CN107077032A - Aligning agent for liquid crystal, liquid crystal orientation film and its liquid crystal has been used to represent element - Google Patents
Aligning agent for liquid crystal, liquid crystal orientation film and its liquid crystal has been used to represent element Download PDFInfo
- Publication number
- CN107077032A CN107077032A CN201580057130.1A CN201580057130A CN107077032A CN 107077032 A CN107077032 A CN 107077032A CN 201580057130 A CN201580057130 A CN 201580057130A CN 107077032 A CN107077032 A CN 107077032A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- formula
- carbon number
- aligning agent
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CCC(CCCC1)CCC1c1ccc(*)cc1 Chemical compound CCC(CCCC1)CCC1c1ccc(*)cc1 0.000 description 6
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
There is provided with high liquid crystal aligning, voltage retention and can realize that quick mitigation, the aligning agent for liquid crystal of high-contrast, liquid crystal orientation film and the liquid crystal of residual charge represent element.A kind of aligning agent for liquid crystal, it contains：At least one kind of polymer in the group being made up of polyamic acid and its imide amination polymer, the polyamic acid is obtained by the polycondensation reaction of the tetracarboxylic dianhydride's composition and the diamine component of the diamines comprising formula (B) of the tetracarboxylic dianhydride comprising formula (A)；And, the compound shown in formula (C).(m is 1~5 integer.X1For the n valency organic groups comprising aliphatic alkyl or aromatic hydrocarbyl of carbon number 1~20, n is 2~6 integer, R1、R2For the alkynyl of the alkyl, the alkenyl of carbon number 2~4 or carbon number 2~4 of hydrogen atom or the optional carbon number 1~4 with substituent, R1、R2At least one of there is the alkyl that is optionally substituted by a hydroxyl group.)
Description
Technical field
The present invention relates to apply parallel electric field to substrate to represent in element come the liquid crystal of the transverse electric field type of drive driven
The aligning agent for liquid crystal that uses, liquid crystal orientation film and its liquid crystal has been used to represent element.
Background technology
All the time, liquid-crystal apparatus is widely used as the expressed portion of PC, mobile phone, television receiver etc..Liquid crystal is filled
Put and for example possess：It is clamped in the liquid crystal layer between device substrate and filter substrate, the picture for applying electric field to liquid crystal layer
Plain electrode and common electrode, the alignment films of liquid crystal molecular orientation for controlling liquid crystal layer, for supplying to pixel electrode
The thin film transistor (TFT) (TFT) that switches over of electric signal etc..It is used as the type of drive of liquid crystal molecule, it is known to TN (twisted nematic,
Twisted Nematic) the longitudinal electric field mode such as mode, VA (vertical orientated, Vertical Alignment) mode；IPS is (flat
Face switch, In Plane Switching) mode, FFS (fringe field switching technology, Fringe Field Switching) mode
Deng Transverse electric-field type.In general, apply voltage with the conventional electrode to being formed at upper and lower base plate and make liquid crystal drive
Longitudinal electric field mode is compared, only the unilateral transverse electric field for forming electrode and applying electric field to the direction parallel to substrate to substrate
Mode has broad angle of visibility characteristic, and it is as can realize that the liquid crystal that high-quality is represented represents that element is known.
But, although the liquid crystal cells angle of visibility excellent of Transverse electric-field type, the electrode part formed in substrate
It is few, therefore, if the voltage retention of liquid crystal orientation film is poor, sufficient voltage will not be applied to liquid crystal, represent contrast reduction.
In addition, electrostatic is likely to accumulate in liquid crystal cells, even if applying the asymmetric voltage produced by driving, electric charge can be also accumulated in
In liquid crystal cells, these accumulated charges can cause the disorder of liquid crystal aligning or in the form of ghost, after image to representing to cause shadow
Ring, so that the expression quality of liquid crystal cell is significantly reduced.When being once again powered up in this state, stage in the early stage, liquid crystal point
Son is not well controlled and produces flicker (flicker) etc..Especially, compared with longitudinal electric field mode, Transverse electric-field type
In pixel electrode and common electrode distance it is near, therefore, highfield acts on alignment films, liquid crystal layer, thus exist it is this not
The problem of good situation easily becomes notable.
And then, IPS modes, FFS type of drive etc. drive what is be horizontally oriented relative to substrate using transverse electric field
In the mode of liquid crystal molecule, the stability of liquid crystal aligning also becomes important.If the stability of orientation is small, liquid crystal is driven for a long time
When, liquid crystal recovers less than original state, and contrast reduces, causes after image.
It is used as the method for charge accumulation caused by asymmetricization for solving to be driven by above-mentioned exchange, it is proposed that with following liquid
The liquid crystal display device of brilliant alignment films, the liquid crystal orientation film possesses：The 1st alignment films formed on electrode；And, in its table
The polymer formed by pyromellitic acid dianhydride and diamines and the 2nd low alignment films of the alignment films of resistance ratio the 1st formed on face, and
And, the charge accumulation caused by asymmetricization of exchange driving can be suppressed by reporting the device, and can quickly be relaxed and stored
Long-pending electric charge (patent document 1).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-167782 publications
The content of the invention
Problems to be solved by the invention
But, as liquid crystal represents the High precision of element in recent years, the level of above-mentioned requirements also becomes higher.In addition,
The side that parallel-oriented liquid crystal molecule is carried out relative to substrate is driven using transverse electric field in IPS modes, FFS type of drive etc.
In formula, the stability of the liquid crystal aligning under harsh and unforgiving environments, electric reliability also become important.Seek to meet complete with high level
The aligning agent for liquid crystal of the these requirements in portion.
It is an object of the present invention to provide can obtain representing member for the liquid crystal of IPS type of drive, FFS type of drive
There are especially important various characteristics for part, there is high liquid crystal aligning and high voltage holding ratio and then because of DC voltage
And the residual charge accumulated quickly relaxes, can be achieved the aligning agent for liquid crystal of the liquid crystal orientation film of high-contrast.
The solution used to solve the problem
The present inventor etc. are had made intensive studies to solve above-mentioned problem, and being as a result found that can be met with high level
The aligning agent for liquid crystal of above-mentioned characteristic, so as to complete the present invention.
Thus, the present invention is a kind of aligning agent for liquid crystal, it is characterised in that it contains：Selected from by polyamic acid and the polyamides
At least one kind of polymer in the group of the imide amination polymer composition of amino acid, the polyamic acid is to make to include following formula (A) institute
Show that tetracarboxylic dianhydride's composition of tetracarboxylic dianhydride occurs polycondensation reaction with the diamine component comprising diamines shown in following formula (B) and obtained
Arrive；And, the compound shown in following formula (C).
(in formula (B), m is 1~5 integer.)
(in formula (C), X1For the n valency organic groups comprising aliphatic alkyl or aromatic hydrocarbyl of carbon number 1~20；N is 2
~6 integer；R1And R2It is each independently hydrogen atom or optionally alkyl, the carbon number 2~4 of the carbon number 1~4 with substituent
Alkenyl or carbon number 2~4 alkynyl；R1And R2At least one of represent the alkyl that is optionally substituted by a hydroxyl group.)
The effect of invention
By using the obtained liquid crystal orientation film of aligning agent for liquid crystal by the present invention, can obtain for IPS type of drive,
The liquid crystal of FFS type of drive represents to have especially important various characteristics for element, has high liquid crystal aligning and height electricity
The residual charge pressed conservation rate and then accumulated by DC voltage quickly relaxes, the liquid crystal that contrast is high represents element.
It is still not clear and why foregoing result is resulted in by the aligning agent for liquid crystal of the present invention, but substantially speculate such as
Under.
In the main polymer chain for constituting it of the liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention, have in main chain
Have and handled and the flexible structure that can be sufficiently tensile and the aromatic series official that can be fully interacted with liquid crystal molecule by brushing
It can roll into a ball, therefore with high liquid crystal aligning.In addition, the carboxyl in compound and polymer shown in formula (C) is when burning till
Reaction, thus improves heat resistance, the decomposition object amount produced when burning till by liquid crystal orientation film is suppressed, therefore with high electricity
Press conservation rate.And then, friendship is formed by the reaction between the compound and the carboxyl of polymer shown in formula (C) in the polymer
It is coupled structure, thus improves film hardness, the influence of brushing cloth is not easily susceptible to when brushing is handled, therefore, used the liquid crystal
The liquid crystal of alignment films represents that element can suppress the contrast caused by brushing and reduce.In addition it is considered that：The liquid crystal of the present invention
Alignment films in the polymer backbone there is pi-electron conjugated system to expand obtained structure, therefore volumetric resistivity value is low, thus make because
DC voltage and the residual charge accumulated quickly relax.
Embodiment
<The imide amination polymer of polyamic acid and the polyamic acid>
The aligning agent for liquid crystal of the present invention contains：Constituted selected from the imide amination polymer by polyamic acid and the polyamic acid
Group at least one kind of polymer, the polyamic acid be make comprising following formula (A) tetracarboxylic dianhydride tetracarboxylic dianhydride into
Point with comprising diamines shown in following formula (B) diamine component generation polycondensation reaction obtained from；And, shown in following formula (C)
Compound.
In formula (B), m is 1~5, is preferably 1~3 integer.
In formula, X1For the n valency organic groups comprising aliphatic alkyl or aromatic hydrocarbyl of carbon number 1~20, preferably carbon
The aliphatic alkyl of number 1~5.N is 2~6, is preferably 3~4 integer.R1And R2It is each independently hydrogen atom or optionally tool
The alkyl that the alkynyl of the alkyl, the alkenyl of carbon number 2~4 or carbon number 2~4 by carbon number 1~4 of substituted base is constituted, preferably appoints
The alkyl of carbon number 1~4 of the choosing with substituent.Also, R1And R2At least one of represent the alkyl that is optionally substituted by a hydroxyl group, preferably
For hydroxyethyl.
<Tetracarboxylic dianhydride's composition>
Tetracarboxylic dianhydride's composition of aligning agent for liquid crystal for manufacturing the present invention contains the tetrabasic carboxylic acid two shown in above-mentioned formula (A)
Acid anhydride.The ratio of tetracarboxylic dianhydride shown in formula (A) is 20~80 moles of %, is preferably relative to whole 1 mole of tetracarboxylic dianhydrides
30~70 moles of %, more preferably 40~60 moles %, more preferably 40~50 moles of %.
<Other tetracarboxylic dianhydrides>
In tetracarboxylic dianhydride's composition for the aligning agent for liquid crystal for manufacturing the present invention, except the tetracarboxylic acid shown in above-mentioned formula (A)
Outside acid dianhydride, the tetracarboxylic dianhydride shown in following formula (1) can also be contained.
In formula (1), X is the organic group of 4 valencys, and its structure is not particularly limited.If including concrete example, it can include
Following formula (X-1)~(X-42) structure.
In formula (X-1), R3~R6It is each independently the alkyl or phenyl of hydrogen atom, carbon number 1~6, more preferably hydrogen
Atom or methyl.
As tetracarboxylic dianhydride, wherein from the viewpoint of the availability of compound, being preferably selected from by following formula (2) institute
Show at least one kind of tetracarboxylic dianhydride in the group of structure composition.
(in formula (2), X1To be at least one kind of in the group of structure composition as shown in above-mentioned formula (X-1)~(X-14).)
Due to can further improve the reliability of gained liquid crystal orientation film, thus be preferably only by (X-1)~(X-7) or
Etc (X-11) structure that aliphatic group is constituted, the more preferably structure shown in (X-1).And then, it is good in order to show
Liquid crystal aligning, be used as X1, particularly preferably following formula (X1-1) or (X1-2).
The ratio of tetracarboxylic dianhydride shown in formula (1) preferably 30~70 is rubbed relative to whole 1 mole of tetracarboxylic dianhydrides
You are %, more preferably 40~60 moles %, more preferably 50~60 moles of %.
<Diamine component>
The diamine component used in the present invention contains the diamines shown in above-mentioned formula (B).In formula (B), m for 1~5 integer,
Preferably 1~3 integer.
Foregoing diamine component is preferably, in addition to the diamines containing formula (B), also containing selected from by following formula (YD-1)
At least one kind of diamines in the group of~(YD-5) structure composition.
In formula (YD-1), A1For the nitrogen atom heterocycle of carbon number 3~15, Z1For hydrogen atom or optionally with substituent
The alkyl of carbon number 1~20.
In formula (YD-2), W1For the alkyl of carbon number 1~10, A21 valency for the carbon number 3~15 with nitrogen atom heterocycle has
Machine group or the disubstituted amido replaced by the aliphatic group of carbon number 1~6.
In formula (YD-3), W2For carbon number 6~15 and with the divalent organic group of 1~2 phenyl ring, W3For the Asia of carbon number 2~5
Alkyl or biphenylene, Z2For hydrogen atom, the alkyl or phenyl ring of carbon number 1~5, a is 0~1 integer.
In formula (YD-4), A3For the nitrogen atom heterocycle of carbon number 3~15.
In formula (YD-5), A4For the nitrogen atom heterocycle of carbon number 3~15, W5For the alkylidene of carbon number 2~5.
A in formula (YD-1), (YD-2), (YD-4) and (YD-5)1、A2、A3And A4Carbon number 3~15 nitrogen atom it is miscellaneous
Ring is not particularly limited.Wherein, pyrrolidines, pyrroles, imidazoles, pyrazoles, oxazoles, thiazole, piperidines, piperazine, pyridine, pyrrole can be included
Piperazine, indoles, benzimidazole, quinoline, isoquinolin etc., more preferably piperazine, piperidines, indoles, benzimidazole, imidazoles, carbazole or pyrrole
Pyridine.
As concrete example, the divalent organic group with nitrogen-atoms shown in following formula (YD-6)~(YD-21) can be included
Group.Due to can suppress by exchange driving caused by charge accumulation, therefore more preferably formula (YD-14)~formula (YD-21), especially
Preferably (YD-14) or (YD-18).
In formula (YD-14) and (YD-21), j is 0~3 integer, preferably 0~1.
In formula (YD-17), h is 1~3 integer, preferably 2~3.
The present invention polyamic acid and polyamic acid imide amination polymer in be selected from by above-mentioned formula (YD-1)~
(YD-5) ratio of at least one kind of diamines in the group of structure composition preferably 10~80 is rubbed relative to whole 1 mole of diamines
You are %, more preferably 20~60 moles %, more preferably 30~50 moles of %.
<Other diamines>
In polyamic acid contained by the aligning agent for liquid crystal of the present invention, except using the diamines shown in above-mentioned formula (B), being selected from
Outside at least one kind of diamines in the group being made up of above-mentioned formula (YD-1)~(YD-5), two shown in following formula (3) can also be used
Amine.Y in following formula (3)2For divalent organic group, its structure is not limited, and can also be mixed two or more.If exemplifying
Its concrete example, then can include following (Y-1)~(Y-102).
Wherein, in order to obtain good liquid crystal aligning, it is preferably linear high diamines, is used as Y2, more preferably Y-7,
Y-21~Y-23, Y-25~Y-27, Y-43~Y-46, Y-48, Y-63, Y-71, Y-73~Y-75, Y-98~Y-101 or Y-
102。
The ratio of diamines shown in formula (3) relative to 1 mole of whole diamines be preferably 0~40 mole of %, more preferably 0~
25 moles of %, more preferably 0~15 mole of %.
<Compound shown in formula (C)>
The aligning agent for liquid crystal of the present invention contains the compound (hereinafter also referred to specific compound) shown in following formula (C).
In above-mentioned formula (C), X1For the n valency organic groups comprising aliphatic alkyl or aromatic hydrocarbyl of carbon number 1~20；n
For 2~6 integer；R1And R2It is each independently hydrogen atom or optionally there is the alkyl by carbon number 1~4, the carbon number of substituent
The alkyl that 2~4 alkenyl or the alkynyl of carbon number 2~4 are constituted, R1And R2At least one of represent the alkyl that is optionally substituted by a hydroxyl group.
Wherein, from the viewpoint of liquid crystal aligning, the X of formula (C)1In be preferably not with the atom of carbonyl Direct Bonding
Form the carbon atom of aromatic rings.
In formula (C), n represents 2~6 integer.From the viewpoint of dissolubility, n is preferably 2~4.
In formula (C), R1And R2Be each independently hydrogen atom or optionally with substituent by carbon number 1~4 alkyl,
The alkyl that the alkenyl of carbon number 2~4 or the alkynyl of carbon number 2~4 are constituted, R1And R2At least one of represent the hydrocarbon that is optionally substituted by a hydroxyl group
Base.Wherein, from the viewpoint of reactivity, R1And R2At least one of be preferably following formula (3) shown in structure, enter one
Step is preferably the structure shown in following formula (4).
In formula (3), R3~R6Any in hydrogen atom, alkyl or the alkyl being optionally substituted by a hydroxyl group is represented independently of one another
Person.
As the preferred concrete example of above-mentioned specific compound, for example following compounds (C-1) can be included.
When the content of specific compound in aligning agent for liquid crystal is excessive, liquid crystal aligning, pre-tilt angle are impacted, content
When very few, it is impossible to obtain the effect of the present invention.Therefore, the content of specific compound is relative to (A) composition in aligning agent for liquid crystal
Polymer be preferably 0.1~20 mass %, more preferably 1~10 mass %.
<The manufacture method of polyamic acid>
It can be manufactured as the polyamic acid of polyimide precursor used in the present invention using method described below.It is specific and
Speech, can be by making tetracarboxylic dianhydride with diamines in presence of organic solvent with -20~150 DEG C, preferably with 0~50 DEG C of reaction
30 minutes~24 hours, preferably react 1~12 hour and manufacture.
From the dissolubility of monomer and polymer, the organic solvent used in above-mentioned reaction preferably N, N- dimethyl methyls
Acid amides, METHYLPYRROLIDONE, gamma-butyrolacton etc., they can use a kind or be mixed with two or more.
From the precipitation for being not susceptible to polymer and it is readily available from the viewpoint of HMW body, the polymerization in reaction system
The concentration of thing is preferably 1~30 mass %, more preferably 5~20 mass %.
Polyamic acid obtained from operating as above is by the way that reaction solution is sufficiently stirred for while being injected into poor solvent
In, polymer can be made to separate out and reclaim.In addition, after being separated out and being cleaned with poor solvent for several times by progress, carrying out normal temperature and doing
Dry or heat drying, results in the powder through refined polyamic acid.Poor solvent is not particularly limited, can enumerate water outlet,
Methanol, ethanol, 2- propyl alcohol, hexane, butyl cellosolve, acetone, toluene etc., preferably water, methanol, ethanol, 2- propyl alcohol etc..
<The manufacture method of polyimides>
The polyimides used in the present invention can be manufactured by carrying out imidizate to foregoing polyamides acid.
It is foregoing obtained to the reaction by diamine component and tetracarboxylic dianhydride when manufacturing polyimides by polyamic acid
It is easy that the chemical imidization of catalyst is added in polyamic acid solution.Chemical imidization is carried out at a lower temperature
The reduction of polymer molecular weight is not susceptible to during imidization reaction, and imidizate, so it is preferred that.
Chemical imidization can be by making the polymer of desired imidizate in organic solvent in base catalyst and acid
It is stirred to carry out in the presence of acid anhydride.As organic solvent, the solvent used when aforementioned polymeric can be used to react.It is used as alkali
Property catalyst, can include pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc..Wherein, it is adapted to promote reaction due to possessing
Alkalescence, therefore preferably pyridine.In addition, as acid anhydrides, acetic anhydride, trihemellitic acid acid anhydride, benzenetetrahydride etc. can be included, its
In, during using acetic anhydride, reaction is easily refined after terminating, so it is preferred that.
Carry out imidizate that can be following：Carry out imidization reaction when temperature for -20~140 DEG C, be preferably 0~
100 DEG C, the reaction time is 1~100 hour.The amount of base catalyst is 0.5~30 times mole of polyamide acidic group, is preferably 2
~20 times moles, the amount of acid anhydrides is 1~50 times mole of polyamide acidic group, is preferably 3~30 times moles.The acyl of resulting polymers
Imines rate can be controlled by adjusting catalytic amount, temperature, reaction time.
Catalyst of addition etc. is remained in solution after the imidization reaction of polyamic acid, it is preferred, therefore, that logical
Cross following means to reclaim gained imide amination polymer, be redissolved and be made the aligning agent for liquid crystal of the present invention with organic solvent.
It is above-mentioned it is such operate obtained from polyimides solution by being sufficiently stirred for while being injected into poor solvent
In, polymer can be separated out.Carry out after separating out and being cleaned with poor solvent for several times, carry out air drying or heat drying, energy
Access the powder through refined polymer.
Foregoing poor solvent is not particularly limited, and can include methanol, 2- propyl alcohol, acetone, hexane, butyl cellosolve, heptan
Alkane, MEK, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene etc., preferably methanol, ethanol, 2- propyl alcohol, acetone etc..
<Aligning agent for liquid crystal>
The aligning agent for liquid crystal of the present invention possesses the form for the solution that component of polymer is dissolved in organic solvent.Point of polymer
Son amount is preferably 2,000~500,000, more preferably 5,000~300,000, more preferably 10 with Weight-average molecular gauge,
000~100,000.In addition, number-average molecular weight is preferably 1,000~250,000, more preferably 2,500~150,000, enter one
Step is preferably 5,000~50,000.
The polymer concentration of the aligning agent for liquid crystal of the present invention can suitably become according to the setting of the thickness of the film of desired formation
More, from forming uniform and flawless film this point, preferably more than 1 mass %, from the storage stability of solution
Viewpoint is set out, and is preferably set to below 10 mass %.The concentration of polymer is particularly preferably 2~8 mass %.
As long as the solvent of the organic solvent uniform dissolution component of polymer contained in aligning agent for liquid crystal is not just limited especially
It is fixed.If including its concrete example, DMF, N, N- diethylformamides, N, N- dimethyl second can be included
Acid amides, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, N- methyl caprolactams, 2-Pyrrolidone, N- vinyl-
2-Pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl sulfone, gamma-butyrolacton, 1,3- dimethyl-imidazolinones, 3- methoxyl groups-N, N- diformazan
Base propionamide etc..They can use a kind or be mixed with two or more.Even in addition, can not be uniformly molten during individualism
The solvent of depolymerization polymer component, as long as in the range of polymer is not separated out, it is possible to mix into above-mentioned organic solvent.
, can be with addition to containing the organic solvent for dissolving component of polymer in the aligning agent for liquid crystal of the present invention
Solvent containing painting film uniformity when aligning agent for liquid crystal being coated on to substrate for improving.The solvent is usually using surface
Power is less than the solvent of above-mentioned organic solvent.As its concrete example, can include ethyl cellosolve, butyl cellosolve, ethyl card must
Alcohol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1- methoxy-2-propanols, 1- ethyoxyl -2- propyl alcohol, 1- fourth oxygen
Base -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propane diols -1- monomethyl ethers -2-
Acetic acid esters, propane diols -1- list ethylether -2- acetic acid esters, butyl cellosolve acetate, DPG, 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 also group
Conjunction uses two or more.
In the aligning agent for liquid crystal of the present invention, in addition to the foregoing, as long as in the range of effect of the present invention is not damaged,
The polymer in addition to the polyimide precursor of the present invention and the polymer of polyimides can also be added；Taken for changing liquid crystal
To the dielectric substance or conductive materials of the electrical characteristics such as the dielectric constant of film, electric conductivity；For improving the close of liquid crystal orientation film and substrate
The silane coupler of conjunction property；The cross-linked compound of the hardness of film, consistency when liquid crystal orientation film is made for improving；And
Imidizate accelerator of imidizate when burning till film for efficiently promoting polyamic acid etc..
<The manufacture method of liquid crystal orientation film>
The liquid crystal orientation film of the present invention is film obtained from above-mentioned aligning agent for liquid crystal is coated on substrate and drying, burnt till.
As the substrate for the aligning agent for liquid crystal that be coated with the present invention, as long as the high substrate of the transparency is just not particularly limited, it can make
With plastic bases such as glass substrate, silicon nitride board, acrylic compounds substrate, polycarbonate substrate etc..The viewpoint for the chemical industry skill that conforms to the principle of simplicity
Set out, preferably use the substrate for being formed with ITO electrode for driving liquid crystal etc..In addition, the liquid crystal of reflection-type is represented in element,
The opaque material such as silicon wafer can be used if being only unilateral substrate, electrode now can also use aluminium etc. can reflected light
Material.
As the coating method of the aligning agent for liquid crystal of the present invention, spin-coating method, print process, ink-jet method etc. can be included.Coating
Drying, firing process after the aligning agent for liquid crystal of the present invention can select arbitrary temperature and time.Generally, in order to fully go
Except contained organic solvent, preferably dried 1 minute~10 minutes with 50~120 DEG C, preferably burn till 5 with 150~300 DEG C thereafter
Minute~120 minutes.The thickness of film after burning till is not particularly limited, when excessively thin, and liquid crystal represents the reliability of element sometimes
Reduction, therefore be 5~300nm, preferably 10~200nm.
As the method that orientation process is carried out to gained liquid crystal orientation film, brushing method, light orientation position logos etc. can be included.
When carrying out brushing processing for liquid crystal orientation film, existing brushing device can be used.It is used as brushing cloth now
Material, cotton, artificial silk, nylon etc. can be included.
As the concrete example of light orientation position logos, following method can be included：Foregoing film coated surface is irradiated along one
Determine the radioactive ray of direction polarization, further heated sometimes with 150~250 DEG C of temperature, so as to assign liquid crystal aligning
Ability.As radioactive ray, ultraviolet and luminous ray with 100~800nm wavelength can be used.Wherein, it is however preferred to have
The ultraviolet of 100~400nm wavelength, the particularly preferably ultraviolet with 200~400nm wavelength.In addition, in order to improve liquid crystal
Orientation, can be while carry out heating while irradiation radioactive ray for applying ilm substrate with 50~250 DEG C.The irradiation of foregoing radioactive ray
Amount is preferably 1~10,000mJ/cm2, particularly preferably 100~5,000mJ/cm2.Aforesaid operations and the liquid crystal orientation film made
Liquid crystal molecule can be made stably to be orientated towards certain direction.
The film of polarization radioactive ray has been irradiated as described above then using comprising the group for selecting Free water and organic solvent to constitute
In at least one kind of solvent carry out contact processing.
As long as the solvent for the analyte that the solvent dissolving used in contact processing is generated by light irradiation, just without special
Limit.As concrete example, water outlet, methanol, ethanol, 2- propyl alcohol, acetone, MEK, 1- methoxy-2-propanols, 1- first can be enumerated
Epoxide -2- propanol acetates, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methoxy methyl propionates, 3- second
Epoxide ethyl propionate, propyl acetate, butyl acetate, cyclohexyl acetate etc..Two or more can be applied in combination in these solvents.
As above-mentioned solvent, from the viewpoint of versatility, security, Free water, 2- propyl alcohol, 1- methoxies are more preferably selected
It is at least one kind of in the group of base -2- propyl alcohol and ethyl lactate composition.Particularly preferably 1- methoxy-2-propanols or ethyl lactate.
In the present invention, film contact with the solution comprising the organic solvent processing for having irradiated polarization radioactive ray passes through at dipping
Reason, spraying (spraying) processing etc. preferably make film fully contact such processing with liquid to carry out.These, it is preferred to, film is existed
Impregnation process preferably 10 seconds~1 hour, the method for more preferably 1~30 minute in solution comprising organic solvent.Contact processing can
To carry out being heated at normal temperatures, preferably implemented with 10~80 DEG C, more preferably with 20~50 DEG C of implementations.In addition, root
According to need can also implement ultrasonic wave etc. be used for improve contact means.
After above-mentioned contact processing, in order to remove the organic solvent in used solution, it can carry out using water, first
The rinsing of the low boiling point solvents such as alcohol, ethanol, 2- propyl alcohol, acetone, MEK (flushing), any one of dry or both.
And then, in order to by solvent seasoning and make the strand reorientation in film, the above-mentioned film handled with solvent contact
It can be heated with more than 150 DEG C.
It is used as heating-up temperature, preferably 150~300 DEG C.Temperature is higher, more can promote the reorientation of strand, but temperature
When too high, it is possible to the decomposition of strand.Therefore, as heating-up temperature, more preferably 180~250 DEG C, particularly preferably
200~230 DEG C.
When heat time is too short, it is possible to the effect of the present invention can not be obtained, when the heat time is long, strand is possible to
Decompose, it is therefore preferable that being 10 seconds~30 minutes, more preferably 1 minute~10 minutes.
The liquid crystal orientation film of the present invention is suitable as the liquid crystal of the Transverse electric-field types such as IPS type of drive, FFS type of drive
The liquid crystal orientation film of element is represented, represents that the liquid crystal orientation film of element is particularly useful as the liquid crystal of FFS type of drive.
<Liquid crystal represents element>
The liquid crystal of the present invention represents that element is obtained as below：The subsidiary liquid crystal obtained by aligning agent for liquid crystal of the invention is obtained to take
To after the substrate of film, liquid crystal cells are made using known method, and element is represented to obtain liquid crystal using the liquid crystal cells.
As one of the preparation method of liquid crystal cells, said so that the liquid crystal of passive-matrix structure represents element as an example
It is bright.Alternatively, it is also possible to be constitute graphical representation each pixel portion be provided with TFT (thin film transistor (TFT), Thin Film
) etc. Transistor the liquid crystal of the active matrix structure of conversion element represents element.
First, prepare transparent glass substrate of electrode, common electrode is set on one substrate, set on another substrate
Segment electrode (segment electrode).ITO electrode can be for example made in these electrodes, be patterned to that the phase can be realized
The graphical representation of prestige.Then, dielectric film is set to cover common electrode and segment electrode on each substrate.Insulating film can such as be made
Into including the SiO formed by sol-gel process2-TiO2Film.
Then, the liquid crystal orientation film of the present invention is formed on each substrate.
Then, another substrate is overlapped in the mutual orientation aspectant mode of film surface on one substrate, around with close
Closure material is bonded.For control base board gap, sept has generally been mixed into advance in encapsulant.It is further preferred, that not setting
Putting part in the face of encapsulant and also having spread in advance is used for the sept in control base board gap.The part of encapsulant is set in advance
Putting can be from the opening portion of outside filling liquid crystal.
Then, by the opening portion set in encapsulant, noted into the space surrounded by two plate bases and encapsulant
Enter liquid crystal material.Thereafter, the opening portion is sealed with bonding agent.Injection can use vacuum impregnation, can also use big
The method that capillarity is utilized in gas.As liquid crystal material, it can use in positive type liquid crystal material and negative type liquid crystal material
It is any.Then, the setting of polarizer is carried out.Specifically, pasted on the surface back to liquid crystal layer side of two plate bases
A pair of polarizers.By the way that via above process, the liquid crystal for resulting in the present invention represents element.The liquid crystal represents that element can be used
The liquid crystal orientation film obtained by the present invention is used as liquid crystal orientation film, therefore ghost characteristic becomes excellent, can be suitably employed in
Big picture and the liquid crystal TV set of high-resolution etc..
Embodiment
Hereinafter, include embodiment etc. to illustrate for the present invention.It should illustrate, the present invention is not limited to these realities
Apply example.Abbreviation used below is as follows.
NMP：METHYLPYRROLIDONE
GBL：Gamma-butyrolacton
BCS：Butyl cellosolve
Acid dianhydride (A)：The tetracarboxylic dianhydride of following formula (A).
Acid dianhydride (B)：The tetracarboxylic dianhydride of following formula (B).
Acid dianhydride (C)：The tetracarboxylic dianhydride of following formula (C).
DA-1：The diamines of following formula (DA-1)
DA-2：The diamines of following formula (DA-2)
Specific compound A：Following compounds (Primid XL552, エ system ス ケ ミ ー company systems)
The assay method of various characteristics described below.
[viscosity]
It is 1.1mL, cone rotor TE-1 in sample size using E type viscosimeters TVE-22H (Toki Sangyo Co., Ltd.'s system)
It is measured at (1 ° 34 ', R24), 25 DEG C of temperature.
[molecular weight]
It is measured, is calculated with polyethylene glycol and PEO conversion by GPC (normal temperature gel permeation chromatography) device
It is worth the number-average molecular weight (Mn) and weight average molecular weight (Mw) of meter.
GPC devices：Shodex company systems (GPC-101)
Post：Shodex company systems (KD803, KD805 series connection)
Column temperature：50℃
Eluent：DMF (is used as additive, lithium bromide monohydrate (LiBrH2O) it is 30mmol/
L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) are that 30mmol/L, tetrahydrofuran (THF) are 10ml/L)
Flow velocity：1.0ml/ minute
Standard curve making standard sample：TOSOH Co., Ltd TSK standards PEO (weight average molecular weight (Mw)
About 900,000,150,000,100,000,30,000) and Polymer Laboratories Ltd. polyethylene glycol (peak values
Molecular weight (Mp) about 12,000,4,000,1,000).It is overlapping in order to avoid peak, respectively for by 900,000,100,000,
12,000 and 1,000 this 4 kinds samples that are mixed to get and by 150,000,30,000 and 4,000 this 3 kinds samples that are mixed to get
This two classes sample of product is measured.
[making of liquid crystal cells]
Make the liquid crystal cells for possessing the composition that FFS mode liquid crystal represents element.
On the attached electroded glass substrate (vertical 30mm × horizontal 50mm × thickness 0.7mm) prepared, as the 1st layer,
Form for constituting counter electrode and possessing the ITO electrode of solid shape pattern.On the 1st layer of counter electrode, the 2nd is used as
Layer, forms the SiN (silicon nitride) of the film forming using CVD (chemical vapor deposition, chemical vapor deposition) methods
Film.The thickness of 2nd layer of SiN film is 500nm, and it is used as interlayer dielectric function.On the 2nd layer of SiN film, is used as
3 layers, configuration by ito film pattern formed by comb teeth-shaped pixel electrode, so as to form the 1st pixel and the 2nd pixel the two pictures
Element.The size of each pixel is：Long 10mm and wide about 5mm.Now, the 1st layer of counter electrode and the 3rd layer of pixel electrode are because of
The effect of 2 layers of SiN film and be electrically insulated.
There is 3rd layer of pixel electrode " く " font electrode key element that middle body bends to be constituted through multiple arrangements
Comb teeth-shaped shape.The width of the width of each electrode key element is 3 μm, between electrode key element at intervals of 6 μm.Form each pixel
" く " font electrode key element for being bent by middle body of pixel electrode constituted through multiple arrangements, therefore the shape of each pixel
Shape is not oblong-shaped, and possesses " く " word being bent in the same manner as electrode key element in middle body, similar to runic
Shape.Also, each pixel is split up and down using its central bent portion as boundary, with the 1st region on the upside of bent portion and
2nd region of downside.
When contrasting the 1st region and 2 region of each pixel, the formation direction of the electrode key element of their pixel electrode is constituted
It is different.That is, during using the brushing direction of aftermentioned liquid crystal orientation film as benchmark, in the 1st region of pixel, so that+10 ° of angle is presented
The mode of degree (clockwise) forms the electrode key element of pixel electrode, in the 2nd region of pixel, (suitable with the angle for being presented -10 °
Hour hands) mode form the electrode key element of pixel electrode.That is, the 1st region of each pixel is constituted as follows with the 2nd region：By
The side for the spinning movement (plane switching) liquid crystal, in real estate for applying voltage between pixel electrode and counter electrode and inducing
To opposite direction each other.
Then, what is prepared with after 1.0 μm of filter filtering gained aligning agent for liquid crystal, being coated on using spin coating is above-mentioned
Attached electroded substrate and the back side are formed with ito film and with the glass substrate highly for 4 μm of column spacer.
After drying 5 minutes on 80 DEG C of hot plate, carried out with 230 DEG C of heated air circulation type baking oven burning till for 20 minutes, so as to form thickness
For 100nm film.Implement the orientation process such as brushing, polarized UV rays irradiation to the coated surface, so as to obtain band liquid crystal aligning
The substrate of film.Using two above-mentioned plate bases as one group, the printing and sealing agent on substrate, and with liquid crystal aligning film surface face-to-face,
Differently- oriented directivity is pasted after another 1 plate base for 0 ° of mode, makes sealant cures to make dummy cell.Should by depressurizing injection normal direction
Liquid crystal MLC-2041 (MERCK CORPORATION systems) is injected in dummy cell, inlet is sealed and obtains FFS driving liquid crystal lists
Member.Thereafter, gained liquid crystal cells are heated 1 hour with 110 DEG C, placed after a Dinner, evaluated for each.
[evaluation of liquid crystal aligning]
The frequency that the liquid crystal cells obtained by above-mentioned preparation method are applied under 60 DEG C of isoperibol to 168 hours is
30Hz and relative transmittance reach 100% alternating voltage.Thereafter, make be between the pixel electrode of liquid crystal cells and counter electrode
Existing short-circuit condition, keeps the state to place at room temperature one day.After placement, liquid crystal cells are arranged on vertical with polarizing axis
Between 2 polarizers that mode is configured, backlight is lighted in the state of no applied voltage, minimum is reached with the brightness of transmitted light
Mode adjusts the arrangement angles of liquid crystal cells.Also, calculating makes liquid crystal cells reach most dark angle from the 2nd region of the 1st pixel
Anglec of rotation when degree rotation is untill the 1st region reaches most dark angle is as angle △.For the 2nd pixel similarly,
2nd region and the 1st region are contrasted, same angle △ is calculated.Also, calculate the angle △ of the 1st pixel and the 2nd pixel
The average value of value evaluates liquid crystal aligning as the angle △ of liquid crystal cells according to the size of the value.That is, angle △ value
Hour, liquid crystal aligning is good.
[evaluation of voltage retention (VHR) (backlight aging patience (voltage retention 1))]
Forming thickness on the attached electroded glass substrate (vertical 30mm × horizontal 50mm × thickness 0.7mm) prepared is
35nm ITO electrode, electrode is vertical 40mm, horizontal 10mm candy strip.Then, by aligning agent for liquid crystal with 1.0 μm of filter
After filtering, it is coated on by spin coating on the above-mentioned attached electroded substrate prepared.Dried 5 minutes on 50 DEG C of hot plate
Afterwards, carried out burning till for 20 minutes with 230 DEG C of IR formulas baking oven, form the film that thickness is 100nm, taken so as to obtain subsidiary liquid crystal
To the substrate of film.The liquid crystal orientation film is subjected to brushing (roller diameter with rayon cloth：120mm, roller rotating speed：1000rpm, movement
Speed：20mm/ seconds, by give as security length：After 0.4mm), the ultrasonic irradiation of 1 minute is carried out in pure water to be cleaned, passes through drum
Wind is made a return journey except water droplet, is then dried 15 minutes with 80 DEG C, is obtained the substrate of subsidiary liquid crystal orientation film.
Prepare the substrate of 2 above-mentioned subsidiary liquid crystal orientation films, spread 4 μm of interval on 1 liquid crystal aligning film surface wherein
After thing, printing and sealing agent from it, by brushing direction as reversely and film surface toward each other in the way of paste another 1 plate base.Its
Afterwards, sealant cures are made to make dummy cell.By depressurizing injection liquid crystal MLC-2041 (MERCK in the injection normal direction dummy cell
CORPORATION systems), seal inlet and obtain liquid crystal cells.Thereafter, gained liquid crystal cells are heated 1 hour with 110 DEG C,
A Dinner is placed at 23 DEG C, so as to obtain VHR determination units.Then, by the unit in 70 DEG C of baking oven in LED/light source
The aging of progress 72 hours under (1000cd).
After the backlight aging for carrying out 72 hours, apply the 1V voltages of 60 microseconds to the unit at a temperature of 60 DEG C, determine
Voltage after 100 milliseconds, voltage can be remained which kind of degree as VHR, VHR backlights be evaluated by the size of the value old
Change patience.That is, the value of the VHR is bigger, then VHR backlights aging patience is better.
[black level evaluation]
It will be arranged on the liquid crystal cells that above-mentioned (making of liquid crystal cells) equally make in the vertical mode of polarizing axis
Between 2 polarizers of configuration, backlight is lighted in the state of no applied voltage, in the way of the brightness of transmitted light reaches minimum
Adjust the arrangement angles of liquid crystal cells.The digital CCD camera " C8800-21C " manufactured using creek pine ホ ト ニ Network ス companies, it is right
The liquid crystal cells are observed, by analysis software " the ExDcam Image capture of the image of shooting the said firm
Software " carries out quantizing for brightness.If the brightness value of the liquid crystal cells is 500~600, " good " is denoted as, if brightness
It is worth for more than 500~600, then is denoted as " bad ".
[relaxation properties of accumulated charge]
It will be arranged on the liquid crystal cells that above-mentioned (making of liquid crystal cells) equally make in the vertical mode of polarizing axis
Between 2 polarizers of configuration, in the state of same potential is made in pixel electrode and counter electrode short circuit, from 2 polarizations
The lower section irradiation LED backlight of piece, the side of minimum is reached with the brightness of the LED backlight transmitted light determined in the top of 2 polarizers
Formula adjusts the angle of liquid crystal cells.
Then, while the liquid crystal cells are applied with the square wave that frequency is 30Hz, while determining the V-T at a temperature of 23 DEG C
Characteristic (voltage-transmission rate characteristic), calculates the alternating voltage that relative transmittance reaches 23%.Then, apply relative transmittance to reach
To 23% alternating voltage and frequency for 30Hz square wave 5 minutes after, overlapping+1.0V DC voltage and its is driven 30 points
Clock.Thereafter, DC voltage is cut off, only applies the rectangle that relative transmittance reaches that 23% alternating voltage and frequency are 30Hz again
Ripple 20 minutes.
The mitigation of accumulated charge is faster, then charge accumulation during overlapping DC voltage in liquid crystal cells is also faster, therefore
On the relaxation properties of accumulated charge, by from the relative transmittance after firm overlapping DC voltage for more than 30% state by
Untill 30 minutes, the situation that relative transmittance is reduced to less than 28% is defined and is evaluated as " good ".Even if by self-overlapped direct current
When voltage was risen by 30 minutes, the situation that relative transmittance is not reduced to less than 28% yet is defined and is evaluated as " bad ".
(synthesis example 1)
Nitrogen atmosphere is made in the 3L four-neck flasks of subsidiary agitating device, DA-1 79.4g (0.33mol) are measured, in addition,
DA-2 64.8g (0.33mol) are measured, NMP 911g and GBL 911g, one side supplying nitrogen are added while stirring and making its molten
Solution.While the diamine solution is stirred, while addition acid dianhydride (C) 65.0g (0.33mol), is stirred at room temperature after 2 hours, adds
Acid adding dianhydride (A) 86.1g (0.29mol), and then NMP 390g and GBL 390g are added, in a nitrogen atmosphere with 40 DEG C of stirrings 30
Hour, so as to obtain polyamic acid solution (PAA-1).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 215mPas.
The Mn of the polyamic acid is that 15,773, Mw is 31,242.
(synthesis example 2)
Nitrogen atmosphere is made in the 3L four-neck flasks of subsidiary agitating device, DA-1 95.3g (0.39mol) are measured, in addition,
DA-2 51.8g (0.26mol) are measured, NMP 939g and GBL 939g, one side supplying nitrogen are added while stirring and making its molten
Solution.While the diamine solution is stirred, while addition acid dianhydride (C) 65.0g (0.33mol), is stirred at room temperature after 2 hours, adds
Acid adding dianhydride (A) 86.1g (0.29mol), and then NMP 402g and GBL 402g are added, in a nitrogen atmosphere with 40 DEG C of stirrings 30
Hour, so as to obtain polyamic acid solution (PAA-2).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 221mPas.
The Mn of the polyamic acid is that 14,773, Mw is 32,212.
(synthesis example 3)
Nitrogen atmosphere is made in the 3L four-neck flasks of subsidiary agitating device, DA-1 79.4g (0.33mol) are measured, in addition,
DA-2 64.8g (0.33mol) are measured, NMP 859g and GBL 859g, one side supplying nitrogen are added while stirring and making its molten
Solution.While the diamine solution is stirred, while addition acid dianhydride (C) 65.0g (0.33mol), is stirred at room temperature after 2 hours, adds
Acid adding dianhydride (B) 63.8g (0.29mol), and then NMP 369g and GBL 369g are added, in a nitrogen atmosphere with 40 DEG C of stirrings 30
Hour, so as to obtain polyamic acid solution (PAA-3).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 207mPas.
The Mn of the polyamic acid is that 13,853, Mw is 28,251.
(synthesis example 4)
Nitrogen atmosphere is made in the 3L four-neck flasks of subsidiary agitating device, DA-1 79.4g (0.33mol) are measured, in addition,
DA-2 64.8g (0.33mol) are measured, NMP 839g and GBL 839g, one side supplying nitrogen are added while stirring and making its molten
Solution.While the diamine solution is stirred, while addition acid dianhydride (C) 122.3g (0.62mol), and then add NMP 360g and GBL
360g, is stirred 30 hours with 40 DEG C, so as to obtain polyamic acid solution (PAA-4) in a nitrogen atmosphere.The polyamic acid solution
25 DEG C of temperature at viscosity be 212mPas.The Mn of the polyamic acid is that 14,255, Mw is 28,373.
(synthesis example 5)
Nitrogen atmosphere is made in the 3L four-neck flasks of subsidiary agitating device, DA-2 129.5g (0.65mol) are measured, added
NMP 884g and GBL 884g, one side supplying nitrogen are while stirring and dissolving it.While the diamine solution is stirred, while addition
Acid dianhydride (C) 65.0g (0.33mol), was stirred at room temperature after 2 hours, added acid dianhydride (A) 86.1g (0.29mol), and then
NMP 379g and GBL 379g are added, are stirred 30 hours with 40 DEG C in a nitrogen atmosphere, so as to obtain polyamic acid solution (PAA-
5).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 225mPas.The Mn of the polyamic acid is that 12,799, Mw is 33,
192。
(synthesis example 6)
Nitrogen atmosphere is made in the 3L four-neck flasks of subsidiary agitating device, DA-1 91.6g (0.38mol) are measured, in addition,
DA-2 74.7g (0.38mol) are measured, NMP 661g and GBL 661g, one side supplying nitrogen are added while stirring and making its molten
Solution.While the diamine solution is stirred, while addition acid dianhydride (C) 67.7g (0.35mol), is stirred at room temperature after 2 hours, adds
Acid adding dianhydride (A) 99.3g (0.34mol), and then NMP 283g and GBL 283g are added, in a nitrogen atmosphere with 40 DEG C of stirrings 30
Hour, so as to obtain polyamic acid solution (PAA-6).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 583mPas.
The Mn of the polyamic acid is that 11,141, Mw is 21,889.
(synthesis example 7)
Nitrogen atmosphere is made in the 3L four-neck flasks of subsidiary agitating device, DA-1 73.3g (0.30mol) are measured, in addition,
DA-2 59.8g (0.30mol) are measured, NMP 674g and GBL 674g, one side supplying nitrogen are added while stirring and making its molten
Solution.While the diamine solution is stirred, while addition acid dianhydride (C) 50.0g (0.26mol), is stirred at room temperature after 2 hours, adds
Acid adding dianhydride (A) 79.4g (0.27mol), and then NMP 288g and GBL 288g are added, in a nitrogen atmosphere with 40 DEG C of stirrings 30
Hour, so as to obtain polyamic acid solution (PAA-7).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 117mPas.
The Mn of the polyamic acid is that 8,953, Mw is 19,521.
(embodiment 1)
The polyamic acid solution (PAA-1) that input is obtained by synthesis example 1 into the 5L conical flasks equipped with stirrer
1861g, and add NMP 578g, 3- glycidoxypropyl group triethoxysilanes 1.8g, specific compound A 5.4g, GBL
122g and BCS 642g, using magnetic stirrer 2 hours, so as to obtain aligning agent for liquid crystal (A-1).
(embodiment 2)
The polyamic acid solution (PAA-2) that input is obtained by synthesis example 2 into the 5L conical flasks equipped with stirrer
1861g, and add NMP 578g, 3- glycidoxypropyl group triethoxysilanes 1.8g, specific compound A5.4g, GBL
122g and BCS 642g, using magnetic stirrer 2 hours, so as to obtain aligning agent for liquid crystal (A-2).
(embodiment 3)
Polyamic acid solution (PAA-6) 371g that input is obtained by synthesis example 6 into the 3L conical flasks equipped with stirrer,
And add NMP 84.6g, 3- glycidoxypropyl group triethoxysilanes 0.53g, specific compound A 1.6g, GBL 201g and
BCS 165g, using magnetic stirrer 2 hours, so as to obtain aligning agent for liquid crystal (A-3).
(embodiment 4)
Polyamic acid solution (PAA-7) 213g that input is obtained by synthesis example 7 into the 2L conical flasks equipped with stirrer,
And add NMP 101g, 3- glycidoxypropyl group triethoxysilanes 0.25g, specific compound A 0.74g, GBL 146g and
BCS 109g, using magnetic stirrer 2 hours, so as to obtain aligning agent for liquid crystal (A-4).
(comparative example 1)
The polyamic acid solution (PAA-3) that input is obtained by synthesis example 3 into the 5L conical flasks equipped with stirrer
1861g, and add NMP 578g, 3- glycidoxypropyl group triethoxysilanes 1.8g, specific compound A 5.4g, GBL
122g and BCS 642g, using magnetic stirrer 2 hours, so as to obtain aligning agent for liquid crystal (B-1).
(comparative example 2)
The polyamic acid solution (PAA-4) that input is obtained by synthesis example 4 into the 5L conical flasks equipped with stirrer
1861g, and add NMP 578g, 3- glycidoxypropyl group triethoxysilanes 1.8g, specific compound A 5.4g, GBL
122g and BCS 642g, using magnetic stirrer 2 hours, so as to obtain aligning agent for liquid crystal (B-2).
(comparative example 3)
The polyamic acid solution (PAA-5) that input is obtained by synthesis example 5 into the 5L conical flasks equipped with stirrer
1861g, and add NMP 578g, 3- glycidoxypropyl group triethoxysilanes 1.8g, specific compound A 5.4g, GBL
122g and BCS 642g, using magnetic stirrer 2 hours, so as to obtain aligning agent for liquid crystal (B-3).
(comparative example 4)
The polyamic acid solution (PAA-1) that input is obtained by synthesis example 1 into the 5L conical flasks equipped with stirrer
1861g, and NMP 583g, 3- glycidoxypropyl group triethoxysilane 1.8g, GBL 122g and BCS 642g are added, utilize
Magnetic stirrer 2 hours, so as to obtain aligning agent for liquid crystal (B-4).
[table 1]
Industrial applicability
By the present invention the obtained liquid crystal orientation film of aligning agent for liquid crystal as IPS type of drive, FFS type of drive liquid crystal
Represent that element, the liquid crystal orientation film of liquid crystal TV set are particularly useful.
It should illustrate, by the Japanese patent application submitted on October 20th, 2014 No. 2014-213835 and 2 months 2015 20
The full content of the specification of Japanese patent application 2015-032093, claims and the summary day submitted is quoted so far,
It is used as the disclosure of description of the invention.
Claims (10)
1. a kind of aligning agent for liquid crystal, it is characterised in that it contains：
At least one kind of polymer in the group being made up of the imide amination polymer of polyamic acid and the polyamic acid, it is described
Polyamic acid is to make tetracarboxylic dianhydride's composition of the tetracarboxylic dianhydride comprising following formula (A) and comprising diamines shown in following formula (B)
Diamine component occur polycondensation reaction obtained from；And
The compound represented with following formula (C),
In formula (B), m is 1~5 integer,
In formula (C), X1For the n valency organic groups comprising aliphatic alkyl or aromatic hydrocarbyl of carbon number 1~20；N for 2~6 it is whole
Number；R1And R2It is each independently hydrogen atom or optionally with substituent by the alkyl of carbon number 1~4, the alkenyl of carbon number 2~4
Or the alkyl that the alkynyl of carbon number 2~4 is constituted, R1And R2At least one of for the alkyl that is optionally substituted by a hydroxyl group.
2. aligning agent for liquid crystal according to claim 1, wherein, 20~80 moles of % in tetracarboxylic dianhydride's composition are
The tetracarboxylic dianhydride of formula (A).
3. aligning agent for liquid crystal according to claim 1 or 2, wherein, 20~80 moles of % in the diamine component are formula
(B) diamines.
4. according to aligning agent for liquid crystal according to any one of claims 1 to 3, wherein, the diamine component contains selected under
At least one kind of diamines in the group for the structure composition for stating formula (YD-1)~(YD-5),
In formula (YD-1), A1For the nitrogen atom heterocycle of carbon number 3~15, Z1For hydrogen atom or the optional carbon number 1 with substituent
~20 alkyl；In formula (YD-2), W1For the alkyl of carbon number 1~10, A2For 1 valency of the carbon number 3~15 with nitrogen atom heterocycle
Organic group or the disubstituted amido replaced by the fatty group of carbon number 1~6；In formula (YD-3), W2For carbon number 6~15 and
Divalent organic group with 1~2 phenyl ring, W3For the alkylidene or biphenylene of carbon number 2~5, Z2For hydrogen atom, carbon number 1~5
Alkyl or phenyl ring, a be 0~1 integer；In formula (YD-4), A3For the nitrogen atom heterocycle of carbon number 3~15；In formula (YD-5),
A4For the nitrogen atom heterocycle of carbon number 3~15, W5For the alkylidene of carbon number 2~5.
5. according to aligning agent for liquid crystal according to any one of claims 1 to 4, wherein, the diamine component contains selected from by having
It is at least one kind of in the group be made up of the divalent organic group of following formula (YD-6)~(YD-21) structure,
In formula (YD-17), h is 1~3 integer；In formula (YD-14) and (YD-21), j is 1~3 integer.
6. according to aligning agent for liquid crystal according to any one of claims 1 to 5, wherein, relative to the polymer of (A) composition, contain
There is the compound shown in 0.1~20 mass % above-mentioned formula (C).
7. according to aligning agent for liquid crystal according to any one of claims 1 to 6, wherein, under the compound shown in above-mentioned formula (C) is
The compound shown in formula (C-1) is stated,
8. a kind of liquid crystal orientation film, it is coating aligning agent for liquid crystal according to any one of claims 1 to 7 and burns till and obtain
's.
9. a kind of liquid crystal represents element, it possesses the liquid crystal orientation film described in claim 8.
10. liquid crystal according to claim 9 represents element, it is IPS type of drive or FFS type of drive.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-213835 | 2014-10-20 | ||
| JP2014213835 | 2014-10-20 | ||
| JP2015032093 | 2015-02-20 | ||
| JP2015-032093 | 2015-02-20 | ||
| PCT/JP2015/079449 WO2016063834A1 (en) | 2014-10-20 | 2015-10-19 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107077032A true CN107077032A (en) | 2017-08-18 |
| CN107077032B CN107077032B (en) | 2021-04-16 |
Family
ID=55760869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580057130.1A Active CN107077032B (en) | 2014-10-20 | 2015-10-19 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6627772B2 (en) |
| KR (1) | KR102420194B1 (en) |
| CN (1) | CN107077032B (en) |
| TW (1) | TWI699386B (en) |
| WO (1) | WO2016063834A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111279255A (en) * | 2017-10-26 | 2020-06-12 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7089227B2 (en) * | 2016-09-13 | 2022-06-22 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| WO2018062438A1 (en) * | 2016-09-29 | 2018-04-05 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| WO2018092811A1 (en) * | 2016-11-18 | 2018-05-24 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN110462505A (en) * | 2017-03-31 | 2019-11-15 | 日产化学株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element |
| KR20200136002A (en) | 2018-04-09 | 2020-12-04 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using same |
| WO2020166623A1 (en) | 2019-02-13 | 2020-08-20 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal element using this |
| WO2020203110A1 (en) | 2019-03-29 | 2020-10-08 | 日産化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and diamine |
| JP7409375B2 (en) | 2019-04-24 | 2024-01-09 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same |
| KR20220027945A (en) | 2019-07-08 | 2022-03-08 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using same |
| CN118355319A (en) | 2021-10-18 | 2024-07-16 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and compound |
| JP2024070838A (en) | 2022-11-11 | 2024-05-23 | 日産化学株式会社 | Liquid crystal orientation agent, liquid crystal orientation film, and liquid crystal display element |
| KR20240101393A (en) | 2022-12-23 | 2024-07-02 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6562420B2 (en) * | 2001-07-31 | 2003-05-13 | Industrial Technology Research Institute | Liquid crystal aligning film |
| US6639006B1 (en) * | 1998-11-12 | 2003-10-28 | Avecia Limited | Composition based on cross-linkable, water-dissipatable acrylic polymers, process and use |
| US6723835B1 (en) * | 1999-09-20 | 2004-04-20 | Avecia Limited | Azopyridone compounds, compositions and use |
| CN101339334A (en) * | 2007-07-06 | 2009-01-07 | Jsr株式会社 | Liquid crystal alignment agent and liquid crystal display unit |
| CN101874097A (en) * | 2007-11-23 | 2010-10-27 | Lg化学株式会社 | Polymerizable liquid crystal composition, homeotropic alignment liquid crystal film made from the compostion and method for preparing the same |
| US20120206681A1 (en) * | 2011-02-10 | 2012-08-16 | Samsung Electronics Co., Ltd. | Liquid crystal display |
| JP2013010889A (en) * | 2011-06-30 | 2013-01-17 | Jnc Corp | Polyamic acid, and liquid crystal orientating agent, liquid crystal oriented film, and liquid crystal display element using the same |
| CN103180294A (en) * | 2010-08-31 | 2013-06-26 | 日产化学工业株式会社 | Diamine, polyimide precursor, polyimide, liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element |
| CN103257479A (en) * | 2012-02-16 | 2013-08-21 | 株式会社日本显示器东 | Liquid crystal display device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012197268A (en) | 2011-03-04 | 2012-10-18 | Toyo Ink Sc Holdings Co Ltd | β-HYDROXYALKYLAMIDE AND CROSSLINKABLE COMPOSITION |
| WO2012121179A1 (en) * | 2011-03-04 | 2012-09-13 | 東洋インキＳｃホールディングス株式会社 | β-HYDROXYALKYL AMIDE AND RESIN COMPOSITION |
| WO2013047693A1 (en) * | 2011-09-30 | 2013-04-04 | 日産化学工業株式会社 | Liquid crystal orientation treatment agent, liquid crystal orientation membrane, and liquid crystal display element |
| KR102072871B1 (en) * | 2012-04-18 | 2020-02-03 | 닛산 가가쿠 가부시키가이샤 | Liquid-crystal alignment material for use in photo-alignment method, liquid-crystal alignment film, and liquid-crystal display element |
| TWI637029B (en) * | 2013-11-15 | 2018-10-01 | 日商日產化學工業股份有限公司 | Liquid crystal alignment agent and liquid crystal display element using same |
-
2015
- 2015-10-19 CN CN201580057130.1A patent/CN107077032B/en active Active
- 2015-10-19 JP JP2016555212A patent/JP6627772B2/en active Active
- 2015-10-19 WO PCT/JP2015/079449 patent/WO2016063834A1/en active Application Filing
- 2015-10-19 KR KR1020177011073A patent/KR102420194B1/en active IP Right Grant
- 2015-10-20 TW TW104134370A patent/TWI699386B/en active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6639006B1 (en) * | 1998-11-12 | 2003-10-28 | Avecia Limited | Composition based on cross-linkable, water-dissipatable acrylic polymers, process and use |
| US6723835B1 (en) * | 1999-09-20 | 2004-04-20 | Avecia Limited | Azopyridone compounds, compositions and use |
| US6562420B2 (en) * | 2001-07-31 | 2003-05-13 | Industrial Technology Research Institute | Liquid crystal aligning film |
| CN101339334A (en) * | 2007-07-06 | 2009-01-07 | Jsr株式会社 | Liquid crystal alignment agent and liquid crystal display unit |
| CN101874097A (en) * | 2007-11-23 | 2010-10-27 | Lg化学株式会社 | Polymerizable liquid crystal composition, homeotropic alignment liquid crystal film made from the compostion and method for preparing the same |
| CN103180294A (en) * | 2010-08-31 | 2013-06-26 | 日产化学工业株式会社 | Diamine, polyimide precursor, polyimide, liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element |
| US20120206681A1 (en) * | 2011-02-10 | 2012-08-16 | Samsung Electronics Co., Ltd. | Liquid crystal display |
| JP2013010889A (en) * | 2011-06-30 | 2013-01-17 | Jnc Corp | Polyamic acid, and liquid crystal orientating agent, liquid crystal oriented film, and liquid crystal display element using the same |
| CN103257479A (en) * | 2012-02-16 | 2013-08-21 | 株式会社日本显示器东 | Liquid crystal display device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111279255A (en) * | 2017-10-26 | 2020-06-12 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN111279255B (en) * | 2017-10-26 | 2023-03-14 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102420194B1 (en) | 2022-07-12 |
| JP6627772B2 (en) | 2020-01-08 |
| CN107077032B (en) | 2021-04-16 |
| JPWO2016063834A1 (en) | 2017-07-27 |
| KR20170071513A (en) | 2017-06-23 |
| TWI699386B (en) | 2020-07-21 |
| TW201629124A (en) | 2016-08-16 |
| WO2016063834A1 (en) | 2016-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107077032A (en) | Aligning agent for liquid crystal, liquid crystal orientation film and its liquid crystal has been used to represent element | |
| JP6558245B2 (en) | LIQUID CRYSTAL ORIENTING LIQUID CRYSTAL Alignment Agent, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY DEVICE USING THE SAME | |
| KR102172129B1 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same | |
| TWI602852B (en) | Optical alignment method with the liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display components | |
| TW201531527A (en) | Liquid crystal aligning agent, and liquid crystal display element using same | |
| TW201518408A (en) | Liquid crystal aligning agent and liquid crystal aligning film using same | |
| CN104823104B (en) | Manufacture method, liquid crystal orientation film and the liquid crystal display cells of liquid crystal orientation film | |
| WO2020100918A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same | |
| TWI820010B (en) | Manufacturing method of liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element | |
| CN110325902A (en) | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element | |
| TWI597305B (en) | A method of manufacturing a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element | |
| KR102278973B1 (en) | Liquid crystal aligning agent and liquid crystal display element using same | |
| JP7299556B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| WO2014092170A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| KR102393693B1 (en) | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element | |
| CN111602088B (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |