CN109923469A - 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 PDF

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CN109923469A
CN109923469A CN201780069120.9A CN201780069120A CN109923469A CN 109923469 A CN109923469 A CN 109923469A CN 201780069120 A CN201780069120 A CN 201780069120A CN 109923469 A CN109923469 A CN 109923469A
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liquid crystal
aligning agent
formula
carbon number
polyimide precursor
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CN109923469B (en
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石川和典
金信郁
中原翔一朗
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

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  • Polymers & Plastics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A kind of aligning agent for liquid crystal contains following (A) ingredients and (B) ingredient.It should be noted that it is following it is various in mark definition such as specification in it is recorded.(A) ingredient: at least one kind of polymer being selected from polyimide precursor and the group for forming polyimides obtained from the polyimide precursor closed loop obtained from being reacted by the diamine component of the diamines containing following formula (1) with tetracarboxylic acid derivatives ingredient, (B) ingredient: with part-structure shown in 2 or more following formula (2) and molecular weight is 2500 compounds below.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
Technical field
The present invention relates to novel aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal to indicate element.
Background technique
Liquid crystal indicates that element is widely used now as the expression device for realizing slim light weight.The usual liquid crystal indicates Element uses liquid crystal orientation film to determine the state of orientation of liquid crystal.
As polymer used in liquid crystal orientation film, it is known that polyimides, polyamide, polyamidoimide etc., usually Aligning agent for liquid crystal made of solvent is dissolved in using by these polymer, its precursor.
In recent years, the LCD TV of big picture and fine indicates member with liquid crystal on the way for this by extensive functionization For part, it is desirable that can be resistant to the characteristic of the long-time service in harsh use environment.Therefore, liquid crystal orientation film used herein needs It is higher than previous reliability.For this problem, proposes and used the aligning agent for liquid crystal of special additive (referring to patent text It offers 1).
Existing technical literature
Patent document
Patent document 1: International Publication No. 2010/074269
Summary of the invention
Problems to be solved by the invention
Recently, liquid crystal indicates that the brightness of backlight (BL) used in element further increases, for liquid crystal orientation film Orientation stability, electrical characteristics are also required considerably beyond previous horizontal excellent light resistance, relaxation properties.
The solution to the problem
The inventors of the present invention have made intensive studies, and are selected from by polyimide precursor as a result, it has been found that passing through and containing and gather this The aligning agent for liquid crystal of the compound of polymer and specific structure in the group of the composition of polyimides made of imide precursor closed loop, It is able to solve the above problem, to reach the present invention, the polyimide precursor is make the diamines containing specific structure two Obtained from amine component is reacted with tetracarboxylic acid derivatives ingredient.
The 1st mode of the invention for reaching above-mentioned purpose is a kind of aligning agent for liquid crystal, contains following (A) ingredients and (B) Ingredient.
(A) ingredient: selected from by polyimide precursor and forming polyimides obtained from the polyimide precursor closed loop Group at least one kind of polymer, the polyimide precursor is the diamine component and tetracarboxylic acid for making the diamines containing following formula (1) Obtained from the reaction of acid derivative ingredient
(in formula (1), R1Indicate hydrogen or 1 valence organic group.Q1Indicate the alkylidene of carbon number 1~5.Cy is to indicate to include azepine Cyclobutane, pyrrolidines, piperidines or hexamethylene imine aliphatic heterocycle divalent group, the loop section at them is optionally bonded Substituted base.R2And R3It is each independently 1 valence organic group.Q and r is each independently 0~4 integer.Wherein, q and r In the case where adding up to 2 or more, multiple R2And R3With above-mentioned definition.)
(B) ingredient: structure and molecular weight with 2 or more following formula (2) are 2500 compounds below
(in formula (2), R1Indicate the alkyl of hydrogen atom or carbon number 1~3, R2And R3Each independently represent hydrogen atom, carbon number 1 ~3 alkyl or *3-CH2-O-R11(R11Indicate the alkyl of hydrogen atom or carbon number 1~3, " *3" indicate and R2And R3It is bonded The connecting key of carbon atom), " *1" and " *2" indicate and the connecting keys of other atoms.)
The 2nd mode of the invention for reaching above-mentioned purpose is the aligning agent for liquid crystal of the 1st mode, wherein the two of previously described formula (1) Amine is indicated with following formula (3).
(in formula (3), R1For hydrogen atom, methyl or tert-butoxycarbonyl, R2And R3It is each independently hydrogen atom or methyl, Q1For the straight-chain alkyl-sub of carbon number 1~5.)
The 3rd mode of the invention for reaching above-mentioned purpose is the aligning agent for liquid crystal of the 1st mode or the 2nd mode, wherein aforementioned The containing ratio of diamines shown in formula (1) is 1 mole of %~80 mole % relative to 1 mole of whole diamine components.
The 4th mode of the invention for reaching above-mentioned purpose is the aligning agent for liquid crystal of any one of the 1st mode~the 3rd mode, Wherein, the compound of aforementioned (B) ingredient is selected from least one of following formula compound.
The 5th mode of the invention for reaching above-mentioned purpose is the 1st mode~the 4th mode aligning agent for liquid crystal, also includes The polyimide precursor for containing the structural unit of following formula (5) is used as (C) ingredient.
(in formula (5), X2For the 4 valence organic groups from tetracarboxylic acid derivatives, Y2For the divalent organic group from diamines, R4For hydrogen atom or the alkyl of carbon number 1~5, Z1And Z2The respective carbon number 1~10 for standing alone as hydrogen atom, optionally there is substituent group The alkynyl of alkyl, the alkenyl of carbon number 2~10 or carbon number 2~10.)
The 6th mode of the invention for reaching above-mentioned purpose is the aligning agent for liquid crystal of the 5th mode, and it includes contain previously described formula (5) X in2For the polyimide precursor of the structural unit of following structures.
The 7th mode of the invention for reaching above-mentioned purpose is a kind of liquid crystal orientation film, by the 1st mode~the 6th mode The aligning agent for liquid crystal of any one obtains.
The 8th mode of the invention for reaching above-mentioned purpose is that a kind of liquid crystal indicates that element, the liquid crystal for having the 7th mode take To film.
The effect of invention
Aligning agent for liquid crystal according to the present invention can obtain the excellent liquid crystal aligning of BL patience, orientation stability, relaxation properties Film.
Specific embodiment
Aligning agent for liquid crystal of the invention contains (A) ingredient and (B) ingredient.It is carried out specifically below for each structure condition It is bright.
< (A) ingredient >
(A) ingredient contained in aligning agent for liquid crystal of the invention refers to being selected from by polyimide precursor and keeps the polyamides sub- Polyimides obtained from amine precursor closed loop composition group at least one kind of polymer, the polyimide precursor be make containing Obtained from the diamine component of the diamines (hereinafter also referred to specific diamines) of following formula (1) is reacted with tetracarboxylic acid derivatives ingredient.
In above-mentioned formula (1), R1Indicate hydrogen or 1 valence organic group, the preferably straight chained alkyl of hydrogen atom or carbon number 1~3, more Preferably hydrogen atom or methyl.
In addition, R1Or the blocking group for generating reaction of leaving away by heat, being replaced into hydrogen atom.From liquid crystal aligning From the viewpoint of the storage stability of agent, which will not leave away at room temperature, preferably in 80 DEG C or more, more preferable 100 DEG C or more, it is 150~200 DEG C particularly preferred at leave away, formed hydrogen atom be suitable.Such as 1,1- dimethyl -2- can be enumerated Chloroethoxycarbonyl, 1,1- dimethyl -2- cyanoethoxy carbonyl, tert-butoxycarbonyl etc., preferably tert-butoxycarbonyl.
Q1The alkylidene for indicating carbon number 1~5, from the viewpoint of convieniently synthesized property, the straight chain of preferably carbon number 1~5 is sub- Alkyl.Cy is the divalent group for indicating the aliphatic heterocycle comprising azetidine, pyrrolidines, piperidines or hexamethylene imine, from From the viewpoint of the simplicity of synthesis, preferably azetidine, pyrrolidines or piperidines.In addition, the loop section at them can be with It is bonded with substituent group.
R2And R3It is each independently 1 valence organic group, q, r are each independently 0~4 integer.Wherein, q's and r is total In the case where being calculated as 2 or more, multiple R2And R3With above-mentioned definition.From the viewpoint of the simplicity of synthesis, preferably R2And R3For Methyl.
In addition, the bonding position of the amino in the phenyl ring of diamines above-mentioned for composition does not limit, it is preferred that amino phase 3 or 4 are in, relative to Q for the nitrogen-atoms on Cy1And R1The nitrogen-atoms being bonded is in 3 or 4 positions, more excellent Phase selection is in 4 for the nitrogen-atoms on Cy, relative to Q1And R1The nitrogen-atoms being bonded is in 4 positions.
Think the structure of one of the main reason for playing effect of the present invention, it is believed that be the diamines by above-mentioned formula (1) in addition to 2 Structure (hereinafter also referred to specific structure) except primary amino group.It is thus regarded that being used even if not using the diamines of above-mentioned formula (1) Diamine compound containing 2 or more specific structures, tetracarboxylic dianhydride with specific structure etc., can also be to of the invention Polymer used in aligning agent for liquid crystal imports specific structure, but synthesizes conveniently above, it is preferable to use the diamines of above-mentioned formula (1).
Diamines shown in above-mentioned formula (1) of the invention is preferably following formula (3) compound represented.
In above-mentioned formula (3), R1For hydrogen atom, methyl or tert-butoxycarbonyl.R2And R3It is each independently hydrogen atom or first Base, Q1For the straight-chain alkyl-sub of carbon number 1~5.
As the concrete example of diamines shown in above-mentioned formula (3), such as following formula (3-1)~following formula (3-10) can be enumerated Shown in diamines.In following formula, Boc indicates tert-butoxycarbonyl.
< (B) ingredient >
(B) ingredient contained in aligning agent for liquid crystal of the invention refer to structure with 2 or more following formula (2), And molecular weight is 2500 compounds below.
In above-mentioned formula (2), R1Indicate the alkyl of hydrogen atom or carbon number 1~3.
R2And R3Each independently represent the alkyl or * of hydrogen atom, carbon number 1~33-CH2-O-R11(R11Indicate hydrogen atom or The alkyl of carbon number 1~3, " *3" indicate and R2And R3The connecting key for the carbon atom being bonded), " *1" and " *2" indicate and other atoms Connecting key.
As R1And R11Carbon number 1~3 alkyl, such as methyl, ethyl, n-propyl, isopropyl can be enumerated.Preferably Hydrogen atom or methyl, more preferable hydrogen atom.It should be noted that R1And R11It can be mutually identical or different.
As R2And R3Carbon number 1~3 alkyl, above-mentioned R can be enumerated1In illustrated by group.Preferably hydrogen atom, *3-CH2- OH or *3-CH2-OCH3.It should be noted that R2And R3It can be mutually identical or different.
As the group (following presentation " R with nitrogen atom bonding in above-mentioned formula (2)4"), can enumerate such as hydrogen atom, 1 valence organic group or divalent organic group with carbonyl and the nitrogen atom bonding in above-mentioned formula (2).It should be noted that R4 In the case where for above-mentioned divalent organic group, in above-mentioned formula (2) nitrogen-atoms and carbonyl be formed together ring structure.
Structure number shown in above-mentioned formula (2) in the compound of (B) ingredient of the invention if 2 or more can, preferably 2 It is 2~6 a~8, more preferable.Group " * possessed by compound (B)4-CH2-O-R1(“*4" indicate and the company of carbon atom Connect key.R1With it is above-mentioned synonymous) " number, preferably every 1 molecule be 2 or more, it is 3~8 more preferable, 3 further preferred~ 6.
The preferred concrete example of structure as above-mentioned formula (2) can enumerate such as following formula (2-1)~following formula (2-6) The compound etc. being respectively shown in.
In above-mentioned formula (2-1)~above-mentioned formula (2-5), " *1" indicate connecting key.In formula (2-5), R5For the alkane of carbon number 1~3 Base." * in above-mentioned formula (2-6)1" and " *5" indicate that the nitrogen-atoms being bonded to above-mentioned formula (2-6) and carbonyl are formed together ring Group connecting key.
The molecular weight of compound (B) is 2500 or less.It is good from the coating of dissolubility and aligning agent for liquid crystal for solvent From the viewpoint of good, which is preferably 2000 or less, further preferred 1200 or less.
As the concrete example of compound (B), can enumerate such as following formula compound represented.
Total 100 parts by weight of the compounding ratio of compound (B) relative to the component of polymer contained in aligning agent for liquid crystal Preferably 0.1 parts by weight~100 parts by weight.The lower limit of the preferred compounding ratio of compound (B) is relative to aligning agent for liquid crystal In 100 parts by weight of total of component of polymer that contain be 1 parts by weight or more, more than further preferred 3 parts by weight.In addition, right Below the upper limit of the compounding ratio, more preferably 50 parts by weight, below further preferred 20 parts by weight.It should be noted that Compound (B) can be used alone or combine two or more come using.
< polyimide precursor and polyimides >
The polyimide precursor contained in aligning agent for liquid crystal of the invention is by containing diamines shown in above-mentioned formula (1) Polyimide precursor obtained from the reacting of diamine component and tetracarboxylic acid derivatives ingredient.Here, polyimide precursor is polyamides Amino acid or poly amic acid ester.
Tetracarboxylic acid derivatives can enumerate acid dianhydride, dicarboxylic diester, diester diacid chloride etc..
Polyamic acid is reacted by diamine component with acid dianhydride to obtain, and poly amic acid ester passes through diamine component and dicarboxylic acids The reaction of diester or diester diacid chloride obtains.
The polyimides contained in aligning agent for liquid crystal of the invention is to make to gather obtained from these polyimide precursor closed loops Acid imide is all useful as the polymer for obtaining liquid crystal orientation film.
The polyimide precursor contained in aligning agent for liquid crystal of the invention is to contain structural unit shown in following formula (4) Polymer.
In above-mentioned formula (4), X1For the 4 valence organic groups from tetracarboxylic acid derivatives, Y1For the divalent of the diamines from formula (1) Organic group, R4For hydrogen atom or the alkyl of carbon number 1~5.From the viewpoint of the easy degree for carrying out acyl Asia by heating, R4Preferably hydrogen atom, methyl or ethyl.
For obtaining in the diamine component of above-mentioned polyimide precursor, for diamines shown in above-mentioned formula (1) containing than There is no limit be easy to get effect of the invention to rate when containing ratio is more.The ratio of diamines shown in above-mentioned formula (1) is relative to complete It rubs 1 mole of portion's diamine component preferably 1 mole of %~80 mole %, more preferable 5 moles of %~60 mole %, further preferred 10 You are %~40 mole %.
X1As long as being not particularly limited for 4 valence organic groups.In polyimide precursor, X1Two or more can be mixed.
If showing X1Concrete example can then enumerate following formula (X1-1)~following formula (X1-44) structure.From acquired From the viewpoint of, more preferably following formula (X1-1)~following formula (X1-14).
In above-mentioned formula (X1-1)~above-mentioned formula (X1-4), R5~R25It is each independently hydrogen atom, halogen atom, carbon number 1 ~6 alkyl, the alkenyl of carbon number 2~6, the alkynyl of carbon number 2~6, carbon number 1~6 containing fluorine atom 1 valence organic group or Phenyl, can be identical or different.From the viewpoint of liquid crystal aligning, R5~R25Preferably hydrogen atom, halogen atom, methyl, Or ethyl, more preferable hydrogen atom or methyl.As the specific structure of above-mentioned formula (X1-1), following formula (X1-1-1) can be enumerated Structure shown in~following formula (X1-1-6).From the viewpoint of from the sensitivity of liquid crystal aligning and light reaction, particularly preferably Following formula (X1-1-1).
In addition, polyimide precursor of the invention is other than above-mentioned formula (4), in the range that will not damage effect of the present invention It is interior also to contain structural unit shown in following formula (5).It should be noted that aligning agent for liquid crystal of the invention includes containing upper It, can be for under in the case where stating the polyimide precursor other than the polyimide precursor of structural unit shown in formula (4) State the polyimide precursor of structural unit shown in formula (5).
In above-mentioned formula (5), R4It is identical as the definition of above-mentioned formula (4).X2For 4 valence organic groups, including preference, with X in above-mentioned formula (4)1Definition it is identical.But aligning agent for liquid crystal of the invention is in addition to containing structure shown in above-mentioned formula (4) In the case where polyimide precursor other than the polyimide precursor of unit also comprising the structural unit containing above-mentioned formula (5), from From the viewpoint of the effect performance of obtained liquid crystal orientation film, particularly preferably above-mentioned formula (X1-8).Z1And Z2Each independently For hydrogen atom, the alkyl for the carbon number 1~10 that can have substituent group, the alkenyl of carbon number 2~10 or the alkynyl of carbon number 2~10.
The concrete example of alkyl as carbon number 1~10, can enumerate methyl, ethyl, propyl, butyl, tert-butyl, hexyl, Octyl, decyl, cyclopenta, cyclohexyl, dicyclohexyl etc..
As the alkenyl of carbon number 2~10, more than one CH for being present in abovementioned alkyl can be enumerated2-CH2It is replaced into CH= Group made of CH.More specifically, vinyl, allyl, 1- acrylic, isopropenyl, 2- cyclobutenyl, 1,3- can be enumerated Butadienyl, 2- pentenyl, 2- hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc..
As the alkynyl of carbon number 2~10, more than one CH for being present in abovementioned alkyl can be enumerated2-CH2It is replaced into C ≡ C Made of group.More specifically, acetenyl, 1- propinyl, 2-propynyl etc. can be enumerated.
The alkynyl of the alkyl of above-mentioned carbon number 1~10, the alkenyl of carbon number 2~10 and carbon number 2~10 is including substituent group The carbon number of total can have substituent group in the range of being no more than 10, and then can form ring structure by substituent group.It needs It is bright, form that ring structure refers between substituent group or substituent group with a part of of female skeleton is bonded formation by substituent group Ring structure.
As the example of substituent group, halogen radical, hydroxyl, sulfydryl, nitro, aryl, organic oxygroup, organic sulfur can be enumerated Base, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide groups, alkyl, alkenyl, alkynyl etc..
In polyimide precursor, usually the reactivity of amino, liquid crystal aligning are possible to drop if importing bulk structure It is low, therefore as Z1And Z2, more preferably hydrogen atom or can have substituent group carbon number 1~5 alkyl, particularly preferably hydrogen Atom, methyl or ethyl.
In above-mentioned formula (5), Y2For the bivalent organic group from the diamine component other than above-mentioned formula (1), for its structure It is not particularly limited.If enumerating Y2Concrete example can then enumerate following formula (Y-1)~following formula (Y-49) and following formula (Y- 57)~following formula (Y-114).In addition, diamine component can mix two or more.
In above-mentioned formula (Y-158), above-mentioned formula (Y-162)~above-mentioned formula (Y-165), n be 1~6 integer.
Boc in above-mentioned formula (Y-174), above-mentioned formula (Y-175), above-mentioned formula (Y-178) and above-mentioned formula (Y-179) indicates uncle Butoxy carbonyl.
The manufacturing method > of < polyamic acid
As the polyamic acid of polyimide precursor used in aligning agent for liquid crystal of the invention, can make containing the present invention The diamine component of diamines reacted with tetracarboxylic acid derivatives ingredient to obtain.
Specifically, can be synthesized by reacting tetracarboxylic dianhydride and diamines in presence of organic solvent.
It is if enumerating concrete example if polyamic acid generated dissolution is not particularly limited as organic solvent N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl caprolactam, dimethyl are sub- Sulfone, gamma-butyrolacton etc..In addition, methyl ethyl ketone, cyclohexanone, ring penta can be used in the case that the dissolubility of polyimide precursor is high Organic solvent shown in ketone, 4- hydroxy-4-methyl-2-pentanone or following formula (D-1)~following formula (D-3).
In above-mentioned formula (D-1), D1The alkyl for indicating carbon number 1~3, in above-mentioned formula (D-2), D2Indicate the alkyl of carbon number 1~3, In above-mentioned formula (D-3), D3Indicate the alkyl of carbon number 1~4.
They can be used alone or mix to use.In turn, even if not dissolving the molten of polyamic acid when being single use Agent, in the range of polyamic acid generated is not precipitated, also may be mixed in above-mentioned solvent come using.In addition, organic solvent In moisture become the reason of inhibiting polymerization reaction and then hydrolyzing polyamic acid generated, therefore organic solvent preferably makes With as far as possible by the organic solvent of dehydration and drying.
As the method for mixing diamine component and tetracarboxylic dianhydride in organic solvent, can enumerate by diamines dispersion or It is dissolved in the stirring of solution made of organic solvent, tetracarboxylic dianhydride directly or is dispersed or dissolved in organic solvent to add Method；The method of the addition diamines of solution made of organic solvent is dispersed or dissolved in tetracarboxylic dianhydride；Either alternatively or simultaneously by four The method etc. that carboxylic acid dianhydride and diamines are added to organic solvent can be any one method among them.
The temperature when synthesis of polyamic acid can choose -20 DEG C~150 DEG C of arbitrary temp, it is preferred that being in -5 DEG C In the range of~100 DEG C, it is 0 DEG C~80 DEG C more preferable.
In addition, the reaction time can arbitrarily select in the time of the polymerization-stable than polyamic acid long range, still Preferably 30 minutes~24 hours, it is 1 hour~12 hours more preferable.
Reaction can be carried out with arbitrary concentration, but if the diamine component of raw material and the concentration of tetracarboxylic dianhydride are too low It is difficult to obtain the polymer of high molecular weight, the viscosity of reaction solution is excessively high and be difficult to uniform stirring if excessive concentration, therefore preferably For 1 mass of mass %~50 %, the more preferable 5 mass mass of %~20 %.It can also be carried out with initial reaction stage with high concentration, then be chased after Added with solvent.
In the synthetic reaction of polyamic acid, the ratio between the molal quantity of the molal quantity of tetracarboxylic dianhydride relative to diamine component is preferred It is 0.8~1.2.In the same manner as common polycondensation reaction, molecular weight of the molar ratio closer to 1.0 polyamic acids generated It is bigger.
The polyamic acid obtained as described above is injected into poor solvent while reaction solution is sufficiently stirred, thus may be used Polymer to be precipitated, is recycled.It is additionally carried out and is precipitated for several times, after being washed with poor solvent, room temperature or heat drying, it is possible thereby to Obtain the powder of purified polyamic acid.
Poor solvent is not particularly limited, can enumerate water outlet, methanol, ethyl alcohol, 2- propyl alcohol, hexane, butyl cellosolve, Acetone, toluene etc., preferably water, methanol, ethyl alcohol, 2- propyl alcohol etc..
The manufacture > of < poly amic acid ester
The system of poly amic acid ester [1], [2] or [3] shown in following as polyimide precursor of the invention Method manufacture.
When [1] being manufactured by polyamic acid
Poly amic acid ester can be manufactured by the way that the polyamic acid manufactured as mentioned before to be esterified.
Specifically, can by make polyamic acid and esterifying agent in presence of organic solvent, -20 DEG C~150 DEG C, it is excellent It selects and reacts 30 minutes~24 hours, preferably 1 hour~4 hours at 0 DEG C~50 DEG C to manufacture.
As esterifying agent, the esterifying agent that can be readily removable preferably by purifying can enumerate N, N- dimethyl Formamide dimethylacetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N, N- bis- Methylformamide di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1- methyl -3- p-methylphenyl three Nitrence, 1- ethyl -3- p-methylphenyl triazenes, 1- propyl -3- p-methylphenyl triazenes, 4- (4,6- dimethoxy -1,3,5- three Piperazine -2- base) -4- methylmorpholinium chloride etc..The additive amount of esterifying agent relative to 1 mole of repetitive unit of polyamic acid preferably 2 molar equivalents~6 molar equivalents.
As organic solvent, such as n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone or γ-Ding Nei can be enumerated Ester, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or 1,3- dimethyl-2-imidazolidinone.In addition, poly- In the case that imide precursor is high to the dissolubility of solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4- hydroxyl -4- first can be used Solvent shown in base -2 pentanone or previously described formula (D-1)~previously described formula (D-3).
Solvent can be used alone or mix to use.In turn, even the solvent of insoluble polyimide precursor, in institute In the range of the polyimide precursor of generation is not precipitated, also may be mixed in aforementioned solvents come using.In addition, the moisture in solvent The reason of as inhibiting polymerization reaction and then hydrolyzing polyimide precursor generated, therefore it is preferable to use by de- for solvent The dry solvent of water.
Solvent used in above-mentioned reaction is from the viewpoint of the dissolubility of polymer, preferably N, N- dimethyl formyl Amine, n-methyl-2-pyrrolidone or gamma-butyrolacton, they can be used a kind or mix two or more come using.It is dense when manufacture Degree is from the viewpoint of the precipitation for being not likely to produce polymer and being easy to get high molecular weight body, preferably 1 matter of mass %~30 Measure %, the more preferable 5 mass mass of %~20 %.
[2] by tetracarboxylic acid acid diesters diacid chloride with diamines when reacting to manufacture
Poly amic acid ester can be manufactured by tetracarboxylic acid acid diesters diacid chloride with the diamine component containing diamines of the invention.
Specifically, can be by making tetracarboxylic acid acid diesters diacid chloride and diamines in the presence of alkali and organic solvent, -20 DEG C 30 minutes~24 hours, preferably 1 hour~4 hours are reacted at~150 DEG C, preferably 0 DEG C~50 DEG C to manufacture.
As alkali, pyridine, triethylamine, 4-dimethylaminopyridine etc. can be used, but in order to leniently be reacted, Preferably pyridine.The additive amount of alkali from for the amount easily removed and from the viewpoint of being easy to get high molecular weight body, relative to Tetracarboxylic acid acid diesters diacid chloride is preferably 2 times moles~4 times moles, 2 times moles~3 times moles more preferable.
Solvent used in above-mentioned reaction is from the viewpoint of the dissolubility of monomer and polymer, preferably N- methyl- 2-Pyrrolidone or gamma-butyrolacton, they can be used a kind or mix two or more come using.
Polymer concentration when manufacture is examined from being not likely to produce polymer and be precipitated and be easy to get the viewpoint of high molecular weight body Consider, preferably 1 mass of mass %~30 %, the more preferable 5 mass mass of %~20 %.
In addition, the hydrolysis of tetracarboxylic acid acid diesters diacid chloride in order to prevent, solvent used in the manufacture of poly amic acid ester is preferred It is dehydrated as far as possible, being mixed into for extraneous gas is preferably prevented in nitrogen atmosphere.
When [3] being manufactured by tetracarboxylic acid acid diesters and diamines
Poly amic acid ester can be by manufacturing tetracarboxylic acid acid diesters and diamine component polycondensation containing diamines of the invention.
Specifically, can by making tetracarboxylic acid acid diesters and diamines in the presence of condensing agent, alkali and organic solvent, 0 DEG C 30 minutes~24 hours, preferably 3 hours~15 hours are reacted at~150 DEG C, preferably 0 DEG C~100 DEG C to manufacture.
As condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyl -3- (3- dimethyl can be used Aminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, tetrafluoro Boric acid O- (benzotriazole -1- base)-N, N, N ', N '-tetramethylurea, hexafluorophosphoric acid O- (benzotriazole -1- base)-N, N, N ', N '-tetramethylurea, (thio -3- benzoxazolyl of 2,3- dihydro -2-) phosphonic acids diphenyl etc..The additive amount of condensing agent is opposite In tetracarboxylic acid acid diesters be preferably 2 times moles~3 times moles, it is 2 times moles~2.5 times moles more preferable.
As alkali, the tertiary amines such as pyridine, triethylamine can be used.The additive amount of alkali is from the amount to easily remove and is easy To from the viewpoint of high molecular weight body, relative to diamine component be preferably 2 times moles~4 times moles, 2.5 times moles more preferable~ 3.5 times moles.
In addition, by the way that lewis acid is added as additive, reaction is effectively performed in above-mentioned reaction.As Louis The lithium halides such as acid, preferably lithium chloride, lithium bromide.Lewis acidic additive amount relative to diamine component be preferably 0 times mole~ 1.0 times moles, it is 0 times mole~0.7 times mole more preferable.
Among the manufacturing method of above-mentioned 3 kinds of poly amic acid ester, the poly amic acid ester of high molecular weight, especially excellent in order to obtain It is selected as the preparation method of above-mentioned [1] or above-mentioned [2].
By the solution of the poly amic acid ester obtained as described above, poor solvent is injected into while being sufficiently stirred, thus Polymer can be precipitated.It is precipitated for several times, after being washed with poor solvent, room temperature or heat drying, and available process The powder of the poly amic acid ester of purifying.Poor solvent is not particularly limited, water outlet, methanol, ethyl alcohol, hexane, fourth can be enumerated Base cellosolve, acetone, toluene etc..
The manufacturing method > of < polyimides
Polyimides used in the present invention can be manufactured by the way that aforementioned polyimide precursor is carried out imidizate.
In polyimides of the invention, the closed loop rate (acid imide rate) of amide acidic group or amic acid ester group is not necessarily required It is 100%, depending on the application, purpose arbitrarily adjusts.
As the method for making polyimide precursor closed loop, it can enumerate and without using catalyst heat polyimide precursor Hot-imide, the catalysis imidizate using catalyst.
In the case that polyimide precursor is carried out hot-imide, preferably the solution of polyimide precursor is heated to 100 DEG C~400 DEG C, preferably 120 DEG C~250 DEG C, the water or alcohol that are generated using imidization reaction are removed to same outside system Shi Jinhang.
The catalysis imidizate of polyimide precursor can by the solution of polyamic acid add basic catalyst and Acid anhydrides stirs at -20 DEG C~250 DEG C, preferably 0 DEG C~180 DEG C to carry out.The amount of basic catalyst is the 0.5 of amide acidic group Mole times~30 moles times, preferably 2 moles times~20 moles times, the amount of acid anhydrides is 1 mole times~50 moles times of amide acidic group, It is preferred that 3 moles times~30 moles times.
As basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated, wherein pyridine by In have for reacting it is appropriate alkalinity and it is preferred that.
As acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, wherein if using acetic anhydride Purifying after reaction becomes easy, therefore preferably.It can be passed through using the acid imide rate that catalyst imidizate is realized It adjusts catalytic amount and reaction temperature, reaction time controls.
By polyimides reaction solution recycle component of polymer in the case where, by reaction solution put into poor solvent into Row precipitating.As poor solvent used in precipitating, methanol, acetone, hexane, butyl cellosolve, heptane, first can be enumerated Ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene, water etc..It is excellent that polymer obtained from poor solvent is precipitated will be put into After choosing filtering, recycling, under normal pressure or decompression, room temperature or heating are dried.
< aligning agent for liquid crystal >
Aligning agent for liquid crystal is the coating fluid for making liquid crystal orientation film, contains for its main component and is used to form resin coating The resin component of film and the organic solvent composition for dissolving the resin component.Aligning agent for liquid crystal of the invention, as resin at Point, using selected from by above-mentioned polyimide precursor and the group for forming polyimides obtained from the polyimide precursor closed loop At least one of polymer.
The concentration of polymer in aligning agent for liquid crystal can suitably become according to the setting for the thickness for thinking film to be formed More.From being formed uniformly and from the viewpoint of not having defective film, preferably 1 mass % or more, from the storage stability of solution From the viewpoint of, preferably 10 mass % or less.Particularly preferred polymer concentration is 2 mass of mass %~8 %.
In addition resin component in aligning agent for liquid crystal can also be mixed of the invention with all polymer of the invention Other polymer other than polymer.As above-mentioned other polymer, it can enumerate and use above-mentioned formula (1) institute as diamine component Polyimide precursor obtained from diamines other than showing or polyimides.
If the organic solvent component of polymer uniform dissolution contained in aligning agent for liquid crystal is not particularly limited.If enumerating Its concrete example can then enumerate N,N-dimethylformamide, N, N- diethylformamide, DMAC N,N' dimethyl acetamide, N- methyl- 2-Pyrrolidone, N- ethyl-2-pyrrolidone, N- methyl caprolactam, 2-Pyrrolidone, n-vinyl-2-pyrrolidone, two Methyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinone, 3- methoxyl group-N, N- dimethylpropionamide etc.. They can be used a kind or mix two or more come using.In addition, even if cannot equably dissolve polymer when being single use The solvent of ingredient, if in polymer will not be precipitated in the range of if can also be mixed with above-mentioned organic solvent.
Aligning agent for liquid crystal, can be also containing for improving liquid other than the organic solvent for dissolving component of polymer Brilliant alignment agent is applied to the solvent for applying film uniformity when substrate.The usually used table low compared with above-mentioned organic solvent of above-mentioned solvent The solvent of face tension.As its concrete example, can enumerate ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl card must Alcohol, ethylcarbitol acetate, ethylene glycol, 1- methoxy-2-propanol, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 2- Butoxy -1- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl Ether -2- acetic acid esters, propylene glycol -1- list ethylether -2- acetic acid esters, butyl cellosolve acetate, dipropylene glycol, a contracting dipropyl Glycol monomethyl ether, dipropylene glycol dimethyl, diacetone alcohol, diethylene glycol diethyl ether, 2,6- 2,6-dimethyl-4-heptanol, Diisobutyl ketone, 4- methoxyl group -4-methyl-2 pentanone, 4- hydroxy-2-butanone and 2- methyl -2- hexanol, 2- (2- ethoxy-c Oxygroup) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc..These solvents can group It closes and uses two or more.
Above-mentioned solvent is the low poor solvent of the dissolubility of resin.These solvents are preferably to contain in aligning agent for liquid crystal Organic solvent 5 mass of mass %~60 %, the more preferable 10 mass mass of %~50 %.
In aligning agent for liquid crystal, in addition to that mentioned above, it can also be added if in the range of will not damage effect of the present invention The electricity of the electrical characteristics such as the polymer other than polymer of the invention, the dielectric constant for changing liquid crystal orientation film, electric conductivity is situated between Body or conductive materials, the silane coupling agent of adaptation for improving liquid crystal orientation film and substrate form liquid crystal and take for improving The hardness of film when to film, the cross-linked compound of consistency and then the acyl for making polyimide precursor when being burnt into film The imidizate promotor etc. that imidization is effectively performed.
In the case where comprising cross-linked compounds such as the compound containing functional silanes, the compounds containing epoxy group, Its amount is preferably 0.1 mass parts~30 mass parts, more preferable 1 mass parts~20 mass relative to 100 mass parts of resin component Part, particularly preferred 1 mass parts~10 mass parts.
The manufacturing method > of < liquid crystal orientation film
Liquid crystal orientation film is film obtained from being coated on substrate by above-mentioned aligning agent for liquid crystal, be dried, be burnt into.
As the substrate of coating of liquid crystalline alignment agent, it is not particularly limited if the high substrate of the transparency, glass can be used Plastic bases such as glass substrate, silicon nitride board, acrylic compounds substrate, polycarbonate substrate etc..It is used for especially with being formed with Drive the substrate of ITO electrode etc. of liquid crystal, from the viewpoint of the chemical industry skill that conforms to the principle of simplicity preferably.
In addition, if being only unilateral substrate, silicon wafer also can be used for the liquid crystal of reflection-type indicates element Etc. opaque substrate, the material of the meeting reflected light such as aluminium is also can be used in electrode at this time.
As the coating method of aligning agent for liquid crystal, spin-coating method, print process, ink-jet method etc. can be enumerated.In addition, as using The method of coating fluid, there are dipping, roll coater, slit coater, spin coaters etc., can use them according to purpose.
Drying, firing process after coating of liquid crystalline alignment agent can choose arbitrary temperature and time.Generally for filling The organic solvent for dividing removal contained, dry 1 minute~10 minutes, preferably 3 at 50 DEG C~120 DEG C, preferably 50 DEG C~80 DEG C Minute~5 minutes, then it is burnt into 5 minutes~120 minutes, preferably 10 points at 150 DEG C~300 DEG C, preferably 200 DEG C~240 DEG C Clock~40 minute.
The thickness of film after firing is not particularly limited, liquid crystal indicates that the reliability of element is possible to if excessively thin It reduces, therefore is 5nm~300nm, preferably 10nm~200nm.
As the method for carrying out orientation process for obtained liquid crystal orientation film, rubbing manipulation can be enumerated, at light orientation Logos etc..Rayon cloth, nylon cloth, cotton etc. can be used in friction treatment.Vertically oriented liquid crystal orientation film is due to being difficult to Uniform state of orientation is obtained by friction treatment, therefore in the case where being used as vertical orientation with aligning agent for liquid crystal, It can not rub to use.
As the concrete example of light orientation position logos, it can enumerate and fixed-direction polarisation is radiated at for aforementioned film coated surface Radiation, as needed so that 150 DEG C~250 DEG C at a temperature of heated, the method for assigning liquid crystal aligning ability. As radiation, the ultraviolet light and luminous ray of the wavelength with 100nm~800nm can be used.Wherein, it is however preferred to have The ultraviolet light of the ultraviolet light of the wavelength of 100nm~400nm, the particularly preferably wavelength with 200nm~400nm.
In addition, can will apply while ilm substrate heats at 50 DEG C~250 DEG C in order to improve liquid crystal aligning and irradiate spoke Ray.
The exposure of radiation is preferably 1mJ/cm2~10000mJ/cm2, particularly preferred 100mJ/cm2~5000mJ/ cm2.The liquid crystal orientation film made as described above can make liquid crystal molecule in fixed-direction stable orientations.
The film of the above-mentioned radiation for having irradiated polarisation can be then with containing selected from least one of water and organic solvent Solvent carry out contact treatment.
As solvent used in contact treatment, do not have then if the solvent for the decomposition product that dissolution is generated by light irradiation It is particularly limited to.As concrete example, can enumerate water outlet, methanol, ethyl alcohol, 2- propyl alcohol, acetone, methyl ethyl ketone, 1- methoxy-2-propanol, 1- methoxy-2-propanol acetic acid esters, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methoxy methyl propionate, 3- ethoxyl ethyl propionate, propyl acetate, butyl acetate, cyclohexyl acetate etc..Two or more can be applied in combination in these solvents.
From the viewpoint of versatility, safety, Free water, 2- propyl alcohol, 1- methoxy-2-propanol and cream are more preferably selected At least one of the group of acetoacetic ester composition.Particularly preferably 1- methoxy-2-propanol or ethyl lactate.
In the present invention, the contact treatment of the film and the solution containing organic solvent that have irradiated the radiation of polarisation preferably passes through The films such as impregnation, spraying (spray) processing and liquid come into full contact with such processing and carry out.Wherein, preferably having Impregnation film preferably 10 seconds~1 hour, more preferable 1 minute~30 minutes methods in the solution of solvent.Contact treatment can Think room temperature or heating, it is preferred that 10 DEG C~80 DEG C, it is 20 DEG C~50 DEG C more preferable at implement.It can be real according further to needs The means of the raisings such as Shih-chao's sound wave contact.
After above-mentioned contact treatment, in order to remove the organic solvent in used solution, water, methanol, second can use The low boiling point solvents such as alcohol, 2- propyl alcohol, acetone, methyl ethyl ketone done the wash (flushing), it is dry in any one or both.
And then carried out the film of contact treatment using solvent for the reorientation of the strand in the drying of solvent and film, It can be heated at 150 DEG C or more.
As the temperature of heating, preferably 150 DEG C~300 DEG C.The temperature the high, the reorientation of strand more is promoted, But the decomposition with strand is possible to if temperature is excessively high.Therefore it is used as heating temperature, more preferably 180 DEG C~250 DEG C, it is 200 DEG C~230 DEG C particularly preferred.
The time heated may not be obtained effect of the invention if too short, if too long strand is possible to point Solution, thus preferably 10 seconds~30 minutes, it is 1 minute~10 minutes more preferable.
< liquid crystal indicates element >
Liquid crystal indicates that element is to utilize after obtaining the substrate with liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention Known method makes liquid crystal cells, and forming liquid crystal using the liquid crystal cells indicates that element forms.
The liquid crystal of passive-matrix structure is indicated that element carries out as an example by an example of the production method as liquid crystal cells Explanation.It should be noted that or being provided with thin film transistor (TFT) (TFT, Thin constituting each pixel portion that image is shown Film Transistor) etc. the active matrix structure of switch elements liquid crystal indicate element.
Prepare the substrate of transparent glass system first, common electrode is set on a substrate, section is set on another substrate Electrode.These electrodes can for example form ITO electrode, be patterned in a manner of it can carry out desired image and indicate.Then Common electrode and segment electrode are covered on each substrate insulating film is arranged.Insulating film can such as form and utilize sol-gel method Formed by SiO2-TiO2The film of formation.
Then liquid crystal orientation film of the invention is formed on each substrate.Then make mutual alignment films face it is opposed come in a base Plate is overlapped another substrate, is bonded periphery with sealing material.In sealing material, for control base board gap, it is ordinarily incorporated into spacer. Additionally, it is preferred that also spreading the spacer of substrate gap control in the face inner part for being not provided with sealing material.In sealing material A part setting can be by the opening portion of external filling liquid crystal.
Then it by being set to the opening portion of sealing material, is injected in the space that 2 pieces of substrates of Xiang Yong and sealing material surround Liquid crystal material.Then the opening portion is sealed with bonding agent.Injection can be used vacuum impregnation, benefit in an atmosphere also can be used With the method for capillarity.In addition, being added dropwise liquid crystal after describing sealing material on substrate, lower fitting is depressurized, it thus can also be with Filling liquid crystal.
As liquid crystal material, any one in positive type liquid crystal material and negative type liquid crystal material can be used.Especially it is In the case where using the voltage retention negative type liquid crystal material lower than positive type liquid crystal material, if using liquid crystal aligning of the invention Then image retention speciality is also excellent for film.
Then the setting of polarizer is carried out.Specifically, the face stickup with liquid crystal layer opposite side in 2 pieces of substrates is a pair of partially Tabula rasa.By passing through the above process, obtaining liquid crystal of the invention indicates element.The liquid crystal indicates element due to as liquid crystal aligning The liquid crystal orientation film that film is obtained using the manufacturing method using liquid crystal orientation film of the invention, therefore image retention speciality is excellent, is suitable for The multifunctional portable telephone (smart phone) of fine, tablet-type personal computer, LCD TV etc..
Embodiment
Embodiment is exemplified below out to be more particularly described the present invention.But the present invention is not limited by these embodiments Fixed, explanation.The abbreviation of the compound used later and the measuring method of each characteristic are as described below.
The abbreviation > of < compound
In following formula DA-5 and following formula DA-6, " Boc " is tert-butoxycarbonyl.
The abbreviation > of < compound
Bis- (4- aminophenethyl) ureas of DA-7:1,3-
DA-8:4- (2- methylaminoethyl) aniline
NMP:N- N-methyl-2-2-pyrrolidone N
BCS: butyl cellosolve
GBL: gamma-butyrolacton
< viscosity >
In synthesis example, the viscosity of polymer solution be using E type viscosimeter TVE-22H (Toki Sangyo Co., Ltd.'s system), It is measured at sample size 1.1mL, cone rotor TE-1 (1 ° 34 ', R24), 25 DEG C of temperature.
The production > of < liquid crystal expression element
Prepare electroded substrate first.Substrate is the size of 30mm × 35mm and the glass substrate of thickness 0.7mm.In base The IZO electrode for constituting the pattern for having solid shape of opposite electrode is formed on plate as the 1st layer.The 1st layer of opposite electrode it On, as the 2nd layer, form SiN (silicon nitride) film using CVD method film forming.The film thickness of 2nd layer of SiN film is 500nm, as Interlayer dielectric functions.On the 2nd layer of SiN film, as the 3rd layer, the comb teeth-shaped for forming IZO film figureization is configured Pixel electrode forms the 1st pixel and the 2nd pixel both pixels.The size of each pixel is vertical 10mm, horizontal about 5mm.At this time the 1st The opposite electrode and the 3rd layer of pixel electrode of layer are electrically insulated by the effect of the 2nd layer of SiN film.
3rd layer of pixel electrode has the multiple comb teeth being arranged to make up of electrode member of the curved く word shape of center portion The shape of shape.The width of the width direction of each electrode member between 3 μm, electrode member between be divided into 6 μm.Form each pixel Pixel electrode, which is that the electrode member of the curved く word shape of center portion is multiple, to be arranged to make up, therefore the shape of each pixel is not grown Square shape has the shape similar to く word of the curved too word of center portion in the same manner as electrode member.And each pixel by its The bending part in center is divided into up and down as boundary line, the 1st region of the upside with bending part and the 2nd region of downside.
The formation side of the electrode member of their pixel electrode is constituted if the 1st region of more each pixel and the 2nd region To difference.That is, in the case that the frictional direction of aftermentioned liquid crystal orientation film is as benchmark, in the 1st region of pixel, with pixel electricity The mode that the electrode member of pole forms+10 ° of angle (rotating clockwise) is formed, in the 2nd region of pixel, with pixel electrode The mode that electrode member forms -10 ° of angle (rotation counterclockwise) is formed.That is, in the 1st region of each pixel and the 2nd region, with The spinning movement applied in the real estate of the liquid crystal induced by the voltage between pixel electrode and opposite electrode is (coplanar to open Close) direction be mutual opposite direction mode constitute.
Then will after 1.0 μm of the filter filtering of obtained aligning agent for liquid crystal, be spun on respectively prepared it is above-mentioned Electroded substrate and as counter substrate, overleaf form a film ito film and have height 4 μm columnar spacer glass Substrate.Then dry in 80 DEG C of heating plate to be burnt into 20 minutes at 230 DEG C after five minutes, the film of film thickness 60nm is formed, Polyimide film is obtained on each substrate.On the polyimide film, rayon cloth friction (roller is utilized with defined frictional direction Diameter: 120mm, revolving speed: 500rpm, movement speed: 30mm/ second, fill in length: after 0.3mm), carried out in pure water 1 minute it is super Sound wave irradiation, it is 10 minutes dry at 80 DEG C.
Then above-mentioned 2 with liquid crystal orientation film kind substrate is used, is combined in such a way that respective frictional direction is antiparallel, it is residual Stay liquid crystal injecting port, sealing surrounding, the dummy cell that production unit gap is 3.8 μm.Vacuum injection liquid under to the dummy cell room temperature After brilliant (MLC-2041, Merck Ltd. system), inlet is sealed, the liquid crystal cells of antiparallel orientations are formed.Obtained liquid crystal Unit, which constitutes FFS (boundary electric field switching) mode liquid crystal, indicates element.Then obtained liquid crystal cells are heated at 120 DEG C 1 hour, each evaluation was used for after placing a Dinner.
The evaluation > of the relaxation properties of < charge accumulation
The evaluation of ghost is carried out using optical system below etc..Made liquid crystal cells are set to polarizing axis just Between 2 pieces of polarizers that the mode of friendship configures, LED backlight is set to turn on light in the state that no voltage is applied, through the bright of light Spend the arrangement angles of least way adjustment liquid crystal cells.
Then, V-T curve (voltage-transmission is measured while applying the alternating voltage of frequency 30Hz for the liquid crystal cells Rate curve), the alternating voltage that relative permeability is 23% is calculated as driving voltage.
In ghost evaluation, while applying the alternating voltage driving liquid crystal cells for the frequency 30Hz that relative permeability is 23% Apply the DC voltage of 1V, drives 40 minutes.Then make the application for applying DC voltage value 0V, only stopping DC voltage, It is driven 15 minutes under the state.
For evaluation for, from start DC voltage application time point until process 45 minutes until, relative permeability It is reduced in 25% situation below, is defined as " good " and is evaluated.Until relative permeability is reduced to 25% or less In the case where needing 45 minutes or more, it is defined as " bad " and is evaluated.
Also, the temperature condition for the state that the ghost evaluation carried out according to the above method is 23 DEG C in the temperature of liquid crystal cells Lower progress.
The estimation of stability > of < liquid crystal aligning
Using the liquid crystal cells, under 60 DEG C of isoperibol, with frequency 30Hz apply 10VPP alternating voltage 168 it is small When.Then state short-circuit between the pixel electrode and opposite electrode of liquid crystal cells is formed, is directly placed one day at room temperature.
After placement, liquid crystal cells are set between the 2 pieces of polarizers configured in the orthogonal mode of polarizing axis, are not being applied Backlight is set to turn on light in the state of voltage, with the arrangement angles through the brightness least way of light adjustment liquid crystal cells.Then Rotation angle when liquid crystal cells is rotated until the most dark angle in the 1st region by the most dark angle in the 2nd region of the 1st pixel It is calculated as angle delta.Similarly for the 2nd pixel, compare the 2nd region and the 1st region, calculate same angle delta.It connects , it is calculated the average value of the 1st pixel and the angle delta value of the 2nd pixel as the angle delta of liquid crystal cells.The liquid crystal cells In the case that the value of angle delta is more than 0.1 degree, it is defined as " bad " and is evaluated.The value of the angle delta of the liquid crystal cells is no more than In the case where 0.1 degree, it is defined as " good " and is evaluated.
The evaluation > of < BL patience
By made liquid crystal cells on the BL of 2000nit aging 1 week.For unit after aging, in 60 DEG C of temperature The lower 60 μ sec of voltage for applying 1V of degree, the voltage after measuring 100msec evaluate voltage retention.
At this point, voltage retention maintain 80% or more in the case where be defined as " good ", less than 80% in the case where define It is evaluated for " bad ".
The evaluation > of < friction patience
Aligning agent for liquid crystal is coated on ito substrate, and after carrying out predrying, is burnt into using 230 DEG C of IR formula baking oven, Obtain the substrate with liquid crystal orientation film.Rayon cloth friction (roller revolving speed: 1000rpm, objective table is utilized for the liquid crystal orientation film Movement speed: 20mm/ seconds, fill in length: 0.4mm).This substrate is observed using microscope, film surface do not find by It is used as " good " in the case where friction caused striped, finds the case where striped as " bad " to be evaluated.
< synthesis example >
(synthesis example 1)
After putting into DA-3 34.36g (0.12 mole) in the 500mL flask with agitating device and nitrogen ingress pipe, it is added NMP 335.12g is simultaneously stirred, is dissolved.While the solution is stirred under water cooling, add CA-1 22.77g (0.10 mole), And then NMP83.80g is added, it is stirred 12 hours at 50 DEG C, obtains polyamic acid solution (PAA-1).
(synthesis example 2)
DA-3 25.20g (0.088 mole) and DA- are put into the 500mL flask with agitating device and nitrogen ingress pipe After 6 8.77g (0.022 mole), NMP 333.97g is added and stirs, dissolve.While the solution is stirred under water cooling, add Add CA-1 22.96g (0.11 mole), and then NMP 326g is added, is stirred 12 hours at 50 DEG C, obtain polyamic acid solution (PAA-2)。
(synthesis example 3)
DA-3 25.20g (0.088 mole) and DA- are put into the 500mL flask with agitating device and nitrogen ingress pipe After 5 8.72g (0.022 mole), NMP 334.28g is added and stirs, dissolve.While the solution is stirred under water cooling, add Add CA-1 23.06g (0.11 mole), and then NMP83.57g is added, is stirred 12 hours at 50 DEG C, obtain polyamic acid solution (PAA-3)。
(synthesis example 4)
After putting into DA-4 19.13g (0.096 mole) in the 500mL flask with agitating device and nitrogen ingress pipe, add Enter solvent (NMP:GBL=50wt%:50wt%) 232.72g and is stirred, dissolves.The solution is stirred under water cooling same When, it adds CA-2 14.12g (0.072 mole), and then after addition solvent (NMP:GBL=50wt%:50wt%) 84.63g, stir It mixes 2 hours.Then after putting into DA-1 4.76g (0.024 mole), NMP42.31g is added and is stirred, dissolves.Again in water CA-3 9.00g (0.03 mole) is added while cold lower stirring, and then solvent (NMP:GBL=50wt%:50wt%) is added 326g obtains polyamic acid solution (PAA-4) after stirring 2 hours.
(synthesis example 5)
DA-4 23.91g (0.12 mole) and DA-1 are put into the 500mL flask with agitating device and nitrogen ingress pipe After 5.95g (0.03 mole), NMP 255.76g is added and stirs, dissolve.While the solution is stirred under water cooling, addition CA-2 6.47g (0.033 mole), and then after addition NMP73.01g, it stirs 2 hours.Then CA-4 28.15g (0.11 is put into Mole) after, NMP36.54g is added, is stirred 12 hours at 50 DEG C, obtains polyamic acid solution (PAA-5).
(synthesis example 6)
DA-4 23.91g (0.12 mole) and DA-2 are put into the 500mL flask with agitating device and nitrogen ingress pipe After 4.56g (0.03 mole), NMP 241.76g is added and stirs, dissolve.While the solution is stirred under water cooling, addition CA-2 13.71g (0.070 mole), and then after addition NMP69.07g, it stirs 2 hours.Then CA-4 18.77g is put into After (0.075 mole), NMP34.54g is added, is stirred 12 hours at 50 DEG C, obtains polyamic acid solution (PAA-6).
(synthesis example 7)
DA-4 28.69g (0.144 mole) and DA- are put into the 500mL flask with agitating device and nitrogen ingress pipe After 1 7.14g (0.036 mole), NMP 296.56g is added and stirs, dissolve.While the solution is stirred under water cooling, add Add CA-2 16.41g (0.084 mole), and then after addition NMP84.73g, stirs 2 hours.Then CA-4 22.52g is put into After (0.09 mole), NMP42.37g is added, is stirred 12 hours at 50 DEG C, obtains polyamic acid solution (PAA-7).
(synthesis example 8)
DA-5 18.98g (0.048 mole) and DA- are put into the 500mL flask with agitating device and nitrogen ingress pipe After 7 14.28g (0.048 mole), NMP 312.67g is added and stirs, dissolve.While the solution is stirred under water cooling, It adds CA-1 20.04g (0.092 mole), and then after addition NMP78.17g, is stirred 12 hours at 50 DEG C, obtain polyamic acid Solution (PAA-8).
(synthesis example 9)
DA-7 26.85g (0.09 mole) and DA-8 are put into the 500mL flask with agitating device and nitrogen ingress pipe After 9.01g (0.06 mole), NMP 289.28g is added and stirs, dissolve.While the solution is stirred under water cooling, addition CA-2 27.94g (0.14 mole), and then after addition NMP72.32g, it stirs 2 hours, obtains polyamic acid solution (PAA-9).
(comparative example 1)
Take PAA-1 1.51g, PAA-4 6.99g in the 20ml sample cell for having stirrer is added, be added NMP1.51g, GBL3.13g, BCS6.00g, the GBL solution 0.86g containing 1 weight % of AD-1 were obtained with magnetic stirrer 30 minutes Aligning agent for liquid crystal (A-1).
(comparative example 2)
Take PAA-1 1.33g, PAA-5 4.27g in the 20ml sample cell for having stirrer is added, be added NMP4.40g, GBL5.36g, BCS4.00g, the GBL solution 0.64g containing 1 weight % of AD-1 were obtained with magnetic stirrer 30 minutes Aligning agent for liquid crystal (A-2).
(comparative example 3)
Take PAA-2 1.33g, PAA-6 4.27g in the 20ml sample cell for having stirrer is added, be added NMP4.40g, GBL5.36g, BCS4.00g, the GBL solution 0.64g containing 1 weight % of AD-2 were obtained with magnetic stirrer 30 minutes Aligning agent for liquid crystal (A-3).
(comparative example 4)
Take PAA-8 2.00g, PAA-9 6.40g in the 20ml sample cell for having stirrer is added, be added NMP1.60g, GBL5.04g, BCS4.00g, the GBL solution 0.96g containing 1 weight % of AD-2 were obtained with magnetic stirrer 30 minutes Aligning agent for liquid crystal (A-4).
(embodiment 1)
Take PAA-3 1.33g, PAA-6 4.27g in the 20ml sample cell for having stirrer is added, be added NMP4.40g, GBL5.36g, BCS4.00g, the GBL solution 0.64g containing 1 weight % of AD-2 were obtained with magnetic stirrer 30 minutes Aligning agent for liquid crystal (B-1).
(embodiment 2)
Take PAA-3 1.33g, PAA-6 4.27g in the 20ml sample cell for having stirrer is added, be added NMP4.16g, GBL5.36g, BCS4.00g, the GBL solution 0.64g containing 1 weight % of AD-2, the nmp solution containing 10 weight % of AD-3 0.24g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (B-2).
(embodiment 3)
Take PAA-3 1.33g, PAA-7 4.27g in the 20ml sample cell for having stirrer is added, be added NMP4.40g, GBL5.36g, BCS4.00g, the GBL solution 0.64g containing 1 weight % of AD-2 were obtained with magnetic stirrer 30 minutes Aligning agent for liquid crystal (B-3).
(embodiment 4)
Take PAA-3 1.33g, PAA-7 4.27g in the 20ml sample cell for having stirrer is added, be added NMP4.16g, GBL5.36g, BCS4.00g, the GBL solution 0.64g containing 1 weight % of AD-2, the nmp solution containing 10 weight % of AD-3 0.24g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (B-4).Using aligning agent for liquid crystal obtained above, into Row BL patience, the relaxation properties of charge accumulation, the stability of liquid crystal aligning and friction patience evaluation.As a result as described in Table 1.
[table 1]
As described above liquid crystal orientation film of the invention friction patience, the evaluation of BL patience, liquid crystal aligning estimation of stability, Good result is showd that in any one in the evaluation of ghost extinction time.

Claims (8)

1. a kind of aligning agent for liquid crystal, containing following (A) ingredients and (B) ingredient,
(A) ingredient: selected from by polyimide precursor and the group for forming polyimides obtained from the polyimide precursor closed loop In at least one kind of polymer, the polyimide precursor is that the diamine component of the diamines containing following formula (1) is made to spread out with tetrabasic carboxylic acid Obtained from biotic component reaction,
In formula (1), R1Indicate hydrogen or 1 valence organic group, Q1Indicate the alkylidene of carbon number 1~5, Cy are to indicate to include azetidin Alkane, pyrrolidines, piperidines or hexamethylene imine aliphatic heterocycle divalent group, be optionally bonded with and take in their loop section Dai Ji, R2And R3It is each independently 1 valence organic group, q and r are each independently 0~4 integer, wherein the total of q and r In the case where 2 or more, multiple R2And R3With above-mentioned definition,
(B) ingredient: with part-structure shown in 2 or more following formula (2) and molecular weight is 2500 chemical combination below Object,
In formula (2), R1Indicate the alkyl of hydrogen atom or carbon number 1~3, R2And R3Each independently represent hydrogen atom, carbon number 1~3 Alkyl or *3-CH2-O-R11, wherein R11Indicate the alkyl of hydrogen atom or carbon number 1~3, " *3" indicate and R2And R3It is bonded The connecting key of carbon atom, " *1" and " *2" indicate and the connecting keys of other atoms.
2. aligning agent for liquid crystal according to claim 1, wherein following formula (3) expression of the diamines of the formula (1),
In formula (3), R1For hydrogen atom, methyl or tert-butoxycarbonyl, R2And R3It is each independently hydrogen atom or methyl, Q1For carbon The straight-chain alkyl-sub of number 1~5.
3. aligning agent for liquid crystal according to claim 1 or 2, wherein the containing ratio of diamines shown in the formula (1) is opposite It is 1 mole of %~80 mole % in 1 mole of whole diamine components.
4. aligning agent for liquid crystal described in any one of claim 1 to 3, wherein the compound of (B) ingredient be selected from At least one of following formula compound,
5. aligning agent for liquid crystal according to any one of claims 1 to 4 also includes the structure list containing following formula (5) The polyimide precursor of member is used as (C) ingredient,
In formula (5), X2For the 4 valence organic groups from tetracarboxylic acid derivatives, Y2For the divalent organic group from diamines, R4For hydrogen The alkyl of atom or carbon number 1~5, Z1And Z2Respectively stand alone as alkyl, the carbon of hydrogen atom, the optionally carbon number 1~10 with substituent group The alkenyl of number 2~10 or the alkynyl of carbon number 2~10.
6. aligning agent for liquid crystal according to claim 5, it includes contain the X in the formula (5)2For the structure of following structures The polyimide precursor of unit,
7. a kind of liquid crystal orientation film is obtained by aligning agent for liquid crystal according to any one of claims 1 to 6.
8. a kind of liquid crystal indicates element, has liquid crystal orientation film as claimed in claim 7.
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