bis- (the chlorocarbonyl) -1,3- dimethylcyclobutane -2,4- dicarboxylic esters of dimethyl 1,3-
1,3DMCBDA：1,2,3,4 cyclobutane tetracarboxylic dianhydride of 1,3- dimethyl
PMDA：Pyromellitic acid anhydride
PMDE-me：Bis- -1,4 dicarboxylic acids of (methoxycarbonyl) benzene of 2,5-
CBDE：Bis- (methoxycarbonyl) the cyclobutane 1,3- dicarboxylic acids of 2,4-
CBDA：1,2,3,4- cyclobutane tetracarboxylic dianhydrides
DADPA：4,4 '-diamino-diphenyl amine
p-PDA：P-phenylenediamine
DBOP：Diphenyl (thio -3- benzoxazolyls of 2,3- dihydros -2-) phosphonate ester
<Solvent>
NMP：N-methyl-2-pyrrolidone
BCS：Butyl cellosolve
GBL：Gamma-butyrolacton
<Viscosity>
The viscosity of polymer solution uses E type viscosimeters TVE-22H (Toki Sangyo Co., Ltd.'s system), in sample size
It is measured under conditions of 1.1mL, cone rotor TE-1 (1 ° 34 ', R24), 25 DEG C of temperature.
<Molecular weight>
The molecular weight of polymer is measured by GPC (room temperature gel permeation chromatography) device, as polyethylene glycol, polycyclic oxygen second
Alkane scaled value calculates number-average molecular weight (hereinafter also referred to Mn) and weight average molecular weight (hereinafter also referred to Mw).
GPC devices：Shodex corporations (GPC-101)
Chromatographic column：Shodex corporations (series connection of KD803, KD805)
Chromatogram column temperature：50℃
Eluent：N,N-Dimethylformamide (as additive, contains lithium bromide-hydrate (LiBrH2O) 30 mmoles
That/L, phosphoric acid anhydrous crystal (orthophosphoric acid) 30 mMs/L, tetrahydrofuran (THF) 10ml/L)
Flow velocity：1.0ml/ minute
Standard curve, which is made, uses standard sample：TOSOH CORPORATION TSK standard polyethylene oxide (Weight-average moleculars
Measure (Mw) about 900000,150000,100000,30000) and Polymer Laboratories Ltd. polyethylene glycol (peak
Position molecular weight (Mp) about 12000,4000,1000).For measuring, in order to avoid overlap of peaks, measure 900000 respectively, 100000,
12000,1000 this 4 kinds of samples mixed and 150000,30000,4000 this 3 kinds of samples mixed this 2 samples
Product.
(synthesis example 1)
Taken in the four-neck flask with agitating device and the 2L of nitrogen ingress pipe p-PDA 1.30g (12.02 mMs),
NMP 46.10g, GBL 106.9g and pyridine is added in DA-A 1.76g (7.21 mMs), DA-B 1.64g (4.81 mMs)
3.58g (0.44 mole), is dissolved.Then 1,3DMCBDA 1.07g (4.81 mmoles are added while the solution stirring
You), it reacts 5 hours under water cooling.For thus obtained solution addition 1,3DMCBDE-Cl 6.02g (18.5 mMs), in water
Cold lower further reaction 14 hours.
Acryloyl chloride 2.39g (2.64 mMs) is added to obtained poly amic acid ester-polyamic acid copolymer solution,
And then after reacting 4 hours, which is put into the isopropanol of 1061ml, the white precipitate that leaching is precipitated by stirring while.
It is then split into 5 isopropanols using 2655ml to wash, is dried, thus obtains poly amic acid ester-polyamic acid of white
Copolymer resin powder (PWD-1).The molecular weight of the poly amic acid ester-polyamic acid copolymer is Mn=13493, Mw=
27207。
Poly amic acid ester obtained above-polyamic acid copolymer toner (PWD-1) is dissolved in GBL, is consolidated
The poly amic acid ester of 12 mass % of body constituent concentration-polyamic acid copolymer solution (Copolymer-1).
(synthesis example 2)
Taken in the four-neck flask with agitating device and the 200mL of nitrogen ingress pipe CBDE 8.40g (3.23 mMs),
NMP 106.57g and triethylamine 6.92g are added in DA-A 5.57g (2.28 mMs), DADPA 3.03g (1.52 mMs)
(6.84 mMs), are dissolved.Then DBOP 24.77g (6.46 mMs), water cooling are added while the solution stirring
Lower reaction 5 hours.Then while futher stirring solution, additional diphenyl phosphate 1.90g (0.76 mM), PMDA
1.08g (0.49 mM), NMP 22.84g, further react 5 hours under water cooling.
Obtained poly amic acid ester-polyamic acid copolymer solution is put into the isopropyl of 2000ml while stirring
Alcohol, the white precipitate that leaching is precipitated are then split into 4 methanol using 407.83ml and wash, be dried, thus obtain white
The poly amic acid ester of color-polyamic acid copolymer toner (PWD-2).
Poly amic acid ester obtained above-polyamic acid copolymer toner (PWD-2) is dissolved in NMP, is consolidated
The poly amic acid ester of 12 mass % of body constituent concentration-polyamic acid copolymer solution (Copolymer-2).
(comparing synthesis example 1)
Taken in the four-neck flask with agitating device and the 2L of nitrogen ingress pipe p-PDA 10.00g (92.4 mMs),
NMP 379.00g, GBL 1023.00g is added in DA-A 13.60g (55.5 mMs), DA-B 12.60g (37.0 mMs)
With pyridine 34.60g (0.43 mole), dissolved.Then 1,3DMCBDE-Cl 58.30g are added while the solution stirring
(179.4 mMs) react 14 hours under water cooling.
To obtained polyamic acid solution addition acryloyl chloride 2.41g (26.6 mMs), and then react 4 hours after,
The solution is put into the isopropanol of 8653ml, the white precipitate that leaching is precipitated while stirring.It is then split into 5 uses
The isopropanol of 21635ml washs, and is dried, and thus obtains the poly amic acid ester toner (PWD-3) of white.The polyamide
The molecular weight of acid esters is Mn=24366, Mw=54808.
Poly amic acid ester toner (PWD-3) obtained above is dissolved in GBL, obtains 12 matter of solid component concentration
Measure the polyamic acid ester solution (PAE-1) of %.
(comparing synthesis example 2)
Taken in the four-neck flask with agitating device and the 15L of nitrogen ingress pipe p-PDA 761.05g (1.75 moles),
DA-A 256.50g (1.05 moles), DA-B 258.56g (0.7 mole) are added NMP 9671.41g, are dissolved.Then will
The solution adds 1,3DMCBDA 761.05g (3.39 moles) while stirring, and the solid component concentration of solution is diluted to NMP
It is 12%.So that the solution is reacted 14 hours under water cooling, obtains polyamic acid solution (PAA-1).The molecular weight of the polyamic acid
For Mn=14366, Mw=28508.
(embodiment 1)
Poly amic acid ester-polyamic acid the copolymerization obtained in synthesis example 1 is taken in the 20ml sample cells for being incorporated with stirrer
Object solution (Copolymer-1) 5.50g, NMP (10 mass % dilutions) the solution 0.28g and then addition NMP that AD-A is added are dilute
Release 3- glycidoxypropyl diethoxy silane solution 0.55g, NMP 1.70g to 1.0 mass %.Then it is added
BCS 2.00g and with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (A-1).The viscosity of A-1 is 35mPaS.I.e.
Make by aligning agent for liquid crystal (A-1) 1 week certainly at -20 DEG C, also without the precipitation of discovery solids, is uniform solution.
(embodiment 2)
Poly amic acid ester-polyamic acid the copolymerization obtained in synthesis example 2 is taken in the 20ml sample cells for being incorporated with stirrer
Object solution (Copolymer-2) 7.50g, NMP (10 mass % dilutions) the solution 0.45g and then addition NMP that AD-A is added are dilute
Release 3- glycidoxypropyl diethoxy silane solution 0.9g, NMP 3.12g to 1.0 mass %.Then BCS is added
3.00g and with magnetic stirrer 30 minutes, obtains aligning agent for liquid crystal (A-2).The viscosity of A-2 is 37mPaS.Even if will
Aligning agent for liquid crystal A-2 is 1 week certainly at -20 DEG C, result is also uniform solution without the precipitation of discovery solids.
(comparative example 1)
Polyamic acid ester solution (the PAE- for comparing and being obtained in synthesis example 1 is taken in the 20ml sample cells for being incorporated with stirrer
1) 7.50g is added NMP (10 mass % dilutions) the solution 0.45g of AD-A and then the 3- for being diluted to 1.0 mass % with NMP is added
Glycidoxypropyl diethoxy silane solution 0.90g, NMP 2.48g.Then BCS 3.00g are added and are stirred with magnetic force
It mixes device to stir 30 minutes, obtains aligning agent for liquid crystal (B-1).The viscosity of B-1 is 32mPaS.By aligning agent for liquid crystal B-1 at -20 DEG C
Lower keeping 1 week, result do not find the precipitation of solids, are uniform solution.
(comparative example 2)
The polyamic acid solution (PAA-1) for comparing and being obtained in synthesis example 2 is taken in the 20ml sample cells for being incorporated with stirrer
8.21g is added NMP (10 mass % dilutions) the solution 0.45g of AD-A and then the 3- rings for being diluted to 1.0 mass % with NMP is added
Oxygen propoxypropyl methyldiethoxysilane solution 0.90g, NMP 3.12g.Then BCS 3.00g are added and use magnetic agitation
Device stirs 30 minutes, obtains aligning agent for liquid crystal (B-2).The viscosity of B-2 is 35mPaS.By aligning agent for liquid crystal B-2 at -20 DEG C
Keeping 1 week, result do not find the precipitation of solids, for uniform solution.
(embodiment 3)
After 1.0 μm of filter filtering of the aligning agent for liquid crystal (A-1) obtained in embodiment 1, it is spun on transparent electricity
It is 5 minutes dry in the heating plate of 80 DEG C of temperature on the glass substrate of pole.Then, it is dried using the heated air circulation type of 230 DEG C of temperature
Case passes through roasting in 10 minutes, obtains the film of the imidizate of film thickness 100nm.Roasting film is irradiated via polarizer
The ultraviolet light 250mJ/cm of 254nm2.Thus the substrate with liquid crystal orientation film is obtained.
In order to evaluate the electrical characteristics of liquid crystal cells, prepares the above-mentioned substrate 2 with liquid crystal orientation film and open, wherein 1 liquid crystal
6 μm of spacer is spread in alignment films.Make light orientation by another 1 real estate to liquid crystal alignment film surface by printing and sealing agent thereon
Direction is orthogonal after being bonded, to be made sealant cures and makes dummy cell.Normal direction dummy cell injection liquid crystal ML- is injected by decompression
7026-100 (Merck Japan systems) seals inlet, obtains IPS liquid crystal cells.For the liquid crystal cells at 120 DEG C into
Row is heat-treated for 30 minutes, is then slowly cooled to room temperature, is carried out the observation of unit, as a result orientation is good.
<The measurement of voltage retention>
Above-mentioned liquid crystal cells are applied with the 60 μ s of voltage of 1V at a temperature of 60 DEG C, measures the voltage after 500ms, voltage
It how much can keep with the form calculus of voltage retention.
As a result, voltage retention of the alignment films 1 formed by alignment agent A-1 at 60 DEG C is 85.4%.
(embodiment 4)
Using the aligning agent for liquid crystal of the present invention obtained in synthesis example 2, evaluation same as Example 3 is carried out.But it is logical
The friction treatment for crossing using orientation process rayon cloth (grow by roller diameter 120mm, rotating speed 1000rpm, movement speed 20mm/ second, indentation
Spend 0.3mm) it carries out.The result is recorded in aftermentioned table 1.
(comparative example 3)
Using the aligning agent for liquid crystal of the present invention obtained in comparative example 1, evaluation same as Example 3 is carried out.The result
It is recorded in aftermentioned table 1.
(comparative example 4)
Using the aligning agent for liquid crystal of the present invention obtained in comparative example 1, evaluation same as Example 3 is carried out.But light
Irradiation passes through the ultraviolet light 500mJ/cm via polarizer irradiation 254nm2Come carry out.
The result of above-described embodiment 3,4 and comparative example 3,4 table 1 as be described hereinafter is recorded.
[table 1]
Industrial availability
The liquid crystal orientation film formed using the aligning agent for liquid crystal of the present invention, not only liquid crystal aligning increases but also voltage is kept
The electrical characteristics such as rate, the residual of DC voltage are also improved.As a result, being widely used in TN elements, STN elements, TFT liquid crystal cells
The liquid crystal of part and then vertical orientating type indicates element etc..
It should be noted that by the specification of Japanese patent application filed in 3 days December in 2015 2015-236340,
Claims, drawings and abstract full content be incorporated in this, the open of the specification as the present invention is introduced.
Claims (12)
1. a kind of aligning agent for liquid crystal, which is characterized in that it contains following ingredient (A) and ingredient (B),
Ingredient (A)：Copolymer with structural unit shown in structural unit shown in following formula (1) and following formula (2),
In formula (1), formula (2), X1And X2It is 4 valence organic groups, Y each independently1And Y2It is divalent organic group each independently,
R1It is the alkyl of carbon number 1~5, A1And A2It is each independently hydrogen atom or optionally there is the alkane of the carbon number 1~10 of substituent group
The alkynyl of base, the alkenyl of carbon number 2~10 or carbon number 2~10,
Ingredient (B)：Compound with 2 or more cross-linking functional groups.
2. aligning agent for liquid crystal according to claim 1, wherein the ingredient (B) is the chemical combination containing 2 or more functional groups
Object, the functional group be selected from hydroxyl, hydroxyalkylamides base, (methyl) be acrylate-based, blocked isocyanate base, oxa- ring
At least one of butane group and epoxy group.
3. aligning agent for liquid crystal according to claim 1, wherein the ingredient (B) is following formula (3) compound represented,
In formula (3), X3It is the n valence organic groups of the aliphatic alkyl containing carbon number 1~20 or aromatic hydrocarbyl, R2And R3Respectively
It is independently hydrogen atom or optionally there is the alkyl of carbon number 1~4, the alkenyl of carbon number 2~4 or the carbon number 2~4 of substituent group
Alkynyl, R2And R3At least one of with following formula (4) indicate, n be 2~6 integer,
In formula (4), R4~R7It is hydrogen atom, alkyl or the alkyl being optionally substituted by a hydroxyl group each independently.
4. aligning agent for liquid crystal described in any one of claim 1 to 3, wherein the copolymer of the ingredient (A) relative to
Its entire infrastructure unit, with 50~95 moles of % of structural unit shown in formula (1) and with shown in formula (2)
5~50 moles of % of structural unit.
5. aligning agent for liquid crystal according to any one of claims 1 to 4, wherein the content of the ingredient (B) relative at
It is 1~30 weight % to divide (A).
6. aligning agent for liquid crystal according to any one of claims 1 to 5, also contain organic solvent, the ingredient (A) and
The total content of the ingredient (B) is 0.5~15 mass % relative to the organic solvent.
7. according to aligning agent for liquid crystal according to any one of claims 1 to 6, wherein the X in the formula (1) and formula (2)1And X2
It is at least one of the group selected from the structure composition shown in following formula each independently,
8. aligning agent for liquid crystal according to any one of claims 1 to 7, wherein the Y in the formula (1) and formula (2)1And Y2
It is at least one of the group selected from the structure composition shown in following formula each independently,
9. the aligning agent for liquid crystal according to any one of claim 2~8, wherein the blocked isocyanate base is following
Organic group shown in formula (6),
10. the aligning agent for liquid crystal according to any one of claim 3~9, wherein formula (3) compound represented is
Following compounds,
11. a kind of liquid crystal orientation film is obtained by aligning agent for liquid crystal according to any one of claims 1 to 10.
12. a kind of liquid crystal indicates element, with the liquid crystal orientation film described in claim 11.
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| PCT/JP2016/085953 WO2017094898A1 (en) | 2015-12-03 | 2016-12-02 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element employing same |
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| TW202028303A (en) * | 2018-10-15 | 2020-08-01 | 日商日產化學股份有限公司 | Polyamic acid ester resin composition |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003026918A (en) * | 2001-07-13 | 2003-01-29 | Hitachi Ltd | Material for oriented liquid crystal film, liquid crystal display element, process for producing it and liquid crystal display device |
| CN102893209A (en) * | 2010-03-15 | 2013-01-23 | 日产化学工业株式会社 | Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film |
| CN102918452A (en) * | 2010-06-07 | 2013-02-06 | 夏普株式会社 | Liquid crystal display device |
| CN103562782A (en) * | 2011-03-31 | 2014-02-05 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element |
| CN104136979A (en) * | 2011-12-28 | 2014-11-05 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment membrane, liquid crystal display element, and method for manufacturing liquid crystal display element |
| CN104516151A (en) * | 2013-10-07 | 2015-04-15 | Jsr株式会社 | Manufacturing method for liquid crystal alignment film, photo-alignment agent and liquid crystal display device |
| WO2015152174A1 (en) * | 2014-04-03 | 2015-10-08 | 日産化学工業株式会社 | Liquid crystal alignment agent containing polyamic acid ester-polyamic acid compolymer, and liquid crystal alignment film using same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3613421B2 (en) | 1996-05-31 | 2005-01-26 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| TW498664B (en) | 1999-09-17 | 2002-08-11 | Qualcomm Inc | Method and apparatus for rotating a phase of a modulated signal |
| CN102893208B (en) * | 2010-03-15 | 2015-07-08 | 日产化学工业株式会社 | Liquid crystal alignment agent containing polyamic acid ester and polyamic acid, and liquid crystal alignment film |
| TWI628214B (en) * | 2012-02-13 | 2018-07-01 | 日產化學工業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN104204925A (en) * | 2012-03-30 | 2014-12-10 | 日产化学工业株式会社 | Polyimide-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| KR102127032B1 (en) | 2013-05-01 | 2020-06-25 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
-
2016
- 2016-12-02 TW TW105139942A patent/TWI751995B/en active
- 2016-12-02 WO PCT/JP2016/085953 patent/WO2017094898A1/en active Application Filing
- 2016-12-02 JP JP2017554210A patent/JP6891814B2/en active Active
- 2016-12-02 CN CN201680080871.6A patent/CN108604029B/en active Active
- 2016-12-02 KR KR1020187018889A patent/KR102710874B1/en active IP Right Grant
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003026918A (en) * | 2001-07-13 | 2003-01-29 | Hitachi Ltd | Material for oriented liquid crystal film, liquid crystal display element, process for producing it and liquid crystal display device |
| CN102893209A (en) * | 2010-03-15 | 2013-01-23 | 日产化学工业株式会社 | Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film |
| CN102918452A (en) * | 2010-06-07 | 2013-02-06 | 夏普株式会社 | Liquid crystal display device |
| CN103562782A (en) * | 2011-03-31 | 2014-02-05 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element |
| CN104136979A (en) * | 2011-12-28 | 2014-11-05 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment membrane, liquid crystal display element, and method for manufacturing liquid crystal display element |
| CN104516151A (en) * | 2013-10-07 | 2015-04-15 | Jsr株式会社 | Manufacturing method for liquid crystal alignment film, photo-alignment agent and liquid crystal display device |
| WO2015152174A1 (en) * | 2014-04-03 | 2015-10-08 | 日産化学工業株式会社 | Liquid crystal alignment agent containing polyamic acid ester-polyamic acid compolymer, and liquid crystal alignment film using same |
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| Publication number | Publication date |
|---|---|
| CN108604029B (en) | 2021-11-26 |
| KR102710874B1 (en) | 2024-09-26 |
| JP6891814B2 (en) | 2021-06-18 |
| TWI751995B (en) | 2022-01-11 |
| TW201734131A (en) | 2017-10-01 |
| WO2017094898A1 (en) | 2017-06-08 |
| JPWO2017094898A1 (en) | 2018-09-20 |
| KR20180089487A (en) | 2018-08-08 |
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