CN109196412A - 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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- CN109196412A CN109196412A CN201780033849.0A CN201780033849A CN109196412A CN 109196412 A CN109196412 A CN 109196412A CN 201780033849 A CN201780033849 A CN 201780033849A CN 109196412 A CN109196412 A CN 109196412A
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- liquid crystal
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- aligning agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Abstract
There is provided being coated with for the alignment films for being able to suppress the influence generation because of wire structures or C/H is bad, the expression inhomogeneities of liquid crystal expression element is bad, thereby reduces the viscosity of aligning agent for liquid crystal and increases resin component ratio aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicates element.A kind of aligning agent for liquid crystal, which is characterized in that contain: at least one kind of polymer in the group that the polyimides by polyimide precursor and as its acid imide compound forms；And the solvent containing following solvents A, solvent B and solvent C.Solvent A: at least one kind of in the group being made of n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, gamma-butyrolacton and dimethyl-imidazolinone.Solvent B: dimethyl ether.Solvent C: following formula (a) compound represented (R1、R2It is each independently the alkyl of the carbon number 1~8 of linear chain or branched chain, R1And R2Carbon number add up to 4 or more.)
Description
Technical field
It is taken the present invention relates to the high aligning agent for liquid crystal of dimensional stability when being suitable for ink-jet membrane formation process and being coated with, by the liquid crystal
The liquid crystal orientation film obtained to agent and the liquid crystal for having the liquid crystal orientation film indicate element.
Background technique
As liquid crystal orientation film, coating is widely used with polyamic acid (also referred to as polyamic acid.) etc. polyimide precursors,
The solution of soluble polyimide is that the liquid crystal of so-called polyimides system obtained from the aligning agent for liquid crystal of principal component and firing takes
To film.
It is commonly known to have spin coating, dip-coating, flexible printing etc. as the membrane formation process of above-mentioned liquid crystal orientation film.In practical, greatly
Use flexible printing more.But flexible printing has following problem: being needed various according to the kind of liquid crystal display panel difference
Resin plate；Version replacement is complicated in manufacturing process；It must form a film on analog baseplate, the system of version to keep film formation process stable
It is made for the problems such as liquid crystal indicates the reason that the manufacturing cost of panel rises.
Therefore, the membrane formation process as the liquid crystal orientation film without using galley, ink-jet method attract attention.Ink-jet method is in base
Fine drop is added dropwise on plate, the method to form a film by the wetting and spreading of liquid.Galley is not used not only, but also can be certainly
By the pattern of ground setting printing, therefore the manufacturing process of liquid crystal expression element can be simplified.In addition, it is not necessary that in flexible printing
It is required to form a film on analog baseplate, to have the advantages that the waste of coating fluid is few.By ink-jet method, liquid crystal display panel can be expected
Cost reduce, production efficiency improve.
By ink-jet method formed liquid crystal orientation film require coated face inside film thickness unevenness it is small and be coated with peripheral portion at
Film precision is high.For the liquid crystal orientation film to be formed a film by ink-jet method, the uniformity and coating of the film thickness in coated face
There is the relationship of compromise in the film-forming accuracy of peripheral portion.That is, in general, the size of the coating peripheral portion of the high material of inner evenness is steady
Qualitative low, film can be from being sized protrusion.On the other hand, the coating inner evenness that coating peripheral portion becomes the material of straight line becomes
It is low.
In order to improve the film-forming accuracy of above-mentioned coating peripheral portion, proposes and alignment films are limited in rule using special structure
Determine the method (referring to patent document 1~3) in range.But these methods have the difficulty for needing special structure.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2004-361623 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2008-145461 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2010-281925 bulletin
Summary of the invention
Problems to be solved by the invention
In recent years, the high-definition of element is indicated with liquid crystal, the TFT design of multilayer wiring is increasingly becoming mainstream.TFT is set
In meter, in order to connect lower layer wiring and upper layer wiring and on substrate formed contact hole (also referred to as C/H).Along with this,
Due to the influence of wire structures, C/H, it is easy to interfere the spreadability of liquid in aligning agent for liquid crystal coating.As a result, on the periphery C/H
Or other parts generate the uneven of such, alignment films the thickness of unevenness of dotted unevenness or striated, liquid crystal watch sometimes
Show that the expression of element becomes uneven.
In addition, for aligning agent for liquid crystal used in ink-jet method, in order to steadily carry out spray of the alignment agent from inkjet nozzle
Out, it is desirable that correspondingly sometimes obtained the resin component ratio set in aligning agent for liquid crystal less for low viscosity.Another party
Face, in order to make liquid crystal orientation film peripheral portion uniform film thickness, and inhibit the width of liquid crystal orientation film, it is necessary to maintain liquid crystal
Increase the resin component ratio in aligning agent for liquid crystal while the low viscosity of alignment agent, seeks this aligning agent for liquid crystal.
The present invention in view of the above problems, provides the liquid crystal orientation film for being able to suppress and generating by the influence of wire structures or C/H
The bad, liquid crystal of film forming indicate the expression of element become viscosity that is non-uniform bad and can reduce aligning agent for liquid crystal and
Increase the aligning agent for liquid crystal of resin component ratio and the liquid crystal orientation film using it.
The solution to the problem
Further investigation is repeated in the present inventor to solve the above-mentioned problems, as a result completes the present invention.
The gist of the invention is a kind of aligning agent for liquid crystal, which is characterized in that is contained: selected from by polyimide precursor and conduct
At least one kind of polymer in the group of the polyimides composition of its acid imide compound；And containing belong to following A, B and C group it is molten
The solvent of agent.
A group: selected from by n-methyl-2-pyrrolidone (NMP), N- ethyl-2-pyrrolidone (NEP), gamma-butyrolacton
(GBL) and 1,3- dimethyl-imidazolinone (DMI) composition group at least one kind of solvent
B group: dimethyl ether (DME)
C group: including the solvent of following formula (a) compound represented
R1、R2It is each independently the alkyl of the carbon number 1~8 of linear chain or branched chain.Wherein, R1And R2Carbon number add up to 4
More than.
The effect of invention
According to the present invention, the film forming for being able to suppress the liquid crystal orientation film generated by the influence of wire structures or C/H can be obtained
Bad, liquid crystal indicates that the expression of element becomes non-uniform bad, and can have high resin while maintaining low viscosity
Component ratio, therefore it is suitable for use with the aligning agent for liquid crystal of the polyimides system of the film forming of ink-jet method, the liquid crystal aligning using it
Film and liquid crystal indicate element.
Specific embodiment
Aligning agent for liquid crystal of the invention contains: selected from by polyimide precursor and as the polyimides of its acid imide compound
At least one kind of polymer (hereinafter also referred to particular polymers in the group of composition.)；And following contain solvent A, solvent B and molten
Solvent (the hereinafter also referred to specific solvent of agent C.).
<specific solvent>
The solvent contained in aligning agent for liquid crystal of the invention contains above-mentioned solvent A, solvent B and solvent C, individually below into
Row explanation.
<solvent A>
Solvent A is selected from by n-methyl-2-pyrrolidone (NMP), N- ethyl-2-pyrrolidone (NEP), gamma-butyrolacton
(GBL) and 1,3- dimethyl-imidazolinone (DMI) composition group at least one kind of solvent.Solvent A makes poly- in aligning agent for liquid crystal
Close object dissolution.
Wherein, preferably n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone or gamma-butyrolacton (GBL), more preferably
For n-methyl-2-pyrrolidone (NMP) or gamma-butyrolacton (GBL).
In aligning agent for liquid crystal of the invention, the content of solvent A is preferably 20~90 relative to the gross mass of aligning agent for liquid crystal
Quality %, more preferably 30~80 mass %, further preferably 50~80 mass %.
<solvent B>
Solvent B is dimethyl ether (DME).Solvent B is the raising for facilitating the coating homogeneity of aligning agent for liquid crystal
With the solvent of lowering viscousity.
In aligning agent for liquid crystal of the invention, the content of solvent B is preferably 5~50 matter relative to the gross mass of aligning agent for liquid crystal
Measure %, more preferably 10~50 mass %.
<solvent C>
Solvent C is made of following formula (a) compound represented.
In formula (a), R1、R2Be each independently straight or branched carbon number 1~8, preferably 3~8, more preferable 3~6
Alkyl.Wherein, R1And R2Carbon number add up to 4 or more, preferably 5~12.
For solvent C shown in formula (a), specific example goes out a-1~a-48 below, but is not limited to these.
Wherein, solvent C from the viewpoint of availability and practicability be preferably a-22, a-13~a-21, a-24, a-26,
A-27, a-31, a-34, a-37 or a-38, more preferably a-22 or a-37.
In aligning agent for liquid crystal of the invention, the content of solvent C is preferably 5~40 matter relative to the gross mass of aligning agent for liquid crystal
Measure %, more preferably 10~30 mass %.
In addition, solvent B and the total content of solvent C relative to the gross mass of aligning agent for liquid crystal be preferably 20~50 mass %,
More preferably 20~40 mass %.In addition, at this point, the content of solvent B is preferably greater than the content of solvent C, especially more preferably than molten
Big 1~20 mass % of the content of agent C.
Aligning agent for liquid crystal of the invention can also contain the solvent other than specific solvent.As its example, fourth can be enumerated
Base cellosolve, 1- butoxy -2- propyl alcohol, butyl cellosolve acetate, dipropylene glycol monomethyl ether, diacetone alcohol, diethylene glycol two
Ether, isoamyl ether, propylene-glycol diacetate, diisobutyl ketone, ethyl carbitol and dimethyl ether, gamma-valerolactone
Deng.Solvent other than specific solvent is preferably 50 mass % or less, more preferably 20 matter relative to the gross mass of aligning agent for liquid crystal
Measure % or less.
<particular polymers>
Polyimide precursor as the particular polymers contained in aligning agent for liquid crystal of the invention preferably has below
Structure shown in formula (1).
In formula (1), X1For the quadrivalent organic radical group from tetracarboxylic acid derivatives.Y1For the bivalent organic group from diamines.
R1For hydrogen atom or the alkylidene of carbon atom number 1~5.Imidization reaction when heating carries out easness, R1
Preferably hydrogen atom, methyl or ethyl, more preferably hydrogen atom or methyl.
A1And A2It is each independently the alkyl of hydrogen atom or carbon number 1~5, the alkenyl of carbon number 2~5 or carbon number 2~5
Alkynyl.From the viewpoint of liquid crystal aligning, A1And A2It is preferred that hydrogen atom or methyl.
Hereinafter, for being illustrated as each ingredient for the raw material for manufacturing above-mentioned polyimide precursor.
<diamines>
Diamine component used in the manufacture of polyimide precursor is not particularly limited, and gathers as shown in above-mentioned formula (1)
The diamines of the raw material of imide precursor is indicated with following formula (2).
In formula (2), A1And A2Also including preference with the A in above-mentioned formula (1)1And A2For identical definition.If example Y1,
(Y-1) below~(Y-170) can then be enumerated.
In formula, the integer that n is 1~6, Me is methyl.
Wherein, preferably (Y-7), (Y-8), (Y-16), (Y-17), (Y-18), (Y-20), (Y-21), (Y-22), (Y-
28), (Y-35), (Y-38), (Y-43), (Y-48), (Y-64), (Y-66), (Y-71), (Y-72), (Y-76), (Y-77), (Y-
80)、(Y-81)、(Y-82)、(Y-83)、(Y156)、(Y-159)、(Y-160)、(Y-161)、(Y-162)(Y-168)、(Y-
169) or (Y-170), particularly preferred (Y-7), (Y-8), (Y-16), (Y-17), (Y-18), (Y-21), (Y-22), (Y-28),
(Y-38), (Y-64), (Y-66), (Y-72), (Y-76), (Y-81), (Y156), (Y-159), (Y-160), (Y-161), (Y-
162) (Y-168), (Y-169) or (Y-170).
<tetracarboxylic acid derivatives>
Tetracarboxylic acid derivatives used in the manufacture of polyimide precursor are not particularly limited, for as above-mentioned formula (1)
Shown in polyimide precursor raw material tetracarboxylic acid derivatives ingredient, can not only enumerate tetracarboxylic dianhydride, can also enumerate
Tetrabasic carboxylic acid, two carboxylic acid halides of two carboxylic acid halides of tetrabasic carboxylic acid, tetracarboxylic acid acid dialkyl ester or tetracarboxylic acid acid dialkyl ester as its derivative.
As tetracarboxylic dianhydride or derivatives thereof, preferably substance shown in following formula (3).
In formula (3), X1For the quadrivalent organic radical group with ester ring type structure, structure is not particularly limited.As specific
Example, can enumerate following formula (X1-1)~(X1-44).
In formula (X1-1)~(X1-4), R3~R23Be each independently hydrogen atom, halogen atom, carbon number 1~6 alkyl,
The monovalent organic group or phenyl of the alkenyl of carbon number 2~6, the alkynyl of carbon number 2~6, carbon number 1~6 containing fluorine atom.From liquid crystal
From the perspective of orientation, R3~R23Preferably hydrogen atom, halogen atom, methyl or ethyl, more preferably hydrogen atom or first
Base.
It should be noted that the concrete example as formula (X1-1), can enumerate following formula (X1-1-1)~(X1-1-6).From
From the perspective of the sensitivity of liquid crystal aligning and light reaction, particularly preferred (X1-1-1).
Tetracarboxylic dianhydride and its derivative for the raw material as polyimide precursor and polyimides of the invention, it is excellent
Choosing, relative to whole tetracarboxylic dianhydrides and its 1 mole of derivative, comprising four shown in 60~100 moles of above-mentioned formulas of % (3)
Carboxylic acid dianhydride or derivatives thereof.In order to obtain with the liquid crystal orientation film of good liquid crystal aligning, more preferable 80~100 rub
You are %, further preferably 90~100 moles of %.
<polyimide precursor>
<manufacturing method of poly amic acid ester>
The poly amic acid ester of one of polyimide precursor used in the present invention can by (1) as shown below,
(2) or the method for (3) manufactures.
(1) the case where being manufactured by polyamic acid
Poly amic acid ester can be synthesized and making and being esterified by tetracarboxylic dianhydride with the polyamic acid that diamines obtains.
Specifically, can by make polyamic acid and esterifying agent in presence of organic solvent -20 DEG C~150 DEG C,
It is preferred that reacting 30 minutes~24 hours, preferably 1~4 hour and synthesizing at 0 DEG C~50 DEG C.
It as esterifying agent, is preferably able to be readily removable by purification, n,N-Dimethylformamide diformazan can be enumerated
Base acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide
Di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1- methyl -3- p-methylphenyl triazenes, 1- ethyl -
3- p-methylphenyl triazenes, 1- propyl -3- p-methylphenyl triazenes, 4- (4,6- dimethoxy -1,3,5- triazine -2- base) -4-
Methylmorpholinium chloride etc..The dosage of esterifying agent is worked as relative to 1 mole of repetitive unit of polyamic acid preferably 2~6 moles
Amount.
Dissolubility preferably N,N-dimethylformamide, N- first of the solvent used in above-mentioned reaction from polymer
Base -2-Pyrrolidone or gamma-butyrolacton, they can be used a kind or are mixed with two or more.Polymer in reaction solution
Concentration is precipitated and being easy to get macromolecule aggressiveness from the viewpoint of being not susceptible to polymer, preferably 1~30 mass %, more
Preferably 5~20 mass %.
(2) the case where manufacturing, is reacted by tetracarboxylic acid acid diesters diacid chloride and diamines
Poly amic acid ester can be manufactured by tetracarboxylic acid acid diesters diacid chloride and diamines.Specifically, can be by making tetrabasic carboxylic acid
Diester diacid chloride reacts 30 points at -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C in the presence of alkali and organic solvent with diamines
Clock~24 hour, preferably 1~4 hour and manufacture.
Pyridine, triethylamine, 4-dimethylaminopyridine etc. can be used in aforementioned bases, for reacting balance progress it is preferred that pyrrole
Pyridine.The dosage of alkali is from the viewpoint of for the amount easily removed and being easy to get macromolecule aggressiveness, relative to tetracarboxylic acid acid diesters two
Acyl chlorides, preferably 2~4 times moles.
Solvent used in above-mentioned reaction is from the dissolubility of monomer and polymer preferably N- methyl -2- pyrrolidines
Ketone or gamma-butyrolacton, they can be used a kind or are mixed with two or more.Polymer concentration in reaction solution is from being not easy to send out
Raw polymer is precipitated and is easy to get from the perspective of macromolecule aggressiveness, preferably 1~30 mass %, more preferably 5~20 matter
Measure %.In addition, the hydrolysis of tetracarboxylic acid acid diesters diacid chloride in order to prevent, solvent used in the synthesis of preferred polyamide acid esters to the greatest extent may be used
It is dehydrated to energy, being mixed into for extraneous gas is preferably prevented in nitrogen atmosphere.
(3) by tetracarboxylic acid acid diesters and diamines manufacture poly amic acid ester the case where
Poly amic acid ester can be manufactured and making tetracarboxylic acid acid diesters with diamines polycondensation.Specifically, can be by making four
Carboxylic acid diesters react at 0 DEG C~150 DEG C, preferably 0 DEG C~100 DEG C in the presence of condensing agent, alkali and organic solvent with diamines
30 minutes~24 hours, preferably 3~15 hours and manufacture.
Triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyl -3- (3- dimethylamino can be used in aforementioned condensation agent
Propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, O- (benzo three
Azoles -1- base)-N, N, N ', N '-tetramethylurea tetrafluoroborate, O- (benzotriazole -1- base)-N, N, N ', N '-tetramethylurea
Hexafluorophosphate, (thio -3- benzoxazolyl of 2,3- dihydro -2-) phosphonic acid diphenyl ester etc..The additive amount of condensing agent relative to
Tetracarboxylic acid acid diesters are preferably 2~3 times moles.
The tertiary amines such as pyridine, triethylamine can be used in aforementioned bases.The dosage of alkali is from for the amount easily removed and being easy to get height
It is preferably 2~4 times moles relative to diamine component from the perspective of molecule aggressiveness.
In addition, in above-mentioned reaction, by the way that lewis acid is added as additive, so that reaction efficiently carries out.As road
The lithium halides such as Lewis acid, preferably lithium chloride, lithium bromide.Lewis acidic additive amount is preferably 0~1.0 times relative to diamine component
Mole.
Among the manufacturing method of above-mentioned 3 poly amic acid esters, the poly amic acid ester of high molecular weight in order to obtain, particularly preferably
The autofrettage of above-mentioned (1) or above-mentioned (2).
It is above-mentioned it is such operate obtained from the solution of poly amic acid ester can be bad molten by being injected into when being sufficiently stirred
Polymer is precipitated in agent.It is precipitated for several times, after being cleaned with poor solvent, room temperature or heat drying, so as to obtain
The powder of the poly amic acid ester of purification.Poor solvent is not particularly limited, and it is molten can to enumerate water outlet, methanol, ethyl alcohol, hexane, butyl
Fine agent, acetone, toluene etc..
<manufacturing method of polyamic acid>
The polyamic acid of polyimide precursor used in the present invention can be manufactured by method as shown below.
Specifically, can by make tetracarboxylic dianhydride and diamines in presence of organic solvent -20 DEG C~150 DEG C,
It is preferred that reacting 30 minutes~24 hours, preferably 1~12 hour and synthesizing at 0 DEG C~50 DEG C.
Organic solvent used in above-mentioned reaction is from the dissolubility of monomer and polymer preferably N, N- dimethyl methyl
Amide, n-methyl-2-pyrrolidone or gamma-butyrolacton, they can be used a kind or are mixed with two or more.Polymer
Concentration is precipitated and preferably 1~30 mass % being easy to get macromolecule aggressiveness, more excellent from the viewpoint of being not susceptible to polymer
It is selected as 5~20 mass %.
It is above-mentioned it is such operate obtained from polyamic acid can be bad by the way that reaction solution to be injected into when being sufficiently stirred
Polymer is set to be precipitated and recycle in solvent.In addition, be precipitated for several times, after being cleaned with poor solvent, room temperature or heat drying,
Powder so as to the polyamic acid refined.Poor solvent is not particularly limited, can enumerate water outlet, methanol, ethyl alcohol, oneself
Alkane, butyl cellosolve, acetone, toluene etc..
<manufacturing method of polyimides>
Polyimides used in the present invention can be by making foregoing polyamides acid esters or polyamic acid carry out imidizate
And it manufactures.When manufacturing polyimides by poly amic acid ester, in foregoing polyamides acid esters solution or make poly amic acid ester toner
It is easy for being dissolved in polyamic acid solution obtained from organic solvent and adding the chemical imidization of basic catalyst.Chemistry
Imidizate carries out imidization reaction at relatively low temperatures, and the molecular weight drop of polymer is not susceptible to during imidizate
It is low, so it is preferred that.
Chemical imidization can be by making the poly amic acid ester for wanting imidizate in organic solvent in base catalysis
Stirring is in the presence of agent to carry out.As organic solvent, the solvent used when aforementioned polymeric reaction can be used.It is urged as alkalinity
Agent can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc..Wherein, triethylamine has for carrying out reaction
For adequately alkalinity, so it is preferred that.
Temperature when carrying out imidization reaction is -20 DEG C~140 DEG C, preferably 0 DEG C~100 DEG C, can be with 1~100
The reaction time of hour carries out.The amount of basic catalyst is 0.5~30 mole times, preferably 2~20 moles of amic acid ester group
Times.The acid imide rate of obtained polymer can be controlled by adjusting catalytic amount, temperature, reaction time.Imidizate
Remain the catalyst etc. of addition in solution after reaction, therefore preferably recycle obtained imide amination polymer, use is organic
Solvent is redissolved, and aligning agent for liquid crystal of the invention is made.
When manufacturing polyimides by polyamic acid, aforementioned poly- by diamine component and reacting for tetracarboxylic dianhydride
It is easy that the chemical imidization of catalyst is added in the solution of amic acid.Chemical imidization carries out acyl Asia at relatively low temperatures
Aminating reaction, the molecular weight that polymer is not susceptible to during imidizate reduce, so it is preferred that.
Chemical imidization can by make to want the polymer of imidizate in organic solvent in basic catalyst and
It stirs and carries out in the presence of acid anhydrides.As organic solvent, the solvent used when aforementioned polymeric reaction can be used.As alkalinity
Catalyst can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc..Wherein, pyridine has for carrying out reaction
For appropriate alkalinity, so it is preferred that.In addition, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated as acid anhydrides,
Wherein become easy using purification when acetic anhydride after reaction, so it is preferred that.
Temperature when carrying out imidization reaction is -20 DEG C~140 DEG C, preferably 0 DEG C~100 DEG C, can be with 1~100
The reaction time of hour carries out.The amount of basic catalyst is 0.5~30 mole times, preferably 2~20 moles times of amide acidic group,
The amount of acid anhydrides is 1~50 mole times, preferably 3~30 moles times of amide acidic group.The acid imide rate of obtained polymer can
To be controlled by adjusting catalytic amount, temperature, reaction time.
Remain the catalyst etc. of addition in solution after the imidization reaction of poly amic acid ester or polyamic acid, therefore
It is preferred that being recycled obtained imide amination polymer by means as described below, it is redissolved with organic solvent, the present invention is made
Aligning agent for liquid crystal.
The solution of above-mentioned such polyimides operated can be by being injected into poor solvent when being sufficiently stirred
And polymer is precipitated.It is precipitated for several times, after being cleaned with poor solvent, room temperature or heat drying, so as to be refined
Poly amic acid ester powder.
Aforementioned poor solvent is not particularly limited, and can enumerate methanol, acetone, hexane, butyl cellosolve, heptane, first and second
Ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene etc..
<aligning agent for liquid crystal>
Solution made of there are aligning agent for liquid crystal of the invention particular polymers to be dissolved in the solvent comprising specific solvent
Form.The molecular weight of the polyimide precursor and polyimides recorded in the present invention with Weight-average molecular meter be preferably 2000~
500000,5000~300000, further preferably 10000~100000 are more preferably.In addition, number-average molecular weight is preferably
1000~250000,2500~150000, further preferably 5000~50000 are more preferably.
The concentration of the polymer of aligning agent for liquid crystal used in the present invention can think the thickness of film to be formed by setting
Degree is to be suitable for change, the preferably 1 weight % or more from the viewpoint of forming uniform and flawless film, from the preservation of solution
10 weight % or less are preferably set to from the perspective of stability.
<other solvents>
In aligning agent for liquid crystal of the invention can containing other than above-mentioned solvent A, B and C solvent (hereinafter also referred to its
His solvent.).It, can be (also referred to as good molten containing the solvent for dissolving polyimide precursor and polyimides as other solvents
Agent), solvent that painting film property, the surface smoothness of liquid crystal orientation film when making coating of liquid crystalline alignment agent improve it is (also referred to as bad molten
Agent).
The concrete example of other solvents is hereinafter enumerated, but is not limited to these examples.
As good solvent, for example, can enumerate n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide,
Methyl ethyl ketone, cyclohexanone, cyclopentanone, 3- methoxyl group-N, N- dimethylpropionamide (IPME) or 4- hydroxy-4-methyl-2-pentanone etc..
As the concrete example of poor solvent, such as ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, uncle can be enumerated
Butanol, 1- amylalcohol, 2- amylalcohol, 3- amylalcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1-
Hexanol, 2- methyl-1-pentene alcohol, 2- methyl -2- amylalcohol, 2- ethyl-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanol, 2-
Octanol, 2- ethyl -1- hexanol, cyclohexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol,
1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,5- pentanediol,
2- methyl -2,4-PD, 2- ethyl -1,3- hexylene glycol, dipropyl ether, butyl oxide, two hexyl ethers, dioxanes, glycol dimethyl ether,
Ethylene glycol diethyl ether, butyl cellosolve, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl two
Alcohol methyl ethyl ether, dibutyl ethylene glycol ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, 3- ethoxybutyl second
Acid esters, 1- methyl amyl acetic acid esters, 2- ethyl-butyl acetic acid esters, 2- ethylhexyl acetate, ethylene glycol acetate, ethylene glycol
Diacetate esters, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethyl alcohol, butyl cellosolve, ethylene glycol list isoamyl
Ether, ethylene glycol monohexylether, 2- (hexyloxy) ethyl alcohol, furfuryl alcohol, diethylene glycol, propylene glycol, 1- butoxy -2- propyl alcohol, 1- (butoxy
Ethyoxyl) propyl alcohol, propylene glycol methyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3 the third two
Alcohol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol list second
Acid esters, ethylene acetate, diethylene glycol monoethyl ether acetic acid esters, diacetone alcohol, propylene-glycol diacetate, isoamyl ether, two
Ethylene glycol monomethyl ether acetate, 2- (2- ethoxy ethoxy) ethylhexoate, diethylene glycol acetic acid esters, triethylene glycol, three second
Glycol monomethyl ether, Triethylene glycol ethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, the third two
Alcohol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3-
Methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, cream
Sour methyl esters, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, diisobutyl ketone, ethyl carbitol etc..
In addition, solvent shown in following formula [D-1]~formula [D-3] can be enumerated as poor solvent.
In formula [D-1], D1The alkyl for indicating carbon number 1~3, in formula [D-2], D2Indicate the alkyl of carbon number 1~3, formula [D-3]
In, D3Indicate the alkyl of carbon number 1~4.
Aligning agent for liquid crystal of the invention may include: have epoxy group, isocyanate group, oxetanyl or ring carbon acid
The cross-linked compound of ester group；With at least one kind of in the group for selecting free hydroxyl, hydroxy alkyl and low-grade alkoxy alkyl composition
The cross-linked compound of substituent group；Or the cross-linked compound with polyunsaturated bond.These substituent groups, polymerism insatiable hunger
There must be 2 or more in cross-linked compound with key.
As the cross-linked compound with epoxy group or isocyanate group, such as bisphenol acetone glycidol can be enumerated
Ether, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl isocyanurate, four glycidols
Base aminodiphenyl support (tetraglycidyl aminodiphenylene), four glycidyl group m-xylene diamine, four shrinks are sweet
Bis- (amino-ethyl) hexamethylenes of oil base -1,3-, tetraphenyl glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol six
Acetyl fluoride diglycidyl ether, 1,3- bis- (1- (2,3- glycidoxy) -1- trifluoromethyl -2,2,2- trifluoromethyl) benzene, 4,
Bis- (2,3- glycidoxy) octafluorobiphenyls of 4-, triglycidyl group-para-aminophenol, four glycidyl group m-xylene diamine,
2- (4- (2,3- glycidoxy) phenyl) -2- (4- (bis- (4- (2,3- glycidoxy) phenyl) ethyls of 1,1-) phenyl) propane
Or bis- (4- (1- (4- (2,3- glycidoxy) phenyl) -1- (4- (1- (4- (2,3- glycidoxy) phenyl) -1- first of 1,3-
Base ethyl) phenyl) ethyl) phenoxy group) -2- propyl alcohol etc..
Cross-linked compound with oxetanyl is with oxetanes shown at least two following formula [4A]
The compound of base.
Specifically, the 58~59 of International Publication bulletin No. WO2011/132751 (2011.10.27 is disclosed) can be enumerated
Cross-linked compound shown in formula [the 4a]~formula [4k] recorded in page.
As the cross-linked compound with cyclocarbonate radical, for the acid of ring carbon shown at least two following formula [5A]
The cross-linked compound of ester group.
Specifically, page 76~82 of International Publication bulletin No. WO2012/014898 (2012.2.2 is disclosed) can be enumerated
Cross-linked compound shown in the formula [5-1] of middle record~formula [5-42].
As the cross-linked compound at least one kind of substituent group in the group for selecting free hydroxyl and alkoxy to form, example
The amino resins with hydroxyl or alkoxy can be such as enumerated, for example, melamine resin, urea resin, guanamine resin, sweet
Urea-formaldehyde resins, succinyl amine-formaldehyde resin or ethylene urea-formaldehyde resins etc..Specifically, the hydrogen that amino can be used is former
Melamine derivative made of son is replaced by methylol or alkoxy methyl or the two, benzoguanamine derivative or glycoluril.
The melamine derivative or benzoguanamine derivative can be 2 aggressiveness or 3 aggressiveness.Their preferably every 1 triazine rings have flat
Equal 3~6 methylols or alkoxy methyl.
As above-mentioned melamine derivative or the example of benzoguanamine derivative, every 1 three of commercially available product can be enumerated
Replace the MX-750 for there are average 3.7 methoxies on piperazine ring, replace on every 1 triazine ring and there are average 5.8 methoxy methyls
The MW-30 (more than, Sanwa Chemical Co., Ltd. system) of base, Cymel300,301,303,350,370,771,325,
327, the methoxymethylated melamines such as 703,712, Cymel235,236,238,212,253,254 etc. are methoxymethylated
Contain carboxyl as the butoxymethyls melamine such as butoxymethyl melamine, Cymel506,508, Cymel1141
Methoxymethylated isobutoxymethyl melamine, the methoxymethylated ethoxyl methyl benzo such as Cymel1123
The butoxymethyls benzene such as the methoxymethylated butoxymethyl benzoguanamine such as guanamines, Cymel1123-10, Cymel1128
And carboxylic methoxymethylated ethoxyl methyl benzoguanamine as guanamines, Cymel1125-80 (more than, Mitsui
Cyanamid Co., Ltd. system).In addition, the example as glycoluril, can enumerate the butoxymethyls such as Cymel1170 glycoluril,
Methoxyl groups methylolation glycoluril such as methylolations glycoluril such as Cymel1172 etc., Powderlink1174 etc..
As benzene or phenoloid with hydroxyl or alkoxy, such as 1,3,5- tri- (methoxy) can be enumerated
Benzene, 1,2,4- tri- (i-propoxymethyl) benzene, bis- (sec-butoxymethyl) benzene of 1,4- or 2,6- bishydroxymethyl-are to tert-butyl benzene
Phenol.
More specifically, can enumerate International Publication bulletin No. WO2011/132751 (2011.10.27 is disclosed) 62~
Recorded in page 66, formula [6-1]~formula [6-48] cross-linked compound.
As the cross-linked compound with polyunsaturated bond, such as trimethylolpropane tris (methyl) can be enumerated
Acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyl-oxies
Base oxethyl trimethylolpropane or poly- (methyl) acrylate of glycerine polyglycidyl ether etc. have 3 polymerisms in the molecule
The cross-linked compound of unsaturated group；And then ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate,
Tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, poly- third
Glycol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene oxide
Bisphenol A-type two (methyl) acrylate, propylene oxide bisphenol type two (methyl) acrylate, 1,6-HD two (methyl) propylene
Acid esters, glycerol two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl)
Acrylate, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, phthalic acid 2-glycidyl ester two (methyl) third
Olefin(e) acid ester or hydroxy new pentane acid neopentyl glycol two (methyl) acrylate etc. have 2 polymerism unsaturated groups in the molecule
Cross-linked compound；And (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2-
Hydroxybutyl, (methyl) acrylic acid 2- phenoxy group -2- hydroxy propyl ester, 2- (methyl) acryloxy -2- hydroxypropyl benzene diformazan
Acid esters, 3- chlorine-2-hydroxyl propyl (methyl) acrylate, glycerol list (methyl) acrylate, 2- (methyl) acryloxy second
Base phosphate or N- methylol (methyl) acrylamide etc. are in the molecule with the bridging property chemical combination of 1 polymerism unsaturated group
Object etc..
In turn, following formula [7A] compound represented also can be used.
(in formula [7A], E1Indicate selected from by cyclohexane ring, connection cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus,
Group in the group of fluorenes ring, anthracene nucleus or phenanthrene ring composition, E2Indicate that the group selected from following formula [7a] or formula [7b], n indicate 1~4
Integer).
Cross-linked compound used in aligning agent for liquid crystal of the invention can be a kind, can also combine two or more.
The content of cross-linked compound in aligning agent for liquid crystal of the invention is relative to whole 100 mass parts of component of polymer
Preferably 0.1~150 mass parts.Wherein, target effect is shown in order to promote cross-linking reaction, preferably 0.1~100 matter
Measure part.More preferably 1~50 mass parts.
Aligning agent for liquid crystal of the invention can contain the uniform of the film thickness of liquid crystal orientation film when making coating of liquid crystalline alignment agent
Property, surface smoothness improve compound.
The compound that uniformity, surface smoothness as the film thickness for making liquid crystal orientation film improve, can enumerate fluorine system table
Face activating agent, silicone based surfactants, nonionic surfactants etc..
Specifically, can for example enumerate Ftop EF301, EF303, EF352 (more than, Tochem Products Co.,
Ltd. make), MegaFac F171, F173, R-30 (more than, Dainippon Ink and Chemicals, Inc. system),
Fluorad FC430, FC431 (more than, Sumitomo 3M corporation), Asahi Guard AG710, Surflon S-382,
SC101, SC102, SC103, SC104, SC105, SC106 (more than, Asahi Glass Co., Ltd's system) etc..
The dosage of surfactant is preferably relative to 100 mass parts of whole component of polymer contained in aligning agent for liquid crystal
0.01~2 mass parts, more preferably 0.01~1 mass parts.
In turn, in aligning agent for liquid crystal, the charge of element is promoted to escape as the charge movement promoted in liquid crystal orientation film
Compound, can also add and remember in page 69~73 of International Publication bulletin No. WO2011/132751 (2011.10.27 is disclosed)
Nitrogen-containing hetero cyclammonium shown in carry, formula [M1]~formula [M156].The amine can be directly appended in aligning agent for liquid crystal, be preferably made
0.1~10 mass % of concentration, preferably 1~7 mass % solution after add.The solvent does not have as long as dissolving particular polymers
It is particularly limited to.
In aligning agent for liquid crystal of the invention, in addition to above-mentioned poor solvent, cross-linked compound, take resin coating or liquid crystal
Except the compound improved to uniformity, the surface smoothness of the film thickness of film and the compound for promoting charge to escape, it can also contain
Have so that the adherence of liquid crystal orientation film and substrate improve for the purpose of silane coupling agent, and then with when being burnt into film efficiency it is good
The imidizate promotor etc. for the purpose of the imidizate based on heating of polyimide precursor is carried out well.
<liquid crystal orientation film liquid crystal indicates element>
Liquid crystal orientation film of the invention is that above-mentioned aligning agent for liquid crystal is coated on substrate, obtained from being dried, being burnt into
Film.As the substrate for being coated with aligning agent for liquid crystal of the invention, it is not particularly limited as long as the high substrate of the transparency, it can also be with
Use plastic bases such as glass substrate, silicon nitride board, acrylic compounds substrate, polycarbonate substrate etc..At this point, using being formed with
It is preferred from the viewpoint of the simplification of technique when the substrate of the ITO electrode for driving liquid crystal etc..In addition, reflection-type
Liquid crystal indicates in element, if only unilateral substrate, then also can be used the opaque materials such as silicon wafer, electrode at this time can also be with
Use the material of the reflected lights such as aluminium.
The coating method of aligning agent for liquid crystal is industrially generally by silk-screen printing, offset printing, flexible printing or spray
The method of the progress such as method of the use of ink and water.As other coating methods, it is known to infusion process, roll coater method, slit coater method, spinner method
Or spray-on process etc..
Wherein, polymer can contained component ratio, polymer as described above by aligning agent for liquid crystal of the invention
Molecular weight maintains higher while realizing the low viscosity of aligning agent for liquid crystal, therefore can be suitably used for the painting based on ink-jet method
Cloth, membrane formation process.
After aligning agent for liquid crystal is applied on substrate, it can use hot plate, thermal cycle type baking oven or IR (infrared ray) type and dry
The heating meanss such as case, evaporate solvent, so that liquid crystal orientation film be made.Drying, firing process after coating of liquid crystalline alignment agent can
To select arbitrary temperature and time.Generally for the contained solvent of abundant removal, it can enumerate: be burnt at 50~120 DEG C
At 1~10 minute, 5~120 minutes conditions are then burnt at 150~300 DEG C.The thickness mistake of liquid crystal orientation film after firing
Bao Shi, liquid crystal indicates that the reliability of element reduces sometimes, therefore preferably 5~300nm, more preferably 10~200nm.
Aligning agent for liquid crystal of the invention can pass through polish-brush processing, light orientation processing etc. on being applied to substrate and after being burnt into
Carry out orientation process, in addition without orientation process in vertically oriented purposes etc., thus as liquid crystal orientation film come using.Mill
Known method, apparatus can be used in the orientation process such as brush processing, light orientation processing.
An example of production method as liquid crystal cells is said so that the liquid crystal of passive-matrix structure indicates element as an example
It is bright.It should be noted that or being equipped with the switching such as TFT (thin film transistor (TFT)) member constituting each pixel portion that image indicates
The liquid crystal of the active matrix structure of part indicates element.
Specifically, preparing the substrate of transparent glass system, ordinary electrode is set on one substrate, in another substrate
Upper setting segmented electrode.These electrodes can for example use ITO electrode, be schemed to can be carried out desired image expression
Case.Then, on each substrate, insulating film is set in a manner of covering ordinary electrode and segmented electrode.Insulating film such as can be with
Using the SiO formed by sol-gel method2-TiO2Film.
Then, liquid crystal orientation film is formed on each substrate, on one substrate takes another substrate with mutual liquid crystal
The mode opposite to film surface is overlapped, and periphery is bonded with sealant.In sealant, for control base board interval, can usually it mix
Enter to have spacer, additionally, it is preferred that the face inner part in not set sealant is also scattered with the spacer of substrate gap control.?
A part of sealant is provided with can be from the opening portion of external filling liquid crystal.Then, by being set to the opening portion of sealant, to
Liquid crystal material is injected in the space surrounded by 2 substrates and sealant, then, which is sealed with bonding agent.Injection can
To use vacuum impregnation, the method for utilizing capillarity in an atmosphere also can be used.Eurymeric can be used in liquid crystal material
Any one of liquid crystal material, negative type liquid crystal material, preferably negative type liquid crystal material.Then, the setting of polarizing film is carried out.Specifically
For, in a pair of of polarizing film of face stickup with liquid crystal layer opposite side of 2 substrates.
Embodiment is enumerated below, the present invention is described in more detail, but the present invention is not limited to them.Following abbreviations used are such as
It is lower described.
Bis- (4- amino-benzene oxygen) pentanes of DA-1:1,5-
DA-2:4,4 '-diaminodiphenyl-methane
DA-3:4,4 '-diamino-diphenyl amine, CA-1: pyromellitic acid anhydride
CA-2:1,2,3,4- cyclobutane tetracarboxylic dianhydride
CA-3:3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride
NMP:N- N-methyl-2-2-pyrrolidone N, GBL: gamma butyrolactone,
BCS: butyl cellosolve, PB:1- butoxy -2- propyl alcohol
DME: dimethyl ether
DPM: dipropylene glycol monomethyl ether
DAA: diacetone alcohol, DEDG: diethylene glycol diethyl ether
DIBC:2,6- 2,6-dimethyl-4-heptanol
AD-1: the compound of following formula
<measurement of viscosity>
The viscosity of polyamic acid, aligning agent for liquid crystal etc. is using E type viscosimeter (Toki Sangyo Co., Ltd.'s system) in temperature 25
It is measured at DEG C.
<measurement of solid component concentration>
Solution 1.0g is weighed in aluminum cup, after heating under conditions of 200 DEG C, 2 hours, measurement remains on cup
Amount of solid measures the solid component concentration of solution.
[manufacture of polyamic acid A1]
DA-1 171.8g is added in the 2000ml flask with agitating device and with nitrogen ingress pipe, adds NMP
1676g is stirred to dissolve in supplying nitrogen.CA-1 113.8g is added when stirring the diamine solution under water cooling, into
And NMP is added in such a way that solid component concentration becomes 12 weight %, 20 are stirred when heating under 50 degree in a nitrogen atmosphere
Hour, obtain the solution (viscosity: 90mPas) of polyamic acid (A1).Polyamic acid (A1) solution is weighed in aluminum cup
1.0g, solid component concentration when handling under conditions of 200 DEG C 2 hours are 11.2 weight %.
[manufacture of polyamic acid solution a1]
Relative to polyamic acid (A1) solution 535.7g, NMP 264.3g and BCS 200.0g is added, solid component is obtained
The concentration of concentration is polyamic acid solution (a1) solution of 6.0 weight %.
[manufacture of polyamic acid solution a2]
Relative to polyamic acid (A1) solution 535.7g, NMP 264.3g and PB 200.0g is added, it is dense to obtain solid component
The concentration of degree is polyamic acid solution (a2) solution of 6.0 weight %.
[manufacture of polyamic acid solution a3]
Relative to polyamic acid (A1) solution 535.7g, NMP 264.3g and DME 200.0g is added, solid component is obtained
The concentration of concentration is the polyamic acid solution (a3) of 6.0 weight %.
[manufacture of polyamic acid A2]
DA-1 100.8g and DA-5 34.9g is added in the 2000ml flask with agitating device and with nitrogen ingress pipe,
NMP 1337g is added, is stirred to dissolve in supplying nitrogen.CA-1 is added when stirring the diamine solution under water cooling
92.2g, and then NMP is added in such a way that solid component concentration becomes 12 weight %, in a nitrogen atmosphere when being heated to 50 DEG C
Stirring 20 hours, obtains the solution (viscosity: 520mmPas) of polyamic acid (A2).
[manufacture of polyamic acid B1]
In the 2000ml four-hole boiling flask with agitating device and with nitrogen ingress pipe be added DA-3 87.7g, addition NMP with
Solvent (following solvent 1) 1052.5g made of GBL is blended with the ratio of each 50 weight %, stirring in supplying nitrogen keeps its molten
Solution.1 382.7g of CA-2 70.1g and solvent is added when stirring the diamine solution under water cooling, in a nitrogen atmosphere in water
Cold lower stirring 3 hours.Then, it adds DA-2 21.8g and 1 191.3g of solvent and stirs.After DA-2 dissolution, CA-3 is added
1 287.0g of 33.0g and solvent is stirred 3 hours under water cooling in a nitrogen atmosphere again, to obtain solid component concentration and be
The solution (viscosity: 65mPas) of the polyamic acid (B1) of 9.8 weight %.Polyamic acid (B1) solution is weighed in aluminum cup
1.0g, solid component concentration when handling under conditions of 200 DEG C 2 hours are 9.8 weight %.
[manufacture of polyamic acid B2]
DA-3 95.6g and DA-4 are added in the 2000ml four-hole boiling flask with agitating device and with nitrogen ingress pipe
18.2g adding NMP 967g, stirred to dissolve in supplying nitrogen.It is added when stirring the diamine solution under water cooling
CA-2 54.8g and NMP 276g is stirred 3 hours under water cooling in a nitrogen atmosphere.Then, CA-4 75.0g is added and with solid
Body constituent concentration adds NMP as the mode of 15 weight %, stirs 12 hours, obtains when heating at 50 DEG C in a nitrogen atmosphere
To polyamic acid (B2) solution (viscosity: 302mmPas).
[embodiment 1]
Polyamic acid (B1) solution 153.4g is weighed, NMP 1.3g is added into the solution, addition has 3- glycidoxy
GBL solution 38.5g, GBL 95.9g, DME 53.5g and the DIBC 50.0g of 1.3 weight % of propyl-triethoxysilicane, in room
Temperature lower stirring 1 hour.Then, a3 107.5g is added, and then is stirred 1 hour, to obtain solid component: NMP:GBL:DME:
The ratio of DIBC is solution (C1) 500.0g of 4.3:30:40.7:15:10 (weight %).
[embodiment 2]
Polyamic acid (B1) solution 153.4g is weighed, NMP 1.3g and addition are added into the solution 3- glycidoxy
GBL solution 38.5g, GBL 120.9g, DME 28.5g and the DIBC 50.0g of 1.3 weight % of propyl-triethoxysilicane, in room
Temperature lower stirring 1 hour.Then, a3 107.5g is added, and then is stirred 1 hour, to obtain solid component: NMP:GBL:DME:
Solution (C2) 500.0g of DIBC=4.3:30:40.7:10:10 (weight %).
[embodiment 3]
By polyamic acid (B2) the solution 106.6g's of polyamic acid (A2) the solution 33.3g of 12 weight % and 15 weight %
After mixed liquor stirs 30 minutes, NMP 11.1g is added to it, addition has 1.0 weight of 3- epoxy propoxy propyl triethoxysilane
Nmp solution 20.0g, GBL 204.0g, DME 75.0g and the DIBC 50.0g for measuring %, are stirred at room temperature 3 hours, thus
Polymer solids ingredient ratio to A2 and B2 is 2:8, solid component: NMP:GBL:DME:DIBC=4.2:30:40.8:15:10
Solution (C8) 500.0g of (weight %).
[embodiment 4]
By polyamic acid (B2) the solution 106.6g's of polyamic acid (A2) the solution 33.3g of 12 weight % and 15 weight %
After mixed liquor stirs 30 minutes, NMP 5.1g is added to it, addition has 1.0 weight of 3- epoxy propoxy propyl triethoxysilane
Measure the nmp solution 20.0g of %, be added have the nmp solution 6.0g of 10 weight % of AD-1, GBL 204.0g, DME 75.0g and
DIBC 50.0g is stirred at room temperature 3 hours, so that the polymer solids ingredient ratio for obtaining A2 and B2 is 2:8, solid component:
Solution (C9) 500.0g of NMP:GBL:DME:DIBC=4.2:30:40.8:15:10 (weight %).
[comparative example 1]
Polyamic acid (B1) solution 153.4g is weighed, NMP 1.3g is added into the solution, addition has 3- glycidoxy
GBL solution 38.5g, GBL 145.9g and the DME 53.5g of 1.3 weight % of propyl-triethoxysilicane, it is small to be stirred at room temperature 1
When.Then, a3 107.5g is added, and then is stirred 1 hour, to obtain solid component: NMP:GBL:DME=4.3:30:
Solution (C3) 500.0g of 50.7:15 (weight %).
[comparative example 2]
Polyamic acid (B1) solution 153.4g is weighed, NMP 1.3g is added into the solution, addition has 3- glycidoxy
GBL solution 38.5g, GBL 145.9g and the BCS 53.5g of 1.3 weight % of propyl-triethoxysilicane, it is small to be stirred at room temperature 1
When.Then, a1 107.5g is added, and then is stirred 1 hour, to obtain solid component: NMP:GBL:BCS=4.3:30:
Solution (C4) 500.0g of 50.7:15 (weight %).
[comparative example 3]
Polyamic acid (B1) solution 153.4g is weighed, NMP 1.3g is added into the solution, addition has 3- glycidoxy
GBL solution 38.5g, GBL 95.9g, BCS 53.5g and the DPM 50.0g of 1.3 weight % of propyl-triethoxysilicane, in room temperature
Lower stirring 1 hour.Then, a1 107.5g is added, and then is stirred 1 hour, to obtain solid component: NMP:GBL:BCS:DPM
Solution (C5) 500.0g of=4.3:30:40.7:15:10 (weight %).
[comparative example 4]
Polyamic acid (B1) solution 153.4g is weighed, NMP 1.3g is added into the solution, addition has 3- glycidoxy
GBL solution 38.5g, GBL 95.9g, DME 53.5g and the DPM 50.0g of 1.3 weight % of propyl-triethoxysilicane, in room temperature
Lower stirring 1 hour.Then, a3 107.5g is added, and then is stirred 1 hour, to obtain solid component: NMP:GBL:DME:DPM
Solution (C6) 500.0g of=4.3:30:40.7:15:10 (weight %).
[comparative example 5]
Polyamic acid (B1) solution 153.4g is weighed, NMP 1.3g is added into the solution, addition has 3- glycidoxy
GBL solution 38.5g, GBL 95.9g, PB 53.5g and the DPM 50.0g of 1.3 weight % of propyl-triethoxysilicane, in room temperature
Lower stirring 1 hour.Then, a2 107.5g is added, and then is stirred 1 hour, to obtain solid component: NMP:GBL:PB:DPM
Solution (C7) 500.0g of=4.3:30:40.7:15:10 (weight %).
Are measured by viscosity, is shown in table 2 after being filtered with 1 μm of the filter in aperture for Examples 1 to 4 and the Comparative Examples 1 to 5.
Then, implement coating evaluation below.
[ink-jet application evaluation]
For the Examples 1 to 4 and the Comparative Examples 1 to 5 of above-mentioned preparation, using ink-jet coating apparatus (ISHIIHYOKI CO.,
LTD. make) it is applied in TFT substrate.In 127 μm of injector spacing, coating speed 250mm/ seconds, sendout 70pL, spreading area 36
It is carried out under the application conditions of × 36mm.In addition, coating is with the coating of following condition: carrying out predrying in 1 minute on 110 DEG C of hot plate
Afterwards, when using IR baking oven to be burnt under conditions of 15 minutes at 230 DEG C, the thickness of film becomes 120nm.
[evaluation method of film]
For by coated substrate at 110 DEG C film obtained from predrying, compare the shadow because of contact hole or wiring
The uneven degree for ringing the point or striated that generate, is evaluated with 4 grades below.
It can be set as Lv4 when visual confirmation significantly unevenness in whole face, part can be set as Lv3, mesh when visual confirmation unevenness
It being set as Lv2 when depending on can't see unevenness, being set as Lv1 when also absolutely not uneven under an optical microscope.
In addition, be also coated on the glass substrate that surface is vapor-deposited with chromium, for film end there are tone variations
The width of the part of (film thickness is uneven) is evaluated with vernier caliper measurement length as Halo size.It should be noted that recognizing
Value for Halo size is smaller, good film.
In turn, actual measurement paint film width is steady as size using the difference of measured value and setting value for setting dispensing area
It is qualitative to evaluate.It should be noted that in the evaluation, it is believed that value is smaller, good film.
These results are shown in table 1,2.
[table 1]
[table 2]
It should be noted that Japanese patent application 2016-072567 explanation that on March 31st, 2016 is filed an application
The full content that book, claims, drawing and description are made a summary is quoted so far, the disclosure as specification of the invention
And it is incorporated to.
Claims (14)
1. a kind of aligning agent for liquid crystal, which is characterized in that contain:
At least one kind of polymer in the group that the polyimides by polyimide precursor and as its acid imide compound forms；
And
Solvent containing following solvents A, solvent B and solvent C,
Solvent A: selected from by n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, gamma-butyrolacton and dimethyl-imidazolinone
It is at least one kind of in the group of composition,
Solvent B: dimethyl ether,
Solvent C: following formula (a) compound represented,
R1、R2It is each independently the alkyl of the carbon number 1~8 of straight or branched, wherein R1And R2Carbon number add up to 4 with
On.
2. aligning agent for liquid crystal according to claim 1, wherein solvent A is n-methyl-2-pyrrolidone or gamma-butyrolacton.
3. aligning agent for liquid crystal according to claim 1, wherein solvent C is selected from the group being made of following formula a-1~a-48
In it is at least one kind of,
4. aligning agent for liquid crystal described in any one of claim 1 to 3, wherein solvent C be selected from by following formula a-22 and
It is at least one kind of in the group of formula a-37 composition,
5. aligning agent for liquid crystal according to any one of claims 1 to 4, wherein polyimide precursor has following formula (1)
Shown in structure,
X1For the quadrivalent organic radical group from tetracarboxylic acid derivatives, Y1For the bivalent organic group from diamines, R1For hydrogen atom or
The alkylidene of carbon atom number 1~5, A1And A2Be each independently the alkyl of hydrogen atom or carbon number 1~5, the alkenyl of carbon number 2~5,
Or the alkynyl of carbon number 2~5.
6. aligning agent for liquid crystal according to any one of claims 1 to 5, wherein the gross mass relative to aligning agent for liquid crystal
Solvent A containing 20~80 mass %.
7. aligning agent for liquid crystal described according to claim 1~any one of 6, wherein the gross mass relative to aligning agent for liquid crystal
Solvent B containing 1~30 mass %.
8. aligning agent for liquid crystal according to any one of claims 1 to 7, wherein the gross mass relative to aligning agent for liquid crystal
Solvent C containing 1~30 mass %.
9. aligning agent for liquid crystal described according to claim 1~any one of 8, wherein total matter relative to aligning agent for liquid crystal
Measure %, the solvent A containing 50~80 mass %, the solvent B containing 1~30 mass %, the solvent C containing 1~20 mass %.
10. aligning agent for liquid crystal described according to claim 1~any one of 9, wherein the gross mass relative to aligning agent for liquid crystal
Contain solvent B containing the solvent B and solvent C for adding up to 10~60 mass %, and compared to solvent C more.
11. aligning agent for liquid crystal described according to claim 1~any one of 9, wherein contain 1~20 matter compared to solvent C more
Measure the solvent B of %.
12. aligning agent for liquid crystal described according to claim 1~any one of 11 is used for ink-jet method film forming.
13. a kind of liquid crystal orientation film, the aligning agent for liquid crystal as described in any one of claim 1~12 is obtained.
14. a kind of liquid crystal indicates element, has liquid crystal orientation film described in claim 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-072567 | 2016-03-31 | ||
| JP2016072567 | 2016-03-31 | ||
| PCT/JP2017/013419 WO2017170943A1 (en) | 2016-03-31 | 2017-03-30 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
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| JP (1) | JP6866892B2 (en) |
| KR (1) | KR102292494B1 (en) |
| CN (1) | CN109196412B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114058379A (en) * | 2020-07-31 | 2022-02-18 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element |
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| JP6904216B2 (en) * | 2017-10-30 | 2021-07-14 | Jnc株式会社 | A liquid crystal alignment agent for forming a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element using the same. |
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| KR102292494B1 (en) | 2021-08-20 |
| KR20180124127A (en) | 2018-11-20 |
| TWI823833B (en) | 2023-12-01 |
| CN109196412B (en) | 2021-08-24 |
| JP6866892B2 (en) | 2021-04-28 |
| WO2017170943A1 (en) | 2017-10-05 |
| JPWO2017170943A1 (en) | 2019-03-07 |
| TW201809231A (en) | 2018-03-16 |
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