CN101910929B - Liquid crystal aligning agent and liquid crystal display device using the same - Google Patents

Liquid crystal aligning agent and liquid crystal display device using the same Download PDF

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CN101910929B
CN101910929B CN2008801231523A CN200880123152A CN101910929B CN 101910929 B CN101910929 B CN 101910929B CN 2008801231523 A CN2008801231523 A CN 2008801231523A CN 200880123152 A CN200880123152 A CN 200880123152A CN 101910929 B CN101910929 B CN 101910929B
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liquid crystal
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aligning agent
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CN101910929A (en
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三木德俊
后藤耕平
矢田研造
保坂和义
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Nissan Chemical Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings

Abstract

Disclosed is a liquid crystal aligning agent characterized by containing the component (A) described below and the component (B) described below. Component (A): a polyimide which is a polymer obtained by imidizing a polyamide acid having a repeating unit represented by the structural formula [1] below and containing a carboxyl group in a molecule Component (B): an amine compound having a primary amino group and a nitrogen-containing aromatic heterocyclic ring in a molecule, wherein the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. (In the formula [1], R1 represents a tetravalent organic group, and R2 represents a divalent organic group including a structure represented by the following formula [2].) In the formula [2], X1 represents 1,4-phenylene or 1,4-cyclohexylene, and X2 represents an alkyl group having 3-12 carbon atoms, an alkoxy group having 3-12 carbon atoms, a fluoroalkyl group having 3-12 carbon atoms or a fluoroalkoxy group having 3-12 carbon atoms.

Description

Aligning agent for liquid crystal and the liquid crystal display cells for having used the inorganic agent
Technical field
The present invention relates to the aligning agent for liquid crystal used when making liquid crystal orientation film and the liquid crystal display cells for having used the inorganic agent.
Background technology
At present, it is used as the liquid crystal orientation film of liquid crystal display cells, so-called polyimide liquid crystal orientation film is mainly used, the polyimide liquid crystal orientation film is burnt till and is made afterwards by the aligning agent for liquid crystal (also referred to as aligning agent for liquid crystal) being coated with using the solution of the polyimide precursors such as polyamic acid or soluble polyimide as principal component.
One of characteristic required by liquid crystal orientation film is the control for the so-called liquid crystal pretilt angle that liquid crystal molecule is remained to arbitrary value relative to the orientation inclination angle of real estate.The big I of the known pre-tilt angle is made up of the structure of the polyimides of liquid crystal orientation film selection to change.
In the technology that pre-tilt angle is controlled using the structure of polyimides, the method that a part for diamines with side chain as polyimides raw material is used according to the use ratio of the diamines due to that can increase pre-tilt angle, therefore easily controllable purpose pre-tilt angle, the method that can be used as increasing pre-tilt angle.It is used as the side-chain structure of the diamines for the pre-tilt angle for increasing liquid crystal, it is proposed that steroid skeleton (referring for example to patent document 1), the side-chain structure comprising the ring structure such as phenyl or cyclohexyl (referring for example to patent document 2).It also proposed diamines of the side chain with 3 or 4 such ring structures (referring for example to patent document 3).
On the other hand, in the manufacturing process of liquid crystal orientation film, when the solution of polyamic acid solution or solvent-soluble polyimide is applied into substrate, industrial circle is typically implemented by flexible printing etc..The solvent of coating fluid, in order to form homogeneous and flawless film, has also been mixed into butyl cellosolve etc. in addition to the solvent to the favorable solubility of polymer such as METHYLPYRROLIDONE or gamma-butyrolacton.But, the ability of butyl cellosolve equal solvent dissolving polyamic acid or polyimides, therefore the problem of polymer separates out such can be caused during a large amount of mixing (referring for example to patent document 4).Particularly the problem is more highlighted in the solution of solvent-soluble polyimide.In addition, the tendency that the coating homogeneity that there is solution using polyimides obtained by the diamines with foregoing side chain declines, therefore the coatings such as butyl cellosolve, which must be increased, improves the combined amount of solvent, and the mixing allowance of the solvent also turns into the key property of polyimides.
In addition, with the high resolution of liquid crystal display cells, from the point of view of the control declined from the contrasts of liquid crystal display cells or persistence of vision are reduced, the voltage retention of liquid crystal orientation film used is high, accumulated charge when being applied with DC voltage is few and the release of residual charge that is being accumulated by DC voltage it is fast as characteristic it is more and more important.
In polyimide liquid crystal orientation film, it is used as the liquid crystal orientation film that the time untill the after image disappearance produced by DC voltage is short, known have a liquid crystal orientation film (referring for example to patent document 5) for having used the also aligning agent for liquid crystal of the tertiary amine containing specific structure in addition to the polyamic acid of polyamic acid or imido-, or has used containing using liquid crystal orientation film (referring for example to patent document 6) of aligning agent for liquid crystal of soluble polyimide of specific diamines with pyridine skeleton etc. etc. in raw material.In addition, the after image for being used as voltage retention high and being produced by DC voltage disappear untill time short liquid crystal orientation film, it is known that have the liquid crystal orientation film for having used except polyamic acid or its imide amination polymer etc. in addition to and also having included the minimal amount of aligning agent for liquid crystal for being selected from the compound that intramolecular contains the compound that the compound and intramolecular that the compound of 1 carboxyl, intramolecular contain 1 carboxylic acid anhydride group contain 1 tertiary amino (referring for example to patent document 7).
But, big picture and high-resolution LCD TV is widely used in recent years, liquid crystal display cells in the purposes are compared with the current display applications shown based on word or still frame, it is tightened up for the requirement of after image, and requires to possess the resistance characteristics that can be used for a long time under harsh use environment.Therefore, reliability for the liquid crystal orientation film of the purposes necessarily be greater than existing liquid crystal orientation film, for the electrical characteristics of liquid crystal orientation film, initial characteristic is not required nothing more than well, is also required after being for example exposed to for a long time under high temperature, even long-time can also maintain good characteristic after being exposed to the ultraviolet of backlight.
Patent document 1：Japanese Patent Laid-Open 4-281427 publications
Patent document 2：Japanese Patent Laid-Open 9-278724 publications
Patent document 3：Japanese Patent Laid-Open 2004-67589 publications
Patent document 4：Japanese Patent Laid-Open 2-37324 publications
Patent document 5：Japanese Patent Laid-Open 9-316200 publications
Patent document 6：Japanese Patent Laid-Open 10-104633 publications
Patent document 7：Japanese Patent Laid-Open 8-76128 publications
The announcement of invention
The present invention provides the characteristic for possessing the pre-tilt angle for increasing liquid crystal when being formed as liquid crystal orientation film, can make liquid crystal vertical-tropism with less use ratio and the aligning agent for liquid crystal that separates out is not easy to when being mixed with Weak solvent in the coating fluid of aligning agent for liquid crystal.The aligning agent for liquid crystal for the liquid crystal orientation film that following characteristic is also equipped with addition to the characteristic can be obtained by also providing, it is high that these characteristics include voltage retention, the release for the residual charge accumulated after being exposed to even if long-time under high temperature by DC voltage is also quickly, and can also suppress the decline of voltage retention after the ultraviolet of backlight even if long-time.In addition, the present invention further provides can the high liquid crystal display cells of long term reliability under harsh use environment.
Present inventor have found the new aligning agent for liquid crystal that may achieve the purpose after conscientiously being studied to achieve the above object.The present invention is the invention completed based on these achievements in research, including following technology contents.
(1) aligning agent for liquid crystal, the inorganic agent is characterised by, containing following (A) compositions and following (B) compositions,
(A) composition：Polyimides, the polyimides is polymer obtained by the polyamic acid imidizate for the structural formula for making the repeat unit with following formula [1] expression, and the intramolecular of the polymer has carboxyl,
(B) composition：Intramolecular has the amines that 1 primary amino radical and nitrogenous heteroaromatic and the primary amino radical are combined with aliphatic alkyl or non-aromatic ring type alkyl,
Figure BPA00001171770500031
In formula [1], R1For 4 valency organic groups, R2For the divalent organic group containing following formula [2],
Figure BPA00001171770500032
In formula [2], X1For Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, X2For wantonly a kind in the alkyl of carbon number 3~12, the alkoxy of carbon number 3~12, the fluoro-alkyl of carbon number 3~12, the fluoroalkyl of carbon number 3~12.
(2) R in the aligning agent for liquid crystal that above-mentioned (1) is recorded, formula [1]2For the divalent organic group containing following formula [3],
Figure BPA00001171770500041
In formula [3], n is 2~11 integer, and the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is transisomer.
(3) R in the aligning agent for liquid crystal that above-mentioned (1) is recorded, formula [1]2For the divalent organic group containing following formula [4],
Figure BPA00001171770500042
In formula [4], n is 2~11 integer, and the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is transisomer.
(4) aligning agent for liquid crystal that any one of above-mentioned (1)~(3) are recorded, (A) composition is polymer obtained by the polyamic acid imidizate for forming the structural formula of the repeat unit represented as formula [1], and the amount of the carboxyl of the polymer is calculated as 0.1~3 with the average value of the repeat unit relative to the polymer.
(5) aligning agent for liquid crystal that any one of above-mentioned (1)~(4) are recorded, (A) polymer obtained by the polyamic acid imidizate that the structural formula of unit of the part repeat unit as being represented with following formula [5] is formed in structural formula of the composition to make the repeat unit of the formula [1] expression, the amount of the carboxyl of the polymer is calculated as 0.1~3 with the average value of the repeat unit relative to the polymer
Figure BPA00001171770500043
In formula [5], R3For 4 valency organic groups, R4For divalent organic group, R3Or R4At least one party there is carboxyl.
(6) aligning agent for liquid crystal that any one of above-mentioned (1)~(5) are recorded, (B) composition is the amines that following formula [6] is represented,
Figure BPA00001171770500044
In formula [6], Y1For the divalent organic group with aliphatic alkyl or non-aromatic ring type alkyl, Y2For nitrogenous heteroaromatic.
(7) aligning agent for liquid crystal that any one of above-mentioned (1)~(5) are recorded, (B) composition is the amines that following formula [7] is represented,
Figure BPA00001171770500051
In formula [7], Y3Aliphatic alkyl or non-aromatic ring type alkyl for the divalent of carbon number 1~10, Y4For singly-bound ,-O- ,-NH- ,-S- ,-SO2- or carbon number 1~19 divalent organic group, Y3And Y4The carbon atom being had adds up to 1~20, Y5For nitrogenous heteroaromatic.
(8) aligning agent for liquid crystal that above-mentioned (7) are recorded, (B) composition is the Y of formula [7]3、Y4And Y5The amines that the combination of the group or ring of following record is formed is respectively selected from,
Y3For a kind of the straight or branched alkylidene selected from carbon number 1~10, the unsaturated alkylene of carbon number 1~10, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three ring eicosane rings, three ring docosane rings, bicycloheptane ring, decahydro naphthalene nucleus, ENB ring and adamantane ring
Y4For selected from singly-bound ,-O- ,-NH- ,-S- ,-SO2-, the alkyl of carbon number 1~19 ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-CF2-、-C(CF3)2-、-CH(OH)-、-C(CH3)2-、-Si(CH3)2-、-O-Si(CH3)2-、-Si(CH3)2-O-、-O-Si(CH3)2- O-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three ring eicosane rings, three ring docosane rings, bicycloheptane ring, decahydro naphthalene nucleus, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring, 1,8- perinaphthene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenthazine ring, oxadiazole rings, acridine ring, piperazine ring, piperidine ring, 1 kind of dioxane ring and morpholine ring,
Y5For a kind selected from pyrrole ring, imidazole ring, oxazole rings, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenthazine Huan, oxadiazole rings and acridine ring.
(9) aligning agent for liquid crystal that any one of above-mentioned (1)~(8) are recorded, the carboxyl included in polyimides relative to (A) composition of 1 mole, contains (B) composition with the ratio of 0.01~2 mole times of amount.
(10) organic solvent of the amines of the polyimides containing (A) composition and (B) composition is mixed under the aligning agent for liquid crystal that any one of above-mentioned (1)~(9) are recorded, heating and is obtained.
(11) liquid crystal orientation film, the aligning agent for liquid crystal recorded by any one of above-mentioned (1)~(10) is formed.
(12) liquid crystal display cells, the liquid crystal orientation film for possessing above-mentioned (11) record.
The aligning agent for liquid crystal of the present invention can be obtained by relatively easier method.In addition, the aligning agent for liquid crystal of the present invention possesses the characteristic for the pre-tilt angle for increasing liquid crystal when being formed as liquid crystal orientation film, liquid crystal vertical-tropism can just be made with less use ratio.In addition, being not easy to separate out when being mixed with Weak solvent in the coating fluid of aligning agent for liquid crystal.Voltage retention height can be obtained and even if the liquid crystal orientation film discharged also quickly for the residual charge accumulated after exposure for a long time at high temperature by DC voltage.
The reliability for possessing the liquid crystal display cells of the liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention is high, it is adaptable to big picture and high-resolution liquid crystal TV set etc..
The best mode carried out an invention
The aligning agent for liquid crystal of the present invention is containing conduct, (A) intramolecular obtained by the polyamic acid imidizate of the structural formula of the repeat unit for making to represent with the formula [1] of composition has the polyimides of carboxyl, (hereinafter also referred to specific polyimides) and conduct, (B) intramolecular of composition has the amines that 1 amino and nitrogenous heteroaromatic and the amino are combined with aliphatic alkyl or non-aromatic ring type alkyl, the aligning agent for liquid crystal of (hereinafter also referred to specific amines).In this specification, the amino (- NH2), hereinafter also referred to primary amino radical synonymous with primary amino radical.
The raw material of specific polyimides in the aligning agent for liquid crystal of the present invention has the specific diamines (hereinafter also referred to specific diamines) of the substituent for the characteristic for increasing pre-tilt angle using side chain.Therefore, in the case of having used the specific diamines, gained aligning agent for liquid crystal can make liquid crystal vertical-tropism with less use ratio.
In addition, by reducing use ratio, the organic solvent solubility of polymer improves, is not easy to separate out when being mixed with Weak solvent in the coating fluid of aligning agent for liquid crystal.
In the aligning agent for liquid crystal of the present invention, amino in specific amines and the carboxyl in specific polyimides are into salt, the amido link of the disengaging of adjoint water or alcohol is either formed for the carboxyl or carboxylic acid ester groups in specific polyimides or the bonding reaction of the open loop with imino group has been carried out for the imino group in specific polyimides.In addition, in firing process when making liquid crystal orientation film, because of the disengaging of water amido link is formed with the amino of the carboxyl in specific polyimides into salt.As a result, although the aligning agent for liquid crystal of the present invention simply using so simple method is mixed in organic solvent, specific amines and specific polyimides are efficiently combined in the liquid crystal orientation film of gained.
On the other hand, the nitrogenous heteroaromatic in specific amines is played a role by its conjugated structure as the jump of electronics, so promoting the transfer of the electric charge in gained liquid crystal orientation film.In addition, when being formed as liquid crystal orientation film, nitrogenous heteroaromatic, by being combined into electrostatic interaction as salt or hydrogen bond, is moved with the carboxyl in specific polyimides between the nitrogenous heteroaromatic in carboxyl and specific amines of the electric charge in specific polyimides.Further, since the specific amines and specific polyimides there occurs chemical bond, thus be transferred to the electric charge at nitrogenous heteroaromatic position can be efficiently in polyimide molecule or intermolecular movement.
Based on above-mentioned situation, aligning agent for liquid crystal of the invention possesses the characteristic for the pre-tilt angle for increasing liquid crystal when being formed as liquid crystal orientation film, can just make liquid crystal vertical-tropism with less use ratio.In addition, being not easy to separate out when being mixed with Weak solvent in the coating fluid of aligning agent for liquid crystal.Voltage retention height can be obtained and even if the liquid crystal orientation film discharged also quickly for the residual charge accumulated after exposure for a long time at high temperature by DC voltage.
<(A) composition/specific polyimides>
In the present invention, as (A) as long as the specific polyimides of composition make the polyamic acid imidizate of the structural formula of the repeat unit represented with formula [1] obtained by intramolecular there is the polyimides of carboxyl, its structure is not particularly limited.The polyimides can more easily be made using tetracarboxylic dianhydride and diamines as raw material, preferably make with formula [1] represent repeat unit structural formula polyamic acid imidizate obtained by polymer.
Figure BPA00001171770500071
In formula [1], R1For 4 valency organic groups, R2For the divalent organic group containing following formula [2],
Figure BPA00001171770500081
In formula [2], X1For Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, the ring of Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene can have substituent as needed.X2For the base of carbon number 3~12, preferably 3~6 alkyl, carbon number 3~12, preferably 3~6 fluoro-alkyl, carbon number 3~12, preferably 3~6 alkoxy or carbon number 3~12, preferably 3~6 fluoroalkyl.Alkyl, fluoro-alkyl, alkoxy and fluoroalkyl can be straight-chain or branch-like, but preferably straight-chain, in addition, can have suitable substituent.
The phenyl ring of main chain in formula [2] is incorporated into-NH- of the polymer of formula [1], is not particularly limited for the binding sites combined of-NH- in phenyl ring.As concrete example, shown in such as following formula [8], relative to the Z of formula [2]1, 2,3,2,4,2,5,2,6,3,4,3,5 can be enumerated.Wherein, from the point of view of reactivity of synthesizing polyamides when sour, preferably 2,4,2,5,3,5.If further contemplate diamines synthesis it is ease, more preferably be 2,4 or 2,5.
X in formula [2]1The effect of the pre-tilt angle of the increasing liquid crystal of the structure represented for the following formula [3] of Isosorbide-5-Nitrae-trans- cyclohexylidene and [4] is obvious, therefore preferably.The structure that particularly formula [3] is represented this is better, therefore more preferably.
Figure BPA00001171770500083
In formula [3], n be 2~11 integer, preferably 2~6 integer, the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is respectively transisomer.
Figure BPA00001171770500084
In formula [4], n be 2~11 integer, preferably 2~6 integer, the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is respectively transisomer.
The preferred concrete example for the structure that the formula [2] of the present invention is represented is represented with following formula [9]~[12].N in formula [9]~[12] separately preferably 2~11 integer, particularly preferably 2~6 integer.The cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene in formula [9]~[12] is respectively transisomer.
Figure BPA00001171770500091
The specific diamines that the specific polyimides of structure comprising formula [2] can use following formula [13] to represent obtains for raw material.
Figure BPA00001171770500092
In formula [13], X1And X2Definition it is identical with formula [2].
The method for the diamines that formula [13] is represented is not particularly limited, and following method can be enumerated as method for optimizing.
Figure BPA00001171770500093
In formula [14], X1And X2Definition it is identical with formula [2].
The dinitro compound of synthesis type [14], by common method reduce nitro so that it becomes amino and be made.
The dinitro compound of formula [14] can be obtained by reactions such as the compounds and dinitrofluorobenzene of the hydroxyl that following formula [15] is represented.
Figure BPA00001171770500101
In formula [15], X1And X2Definition it is identical with formula [2].
Comprising formula [3], [4], the structure of [9]~[12] specific polyimides also can by with above identical method be made.
In formula [1], R1And R2It can be one species respectively, can also have different R respectively1And R2, as repeat unit by different multiple combinations.
For the purpose of the pre-tilt angle for increasing liquid crystal, the structure of 1 mole of more than % formula [2] is preferably used.So as to for the purpose of liquid crystal vertical-tropism, preferably use the structure of 10 moles of more than % formula [2], more preferably 15 moles more than %.Specific polyimides comprising formula [3], [4], the structure of [9]~[12] is similarly such.
Specific polyimides is by the way that the acid imide rate general control during polyamic acid imidizate is being obtained less than 100%.
In addition, the polyimides that specific polyimides may also comprise the polyamic acid imidizate for the construction unit that repeat unit is represented comprising following formula [5] in the structural formula by the repeat unit for representing formula [1] and obtain.
Figure BPA00001171770500102
In formula [5], R3For 4 valency organic groups, R4For divalent organic group, R3Or R4At least one party there is carboxyl.
Now, acid imide rate can be 100%.
The reasons why based on that can obtain high voltage holding ratio, the acid imide rate of specific polyimides is advisable with more than 20%, and more preferably more than 40%.
Carboxyl amount in the reasons why based on the effect for efficiently obtaining the present invention, specific polyimides is using preferably 0.1~4 based on the average value as the repeat unit of the structural formula of polyimides, more preferably 0.3~3, particularly preferably 0.5~2.5.Repeat unit now refers to also include containing not by the repeat unit of the unit of the acid amides acidic group of imidizate.For example, obtained by the polyamic acid imidizate that is formed as the repeat unit that formula [1] is represented during polyimides, it is made up of during acid imide rate less than 100% combination of following formula [16a]~[16d] structure, comprising whole formula [16a]~[16d] in the repeat unit when above calculates carboxyl amount.
Figure BPA00001171770500111
In the present invention, the amount (the hereinafter also referred to average value of carboxyl) of the carboxyl in specific polyimides is tried to achieve as the P of following (i) and the Q sums of (ii).
(i) average value of the repeat unit relative to the structural formula as polyimides of the carboxyl of the amic acid of non-imidizate is derived from：P
(ii) R of the formula [5]3、R4Comprising carboxyl the repeat unit relative to the structural formula as polyimides average value：Q
The P of (i) can be calculated with acid imide rate (z) by following formula (1).Acid imide rate (z) is for example by described later<The measure of acid imide rate>Try to achieve.
P=2 × (1-z/100) (1)
On the other hand, the Q of described (ii) by the formula [5] R3Comprising carboxyl the repeat unit relative to the structural formula as polyimides average value：Q1And R4Comprising carboxyl the repeat unit relative to the structural formula as polyimides average value：Q2Sum is tried to achieve.
The R3、R4It is some or all of tetracarboxylic dianhydride's residue (R as the raw material for obtaining specific polyimides respectively3), diamines residue (R4)。
Therefore, the Q1The mole fraction of the tetracarboxylic dianhydride represented by the following formula [V1] in total mole of the tetracarboxylic dianhydride for obtaining specific polyimides is calculated by following formula (3).
Figure BPA00001171770500112
Q1=β1×W1/W2      (3)
Here, β1Represent R3Comprising carboxyl number, W1The mole of the tetracarboxylic dianhydride of expression [V1], W2Represent total mole of tetracarboxylic dianhydride.
The Q2The mole fraction of the diamines represented by the following formula [V2] in total mole of the diamines for obtaining specific polyimides is calculated by following formula (4).
H2N-R4-NH2         [V2]
Q2=β2×W3/W4     (4)
Here, β2Represent R4Comprising carboxyl number, W3The mole of the diamines represented for formula [V2], W4Represent total mole of diamines.
Therefore, carboxyl amount can be tried to achieve by following formula (5).
Carboxyl amount in specific polyimides
=P+Q1+Q2
=2 × (1-z/100)+β1×W1/W2+β2×W3/W4   (5)
In the present invention, the regulation of the carboxyl amount in specific polyimides can use following any method：
(1) method by controlling acid imide rate to be adjusted,
(2) according to the R of formula [5]3Or R4Comprising the structural formula of repeat unit that represents of carboxyl number and formula [1] in formula [5] ratio come the method that is adjusted.In addition, also can and with the method for (1) and (2).
R from formula [1]1And R2The selection free degree from the point of view of, the preferred method of (1).From the point of view of the selection free degree of the acid imide rate of specific polyimides, the preferred method of (2).In addition, occur from firing process when making liquid crystal orientation film because carrying out imidization reaction specific amines depart from or the cut-off possibility of polyimides chain it is small from the point of view of, the preferred method of (2).
When the carboxyl amount in specific polyimides is adjusted the method for (1) more than, for the R in formula [1]1And R2It is not particularly limited.In addition, R1And R2It can be one species respectively in formula [1], can also have different R respectively1And R2Structure, as repeat unit by different multiple combinations.
R in formula [1]1Concrete example enumerate it is as follows.
Figure BPA00001171770500131
Figure BPA00001171770500141
Wherein, even A-6, A-16, A-18~A-22, A-25, A-37, A-38 are due to the high polyimides of acid imide rate, its dissolubility in organic solvent is also very high, therefore preferably.
In addition, R110 moles of more than % when there is ester ring type structure or aliphatic structure as A-1~A-25, voltage retention is improved, therefore preferably.Particularly R1And release faster liquid crystal orientation film of the aligning agent for liquid crystal of 2 kinds of groups selected from A-1, A-16, A-19 due to electric charge can be obtained has been used, therefore preferably.
In formula [1], R2The organic group beyond the structure of formula [2] expression can be contained.Its concrete example is as follows.
Figure BPA00001171770500151
Figure BPA00001171770500171
Figure BPA00001171770500181
Figure BPA00001171770500191
Figure BPA00001171770500201
In B-112 and B-113, Q represents-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH2-, any of -0-,-CO-,-NH-.
When the carboxyl amount in specific polyimides being adjusted by the method for (2), as long as R3Or R4Either one possess carboxyl, its structure is not particularly limited.In addition, the preferred R of carboxyl quantity3And R4Possesses 0~2 (R respectively3And R4Either one possess at least one carboxyl).
From the ease and raw material of synthesis of polyimides obtain it is ease from the point of view of, preferably R4With carboxyl.It is used as carboxylic R4, B-102~B-113 can be enumerated.Now, carboxylic R4But can be used a kind also two or more be used in combination.In addition, R4For R during with carboxyl3Structure be not particularly limited, can enumerate A-1~A-45 as concrete example.
<The preparation method of specific polyimides>
Preparation method to the specific polyimides as (A) composition for the present invention is not particularly limited, and is typically adopted with the following method：Make the tetrabasic carboxylic acid composition being made up of one or more selected from tetrabasic carboxylic acid and its derivative and the diamine component reaction being made up of one or more diamine compounds, synthesis possesses the polyamic acid of the structural formula of the repeat unit of formula [1] expression, by polyamic acid imidizate formation polyimides.
Now the polyamic acid of gained can be formed as homopolymer or copolymer by being suitably selected as the tetrabasic carboxylic acid composition and diamine component of raw material.
Tetrabasic carboxylic acid and its derivative described here refers to tetrabasic carboxylic acid, the carboxylic acid halides of tetrabasic carboxylic acid two or tetracarboxylic dianhydride.Wherein, tetracarboxylic dianhydride is because high with the reactivity of diamine compound, therefore preferably.
The concrete example of preparation method as shown below for specific polyimides.
For example, in 1-METHYLPYRROLIDONE, N, N '-dimethyl acetamide, N, at least one kind of tetrabasic carboxylic acid composition comprising the tetracarboxylic dianhydride represented selected from formula [17] and at least one kind of diamine component comprising the diamine compound represented selected from formula [18] is carried out polycondensation reaction in the organic solvents such as N '-dimethyl formamide, gamma-butyrolacton, polyamic acid can be obtained.
Figure BPA00001171770500211
R in formula [17]1Definition it is identical with formula [1].
H2N-R2-NH2        [18]
R in formula [18]2Definition it is identical with formula [1].
Now, -20 DEG C~150 DEG C of arbitrary temp, preferably -5 DEG C~100 DEG C of temperature range may be selected in reaction temperature.
Constitute total molal quantity of the compound of tetrabasic carboxylic acid composition and constitute the ratio between total molal quantity of diamine compound of diamine component preferably 0.8: 1~1.2: 1, particularly preferably 0.9: 1~1.1: 1.The mol ratio is bigger closer to the degree of polymerization of the polymer of 1.0 generations.
In addition, in order to obtain formula [1] expression repeat unit structural formula in repeat unit part or all possess formula [5] expression unit polyamic acid, can be used R1Carboxylic tetracarboxylic dianhydride and/or R2Carboxylic diamines.
As making the method for polyamic acid imidizate, the method for generally comprising the hot-imide by heating, the method that catalysis imidizate is carried out using catalyst, the catalysis imidizate of imidization reaction is carried out at relatively low temperatures because the molecular weight of the polyimides of gained is difficult to decline, therefore preferably.
Be catalyzed imidizate can be by organic solvent, being stirred and implementing in the presence of base catalyst and acid anhydrides to polyamic acid.Reaction temperature now is -20~250 DEG C, more preferably 0~180 DEG C.Imidizate can be carried out quickly when reaction temperature is high, if but temperature is too high, and the molecular weight of polyimides declines sometimes.The amount of base catalyst is 0.5~30 mole times of acid amides acidic group, and preferably 2~20 moles times, the amount of acid anhydrides is 1~50 mole times of acid amides acidic group, preferably 3~30 moles times.If the amount of base catalyst or acid anhydrides is few, reaction can not be carried out fully, if excessively, it is difficult to remove completely after reaction terminates.As the base catalyst now used, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated, wherein, pyridine, which possesses, makes reaction carry out required suitable alkalescence, therefore preferably.As acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, if wherein using acetic anhydride, reaction terminate after it is refined become easy, therefore preferably.As organic solvent, as long as can dissolve polyamic acid, it is not particularly limited.Its concrete example can enumerate N, N '-dimethyl formamide, N, N '-dimethyl acetamide, METHYLPYRROLIDONE, N- methyl caprolactams, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton etc..It can be controlled using the acid imide rate for being catalyzed imidizate by adjusting catalytic amount and reaction temperature, reaction time.
The polyimides of generation can be obtained by the precipitation for reclaiming the reaction solution input Weak solvent of the above and generating.It is not particularly limited, can be enumerated such as methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water for the Weak solvent now used.The polyimides for putting into Weak solvent and precipitating can be formed as powder after filtration in normal pressure or the lower progress air drying of decompression or heat drying.If the polyimide powder to be repeated to the operation for being dissolved in organic solvent formation precipitation of 2~10 times, polyimides can also be refined.The refining step can not preferably implemented during cleared impurity by primary sedimentation reclaimer operation.
Be not particularly limited for the molecular weight of specific polyimides that the present invention is used, from disposable and film forming when characteristic stability from the point of view of, weight average molecular weight preferably 2000~200000, more preferably 4000~50000.Molecular weight is tried to achieve by GPC (gel permeation chromatography).
<(B) composition/specific amines>
The specific amines as (B) composition for the present invention is the amines that there is intramolecular 1 amino and nitrogenous heteroaromatic and the amino to be combined with the aliphatic alkyl or non-aromatic ring type alkyl of divalent.
The specific amines is because intramolecular is only comprising 1 amino, therefore the problem of the precipitation or gelation of polymer can be avoided the occurrence of when preparing aligning agent for liquid crystal or in the preservation of aligning agent for liquid crystal.
Primary amino radical contained by specific amines from specific polyimides into salt or bonding reaction it is ease from the point of view of, it is necessary to combined in intramolecular with the aliphatic alkyl or aromatic free non-aromatic ring type alkyl of divalent.
As the concrete example of aliphatic alkyl, straight-chain alkylidene, the alkylidene with branched structure, divalent alkyl containing unsaturated bond etc. can be enumerated.The carbon number of aliphatic alkyl preferably 1~20, more preferably 1~15, further more preferably 1~10.
As the concrete example of divalent non-aromatic ring type alkyl, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three ring eicosane rings, three ring docosane rings, bicycloheptane ring, decahydro naphthalene nucleus, ENB ring, adamantane ring etc. can be enumerated.The preferably ring of the ring of carbon number 3~20, preferably carbon number 3~15, the further preferably non-aromatic ring type alkyl of the ring of carbon number 3~10.
The nitrogenous heteroaromatic that specific amines is included is the aromatics for possessing the structure that at least one is selected from following formula [20a], formula [20b] and formula [20c], preferably possess the aromatics of 1~4 structure selected from following formula [20a], formula [20b] and formula [20c], more preferably 1~4.
Figure BPA00001171770500231
In formula, Z2For the straight or branched alkyl of carbon number 1~5.
As the concrete example of nitrogenous heteroaromatic, pyrrole ring, imidazole ring, oxazole rings, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenthazine Huan, oxadiazole rings, acridine ring etc. can be enumerated.The carbon atom of these nitrogenous heteroaromatics can possess containing heteroatomic substituent.As more preferable specific amines, the amines of following formula [6] expression can be enumerated.
Figure BPA00001171770500241
In formula, Y1For the divalent organic group with aliphatic alkyl or non-aromatic ring type alkyl, Y2For nitrogenous heteroaromatic.
In formula [6], as long as Y1For the divalent organic group with aliphatic alkyl or non-aromatic ring type alkyl, it is not particularly limited.
Preferred Y in formula [6]1For a kind of the divalent organic group with the aliphatic alkyl selected from carbon number 1~20 and the non-aromatic ring type alkyl of carbon number 3~20.As non-aromatic ring type alkyl, above structure can be enumerated.Aliphatic alkyl, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, ENB ring, adamantane ring of carbon number 1~15 etc. can more preferably be enumerated.It is special it is good be carbon number 1~10 straight or branched alkyl.
In addition, Y1Comprising the arbitrary aliphatic alkyl not adjacent with amino or non-aromatic ring type alkyl in-CH2- can be by-O- ,-NH- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-S- ,-S (O)2-、-CF2-、-C(CF3)2-、-C(CH3)2-、-Si(CH3)2-、-O-Si(CH3)2-、-Si(CH3)2-O-、-O-Si(CH3)2- O-, divalent ring type alkyl or heterocyclic substituted, the hydrogen atom combined with arbitrary carbon atom can be replaced containing fluoroalkyl, heterocycle, fluorine atom or hydroxyl by the straight or branched alkyl of carbon number 1~20, ring type alkyl, carbon number 1~10.
It is used as the concrete example of divalent ring type alkyl, phenyl ring can be enumerated, naphthalene nucleus, tetrahydric naphthalene ring, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring, 1, 8- perinaphthene rings, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three ring eicosane rings, three ring docosane rings, bicycloheptane ring, decahydro naphthalene nucleus, ENB ring, adamantane ring etc..
As the concrete example of divalent heterocycle, pyrrole ring, imidazole ring, oxazole rings, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenthazine Huan, oxadiazole rings, acridine ring etc. can be enumerated.
Y in formula [6]2It is same with more than for nitrogenous heteroaromatic, for the aromatic ring hydrocarbon containing at least one structure selected from formula [20a], formula [20b] and formula [20c].As its concrete example, above structure can be enumerated.Wherein preferred pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, quinoxaline ring, azepines ring, diaza
Figure BPA00001171770500251
Ring, naphthyridines ring, azophenlyene ring, diaza naphthalene nucleus.
In addition, from the point of view of the complexity of electrostatic interaction as the carboxyl into salt or hydrogen bond in nitrogenous heteroaromatic and specific polyimides, Y1Preferably with discord Y2Comprising formula [20a], formula [20b] or the adjacent substituent of formula [20c] combine.
Formula [6] is used as Y2The carbon atom of nitrogenous heteroaromatic can have the substituent of halogen atom and/or organic group, the organic group can contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
Preferred Y in formula [6]1And Y2Combination be：Y1For a kind of the divalent organic group with the aliphatic alkyl selected from carbon number 1~20 and the non-aromatic ring type alkyl of carbon number 3~20, Y2Selected from pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, quinoxaline ring, azepines ring, diaza
Figure BPA00001171770500252
Ring, naphthyridines ring, azophenlyene ring, diaza naphthalene nucleus.
Y2The carbon atom of nitrogenous heteroaromatic can have the substituent of halogen atom and/or organic group, the organic group can contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
As more preferable specific amines, the amines of following formula [7] expression can be enumerated.
In formula, Y3Aliphatic alkyl or non-aromatic ring type alkyl for the divalent of carbon number 1~10, Y4For singly-bound ,-O- ,-NH- ,-S- ,-SO2- or carbon number 1~19 divalent organic group, Y3And Y4The carbon atom being had adds up to 1~20, Y5For nitrogenous heteroaromatic.
Y in formula [7]3Aliphatic alkyl or non-aromatic ring type alkyl for the divalent of carbon number 1~10.Its concrete example can enumerate the straight or branched alkylidene of carbon number 1~10, the unsaturated alkylene of carbon number 1~10, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three ring eicosane rings, three ring docosane rings, bicycloheptane ring, decahydro naphthalene nucleus, ENB ring, adamantane ring etc..Straight or branched alkylidene, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, ENB ring or the adamantane ring of carbon number 1~10 can more preferably be enumerated.It is special it is good be carbon number 1~10 straight or branched alkylidene.
Y3Comprising the arbitrary aliphatic alkyl not adjacent with amino or non-aromatic ring type alkyl in-CH2- can be by-O- ,-NH- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-S- ,-S (O)2-、-CF2-、-C(CF3)2-、-C(CH3)2-、-Si(CH3)2-、-O-Si(CH3)2-、-Si(CH3)2-O-、-O-Si(CH3)2- O-, divalent ring type alkyl or heterocyclic substituted.In addition, the hydrogen atom combined with arbitrary carbon atom can be replaced containing fluoroalkyl, heterocycle, fluorine atom or hydroxyl by the straight or branched alkyl of carbon number 1~20, ring type alkyl, carbon number 1~10.The definition of ring type alkyl and heterocycle described here and the Y of formula [6]1Described in it is identical.
Y in formula [7]4For singly-bound ,-O- ,-NH- ,-S- ,-SO2- or carbon number 1~19 divalent organic group.The divalent organic group of the carbon number 1~19 is the divalent organic group with 1~19 carbon atom, can contain oxygen atom, nitrogen-atoms, sulphur atom, silicon atom etc..
It is used as Y4Concrete example, singly-bound ,-O- ,-NH- ,-S- ,-SO can be enumerated2-, the alkyl of carbon number 1~19 ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-CF2-、-C(CF3)2-、-CH(OH)-、-C(CH3)2-、-Si(CH3)2-、-O-Si(CH3)2-、-Si(CH3)2-O-、-O-Si(CH3)2- O-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three ring eicosane rings, three ring docosane rings, bicycloheptane ring, decahydro naphthalene nucleus, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring, 1,8- perinaphthene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenthazine ring, oxadiazole rings, acridine ring, piperazine ring, piperidine ring, dioxane ring, morpholine ring etc..
It is used as Y4, two or more of them can be contained.As containing Y of more than two kinds4Concrete example ,-N H-C H can be enumerated2 -、- N H - C 2 H 4 -、-N H - C 3 H 6 -、-NH - C 4 H 8 -、- S - C H 2 -、- S - C 2 H 4 -、- S - C 3 H 6 -、- S - C 4 H 8 -、- O - C H 2 -、- O - C 2 H 4 -、- O - C 3 H 6 -、- O - C 4 H 8 -、- N H - C O - C H 2 -、- N H - C O - C 2H 4 -、- N H - C O - C 3 H 6 -、- N H - C O - C 4 H 8 -、- C O - C H 2-、- C O - C 2 H 4 -、- C O - C 3 H 6 -、- C O - C 4 H 8 -、-C O - N H - C H 2 -、-C O - N H - C 2 H 4 -、- C O - N H - C 3H 6 -、- C O - N H - C 4 H 8 -、- N H - C H 2 - C H ( C H 3 ) -、- N H - C 2 H 4 - C H ( C H 3 ) -、- N H - C 3 H 6 - C H ( C H 3 )-、- N H - C 4 H 8 - C H ( C H 3 ) -、- S - C H 2-C H ( C H 3 )-、- S - C 2 H 4 - C H ( C H 3 ) -、- S - C 3H 6 - C H ( C H 3 )-、- S - C 4H 8 - C H ( C H 3 ) -、- O - C H 3 -C H ( C H 3 )-、- O - C 2 H 4 - C H ( C H 3 ) -、- O - C 3 H 6 - C H ( C H 3 )-、- O - C 4 H 8 - C H ( C H 3 ) -、- N H - C O - C H 2 - C H ( CH 3 ) -、- N H - C O - C 2 H 4 - C H ( C H 3 ) -、- N H - C O -C 3 H 6 - C H ( C H 3 )-、- N H - C O - C 4 H 8 - C H ( C H 3 )-、- C H( O H ) - C H 2 -、- C H( O H )- C 2 H 4 -、- C H ( OH ) - C 3 H 6 -、- C H ( O H ) - C 4H 8 -、- C H ( C H 2 O H )- C H 2 -、- C H ( C H 2 O H ) -C 2 H 4 -、- C H ( C H 2 O H )- C 3 H 6 -、- C H ( C H 2 O H ) - C 4H 8 -、- N H - C H ( C H2 O H ) - C H 2-、- C O - N H - C H ( C H 2 O H ) - C H 2 -、-N H - C O - C H ( C H 2 O H ) - C H 2 -、- C O - C H( C H 2 O H )- C H 2 -、- S - C H ( C H 2 O H ) - C H 2 -、- O - C H ( C H 2O H ) - C H 2 -、- C H ( N ( C H 3 ) 2 ) -、- C 6 H 4 - O -、-C 6 H 4 - N H -、- C 6 H 4 - C O - N H -、- C 6 H 4 - N H - C O-、- C 6 H 4 - C O -、- C 6 H 4 - C H 2 -、- C 6 H 4- S-etc..
Y in formula [7]5It is nitrogenous heteroaromatic, with the Y in formula [6]2Definition it is identical, therefore, Y5Definition and Y2It is identical.As its concrete example, the Y with more than can be enumerated2Identical structure.Wherein preferred pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, quinoxaline ring, azepines ring, diaza
Figure BPA00001171770500271
Ring, naphthyridines ring, azophenlyene ring or diaza naphthalene nucleus.
In addition, from the point of view of the complexity of electrostatic interaction as the carboxyl into salt or hydrogen bond in nitrogenous heteroaromatic and specific polyimides, Y4Preferably with discord Y5Comprising formula [20a], formula [20b] or the adjacent carbon atom of formula [20c] combine.
Formula [7] is used as Y5The carbon atom of nitrogenous heteroaromatic can have the substituent of halogen atom and/or organic group, the organic group can contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
Y in formula [7]3、Y4And Y5Preferred compositions be：Y3For the straight or branched alkylidene of carbon number 1~10, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, ENB ring or adamantane ring, Y4For singly-bound, the straight or branched alkylidene of carbon number 1~10 ,-O-,-N H-,-C O-O-,-O-C O-,-C O-N H-,-N H-CO-,-C O-,-S-,-S O2 -、- C F 2 -、- C ( C F 3 ) 2 -、- S i ( C H 3 ) 2 -、- O - S i ( C H 3 ) 2 -、- S i ( C H 3 ) 2- O -、- O - S i ( C H 3) 2 - O -、- C H ( O H ) -、- N H - CH 2 -、- N H - C 2 H 4 -、- N H - C 3 H 6 -、- N H - C 4 H 8 -、- S - C H 2 -、- S - C 2 H 4 -、- S - C 3 H 6 -、- S - C 4 H 8 -、- O - C H 2 -、- O - C 2 H 4 -、- O - C 3 H 6 -、- O - C 4 H 8 -、- N H - C O - C H 2 -、- N H - C O - C 2 H 4 -、- N H - C O - C3 H 6 -、- N H - C O - C 4 H 8 -、- C O - C H 2 -、- C O - C 2H 4 -、- C O - C 3 H 6 -、- C O - C 4 H 8 -、- C O - N H - C H2 -、- C O - N H - C 2 H 4 -、- C O - N H - C 3 H 6 -、- C O -N H - C 4 H 8 -、- N H - C H 2 - C H ( C H 3 ) -、- N H - C 2 H4 - C H ( C H 3 ) -、- N H - C 3 H 6 - C H ( C H 3 ) -、- N H -C 4 H 8 - C H ( C H 3 ) -、- S - C H 2 - C H ( C H 3 ) -、- S -C 2 H 4 - C H ( C H 3 ) -、- S - C 3 H 6 - C H ( C H 3 ) -、- S- C 4 H 8 - C H ( C H 3 ) -、- O - C H 3 -C H ( C H 3 ) -、- O- C 2 H 4 - C H ( C H 3 ) -、- O - C 3 H 6 - C H ( C H 3 ) -、-O - C 4 H 8 - C H ( C H 3 ) -、- N H - C O - C H 2 - C H ( C H 3 )-、- N H - C O - C 2 H 4 -C H ( C H 3 ) -、- N H - C O - C 3 H6 - C H ( C H 3 ) -、- N H - C O - C 4 H 8 - C H ( C H 3 ) -、-C H ( O H ) - C H 2 -、- C H ( O H ) - C 2 H 4 -、- C H ( O H )- C 3 H 6 -、- C H ( O H ) - C 4 H 8 -、- C H ( C H 2 O H ) - CH 2 -、- C H ( C H 2 O H ) - C 2 H 4 -、- C H ( C H 2 O H ) - C3 H 6 -、- C H ( C H 2 O H ) -C 4 H 8 -、- N H - C H ( C H 2 OH ) - C H 2 -、- C O - N H - C H ( C H 2 O H ) - C H 2 -、- N H- C O - C H ( C H 2 O H ) - C H 2 -、- C O - C H ( C H 2 O H ) -C H 2 -、- S - C H ( C H 2 O H ) - C H 2 -、- O - C H ( C H 2 OH ) - C H 2 -、- C H ( N ( C H 3 ) 2 ) -、- C 6 H 4 - O -、- C6 H 4 - N H -、- C 6 H 4 - C O - N H -、- C 6 H 4 - N H - C O -、- C 6 H 4 - C O -、- C 6 H 4 - C H 2 -、- C 6 H 4- S-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring or 1,8- perinaphthene rings, Y5For pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, quinoxaline ring, azepines ring, diazaRing, naphthyridines ring, azophenlyene ring or diaza naphthalene nucleus.Y5The carbon atom of nitrogenous heteroaromatic can have the substituent of halogen atom and/or organic group, the organic group can contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
Y in formula [7]3、Y4And Y5More preferably combination be：Y3For the straight or branched alkylidene of carbon number 1~5, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, ENB ring or adamantane ring, Y4For singly-bound, the straight or branched alkylidene of carbon number 1~5 ,-O-,-N H-,-C O-O-,-O-C O-,-C O-N H-,-N H-C O-,-CO-,-S-,-S (O)2 -、- C H ( O H ) -、- N H - C H 2 -、- S - C H 2 -、- O - C H 2 -、- O - C 2 H 4 -、- N H - C O - CH 2 -、- C O - C H 2 -、- C O - N H - C H 2 -、- N H - C H 2 -C H ( C H 3 ) -、- S - C H 2 - C H ( C H 3 ) -、- O - C H 3 - CH ( C H 3 ) -、- N H - C O - C H 2 - C H (C H 3) -、- C H ( OH ) - C H 2 -、- C H ( O H ) - C 2 H 4 -、- C H ( C H 2 O H ) -C H 2 -、- N H - C H ( C H 2 O H ) - C H 2 -、- C O - N H - C H( C H 2 O H ) - C H 2 -、- N H - C O - C H ( C H 2 O H ) - C H 2-、- C O - C H (C H 2 O H ) - C H 2 -、- S - C H (C H 2 O H )- C H 2 -、- O - C H ( C H 2 O H ) - C H 2 -、- C H ( N ( C H 3 )2 ) -、- C 6 H 4 - O -、- C 6 H 4 - N H -、- C 6 H 4 - C O - N H-、- C 6 H 4 -  N H - C O -、- C 6 H 4 - C O -、- C 6 H 4 - C H 2-、- C 6 H 4- S-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring or 1,8- perinaphthene ring, Y5For pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, quinoxaline ring, azepines ring, diazaRing, naphthyridines ring, azophenlyene ring or diaza naphthalene nucleus.Y5The carbon atom of nitrogenous heteroaromatic can have the substituent of halogen atom and/or organic group, the organic group can contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
Y in formula [7]3、Y4And Y5Even more preferably combination be：Y3For the straight or branched alkylidene of carbon number 1~5, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, Y4For singly-bound, the straight or branched alkylidene of carbon number 1~5 ,-O-,-N H-,-C O-O-,-O-C O-,-C O-N H-,-N H-C O-,-C O-,-C H (O H)-,-NH-C H2 -、- S - C H 2 -、- O - C H 2 -、- N H - C O - C H 2-、- C O - C H 2 -、- C O - N H - C H 2 -、- N H - C H 2 - C H( C H 3 ) -、- S - C H 2 - C H ( C H 3 ) -、- O - C H 3 - C H ( CH 3 ) -、- N H - C O - C H 2 - C H ( C H 3 ) -、- C H ( O H ) -C H 2 -、- C H ( O H ) - C 2 H 4 -、- C H ( C H 2 O H ) - C H 2-、- N H - C H ( C H 2 O H ) - C H 2 -、- C O - N H - C H ( C H2 O H ) - C H 2 -、- N H - C O - C H ( C H 2 O H ) - C H 2 -、-C O - C H ( C H 2 O H ) - C H 2 -、- S - C H ( C H 2 O H ) - C H2 -、- O - C H ( C H 2 O H ) - C H 2 -、- C H ( N ( C H 3 ) 2 )-、- C 6 H 4 - O -、- C 6 H 4 - N H -、- C 6 H 4 - C O - N H -、-C 6 H 4 - N H - C O -、- C 6 H 4 - C O -、- C 6 H 4 - C H 2 -、- C 6 H 4- S-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring or anthracene nucleus, Y5For pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring.Y5The carbon atom of nitrogenous heteroaromatic can have the substituent of halogen atom and/or organic group, the organic group can contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
Y in formula [7]3、Y4And Y5Particularly preferably combination be：Y3For the straight or branched alkylidene, cyclobutane ring or cyclohexane ring of carbon number 1~5, Y4For singly-bound ,-O- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CH (OH)-, phenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus, Y5For pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring.Y5The carbon atom of nitrogenous heteroaromatic can have the substituent of halogen atom and/or organic group, the organic group can contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
As the concrete example of the specific amines for the present invention, M1~M156 compound can be enumerated.
Figure BPA00001171770500311
Figure BPA00001171770500321
Figure BPA00001171770500331
Figure BPA00001171770500351
Figure BPA00001171770500361
As more preferable compound, 6 ~ M of M 8, M 10, 16 ~ M of M 21, 31 ~ M of M 36, 40 ~ M of M 45, 47 ~ M of M 57, 59 ~ M of M 63, M 68, M 69, 72 ~ M of M 82, 95 ~ M of M 98, 10 0 ~ M of M 1 03, 10 8 ~ M of M 125, 12 8 ~ M of M 137, 13 9 ~ M of M 143, the further more preferably 6 ~ M of M 8 of the can be enumerated. of 14 9 ~ M of M 156, 16 ~ M of M 20, 32 ~ M of M 36, M 40, M 41, M 44, 49 ~ M of M 54, 59 ~ M of M 62, M 68, M 69, 75 ~ M of M 82, 100 ~ M of M 103, 108 ~ M of M 112, 114 ~ M of M 116, 118 ~ M of M 121, M 125, 13 4 ~ M of M 136, M 139, M 140, M 143, M 150, the 6.. of 152 ~ M of M 15
<Aligning agent for liquid crystal>
The aligning agent for liquid crystal of the present invention generally mixes the specific polyimides as (A) composition and obtained as the specific amines of (B) composition in organic solvent.The specific polyimides and specific amines of mixing can be respectively that one kind a variety of can be also used in combination.
It is used as mixed method, it can be used reaction solution obtained by the polyamic acid imidizate as the precursor of specific polyimides (solution of specific polyimides), but can generally enumerate the powder of specific polyimides obtained by refined and be dissolved in the method that specific amines is added in solution obtained by organic solvent.As long as the organic solvent now used can dissolve specific polyimides, it is not particularly limited.The concrete example of the organic solvent is enumerated as follows.
Such as N can be enumerated, N '-dimethyl formamide, N, N '-dimethyl acetamide, METHYLPYRROLIDONE, N- methyl caprolactams, 2-Pyrrolidone, N- ethyl pyrrolidones, NVP, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 1, 3- dimethyl-2-imidazolidinones, cinene, ethylamino ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanones etc..These solvents can be used in mixed way with two or more.
When the specific polyimides is dissolved in organic solvent, in order to promote the dissolving of specific polyimides to heat.If heating-up temperature is too high, the molecular weight and molecular weight of polyimides, therefore temperature is preferably 30~100 DEG C sometimes.Concentration for specific polyimide solution is not particularly limited, and it is easy to homogeneous with specific amines and mixed when the specific polyimides concentration in solution is 1~20 mass %, therefore preferably, more preferably 3~15 mass %, particularly preferably 3~10 mass %.
Specific amines can directly make an addition to the specific polyimide solution, but preferably be formed as adding after the mass % of concentration 0.1~10 solution with appropriate solvent.As the solvent, the solvent of the specific polyimides can be enumerated.
Preferably heated after mixing specific polyimides and specific amines in organic solvent.By heating, the ratio increase of bound specific amines and specific polyimides in the state of aligning agent for liquid crystal, the movement for being formed as electric charge during liquid crystal orientation film can be more efficient.Preferably 10~100 DEG C, more preferably 20~80 DEG C of temperature when being heated after mixing.
The reasons why stability of effect and lossless aligning agent for liquid crystal based on the efficient acquisition present invention, relative to the mole of carboxyl 1 contained by specific polyimides, preferably 0.01~2 mole of the consumption of specific amines times, more preferably 0.05~1 mole times, particularly preferably 0.08~0.8 mole times.
The aligning agent for liquid crystal of the present invention can also contain the solvent or compound as other compositions in addition to specific polyimides, specific amines, solvent or compound that thickness homogeneity such as when making to be coated with aligning agent for liquid crystal and surface smoothness are improved, make the compound that the adaptation of liquid crystal orientation film and substrate is improved.Other compositions can be added during specific polyimides and specific amines is mixed, and be added again after also being mixed to form their mixed solution.
Thickness homogeneity and the concrete example of the solvent of surface smoothness raising is set to enumerate as follows.
Such as isopropanol can be enumerated,Methoxy amylalcohol,Methyl cellosolve,Ethyl cellosolve,Butyl cellosolve,Methylcellosolve acetate,Ethyl cellosolve acetate,Butyl carbitol,Ethyl carbitol,Ethylcarbitol acetate,Ethylene glycol,Ethylene glycol acetate,Ethylene glycol monoisopropyl ether,Ethylene glycol monobutyl ether,Propane diols,Propylene glycol monoacetate,Propylene glycol monomethyl ether,Propylene glycol t-butyl ether,Dipropylene glycol monomethyl ether,Diethylene glycol (DEG),Diglycol monotertiary acetic acid esters,Diethylene glycol dimethyl ether,Dipropylene glycol monoacetate monomethyl ether,Dipropylene glycol monomethyl ether,DPE,Dipropylene glycol monoacetate list ether,Dipropylene glycol monopropyl ether,Dipropylene glycol monoacetate list propyl ether,3- methyl -3- methoxybutyl acetic acid esters,Tripropylene glycol methyl ether,3- methyl -3- methoxybutanols,Di Iso Propyl Ether,Ethyl isobutyl ether,Diisobutylene,Pentyl acetate,Butyl butyrate,Butyl ether,DIBK,Methylcyclohexene,Propyl ether,Hexyl ether,N-hexane,Pentane,Normal octane,Ether,Methyl lactate,Ethyl lactate,Methyl acetate,Ethyl acetate,N-butyl acetate,Propylene glycol acetate list ether,Methyl pyruvate,Ethyl pyruvate,3- methoxy methyl propionates,3- ethoxy-propionic acid methyl ethyl esters,3- methoxypropionates,3- ethoxy-propionic acids,3- methoxypropionic acids,3- methoxy propyl propyl propionates,3- methoxy propyl acid butyl esters,1- methoxy-2-propanols,1- ethyoxyl -2- propyl alcohol,1- butoxy -2- propyl alcohol,1- phenoxy group -2- propyl alcohol,Propylene glycol monoacetate,Propylene-glycol diacetate,Propane diols -1- monomethyl ether -2- acetic acid esters,Propane diols -1- list ether -2- acetic acid esters,DPG,2- (2- ethoxy-cs epoxide) propyl alcohol,Methyl lactate,Ethyl lactate,Lactic acid n-propyl ester,N-butyl lactate,Isoamyl lactate etc. has solvent of low surface tension etc..
These solvents can use a kind a variety of can be also used in mixed way.During using the solvent, 5~80 mass % of all solvents that its amount preferably aligning agent for liquid crystal is included, more preferably 20~60 mass %.
As the compound for improving thickness homogeneity and surface smoothness, fluorine class surfactant, organosilicone surfactants, nonionic surface active agent etc. can be enumerated.
Such as F Top EF301, EF303, EF352 (Tao Kemu (Tokem Products) company system) can more specifically be enumerated, MEGAFAC F171, F173, R-30 (big Japanese ink chemical company system), Frorard FC430, FC431 (Sumitomo 3M company systems), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's system) etc..The use ratio of these surfactants is the mass parts of (A) composition 100 preferably 0.01~2 mass parts included relative to aligning agent for liquid crystal, more preferably 0.01~1 mass parts.
As the concrete example of compound that the adaptation of liquid crystal orientation film and substrate improves is made, the compound as shown below containing functional silanes or the compound containing epoxy radicals can be enumerated.
Such as 3- TSL 8330s can be enumerated,APTES,2- TSL 8330s,2- aminopropyltriethoxywerene werenes,N- (2- amino-ethyls) -3- TSL 8330s,N- (2- amino-ethyls) -3- amino propyl methyl dimethoxysilanes,3- ureido-propyl trimethoxy silanes,3- ureidopropyltriethoxysilanes,N- ethoxy carbonyl -3- TSL 8330s,N- ethoxy carbonyls-APTES,N- triethoxysilylpropyltetrasulfide diethylenetriamines,N- trimethoxy-silylpropyl diethylenetriamines,10- trimethoxysilyls -1,4,The azepine decane of 7- tri-,10- triethoxysilyls -1,4,The azepine decane of 7- tri-,9- trimethoxysilyls -3,6- diaza nonyl acetic acid esters,9- triethoxysilyls -3,6- diaza nonyl acetic acid esters,N- benzyl -3- TSL 8330s,N- benzyls-APTES,N- phenyl -3- TSL 8330s,N- phenyl-APTES,Double (oxygen the ethylidene) -3- TSL 8330s of N-,Double (oxygen the ethylidene)-APTESs of N-,Ethylene glycol diglycidylether,Polyethyleneglycol diglycidylether,Propylene glycol diglycidylether,Tripropyleneglycol diglycidyl ether,Polypropylene glycol diglycidyl ether,Neopentylglycol diglycidyl ether,1,6- hexanediol diglycidyl ethers,Glycerin diglycidyl ether,2,2- dibromoneopentyl glycol diglycidyl ethers,1,3,5,6- four glycidyl groups -2,4- hexylene glycols,N,N,N’,N '-four glycidyl group-m-xylene diamine,1,Double (the N of 3-,N- diglycidyls amino methyl) hexamethylene,N,N,N’,N '-four glycidyl group -4,4 '-diaminodiphenyl-methane etc..
The mass parts of specific polyimide component 100 included relative to aligning agent for liquid crystal, these raisings used and amount preferably 0.1~30 mass parts of the compound of the adaptation of substrate, more preferably 1~20 mass parts.If less than 0.1 mass parts, can not obtain the effect of adaptation raising, if it exceeds 30 mass parts, then the orientation of liquid crystal is deteriorated sometimes.
In the aligning agent for liquid crystal of the present invention except component of polymer of the above composition in addition to it can add specific polyimides in the range of external lossless effect of the present invention or so that the electrical characteristics such as dielectric constant and electric conductivity of liquid crystal orientation film change for the purpose of electrolyte or conductive materials, the cross-linked compound for the purpose of can also adding the film hardness and consistency when being formed as liquid crystal orientation film to improve.
The concentration of solid constituent in the aligning agent for liquid crystal of the present invention can suitably change according to the thickness of purpose liquid crystal orientation film, but based on forming flawless film and the reasons why obtain the suitable thickness as liquid crystal orientation film, it is advisable with 1~20 mass %, more preferably 2~10 mass %.
<Liquid crystal orientation film liquid crystal display cells>
After the aligning agent for liquid crystal of the present invention is coated on substrate and burnt till, orientation process is implemented by friction treatment or illumination etc., or can be used in vertical orientated purposes etc. without orientation process as liquid crystal orientation film.Now, as long as the high substrate of substrate used thereof transparency, is not particularly limited, plastic bases such as glass substrate, acrylic acid substrate or polycarbonate substrate etc. can be used.In addition, from the perspective of technique simplification, preferably using the substrate formd for the ITO electrode of liquid crystal drive etc..In addition, for reflection type liquid crystal display element, can be only in unilateral substrate using opaque materials such as silicon wafers, electrode at this moment can use the material of the reflected lights such as aluminium.
It is not particularly limited for the coating method of aligning agent for liquid crystal, in industrial circle typically using screen painting, hectographic printing, flexible printing, ink-jet method etc..As other coating methods, dip coating, rolling method, slit printing, rotary printing etc. can be enumerated, can be used according to different purposes.
By aligning agent for liquid crystal be coated on burning till after substrate can be made by heater meanses such as hot plates at a temperature of 50~300 DEG C, preferably 80~250 DEG C solvent evaporate and form film.It is unfavorable in terms of the power consumption of liquid crystal display cells if the film after burning till is blocked up, if excessively thin, the reliability of liquid crystal display cells can decline, therefore coating thickness is preferably 5~300nm, more preferably 10~100nm.Liquid crystal is set to be horizontally oriented or during tilted alignment, the film after being irradiated etc. by friction or polarized ultraviolet to burning till is handled.
The liquid crystal display cells of the present invention are to be obtained by the above method by the aligning agent for liquid crystal of the present invention after the substrate with liquid crystal orientation film, liquid crystal cell are made in a known manner, so as to obtain liquid crystal display cells.
Example to enumerate liquid crystal cell making, 1 pair of substrate for preparing to be formed with liquid crystal orientation film can be illustrated, sept is spread on the liquid crystal orientation film of 1 piece of substrate, regard liquid crystal aligning film surface as inner side, with another 1 piece of baseplate-laminating, sealed method after liquid crystal is injected in decompression；Or by baseplate-laminating and sealed method etc. after the liquid crystal that dripped on the liquid crystal orientation film surface for being scattered with sept.The thickness of sept now is preferably 1~30 μm, more preferably 2~10 μm.
As described above, it is high using the reliability of liquid crystal display cells made from the aligning agent for liquid crystal of the present invention, available for big picture and high-resolution LCD TV etc..
Embodiment
Embodiment exemplified below and comparative example, the present invention will be described in more detail, but the explanation of these embodiments not limiting the invention property.
The breviary symbol that is used in the present embodiment is described as follows.
(tetracarboxylic dianhydride)
CBDA：1,2,3,4- cyclobutane tetracarboxylic dianhydride
BODA：Bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydrides
Figure BPA00001171770500411
(diamines)
DBA：3,5- diaminobenzoic acids
PBCH5DAB：1,3- diaminourea -4- { 4- [trans- 4- (trans- 4- pentyl cyclohexyls) cyclohexyl] phenoxy group } benzene
BPCH5DAB：1,3- diaminourea -4- { 4- [4- (trans- 4- pentyl cyclohexyls) phenyl] phenoxy group } benzene
PCH7DAB：1,3- diaminourea -4- [4- (trans- 4- n-heptyls cyclohexyl) phenoxy group] benzene
Figure BPA00001171770500421
(specific amines)
3-AMP：3- aminomethyl pyridines
4-AMP：4- aminomethyl pyridines
AEP：4- (2- amino-ethyls) pyridine
API：1- (3- aminopropyls) imidazoles
2-AMMP：2- (amino methyl) -5- methylpyrazines
Figure BPA00001171770500422
(comparative compound)
Py：Pyridine, AP：3- aminopyridines, HA：Hexylamine
Figure BPA00001171770500423
(organic solvent)
NMP：METHYLPYRROLIDONE
BCS：Butyl cellosolve
<The molecular weight determination of polyimides>
The molecular weight of polyimides in synthesis example is determined as follows using three places (セ Application シ ュ mono-) science Co. Ltd. system normal temperature gel permeation chromatography (GPC) device (SSC-7200), Japanese nitre moral (Shodex) company system post (KD-803, KD-805).
Column temperature：50℃
Eluent：N, N '-dimethyl formamide (is used as additive, lithium bromide monohydrate (LiBrH2O) 30mmol/L, phosphoric acid anhydrous crystal (o- phosphoric acid) 30mmol/L, tetrahydrofuran (THF) 10ml/L)
Flow velocity：1.0mL/ minute
Calibration curve making standard specimen：TOSOH Co., Ltd TSK standards PEO (molecular weight about 9000000,150000,100000,30000) and Polymer Laboratory (Polymer Laboratory) company system polyethylene glycol (molecular weight about 12000,4000,1000).
<The measure of acid imide rate>
The acid imide rate of polyimides in synthesis example is determined as follows.20mg polyimide powders are loaded into NMR test tubes (wasteland's science Co. Ltd. system NMR sampling pipe standards φ 5), addition deuterated dimethylsulfoxide (DMSO-d6, 0.05%TMS melanges) and 0.53ml, it is completely dissolved it using ultrasonic wave.The 500MHz of solution proton NMR is determined with Japan Electronic Data (the タ system of デ mono-) Co. Ltd. system NMR analyzers (JNW-ECA500).Proton determines that the proton peak integrated value of the NH bases from amic acid occurred with the peak integrated value of the proton and near 9.5~10.0ppm tried to achieve by following formula on the basis of the proton of unconverted structure from before and after imidizate since acid imide rate.
Acid imide rate (%)=(1- α x/y) × 100
In above formula, x is the proton peak integrated value of the NH bases from amic acid, and y is reference proton peak integrated value, and α is the number ratio of the reference proton of of the NH matrix relative to 1 from amic acid of polyamic acid (acid imide rate is 0%).
<The computational methods of carboxyl amount>
Calculated according to the method recorded above.
<Synthesis example 1>
Mixing BODA (the 14.11g in NMP (740g), 56.3mmol), DBA (9.15g, 60.1mmol), as the PBCH5DAB (6.53g of side chain diamines, 15.0mmol), after 80 DEG C are reacted 5 hours, CBDA (3.23g, 16.5mmol) and NMP (56.0g) is added, reacted 6 hours in 40 DEG C, obtain polyamic acid solution.
NMP is added in the polyamic acid solution (30.0g), is diluted to add acetic anhydride (3.79g), the pyridine (2.94g) as imidization catalyst after 6 mass %, is reacted 3 hours in 80 DEG C.By in reaction solution input methanol (408ml), gained sediment is filtered out.The sediment is washed with methanol, is dried under reduced pressure in 100 DEG C, polyimide powder (A) is obtained.The acid imide rate of the polyimides is 40%, and number-average molecular weight is 17300, and weight average molecular weight is 46800.Carboxyl amount in the polyimides is 2.00 relative to repeat unit.
<Synthesis example 2>
Mixing BODA (the 5.21g in NMP (26.2g), 20.8mmol), DBA (3.37g, 22.2mmol), as the BPCH5DAB (2.38g of side chain diamines, 5.54mmol), after 80 DEG C are reacted 5 hours, CBDA (1.19g, 6.07mmol) and NMP (20.0g) is added, reacted 6 hours in 40 DEG C, obtain polyamic acid solution.
NMP is added in the polyamic acid solution (30.0g), is diluted to add acetic anhydride (3.74g), the pyridine (2.89g) as imidization catalyst after 6 mass %, is reacted 3 hours in 80 DEG C.By in reaction solution input methanol (410ml), gained sediment is filtered out.The sediment is washed with methanol, is dried under reduced pressure in 100 DEG C, polyimide powder (B) is obtained.The acid imide rate of the polyimides is 41%, and number-average molecular weight is 18300, and weight average molecular weight is 49200.Carboxyl amount in the polyimides is 1.98 relative to repeat unit.
<Synthesis example 3>
Mixing BODA (the 33.87g in NMP (185.0g), 135.3mmol), DBA (19.23g, 126.3mmol), as the PBCH5DAB (23.53g of side chain diamines, 54.1mmol), after 80 DEG C are reacted 5 hours, CBDA (8.62g, 43.9mmol) and NMP (155.8g) is added, reacted 6 hours in 40 DEG C, obtain polyamic acid solution.
NMP is added in the polyamic acid solution (100.2g), is diluted to add acetic anhydride (10.82g), the pyridine (8.34g) as imidization catalyst after 6 mass %, is reacted 3 hours in 80 DEG C.By in reaction solution input methanol (1300ml), gained sediment is filtered out.The sediment is washed with methanol, is dried under reduced pressure in 100 DEG C, polyimide powder (C) is obtained.The acid imide rate of the polyimides is 45%, and number-average molecular weight is 19100, and weight average molecular weight is 50800.Carboxyl amount in the polyimides is 1.80 relative to repeat unit.
<Synthesis example 4>
NMP is added in the polyamic acid solution (251.2g) that synthesis example 3 is obtained, is diluted to add acetic anhydride (53.91g), the pyridine (41.8g) as imidization catalyst after 6 mass %, is reacted 3.5 hours in 90 DEG C.By in reaction solution input methanol (3200ml), gained sediment is filtered out.The sediment is washed with methanol, is dried under reduced pressure in 100 DEG C, polyimide powder (D) is obtained.The acid imide rate of the polyimides is 80%, and number-average molecular weight is 15200, and weight average molecular weight is 45500.Carboxyl amount in the polyimides is 1.10 relative to repeat unit.
<Synthesis example 5>
Mixing BODA (the 15.0g in NMP (131g), 60mmol), DBA (9.74g, 64mmol), as the PCH7DAB (6.09g of side chain diamines, 16mmol), after 80 DEG C are reacted 5 hours, CBDA (3.88g, 19.8mmol) and NMP (30g) is added, reacted 3 hours in 40 DEG C, obtain polyamic acid solution.
NMP is added in the polyamic acid solution (10.0g), is diluted to add acetic anhydride (1.27g), the pyridine (0.98g) as imidization catalyst after 6 mass %, is reacted 3 hours in 80 DEG C.By in reaction solution input methanol (140ml), gained sediment is filtered out.The sediment is washed with methanol, is dried under reduced pressure in 100 DEG C, polyimide powder (E) is obtained.The acid imide rate of the polyimides is 46%, and number-average molecular weight is 20200, and weight average molecular weight is 62500.Carboxyl amount in the polyimides is 1.88 relative to repeat unit.
<Synthesis example 6>
Mixing BODA (the 150.1g in NMP (1290g), 600mmol), DBA (60.9g, 400mmol), as the PCH7DAB (152.2g of side chain diamines, 400mmol), after 80 DEG C are reacted 5 hours, CBDA (38.8g, 198mmol) and NMP (320g) is added, reacted 3 hours in 40 DEG C, obtain polyamic acid solution.
NMP is added in the polyamic acid solution (101.2g), is diluted to add acetic anhydride (21.3g), the pyridine (16.5g) as imidization catalyst after 6 mass %, is reacted 3 hours in 90 DEG C.By in reaction solution input methanol (13005ml), gained sediment is filtered out.The sediment is washed with methanol, is dried under reduced pressure in 100 DEG C, polyimide powder (F) is obtained.The acid imide rate of the polyimides is 81%, and number-average molecular weight is 20400, and weight average molecular weight is 63000.Carboxyl amount in the polyimides is 0.88 relative to repeat unit.
<Embodiment 1>
NMP (12.0g) is added in the polyimide powder (A) (2.12g) that synthesis example 1 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (0.64g) (being 0.064g as 3-AMP), NMP (4.41g) and BCS (15.9g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [1].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
<The making of liquid crystal cell>
Aligning agent for liquid crystal [1] achieved above is spun on to the ito surface of the 3 × 4cm substrate with ITO electrode, carries out carrying out with 210 DEG C of recirculation furnace after 5 minutes burn till in 80 DEG C burning till for 1 hour, acquisition thickness 100nm polyimide coating film.
By the rubbing device of roll neck 120mm rayon cloth, friction treatment is carried out to the substrate with liquid crystal orientation film with rotating speed 300rpm, roller gait of march 20mm/sec, intrusion 0.3mm condition, the substrate with liquid crystal orientation film is obtained.
Prepare 2 pieces of substrates with liquid crystal orientation film, wherein in printing and sealing agent thereon after the bead sept of 6 μm of the surface distribution of 1 piece of liquid crystal orientation film.The liquid crystal aligning film surface of another 1 piece of substrate is carried out into laminating as inner side causes frictional direction to be changed into after opposite direction, makes sealant cures that negative crystal born of the same parents are made.The nematic crystal structure cell that liquid crystal obtains antiparallel orientation is injected in negative crystal born of the same parents by depressurizing injection method.
<The evaluation of pre-tilt angle>
The pre-tilt angle at room temperature that device (Ai Er stones (ELSICON) company system, model PAS-301) determines liquid crystal cell produced above is determined with pre-tilt angle.As a result it is shown in table 1 described later.
In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other as described above operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
<The evaluation of voltage retention>
Liquid crystal cell after being determined to pre-tilt angle at a temperature of 80 DEG C applies the μ s of 4V voltages 60, determines the voltage after 16.67ms and after 1667ms, as voltage retention calculate voltage can keep how much.As a result it is shown in table 2 described later.
<The evaluation of residual charge release>
Liquid crystal cell after being determined for voltage retention applies 10V DC voltages 30 minutes, and short circuit is measured after 1 second within the time of 1800 seconds to the electrostatic produced in liquid crystal cell.Then, determine 50 seconds after and the residual charge after 1000 seconds.Determine and use the type liquid crystal evaluation of physical property device of Dongyang technology (テ Network ニ カ) Co. Ltd. system 6254.As a result it is shown in table 3 described later.
<Evaluation after high temperature placement>
Liquid crystal cell after residual charge is determined determines voltage retention and residual charge after temperature is set as placing 7 days in 100 DEG C of high temperature groove.As a result table 2 described later and table 3 are shown in.
<The evaluation of voltage retention after ultraviolet irradiation>
Apply the μ s of 4V voltages 60 to liquid crystal cell produced above at a temperature of 80 DEG C, determine the voltage after 16.67ms and after 1667ms, as voltage retention calculate voltage can keep how much.After measure, with desk-top UV solidification equipments (HCT3 B28 HEX-1 (gloomy special light sources company system)), 365nm exposure 10J/cm is irradiated to liquid crystal cell2Ultraviolet, voltage retention is determined under identical condition.As a result it is shown in table 4 described later.
<Embodiment 2>
NMP (11.4g) is added in the polyimide powder (B) (2.02g) that synthesis example 2 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (0.61g) (being 0.061g as 3-AMP), NMP (4.21g) and BCS (15.2g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [2].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [2] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 3>
NMP (11.4g) is added in the polyimide powder (C) (2.01g) that synthesis example 3 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (0.60g) (being 0.060g as 3-AMP), NMP (4.18g) and BCS (15.1g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [3].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [3] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 4>
NMP (11.2g) is added in the polyimide powder (C) (1.98g) that synthesis example 3 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (1.98g) (being 0.20g as 3-AMP), NMP (2.87g) and BCS (14.9g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [4].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [4] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 5>
NMP (11.3g) is added in the polyimide powder (D) (2.00g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (0.60g) (being 0.060g as 3-AMP), NMP (4.16g) and BCS (15.0g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [5].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [5] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 6>
NMP (11.3g) is added in the polyimide powder (D) (2.00g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (1.00g) (being 0.10g as 3-AMP), NMP (3.80g) and BCS (15.0g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [6].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [6] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 7>
NMP (12.5g) is added in the polyimide powder (D) (2.21g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (1.55g) (being 0.16g as 3-AMP), NMP (3.80g) and BCS (16.6g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [7].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [7] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 8>
NMP (11.3g) is added in the polyimide powder (D) (2.00g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (2.00g) (being 0.20g as 3-AMP), NMP (2.90g) and BCS (15.0g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [8].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [8] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 9>
NMP (11.5g) is added in the polyimide powder (D) (2.03g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.4-AMP 10 mass %NMP solution (1.42g) (being 0.14g as 4-AMP), NMP (3.49g) and BCS (15.2g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [9].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [9] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 10>
NMP (11.3g) is added in the polyimide powder (D) (2.00g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.AEP 10 mass %NMP solution (1.40g) (being 0.14g as AEP), NMP (3.44g) and BCS (15.0g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [10].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [10] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 11>
NMP (11.4g) is added in the polyimide powder (D) (2.00g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.API 10 mass %NMP solution (1.40g) (being 0.14g as API), NMP (3.44g) and BCS (15.1g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [11].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [11] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Embodiment 12>
NMP (11.6g) is added in the polyimide powder (D) (2.04g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.2-AMMP 10 mass %NMP solution (1.43g) (being 0.14g as 2-AMMP), NMP (3.51g) and BCS (15.3g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [12].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [12] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Comparative example 1>
NMP (11.9g) is added in the polyimide powder (C) (2.10g) that synthesis example 3 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.NMP (4.94g) and BCS (15.9g) is added in the solution, is stirred 15 hours in 50 DEG C, aligning agent for liquid crystal [13] is obtained.The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [13] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Comparative example 2>
NMP (11.8g) is added in the polyimide powder (D) (2.08g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.NMP (4.89g) and BCS (15.6g) is added in the solution, is stirred 15 hours in 50 DEG C, aligning agent for liquid crystal [14] is obtained.The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [14] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Comparative example 3>
NMP (11.3g) is added in the polyimide powder (E) (2.00g) that synthesis example 5 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.NMP (4.71g) and BCS (15.0g) is added in the solution, is stirred 15 hours in 50 DEG C, aligning agent for liquid crystal [15] is obtained.The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [15] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Comparative example 4>
NMP (11.3g) is added in the polyimide powder (D) (2.00g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.Py 10 mass %NMP solution (1.40g) (being 0.14g as Py), NMP (3.44g) and BCS (15.2g) is added in the solution, is stirred 15 hours in 50 DEG C, obtains aligning agent for liquid crystal [16].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [16] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Comparative example 5>
NMP (11.2g) is added in the polyimide powder (D) (1.98g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.AP 10 mass %NMP solution (1.39g) (being 0.14g as AP), NMP (3.41g) and BCS (14.9g) is added in the solution, is stirred 15 hours in 50 DEG C, obtains aligning agent for liquid crystal [17].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [17] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Comparative example 6>
NMP (11.3g) is added in the polyimide powder (D) (2.00g) that synthesis example 4 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.HA 10 mass %NMP solution (1.40g) (being 0.14g as HA), NMP (3.44g) and BCS (15.0g) is added in the solution, is stirred 15 hours in 50 DEG C, obtains aligning agent for liquid crystal [18].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [18] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Comparative example 7>
NMP (11.4g) is added in the polyimide powder (E) (2.01g) that synthesis example 5 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (0.60g) (being 0.06g as 3-AMP), NMP (4.18g) and BCS (15.1g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [21].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [19] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
<Comparative example 8>
NMP (11.4g) is added in the polyimide powder (F) (2.01g) that synthesis example 6 is obtained, dissolves it within 40 hours in 70 DEG C of stirrings.3-AMP 10 mass %NMP solution (1.41g) (being 0.14g as 3-AMP), NMP (3.46g) and BCS (15.1g) is added in the solution, stirred 15 hours in 50 DEG C, obtain aligning agent for liquid crystal [20].The aligning agent for liquid crystal there are no the abnormal conditions such as muddy or precipitation, confirm the homogeneous dissolving of resin component.
Obtained liquid crystal cell is operated similarly to Example 1 with the aligning agent for liquid crystal [20] of acquisition and determines pre-tilt angle.As a result it is shown in table 1 described later.In addition, by polarized light microscope observing in addition to not carrying out friction treatment it is other similarly to Example 1 operate prepared by liquid crystal cell, confirm liquid crystal it is equably vertical orientated.
In addition, carrying out the evaluation of the voltage retention after evaluation and ultraviolet irradiation after the evaluation of voltage retention, the evaluation of residual charge release, high temperature placement to obtained liquid crystal cell similarly to Example 1.As a result table 2 described later, table 3 and table 4 are shown in.
[table 1]
Aligning agent for liquid crystal Side chain diamines Specific amines Pre-tilt angle (initial) (°)
Embodiment 1   [1]   PBCH5DAB   3-AMP   48.3
Embodiment 2   [2]   BPCH5DAB   3-AMP   55.1
Embodiment 3   [3]   PBCH5DAB   3-AMP   88.6
Embodiment 4   [4]   PBCH5DAB   3-AMP   88.8
Embodiment 5   [5]   PBCH5DAB   3-AMP   88.2
Embodiment 6   [6]   PBCH5DAB   3-AMP   88.3
Embodiment 7   [7]   PBCH5DAB   3-AMP   88.6
Embodiment 8   [8]   PBCH5DAB   3-AMP   88.6
Embodiment 9   [9]   PBCH5DAB   4-AMP   88.7
Embodiment 10   [10]   PBCH5DAB   AEP   88.6
Embodiment 11   [11]   PBCH5DAB   API   88.5
Embodiment 12   [12]   PBCH5DAB   2-AMMP   88.6
Comparative example 1   [13]   PBCH5DAB Nothing   88.4
Comparative example 2   [14]   PBCH5DAB Nothing   87.7
Comparative example 3   [15]   PCH7DAB Nothing   88.5
Comparative example 4   [16]   PBCH5DAB   Py   87.5
Comparative example 5   [17]   PBCH5DAB   AP   87.7
Comparative example 6   [18]   PBCH5DAB   HA   87.6
Comparative example 7   [19]   PCH7DAB   3-AMP   10.2
Comparative example 8   [20]   PCH7DAB   3-AMP   88.5
[table 2]
Figure BPA00001171770500561
[table 3]
Figure BPA00001171770500571
[table 4]
Figure BPA00001171770500572
The possibility utilized in industry
The aligning agent for liquid crystal of the present invention possesses the characteristic for the pre-tilt angle for increasing liquid crystal when being formed as liquid crystal orientation film, can make liquid crystal vertical-tropism with less use ratio and be not easy to separate out when being mixed with Weak solvent in the coating fluid of aligning agent for liquid crystal.The aligning agent for liquid crystal for the liquid crystal orientation film that following characteristic is also equipped with addition to the characteristic can be obtained by also providing, it is high that these characteristics include voltage retention, the release for the residual charge accumulated after being exposed to even if long-time under high temperature by DC voltage is also quickly, and can also suppress the decline of voltage retention after the ultraviolet of backlight even if long-time.As a result, available for TN elements, STN elements, TFT liquid crystal cells, it may also be used for vertical alignment-type liquid crystal display device etc..
All the elements of the specification of the Japanese patent application 2007-340890 that 28 days December in 2007 incorporated herein files an application, claims and summary as the specification of the present invention announcement.

Claims (13)

1. aligning agent for liquid crystal, it is characterised in that containing following (A) compositions and following (B) compositions,
(A) composition：Make polyimides obtained by the polyamic acid imidizate of the structural formula of repeat unit that is represented with following formula [1], the intramolecular of the polymer has carboxyl,
(B) composition：Intramolecular has the amines that 1 primary amino radical and nitrogenous heteroaromatic and the primary amino radical are combined with aliphatic alkyl or non-aromatic ring type alkyl,
Figure FSB00000675139400011
In formula [1], R1For 4 valency organic groups, R2For the divalent organic group containing following formula [2],
Figure FSB00000675139400012
In formula [2], X1For Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, X2For the fluoroalkyl of the alkyl of carbon number 3~12, the alkoxy of carbon number 3~12, the fluoro-alkyl of carbon number 3~12 or carbon number 3~12.
2. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that the X in formula [2]2For the fluoroalkyl of the alkyl of carbon number 3~6, the alkoxy of carbon number 3~6, the fluoro-alkyl of carbon number 3~6 or carbon number 3~6.
3. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that the R in formula [1]2For the divalent organic group containing following formula [3],
Figure FSB00000675139400013
In formula [3], n is 2~11 integer, and the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is transisomer.
4. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that the R in formula [1]2For the divalent organic group containing following formula [4],
Figure FSB00000675139400021
In formula [4], n is 2~11 integer, and the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is transisomer.
5. such as aligning agent for liquid crystal according to any one of claims 1 to 4, it is characterized in that, (A) composition is polymer obtained by the polyamic acid imidizate for the structural formula for making the repeat unit with formula [1] expression, and the carboxyl amount that the polymer has is calculated as 0.1~3 with the average value of the repeat unit relative to the polymer.
6. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, (A) part repeat unit has polymer obtained by the polyamic acid imidizate of the structural formula of the unit represented comprising following formula [5] in structural formula of the composition to make the repeat unit of the formula [1] expression, the carboxyl amount of the polymer is calculated as 0.1~3 with the average value of the repeat unit relative to the polymer
Figure FSB00000675139400022
In formula, R3For 4 valency organic groups, R4For divalent organic group, R3Or R4At least one party there is carboxyl.
7. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that (B) composition is the amines that following formula [6] is represented,
In formula [6], Y1For the divalent organic group with aliphatic alkyl or non-aromatic ring type alkyl, Y2For nitrogenous heteroaromatic.
8. aligning agent for liquid crystal as claimed in claim 7, it is characterised in that (B) composition is the amines that following formula [7] is represented,
In formula [7], Y3Aliphatic alkyl or non-aromatic ring type alkyl for the divalent of carbon number 1~10, Y4For singly-bound ,-O- ,-NH- ,-S- ,-SO2- or carbon number 1~19 divalent organic group, Y3And Y4The carbon atom being had adds up to 1~20, Y5For nitrogenous heteroaromatic.
9. aligning agent for liquid crystal as claimed in claim 8, it is characterised in that (B) composition is the Y of formula [7]3、Y4And Y5The amines that the combination of the group or ring of following record is formed is respectively selected from,
Y3For a kind of the straight or branched alkylidene selected from carbon number 1~10, the unsaturated alkylene of carbon number 1~10, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three ring eicosane rings, three ring docosane rings, bicycloheptane ring, decahydro naphthalene nucleus, ENB ring and adamantane ring
Y4For selected from singly-bound ,-O- ,-NH- ,-S- ,-SO2-, the alkyl of carbon number 1~19 ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-CF2-、-C(CF3)2-、-CH(OH)-、-C(CH3)2-、-Si(CH3)2-、-O-Si(CH3)2-、-Si(CH3)2-O-、-O-Si(CH3)2- O-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three ring eicosane rings, three ring docosane rings, bicycloheptane ring, decahydro naphthalene nucleus, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring, 1, 8- perinaphthene rings, pyrrole ring, imidazole ring,Azoles ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenthazine ring,
Figure FSB00000675139400032
Diazole ring, acridine ring, piperazine ring, piperidine ring, two
Figure FSB00000675139400033
1 kind of alkane ring and morpholine ring,
Y5For selected from pyrrole ring, imidazole ring,
Figure FSB00000675139400034
Azoles ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenthazine ring,
Figure FSB00000675139400035
1 kind of diazole ring and acridine ring.
10. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that relative to the carboxyl that has of polyimides of (A) composition of 1 mole, contain (B) composition with the ratio of 0.01~2 mole times of amount.
11. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that the organic solvent of the amines of the polyimides containing (A) composition and (B) composition is mixed under heating and is obtained.
12. liquid crystal orientation film, it is characterised in that formed as the aligning agent for liquid crystal any one of claim 1~11.
13. liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in claim 12.
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