CN108604027A - 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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- CN108604027A CN108604027A CN201680080101.1A CN201680080101A CN108604027A CN 108604027 A CN108604027 A CN 108604027A CN 201680080101 A CN201680080101 A CN 201680080101A CN 108604027 A CN108604027 A CN 108604027A
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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
- 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
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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Abstract
It provides:Can obtain resistance to brushing, the excellent in stability of liquid crystal aligning, charge accumulation mitigation is fast and then the aligning agent for liquid crystal of liquid crystal orientation film and excellent storage stability that flicker (flicker level) after just driving is small.A kind of aligning agent for liquid crystal, contains:Has the poly amic acid ester (A ingredients) of the specific repetitive unit of the structure with formula (Y1 1) and the specific repetitive unit with formula (Y2 1);With the polyamic acid (B component) with specific structure.(definition of the symbol in formula is as described in specification).
Description
Technical field
The present invention relates to the aligning agent for liquid crystal for making liquid crystal orientation film, the liquid crystal that are obtained by foregoing liquid crystal alignment agent to take
To film and the liquid crystal with foregoing liquid crystal alignment films indicates element.
Background technology
Now, liquid crystal indicates that element is widely used in digital camera, PC, portable terminal, TV etc. and largely sets
Graphical representation part in standby.Such liquid crystal indicates that element is formed as supporting the liquid-crystal composition with mobility with two
Substrate clamping and enclosed structure are provided on the face of aforesaid base plate contacted with liquid crystal for making liquid crystal molecular orientation
Liquid crystal orientation film.Liquid crystal orientation film generally makes by the process of coating of liquid crystalline alignment agent on aforesaid base plate.In addition, making liquid
Brilliant molecule in the case of the orientation of direction, for the film obtained by aligning agent for liquid crystal, has carried out brushing processing, light in the face of substrate
Orientation process etc..
Fundamental characteristics required by liquid crystal orientation film is that liquid crystal molecule is made to be orientated along defined direction, but in order to realize high property
The liquid crystal of energy indicates element, it is also necessary to the improvement of various characteristics in addition to this, in turn, and in stable industrial production, liquid crystal
The characteristics such as coating, the storage stability of alignment agent also become important.Such as disclosed in patent document 1, it is not easy to draw to provide
Play the aligning agent for liquid crystal for the purpose of the liquid crystal orientation film of scraping, the scuffing of the film caused by brushing processing.Moreover, patent document 2
In disclose, with provide on the basis of the resistance to brushing of film, the differently- oriented directivity of brushing direction and liquid crystal can be inhibited to be staggered, formed
Voltage retention height when liquid crystal expression element, the liquid crystal aligning for the purpose of the liquid crystal orientation film for the charge that can quickly mitigate accumulation
Agent.
Existing technical literature
Patent document
Patent document 1:International Publication bulletin WO2010/053128 pamphlets
Patent document 2:International Publication bulletin WO2015/122413 pamphlets
Invention content
Problems to be solved by the invention
The high performance increasingly that element is indicated along with liquid crystal in recent years requires ratio so far to liquid crystal orientation film
Also high horizontal realization various characteristics.For example, liquid crystal indicates element due to carrying out High precision, accordingly, with respect to resistance to brushing, than
It is increasingly becoming problem with the small scraping of contact, scuffing.Furthermore it is required that realizing other multifrequency natures simultaneously.
By above, problem of the present invention is that, it provides:It can obtain resistance to brushing, the excellent in stability of liquid crystal aligning, liquid crystal
It indicates the fast liquid crystal orientation film of the mitigation of the charge accumulation of element and then liquid crystal is just made to indicate that the flicker after element driving (is dodged
Bright level) small liquid crystal orientation film and excellent storage stability aligning agent for liquid crystal.
The solution to the problem
The inventors of the present invention study repeatedly, as a result complete the present invention, the present invention is with below for purport.
A kind of aligning agent for liquid crystal, which is characterized in that contain following (A) ingredients and (B) ingredient.
(A) ingredient:Polyamide containing repetitive unit shown in repetitive unit shown in following formula (1) and following formula (2)
Acid esters.
(B) ingredient:Polyamic acid with repetitive unit shown in following formula (3).
(in formula (1) and formula (2), multiple R1It is each independently the alkyl of carbon number 1~6, multiple R2It is each independently hydrogen
The alkyl of atom or carbon number 1~6, Y1For the organic group of divalent shown in following formula (Y1-1), Y2For shown in following formula (Y2-1)
Divalent organic group.)
In formula (Y1-1), 2 R3It is each independently singly-bound ,-O- ,-S- ,-OCO- or-COO-, 2 R4Each independently
For the alkylidene of carbon number 1~3, R5For oxygen atom or sulphur atom.
In formula (Y2-1), A1And A5It is each independently singly-bound, methylene, the alkylidene of carbon number 2~5, azetidine two
Base, pyrrolidines diyl or piperidines diyl, B1And B2Be each independently singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-
NHCO-、-CONCH3Or-NCH3CO-, A2And A4It is each independently the alkylidene of singly-bound, methylene or carbon number 2~5, A3For
The alkylidene of methylene or carbon number 2~6, a are 0 or 1, and R is hydrogen atom or methyl, and D is is substituted by the guarantor of hydrogen atom by heat
Protect group.
In formula (3), X is the organic group of 4 valences, and Y is the organic group of divalent, R6For hydrogen atom or the alkyl of carbon number 1~4.
The effect of invention
According to the present invention it is possible to provide:It can obtain resistance to brushing, the excellent in stability of liquid crystal aligning, liquid crystal and indicate element
Charge accumulation the fast liquid crystal orientation film of mitigation so that so that liquid crystal is indicated that the flicker (flicker level) after element driving is small
Liquid crystal orientation film and excellent storage stability aligning agent for liquid crystal;The liquid crystal orientation film obtained by the aligning agent for liquid crystal;With,
The high performance liquid crystal for having the liquid crystal orientation film indicates element.
Specific implementation mode
< poly amic acid esters (A) >
Poly amic acid ester as aforementioned (A) ingredient is contains repetitive unit shown in above-mentioned formula (1) and following formula (2) institute
The poly amic acid ester of the repetitive unit shown.
In formula (1) and formula (2), multiple R1It is each independently the alkyl of carbon number 1~6, preferably methyl or ethyl.In addition,
In formula (1) and formula (2), multiple R2It is each independently the alkyl of hydrogen atom or carbon number 1~6, preferably hydrogen atom or methyl.
In formula (1), Y1For the organic group of divalent shown in following formula (Y1-1).
In formula (Y1-1), R3、R4、R5As defined in above-mentioned, wherein R3It is preferred that singly-bound ,-O-, R4It is preferred that methylene, R5It is preferred that
Oxygen atom.
Y can be enumerated below1Concrete example, but the present invention is not limited to these.
Among the above, from the viewpoint of the orientation stability of liquid crystal, preferably (Y1-1-1)~(Y1-1-8).In addition, formula (1)
Shown in (containing) ratio of repetitive unit be preferably in whole repetitive units contained in poly amic acid ester as (A) ingredient
1~70 mole of %, more preferable 5~50 moles of %.
In previously described formula (2), Y2For the organic group of divalent shown in following formula (Y2-1).
In formula (Y2-1), A1、A5、B1、B2、A2、A3、A4, R, a be as defined in above-mentioned.Wherein, A1、A5It is preferred that singly-bound, methylene
Base, ethylidene or propylidene.In addition, A1Or A5For aliphatic heterocycles such as azetidine diyl, pyrrolidines diyl, piperidines diyls
When, preferably azetidine -1,3- diyl, pyrrolidines -1,3- diyl or piperidines-Isosorbide-5-Nitrae-diyl, the nitrogen-atoms in more preferable ring
It is bonded with adjacent phenyl ring.
In addition, B1And B2It is preferred that singly-bound or-O-.A2And A4It is preferred that singly-bound, methylene, ethylidene or propylidene.A3It is preferred that
Ethylidene.A preferably 0.The preferred hydrogen atoms of R.
In formula (Y2-1), D is is substituted by the blocking group of hydrogen atom by heat, from the storage stability of aligning agent for liquid crystal
From the perspective of, it is appropriate that, it stays at room temperature and leaves away and take under the heating in the production process of liquid crystal orientation film
On behalf of the group of hydrogen atom.As preferred temperature of leaving away, be 80~200 DEG C, it is 100~200 DEG C more preferable, particularly preferred 150
~200 DEG C.As the concrete example of such group, 1,1- dimethyl -2- chloroethoxycarbonyls, 1,1- dimethyl-can be enumerated
2- cyanoethoxies carbonyl, tert-butoxycarbonyl or 9- fluorenylmethoxycarbonyl groups etc., preferably tert-butoxycarbonyl or 9- fluorenyls
Methoxycarbonyl, particularly preferred tert-butoxycarbonyl.
In the organic group of divalent shown in above-mentioned formula (Y2-1), as A1~A5、B1、B2It, can be with the preferred combination of a
Enumerate the combination of Class1~type 3 as shown below, more preferable Class1 or type 2, particularly preferred Class1.
Class1:A1And A5It independently is the alkylidene of singly-bound, methylene, carbon number 2~5, B1And B2Independently be singly-bound ,-
O-、-COO-、-OCO-、-CONH-、-NHCO-、-CONCH3Or-NCH3CO-, A2And A4It independently is methylene or carbon number 2
~5 alkylidene, A3For methylene or the alkylidene of carbon number 2~6, a is 0 or 1.
It is further preferred that A1And A5It is singly-bound, B1And B2It independently is singly-bound or-O-, A2And A4Independently be methylene,
Or the alkylidene of carbon number 2~5, A3For methylene or the alkylidene of carbon number 2~6, a is 0 or 1.
Type 2:A1And A5It independently is singly-bound, azetidine diyl, pyrrolidines diyl or piperidines diyl, B1And B2
For singly-bound, A2And A4It independently is the alkylidene of methylene or carbon number 2~5, a 0.It is further preferred that A1For azetidine
Diyl, pyrrolidines diyl or piperidines diyl, A2For methylene or the alkylidene of carbon number 2~5, A4、A5、B1And B2For singly-bound, a is
0。
Type 3:A1、A2、A4、A5、B1、B2For singly-bound, A3For methylene or the alkylidene of carbon number 2~6, a 1.
Y can be enumerated below2Concrete example, but the present invention is not limited to these.It should be noted that in following structures
D is identical as the definition of formula (Y2-1).
(containing) ratio of repetitive unit shown in formula (2) is preferably contained in the poly amic acid ester as (A) ingredient
1~70 mole of %, more preferable 5~50 moles of % in whole repetitive units.
It is single as being repeated shown in repetitive unit shown in formula (1) and formula (2) in poly amic acid ester as (A) ingredient
The preferred ratio of member, with molar ratio computing for 1:10~10:1, it is more preferably 1:6~6:1.In addition, the polyamide as (A) ingredient
In whole repetitive units contained in acid esters, the summation of repetitive unit and repetitive unit shown in formula (2) shown in formula (1) is preferred
For 15 moles of % or more, more preferably 30 moles of % or more.
The aforementioned poly amic acid ester as (A) ingredient can have the repetitive unit in addition to previously described formula (1) and formula (2).
The structure of repetitive unit in addition to formula (1) and formula (2) is not particularly limited, if specially enumerating its concrete example, under preferred
State repetitive unit shown in formula (4).
In formula (4), R1、R2It is identical definition, Y with formula (1)3Indicate the divalent in addition to previously described formula (Y1-1) and formula (Y2-1)
Organic group.Y in formula (4)3As long as structure be divalent in addition to previously described formula (Y1-1) and formula (Y2-1) organic group
Just it is not particularly limited.The concrete example of preferred structure described below, but the present invention is not limited to these.
Among above structure, particularly preferred (Y-5), (Y-10)~(Y-16), (Y-18), (Y-24)~(Y-29) etc..
It can be obtained above with known synthetic method as the poly amic acid ester of (A) ingredient.As its example, Ke Yiju
Go out following method:Make the tetracarboxylic acid derivatives ingredient comprising following formula (1a) compound represented with comprising following formula (1b) and
The method of the diamine component polycondensation of (2b) compound represented;Or, making the tetrabasic carboxylic acid for including following formula (1a ') compound represented
Two anhydride components and the diamine component addition polymerization comprising following formula (1b) and (2b) compound represented and after obtaining polyamic acid, by carboxylic
The method etc. of base ester.
H2N-Y1-NH2 (1b) H2N-Y2-NH2 (2b)
In formula, R is hydroxyl or chlorine atom, R1、R2、Y1It is identical definition, Y with formula (1)2It is identical definition with formula (2).
In the aligning agent for liquid crystal of the present invention, the molecular weight of the poly amic acid ester as (A) ingredient is not particularly limited, with weight
Average molecular weight meter is preferably 2000~500000, more preferably 5000~300000, further preferably 10000~100000.
< polyamic acids (B) >
Polyamic acid as aforementioned (B) ingredient has repetitive unit shown in following formula (3).It should be noted that should
The structure of formula contained in polyamic acid (3) can be a kind, or two or more.
In formula (3), X is the organic group of 4 valences, and Y is the organic group of divalent, R6For hydrogen atom or the alkyl of carbon number 1~4.
Polyamic acid with repetitive unit shown in above-mentioned formula (3) can for example obtain as follows:Make following formula (3a) institute
At least one kind of compound shown is obtained at least one kind of compound polycondensation shown in following formula (3b).Therefore, the X in formula (3) can
To include structure corresponding with whole compounds shown in formula (3a).Similarly, the Y and R in formula (3)6Can also include and formula
The corresponding structure of whole compound shown in (3b).
X, Y, R in formula (3a) and formula (3b)6Respectively with X, Y, R in formula (3)6For identical definition.
Hereinafter, the concrete example of the preferred structure of the X in formula (3) is shown, but the present invention is not limited to these.
In above-mentioned (X-1), R7~R10It is each independently the alkyl of hydrogen atom or carbon number 1~6.
X in previously described formula (3) be preferably selected from it is at least one kind of in the group being made of above-mentioned (X-1)~(X-14), it is especially excellent
It is selected as selected from by R in above-mentioned (X-1)7~R10The structure of all hydrogen atoms, (X-2), (X-3), (X-5), (X-6), (X-7),
(X-8), at least one kind of in the group of (X-10), (X-11) and (X-14) composition.
Y in formula (3) is not particularly limited its structure as long as the organic group of divalent, just makes liquid crystal from improving
From the perspective of the improvement for indicating the flicker (flicker level) after element driving, Y is preferably free of and is used as formula (Y1-1) or formula
(Y2-1) repetitive unit.
More specifically, Y is preferably selected from the organic group of the divalent in the group being made of following (i)~(iii).
(i) structure shown in following (c-1) or (c-2).
(ii) it is selected from the combination of the structure in following (c-1)~(c-4).
(iii) include to be selected from following (d-1)~(d- in the centre of the combination of the structure in following (c-1)~(c-4)
3) binding groups in.
In formula (c-1), R indicates hydrogen atom, methyl or carboxyl.
Among the above, it is selected from the combination of the structure in the group being made of (c-1)~(c-4), can be to have used multiple phases
Isostructural combination.In addition, the binding groups in the group being made of (d-1)~(d-3) are not adjacent to each other.Selected from by (i)
The molecular weight of the organic group of divalent in the group of~(iii) compositions is more preferably 1000 or less.It, can as the concrete example of above-mentioned Y
To enumerate aforementioned (Y-1)~(Y-34) etc., but the present invention is not limited to these.Wherein, particularly preferred (Y-5), (Y-8), (Y-
9), (Y-12), (Y-17), (Y-18)~(Y-20) or (Y-29).
In the aligning agent for liquid crystal of the present invention, the molecular weight of the polyamic acid as (B) ingredient is preferred with Weight-average molecular gauge
It is 2000~500000, more preferably 5000~300000, further preferably 10000~100000.
< aligning agent for liquid crystal >
The quality of the poly amic acid ester (A) contained in the aligning agent for liquid crystal of the present invention and polyamic acid (B) (contains) ratio
(poly amic acid ester/polyamic acid) preferably 1/9~9/1, more preferable 2/8~8/2.
The aligning agent for liquid crystal of the present invention is preferably the form of the solution containing poly amic acid ester (A) and polyamic acid (B).On
In the case of stating, the total content of poly amic acid ester (A) and polyamic acid (B) can be according to the thickness for thinking liquid crystal orientation film to be formed
Setting and suitable for change, from forming uniform and flawless film aspect, preferably 0.5 matter of aligning agent for liquid crystal entirety
% or more is measured, from the storage stability aspect of solution, preferably 15 mass % or less.In particular, more preferable 0.5~10 matter
Measure %, particularly preferred 1~10 mass %.
As long as the organic solvent that contains makes poly amic acid ester (A) and polyamic acid (B) in the aligning agent for liquid crystal of the present invention
Component of polymer, which equably dissolves, to be just not particularly limited.If enumerating its concrete example, N, N- dimethyl formyls can be enumerated
Amine, N, N- diethylformamides, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidones, N- first
Base caprolactam, 2-Pyrrolidone, n-vinyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl sulfone, gamma-butyrolacton, 1,3-
Dimethyl -2- imidazolidinones, 3- methoxyl groups-N, N- dimethylpropionamide etc..They can use a kind or be used in mixed way 2 kinds with
On.
It should be noted that the poly amic acid ester (A) contained from the aligning agent for liquid crystal of the present invention and polyamic acid (B)
The viewpoints such as compatibility are set out, and the containing ratio of n-methyl-2-pyrrolidone is preferably 30 relative to the total weight of aligning agent for liquid crystal
~80 mass %.Even in addition, can not individually make the solvent that component of polymer equably dissolves, as long as not being precipitated for polymer
Range, so that it may to be blended in above-mentioned organic solvent.
The present invention aligning agent for liquid crystal in addition to organic solvent, can also contain be useful for improve aligning agent for liquid crystal is coated on
The solvent of painting film uniformity when substrate.Above-mentioned solvent generally uses the solvent that surface tension is low compared with above-mentioned organic solvent.
If enumerating its concrete example, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl card can be enumerated
It must alcohol acetic ester, ethylene glycol, 1- methoxy-2-propanols, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy groups -2-
Propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl ether -2- acetic acid esters, propylene glycol -1- lists ether -
2- acetic acid esters, butyl cellosolve acetate, dipropylene glycol, 2- (2- ethoxy-cs oxygroup) propyl alcohol, methyl lactate, ethyl lactate,
Lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc..These solvents can will be applied in combination on 2 kinds.
The aligning agent for liquid crystal of the present invention can contain the various additions such as silane coupling agent, crosslinking agent, imidizate accelerating agent
Agent.
Silane coupling agent can be added with improving the purpose of the adaptation of liquid crystal orientation film and substrate.In addition, silane is even
It can be a kind to join agent, can also combine two or more.The content of silane coupling agent is excellent relative to 100 mass parts of component of polymer
Select 0.01~5.0 mass parts, more preferable 0.1~2.0 mass parts.
The concrete example of silane coupling agent is enumerated below, but is not limited to these.3-aminopropyltriethoxysilane, 3-
(2- amino-ethyls) TSL 8330,3- (2- amino-ethyls) aminopropylmethyldimethoxysilane, 3- ammonia
Base propyl trimethoxy silicane, 3- phenyl amino propyls trimethoxy silane, 3- triethoxysilyls-N- (1,3- diformazans
Base butane) the amine systems silane coupling agent such as propylamine, 3- aminopropyl diethoxymethylsilanes;Vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyl three (2- methoxy ethoxies) silane, vinyl methyl dimethoxysilane, vinyl
Triacetoxysilane, vinyl silane triisopropoxide, allyltrimethoxysilanis, to styryltrimethoxysilane
Equal ethylene base system silane coupling agent;3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxypropyl group triethoxysilicanes
Alkane, 3- glycidoxypropyls diethoxy silane, 3- glycidoxypropyls dimethoxysilane, 2- (3,4-
Epoxycyclohexyl) the epoxies silane coupling agent such as ethyl trimethoxy silane;3- methacryloyloxypropyl methyl dimethoxies
Base silane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloxypropyl methyl diethoxysilanes,
The methacrylics silane coupling agent such as 3- methacryloxypropyls;3- acryloxypropyl front threes
The acrylic-silanes coupling agent such as oxysilane;The urea groups such as 3- ureidopropyltriethoxysilanes system silane coupling agent;Bis- (3-
(triethoxysilyl) propyl) the thioethers system silane such as disulfide, bis- (3- (triethoxysilyl) propyl) four thioethers
Coupling agent;3- mercapto propyl methyl dimethoxy silanes, 3-mercaptopropyi trimethoxy silane, 3- Octanoylthio -1- propyl
The sulfydryls such as triethoxysilane system silane coupling agent;3- isocyanate propyl triethoxysilanes, 3- isocyanates propyl front threes
The isocyanates such as oxysilane system silane coupling agent;The aldehyde system such as triethoxysilyl butyl aldehyde silane coupling agent;Three ethoxies
The amino such as base silylpropyl methyl carbamate, (3- triethoxysilylpropyltetrasulfides)-t-butylcarbamate
Formic acid esters system silane coupling agent.
Above-mentioned crosslinking agent can be used for the purpose for the film-strength for improving liquid crystal orientation film.In addition, crosslinking agent can be with
It is a kind, two or more can also be combined.The dosage of crosslinking agent is preferably 0.1~50 relative to 100 mass parts of component of polymer
Mass parts, more preferably 1~20 mass parts.
As above-mentioned crosslinking agent, can enumerate:With epoxy group, isocyanate group, oxetanyl, cyclic carbonate ester
The cross-linked compound of base or hydroxyalkylamides base;It is formed with free hydroxyl, hydroxy alkyl and low-grade alkoxy alkyl is selected
Group at least one kind of substituent group cross-linked compound;Or, the cross-linked compound etc. with polyunsaturated bond.This
A little substituent group, polyunsaturated bonds have 2 or more preferably in cross-linked compound.
The concrete example of crosslinking agent is enumerated below, but is not limited to these.As the friendship with epoxy group or isocyanate group
Connection property compound, can enumerate bisphenol acetone glycidol ether, phenol novolac epoxy resins, cresol novolak epoxy tree
Fat, triglycidyl isocyanurate, four glycidyl group aminodiphenyl support (tetraglycidyl amino
Diphenylene), bis- (amino-ethyl) hexamethylenes of four glycidyl group-m-xylene diamine, four glycidyl group -1,3-, four benzene
Base glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl diglycidyl ether, the bis- (1- (2,3- of 1,3-
Glycidoxy) -1- trifluoromethyl -2,2,2- trifluoromethyls) benzene, bis- (2,3- glycidoxies) octafluorobiphenyls of 4,4-, three contracting
Water glyceryl-para-aminophenol, four glycidyl group m-xylene diamine, 2- (4- (2,3- glycidoxies) phenyl) -2- (4-
(bis- (4- (2,3- glycidoxies) phenyl) ethyls of 1,1-) phenyl) propane, the bis- (4- (1- (4- (2,3- glycidoxies) of 1,3-
Phenyl) -1- (4- (1- (4- (2,3- glycidoxies) phenyl) -1- Methylethyls) phenyl) ethyl) phenoxy group) -2- propyl alcohol etc..
As the cross-linked compound with oxetanyl, International Publication bulletin WO2011/132751 can be enumerated
Cross-linked compound shown in formula [4a]~[4k] described in page 58~59 of number pamphlet.As with cyclocarbonate radical
Cross-linked compound can enumerate the formula [5- described in page 76~82 of International Publication bulletin WO2012/014898 pamphlets
1] cross-linked compound shown in~[5-42].
As the cross-linked compound with hydroxyalkylamides base, International Publication bulletin WO2015/ can be enumerated
Cross-linked compound described in page 23 [changing 35] of No. 072554 pamphlet.As with selecting free hydroxyl and alkoxy to form
Group at least one kind of substituent group cross-linked compound, International Publication bulletin WO2011/132751 pamphlets can be enumerated
Page 62~66 described in formula [6-1]~[6-48] shown in cross-linked compound.
As the cross-linked compound with polyunsaturated bond, International Publication bulletin WO2015/ can be enumerated
Cross-linked compound described in [0112] of No. 060357 pamphlet page 58~59~[0113].
Imidizate accelerating agent can make poly amic acid ester for when the film of the aligning agent for liquid crystal of the present invention to be burnt into
(A) and the purpose that carries out well of the imidization reaction efficiency of polyamic acid (B) and use.The dosage of imidizate accelerating agent
Relative to 1 mole of the amic acid position and amic acid esters position that imidization reaction can occur, preferably 0.01 mole or more, more
Preferably 0.05 mole or more, further preferably 0.1 mole or more.In addition, from will be caused to each characteristic of liquid crystal orientation film
Harmful effect be reduced to from the perspective of bottom line, remain on firing after film in imidizate accelerating agent itself it is preferred
It is 2 moles or less, more preferably 1 mole or less, further preferably 0.5 mole or less.
As the concrete example of imidizate accelerating agent, International Publication bulletin WO2010/114103 pamphlets can be enumerated
Page 29 described in, formula (B-1)~(B-17) compound represented, but be not limited to these.
< liquid crystal orientation films >
The liquid crystal orientation film of the present invention is that liquid crystal obtained from aligning agent for liquid crystal using the present invention described in above-mentioned takes
To film.Known method may be used in the method for obtaining liquid crystal orientation film.For example, following liquid crystal orientation film:By liquid crystal aligning
Agent is coated on substrate and drying, firing obtain film, and brushing processing or irradiation polarized UV rays are carried out to gained film, to
Impart the liquid crystal orientation film of liquid crystal aligning ability.
As the substrate of coating of liquid crystalline alignment agent, it is not particularly limited, can uses as long as the high substrate of the transparency
The viewpoint of plastic bases such as glass substrate, silicon nitride board, acrylic compounds substrate, polycarbonate substrate etc., the chemical industry skill that conforms to the principle of simplicity goes out
Hair is, it is preferable to use be formed with the substrate of ITO electrode for liquid crystal drive etc..In addition, the liquid crystal of reflection-type indicates in element, such as
Fruit is only the substrate of unilateral side, then can also use the opaque objects such as Silicon Wafer, the electrode under the above situation that can also use
The material of the reflected lights such as aluminium.As the coating method of aligning agent for liquid crystal, spin-coating method, print process, ink-jet method etc. can be enumerated.
Drying, firing process after coating of liquid crystalline alignment agent can select arbitrary temperature and time.In general, in order to make to contain
Some organic solvents fully remove, 1 minute~10 minutes dry at 50~120 DEG C, are burnt into 5 at 150~300 DEG C later
~120 minutes.The thickness of film after firing is not particularly limited, but when excessively thin, and liquid crystal indicates the reliability of element sometimes
It reduces, is 5~300nm, preferably 10~200nm therefore.
As the method for carrying out orientation process to the film, brushing method, light orientation position logos etc. can be enumerated, with brushing method
In the case of use, aligning agent for liquid crystal of the invention is particularly useful.
< liquid crystal indicates element >
The liquid crystal of the present invention indicates that element is that there is the liquid crystal of above-mentioned liquid crystal orientation film to indicate element.More specifically, lead to
The above method is crossed, after obtaining the substrate with liquid crystal orientation film by the aligning agent for liquid crystal of present embodiment, is made by known method
Liquid crystal cells form liquid crystal and indicate element.
If enumerating an example of liquid crystal cells making, as described below.First, prepare a pair for being formed with liquid crystal orientation film
Substrate.Then, liquid crystal alignment film surface is made to become inside, after making another substrate sticking, decompression injection liquid crystal simultaneously seals.Or, can
After liquid crystal is added dropwise in liquid crystal alignment film surface, substrate sticking is made to be sealed.At this point, in order to ensure to fill between a pair of of substrate
The space of liquid crystal material, it is preferred to use following means:Columnar protrusion is set on one substrate or is spread on one substrate
Spacer or be mixed into sealing material spacer or by they combine etc..Preferably 1~30 μm of the thickness of spacer, more preferably
2~10 μm.
As above-mentioned liquid crystal material, nematic liquid crystal, smectic liquid crystal can be enumerated, wherein preferred nematic liquid crystal can use
Any one of positive type liquid crystal material, negative type liquid crystal material.Then, the setting of polarizing film is carried out.Specifically, it is preferable that 2
Open a pair of of polarizing film of adherency on the face with liquid crystal layer opposite side of substrate.
It should be noted that the liquid crystal orientation film and liquid crystal of the present invention indicate that element is not limited to above-mentioned record, Ke Yiwei
The liquid crystal orientation film and liquid crystal made in other well known methods indicates element.Liquid crystal is obtained by aligning agent for liquid crystal and indicates that element is
Process only e.g., as disclosed in Japanese Laid-Open 2015-135393 bulletins [0074]~19 page [0081] of page 17 etc., in addition
It is also disclosed in lot of documents.
Embodiment
Embodiment is enumerated below, and the present invention is further specifically described.But the unlimited qualitative interpretation of the present invention is this
A little embodiments.The abbreviation of the compound used later and the assay method of each characteristic are as described below.
The abbreviation > of < compounds
In following, " Boc " is tert-butoxycarbonyl.
The abbreviation > of < solvents
NMP:N-methyl-2-pyrrolidone, BCS:Butyl cellosolve
GBL:Gamma-butyrolacton, IPA:Isopropanol
< viscosity >
The viscosity of polymer solution uses E type viscosimeters TVE-22H (Toki Sangyo Co., Ltd.'s system), in sample size
It is measured at 1.1mL, cone rotor TE-1 (1 ° 34 ', R24), 25 DEG C of temperature.
< molecular weight >
The molecular weight of polymer is measured using GPC (room temperature gel permeation chromatography) device, with polyethylene glycol, polyethylene oxide
Scaled value calculates number-average molecular weight (hereinafter also referred to as Mn) and weight average molecular weight (hereinafter also referred to as Mw).
GPC devices:Shodex corporations (GPC-101)
Column:Shodex corporations (series connection of KD803, KD805), column temperature:50℃
Eluent:N,N-Dimethylformamide is (as additive, lithium bromide-hydrate (LiBrH2O) it is 30mmol/
L, phosphoric acid anhydrous crystalline (orthophosphoric acid) is 30mmol/L, tetrahydrofuran (THF) is 10ml/L), flow velocity:1.0ml/ minute
Calibration curve, which is made, uses standard sample:TOSOH Co., Ltd TSK standards polyethylene oxide (weight average molecular weight (Mw)
About 900000,150000,100000,30000) and Polymer LaboratoriesLtd. polyethylene glycol (peak top molecular weights
(Mp) about 12000,4000,1000).For measuring, in order to avoid overlap of peaks, measure respectively by 900000,100000,12000,
1000 this 4 kinds of samples mixed and by 150000,30000,4000 this 3 kinds of samples mixed this 2 kinds of samples.
The resistance to brushings of < evaluate >
After 1.0 μm of filter filtering of aligning agent for liquid crystal, it is spun on the glass substrate with transparent electrode, at 80 DEG C
Hot plate on make its 5 drying minute after, with 230 DEG C be burnt into 20 minutes, obtain the polyimide film of film thickness 100nm.By the polyamides
Imines film is with rayon cloth brushing 1 time (roller diameter 120mm, rotating speed 1000rpm, movement speed 20mm/ seconds, intrusion 0.4mm).
To the micro- sem observation surface state of the film surface confocal laser, have with what is scratched with the presence or absence of 100 times of observation chips of multiplying power
Nothing.The case where having no chip substantially, scratching, is defined as " good " and evaluates, it will be seen that the feelings that a large amount of chips, brushing scratch
Condition is defined as " bad " and is evaluated.
< liquid crystal indicates the making > of element
Prepare electroded substrate first.Substrate is the glass substrate that size is 30mm × 35mm and thickness is 0.7mm.
On substrate, as the 1st layer, forms structure paired electrode and have the IZO electrodes of solid shape pattern.At the 1st layer on electrode,
As the 2nd layer, SiN (silicon nitride) film to form a film using CVD method is formd.The film thickness of 2nd layer of SiN film is 500nm, is made
It is functioned for interlayer dielectric.On the 2nd layer of SiN film, as the 3rd layer, the comb for forming IZO film figures is configured
Dentation pixel electrode, to form the 1st pixel and the 2nd pixel the two pixels.The size of each pixel is:Vertical 10mm and it is horizontal about
5mm.At this point, the 1st layer with the 3rd layer of pixel electrode because of the effect of the 2nd layer of SiN film is in be electrically insulated to electrode.
The comb that 3rd layer of pixel electrode is constituted with " < " shape electrode element that the multiple center portions of arrangement bend
Tooth shape.The width of the width direction of each electrode element is 3 μm, between electrode element between be divided into 6 μm.Form the picture of each pixel
Plain electrode is " < " shape electrode element that the multiple center portions of arrangement bend and constitutes, therefore the shape of each pixel is not
Oblong-shaped, but have the shape of " < " similar to runic that bend in center portion in the same manner as electrode element.
Also, each pixel is divided up and down by boundary of the bending part in the center, with the 1st region and downside on the upside of bending part
2nd region.
When comparing the 1st region and 2 region of each pixel, the formation direction of the electrode element of their pixel electrode is constituted
It is different.That is, using the brushing direction of aftermentioned liquid crystal orientation film as when benchmark, in the 1st region of pixel ,+10 ° of angle is presented
The mode of degree (clockwise) forms the electrode element of pixel electrode, (suitable with the angle for being presented -10 ° in the 2nd region of pixel
Hour hands) mode form the electrode element of pixel electrode.That is, following constituted:In the 1st region of each pixel and the 2nd region, pass through
Apply voltage and the side of the spinning movement (plane conversion) of the liquid crystal that induces in real estate in pixel electrode and between electrode
To opposite direction each other.
Then, with after 1.0 μm of filter filtering gained aligning agent for liquid crystal, it is spun on the above-mentioned belt electrode prepared respectively
Substrate and ito film and the glass substrate with height for 4 μm of column spacer are overleaf formed with as opposite substrate.It connects
It, it is dry in 80 DEG C of heating plate to be burnt into 20 minutes with 230 DEG C after five minutes, the film of film thickness 60nm is formed, in each substrate
On obtain polyimide film.By brushing direction as defined in the polyimide film upper edge with rayon cloth brushing (roller diameter 120mm,
Rotating speed 500rpm, movement speed 30mm/ seconds, intrusion 0.3mm) after, 1 minute ultrasonic irradiation is carried out in pure water, with 80 DEG C
It is 10 minutes dry.
Later, 2 kinds of substrates with liquid crystal orientation film using above-mentioned, the group in such a way that respective brushing direction becomes antiparallel
It closes, remains liquid crystal injecting port, surrounding is sealed, 3.8 μm of dummy cell is divided between production unit.At normal temperatures in the dummy cell
After vacuum injection liquid crystal (MLC-2041, MERCK CORPORATION systems), inlet is sealed, the liquid of antiparallel orientations is formed
Brilliant unit.Gained liquid crystal cells constitute FFS mode liquid crystal and indicate element.Later, gained liquid crystal cells are small with 120 DEG C of heating 1
When, it is used for each evaluation after placing a Dinner.
The evaluation > of the relaxation properties of < charge accumulations
The evaluation of ghost is carried out using following optics system etc..The liquid crystal cells made are set to be become with polarizing axis
Between 2 polarizing films that orthogonal mode configures, LED backlight is lighted in the state of without voltage is applied, with the brightness of transmitted light
As least way, the arrangement angles of liquid crystal cells are adjusted.
Then, while the alternating current flanging that the liquid crystal cells are applied with frequency 30Hz measures V-T curve, (voltage-transmission rate is bent
Line), relative transmittance is calculated as 23% alternating voltage as driving voltage.
In ghost evaluation, side applies relative transmittance and drives liquid crystal list as the alternating voltage of 23% frequency 30Hz
Member, side apply the DC voltage of 1V simultaneously, drive 60 minutes.Later, it is 0V to make application DC voltage value, only stops applying direct current
Voltage further drives 30 minutes in this state.
In evaluation, from start apply DC voltage at the time of by 60 minutes until, relative transmittance is reduced to 30%
" good " in the case of below, is defined as to be evaluated.Relative transmittance is reduced to 30% or less the feelings for needing 60 minutes or more
" bad " under condition, is defined as to be evaluated.
Then, according to the above method ghost evaluation liquid crystal cells temperature be 23 DEG C state temperature condition under into
Row.
The estimation of stability > of < liquid crystal alignings
Using the liquid crystal cells, under 60 DEG C of isoperibol, the alternating voltage 168 for applying 10VPP with frequency 30Hz is small
When.Later, it in the state of the pixel electrode and the short circuit between electrode for making liquid crystal cells, directly places one day at room temperature.
After placement, between liquid crystal cells are set to 2 polarizing films configured in such a way that polarizing axis becomes orthogonal, in nothing
Backlight is lighted in the state of application voltage, the arrangement angles that least way adjusts liquid crystal cells are become with the brightness of transmitted light.
Then, calculating, which makes liquid crystal cells be rotated from the 2nd region of the 1st pixel to the 1st region as most dark angle, becomes most dark angle
Rotation angle when spending is as angle delta.Similarly, the 2nd region of comparison and the 1st region calculate same angle to 2nd pixel
Δ.Then, angle delta of the average value of the angle delta value of the 1st pixel and the 2nd pixel as liquid crystal cells is calculated.The liquid crystal cells
Angle delta value be more than 0.2 degree in the case of, be defined as " bad " and evaluated.The value of the angle delta of the liquid crystal cells does not surpass
In the case of crossing 0.2 degree, it is defined as " good " and is evaluated.
< just drive after flicker level evaluation >
The evaluation of ghost is carried out using following optics system etc..
Between the liquid crystal cells made are set to 2 polarizing films configured in such a way that polarizing axis becomes orthogonal,
Without LED backlight is lighted in the state of application voltage, least way is become with the brightness of transmitted light, adjusts the configuration of liquid crystal cells
Angle.
Then, while the alternating current flanging that the liquid crystal cells are applied with frequency 30Hz measures V-T curve, (voltage-transmission rate is bent
Line), relative transmittance is calculated as 23% alternating voltage as driving voltage.
In the measurement of flicker level, the LED backlight lighted in advance is made temporarily to turn off the light, avoid light place carried on the back LED after 72 hours
Light is lighted again, is started simultaneously with backlight lightening, applying relative transmittance becomes 23% alternating voltage of frequency 30Hz, makes
Liquid crystal cells drive 60 minutes, tracking flicker amplitude.For flickering amplitude, with by photodiode and I-V switching amplifiers
The data acquisition of connection/data logger switching device 34970A (Agilent technologies corporations), which is read, passes through 2
Open the transmitted light of the LED backlight of polarizing film and the liquid crystal cells between it.Flicker level is calculated with mathematical expression below.
Flicker level (%)={ flicker amplitude/(2 × z) } × 100
In above-mentioned formula, z is to be become with relative transmittance with data acquisition/data logger switching device 34970A readings
It is worth obtained from brightness when the alternating voltage driving of 23% frequency 30Hz.
In the evaluation of flicker level, it was by 60 minutes from the time of starting to light LED backlight and apply alternating voltage
Only, it in the case that flicker level is maintained less than 3%, is defined as " good " and is evaluated.Flicker level reaches in 60 minutes
" bad " in the case of 3% or more, is defined as to be evaluated.
Then, the temperature strip for the state for being 23 DEG C in the temperature of liquid crystal cells according to the evaluation of the flicker level of the above method
It is carried out under part.
The evaluation > of < storage stabilities
In the evaluation of storage stability, the viscosity change before and after following room temperatures for adjusting solution are taken care of 1 week is less than 5mPas
In the case of, in the case of being denoted as " good ", 5mPas or more, it is denoted as " bad " and is evaluated.
< synthesis examples >
(synthesis example 1)
In the removable flasks of 7L for adding stirrer, after putting into CE-1 119g (0.46mol), NMP is added
2372g is stirred to dissolve.Then, triethylamine 146g (1.44mol), DA-1 61g (0.26mol), DA-3 21g is added
(0.072mol) and DA-5 49g (0.14mol), stir to dissolve.
While the solution is stirred under water cooling, DBOP 362g (0.94mol) are added on side, and then NMP 326g are added, in room
The lower stirring of temperature 12 hours, obtains the solution of poly amic acid ester.The viscosity of the polyamic acid ester solution is 27.3mPas.
The polyamic acid ester solution is put into the IPA of 20739g, and gained sediment is filtered out.By the sediment methanol
After cleaning, it is dried under reduced pressure for 100 DEG C with temperature, obtains the powder of poly amic acid ester.The molecular weight of the poly amic acid ester is Mn
=12200, Mw=21700.
In the powder of gained poly amic acid ester, NMP is added in such a way that solid component concentration becomes 12 weight %, with 50
DEG C stirring makes it dissolve for 30 hours, obtains polyamic acid ester solution (PAE-1).
(synthesis example 2)
In the 300mL four-hole boiling flasks for adding stirrer, after putting into CE-1 6.85g (26.3mmol), NMP is added
140g is stirred to dissolve.Then, triethylamine 8.5g (84.0mmol), DA-24.10g (16.8mmol) and DA-5 is added
3.82g (11.2mmol), stirs to dissolve.
While the solution is stirred under water cooling, DBOP 20.7g (54.0mmol) are added on side, and then NMP 19.2g are added,
It is stirred at room temperature 12 hours, obtains the solution of poly amic acid ester.The viscosity of the polyamic acid ester solution is 31.4mPas.
The polyamic acid ester solution is put into the IPA of 1218g, and gained sediment is filtered out.By the sediment methanol
After cleaning, it is dried under reduced pressure for 100 DEG C with temperature, obtains the powder of poly amic acid ester.The molecular weight of the poly amic acid ester is Mn
=11600, Mw=20500.
In the powder of gained poly amic acid ester, NMP is added in such a way that solid component concentration becomes 12 weight %, with 50
DEG C stirring makes it dissolve for 30 hours, obtains polyamic acid ester solution (PAE-2).
(synthesis example 3)
In the removable flasks of 5L with agitating device and nitrogen ingress pipe, take DA-4 243.9g (1.22mol) and
Solvent (NMP is added in DA-2 74.8g (0.31mol):GBL=50wt%:50wt%) 3154g is stirred when being sent into nitrogen
It mixes and makes it dissolve.
While the diamine solution is stirred under water cooling, CA-2 129.0g (0.66mol), CA-1 166.8g are added in side
(0.77mol), and then solvent (NMP is added in such a way that solid component concentration becomes 12 weight %:GBL=50wt%:
50wt%), it is stirred 12 hours with 50 DEG C, obtains polyamic acid solution (PAA-1).The viscosity of the polyamic acid solution is
310mPa·s.In addition, Mn=11700, Mw=24300 of the polyamic acid.
(synthesis example 4)
In the 200mL four-hole boiling flasks with agitating device and nitrogen ingress pipe, DA-4 4.1g (20.4mmol), DA- are taken
NMP 173g are added in 6 5.4g (13.6mmol) and DA-2 8.3g (34.0mol), and being stirred when being sent into nitrogen keeps its molten
Solution.
While the diamine solution is stirred under water cooling, CA-2 5.3g (27.2mmol), CA-1 7.4g are added in side
(34.0mmol), and then NMP is added in such a way that solid component concentration becomes 15 weight %, it is stirred 12 hours, is obtained with 50 DEG C
Polyamic acid solution (PAA-2).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 530mPas.In addition, the polyamide
The molecular weight of acid is Mn=11700, Mw=27200.
(embodiment 1)
In the 20ml sample cells for adding stirrer, take PAE-1 2.31g, PAA-1 8.31g, be added NMP 1.31g,
GBL 2.38g, BCS 4.0g, nmp solution 1.2g and the AD-2 0.60g comprising 1 weight %AD-1, use magnetic stirrer
30 minutes, obtain aligning agent for liquid crystal (A-1).
(embodiment 2)
In the 20ml sample cells for adding stirrer, take PAE-1 3.46g, PAA-1 7.18g, be added NMP 0.73g,
GBL 2.38g, BCS 4.0g, nmp solution 1.2g and the AD-2 0.60g comprising 1 weight %AD-1, use magnetic stirrer
30 minutes, obtain aligning agent for liquid crystal (A-2).
(embodiment 3)
In the 20ml sample cells for adding stirrer, take PAE-1 4.62g, PAA-1 6.15g, be added NMP 0.15g,
GBL 2.38g, BCS 4.0g, nmp solution 1.2g and the AD-2 0.60g comprising 1 weight %AD-1, use magnetic stirrer
30 minutes, obtain aligning agent for liquid crystal (A-3).
(comparative example 1)
In the 20ml sample cells for adding stirrer, take PAE-2 2.40g, PAA-2 6.88g, be added GBL 4.92g,
BCS 4.0g, nmp solution 1.2g and the AD-2 0.60g comprising 1 weight %AD-1 were obtained with magnetic stirrer 30 minutes
Aligning agent for liquid crystal (B-1).
Using the aligning agent for liquid crystal obtained among the above, resistance to brushing, the relaxation properties of charge accumulation, liquid crystal aligning are carried out
Stability, just drive after flicker level and storage stability evaluation.Show the result in table 1.
[table 1]
As more than, liquid crystal orientation film of the invention evaluate in resistance to brushing, the evaluation of ghost cancellation time, liquid crystal aligning
Estimation of stability, just drive after flicker level evaluation in embody good result.
Industrial availability
The liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention can required with the level also higher than so far
Realize that various characteristics including IPS type of drive, the wide scope of FFS type of drive liquid crystal indicates to use in element.
It should be noted that by the specification of Japanese patent application filed in 25 days November in 2015 2015-229489,
Claims, drawings and abstract full content introduce so far, as the present invention specification disclosure be introduced into.
Claims (13)
1. a kind of aligning agent for liquid crystal, which is characterized in that containing following (A) ingredients and (B) ingredient,
(A) ingredient:Poly amic acid ester containing repetitive unit shown in repetitive unit shown in following formula (1) and following formula (2),
(B) ingredient:Polyamic acid with repetitive unit shown in following formula (3),
In formula (1) and formula (2), multiple R1It is each independently the alkyl of carbon number 1~6, multiple R2Be each independently hydrogen atom or
The alkyl of carbon number 1~6, Y1For the organic group of divalent shown in following formula (Y1-1), Y2For divalent shown in following formula (Y2-1)
Organic group,
In formula (Y1-1), 2 R3It is each independently singly-bound ,-O- ,-S- ,-OCO- or-COO-, 2 R4It is each independently carbon
The alkylidene of number 1~3, R5For oxygen atom or sulphur atom,
In formula (Y2-1), A1And A5Be each independently singly-bound, methylene, the alkylidene of carbon number 2~5, azetidine diyl,
Pyrrolidines diyl or piperidines diyl, B1And B2Be each independently singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-
CONCH3Or-NCH3CO-, A2And A4It is each independently the alkylidene of singly-bound, methylene or carbon number 2~5, A3For methylene,
Or the alkylidene of carbon number 2~6, a be 0 or 1, R be hydrogen atom or methyl, D to be substituted by the blocking group of hydrogen atom by heat,
In formula (3), X is the organic group of 4 valences, and Y is the organic group of divalent, R6For hydrogen atom or the alkyl of carbon number 1~4.
2. aligning agent for liquid crystal according to claim 1, wherein (Y1-1 is selected from by following (Y1-1-1)~(Y1-1- formula
8) group formed,
3. aligning agent for liquid crystal according to claim 1 or 2, wherein and formula (in Y2-1, A1、A2、A4、A5、B1、B2For singly-bound, A3
For methylene or the alkylidene of carbon number 2~6, a 1.
4. aligning agent for liquid crystal described in any one of claim 1 to 3, wherein in formula (3), Y be selected from by following (i),
(iii) organic group of the divalent and in the group of (iii) composition,
(i) structure shown in following (c-1) or (c-2);
(ii) it is selected from the combination of the structure in the group being made of following (c-1)~(c-4);
(iii) include selected from by following in the centre of the combination of the structure in the group being made of following (c-1)~(c-4)
(d-1)~(d-3) binding groups in the group formed;
In formula (c-1), R indicates hydrogen atom, methyl or carboxyl.
5. aligning agent for liquid crystal according to claim 4, wherein in formula (3), X is selected from by following (X-1)~(X-14) groups
At group at least one kind of 4 valence organic group,
6. aligning agent for liquid crystal according to any one of claims 1 to 5, wherein the ratio of repetitive unit shown in formula (1)
The ratio of repetitive unit shown in rate or formula (2) is in whole repetitive unit contained in the poly amic acid ester as (A) ingredient
1~70 mole of %.
7. according to aligning agent for liquid crystal according to any one of claims 1 to 6, wherein in the poly amic acid ester of (A) ingredient
, containing ratio, that is, molar ratio of repetitive unit shown in formula (1) and repetitive unit shown in following formula (2) be 1:10~10:
1。
8. aligning agent for liquid crystal according to any one of claims 1 to 7, wherein (A) ingredient and (B) ingredient
Total content relative to aligning agent for liquid crystal generally 0.5~15 mass %.
9. according to aligning agent for liquid crystal according to any one of claims 1 to 8, wherein (A) ingredient and (B) ingredient
Quality containing ratio be 1/9~9/1, relative to 100 mass parts of (A) ingredient, described in 100~400 mass parts
(B) ingredient.
10. according to aligning agent for liquid crystal according to any one of claims 1 to 9, wherein contain:Selected from by N, N- dimethyl methyls
Amide, N, N- diethylformamides, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidones, N-
Methyl caprolactam, 2-Pyrrolidone, n-vinyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl sulfone, gamma-butyrolacton, 1,
Organic solvent in the group of 3- dimethyl -2- imidazolidinones and 3- methoxyl groups-N, N- dimethylpropionamide composition.
11. according to aligning agent for liquid crystal according to any one of claims 1 to 10, wherein also contain:Silane coupling agent, crosslinking
Agent or amination accelerating agent.
12. a kind of liquid crystal orientation film is using obtained from the aligning agent for liquid crystal described in any one of claim 1~11.
13. a kind of liquid crystal indicates element, with the liquid crystal orientation film described in claim 12.
Applications Claiming Priority (3)
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JP2015229489 | 2015-11-25 | ||
JP2015-229489 | 2015-11-25 | ||
PCT/JP2016/084841 WO2017090691A1 (en) | 2015-11-25 | 2016-11-24 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
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CN108604027A true CN108604027A (en) | 2018-09-28 |
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JP (1) | JP6747452B2 (en) |
KR (1) | KR20180085003A (en) |
CN (1) | CN108604027A (en) |
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CN113557471A (en) * | 2019-03-12 | 2021-10-26 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same |
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CN109923469B (en) * | 2016-09-13 | 2022-06-28 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
JP7193783B2 (en) * | 2018-01-19 | 2022-12-21 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same |
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CN104845642A (en) * | 2014-02-13 | 2015-08-19 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, phase difference film, manufacturing method for the phase difference film, polymer and compound |
JPWO2015060360A1 (en) * | 2013-10-23 | 2017-03-09 | 日産化学工業株式会社 | Liquid crystal aligning agent containing polyimide precursor and / or polyimide having thermally detachable group |
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JP6638396B2 (en) * | 2013-10-23 | 2020-01-29 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
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TWI673301B (en) * | 2014-05-30 | 2019-10-01 | 日商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 |
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CN102203662A (en) * | 2008-11-06 | 2011-09-28 | 日产化学工业株式会社 | Liquid crystal aligning agent |
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 |
CN104024932A (en) * | 2011-10-27 | 2014-09-03 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
WO2014157143A1 (en) * | 2013-03-25 | 2014-10-02 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
WO2015060363A1 (en) * | 2013-10-23 | 2015-04-30 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
JPWO2015060360A1 (en) * | 2013-10-23 | 2017-03-09 | 日産化学工業株式会社 | Liquid crystal aligning agent containing polyimide precursor and / or polyimide having thermally detachable group |
CN104845642A (en) * | 2014-02-13 | 2015-08-19 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, phase difference film, manufacturing method for the phase difference film, polymer and compound |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113557471A (en) * | 2019-03-12 | 2021-10-26 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same |
CN113557471B (en) * | 2019-03-12 | 2024-07-23 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same |
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TWI704183B (en) | 2020-09-11 |
TW201731958A (en) | 2017-09-16 |
JPWO2017090691A1 (en) | 2018-09-13 |
WO2017090691A1 (en) | 2017-06-01 |
KR20180085003A (en) | 2018-07-25 |
JP6747452B2 (en) | 2020-08-26 |
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