CN103797410A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDF

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CN103797410A
CN103797410A CN201280044626.1A CN201280044626A CN103797410A CN 103797410 A CN103797410 A CN 103797410A CN 201280044626 A CN201280044626 A CN 201280044626A CN 103797410 A CN103797410 A CN 103797410A
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liquid crystal
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carbon number
aligning agent
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CN103797410B (en
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作本直树
石井秀则
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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Abstract

This liquid crystal alignment agent contains a polyamic acid ester having repeating units represented by formula (1), and an organic solvent. (In formula (1): X1 is a tetravalent organic group; Y1 is a divalent organic group; R1 is an alkyl group with one to five carbons, and includes at least one type of structure selected from a group comprising an amino group, an imino group and a nitrogen-containing heterocycle in X1 and/or Y1; and A1 and A2 are each independently a hydrogen atom, or an alkyl group with one to ten carbons, which may have a substituent, an alkenyl group or an alkynyl group.)

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
Technical field
The present invention relates to the aligning agent for liquid crystal that contains poly amic acid ester and liquid crystal orientation film and the liquid crystal display cells being made by this aligning agent for liquid crystal.
Background technology
Conventionally in element, be provided for the liquid crystal orientation film of the state of orientation of controlling liquid crystal for the liquid crystal display cells of LCD TV, liquid crystal display etc.Up to now, as liquid crystal orientation film, the aligning agent for liquid crystal that main use will be principal ingredient with the solution of polyamic acid (polyamic acid is also referred to as polyamide acid) or soluble polyimide is coated glass substrate etc. and is burnt till the polyimide liquid crystal orientation film obtaining.
Be accompanied by the high-precision refinement of liquid crystal display cells, reduce and reduce the requirement considerations such as ghost phenomena from suppressing the contrast of liquid crystal display cells, in liquid crystal orientation film, following characteristic becomes important gradually:, except embodying good liquid crystal aligning and stable tilt angle, also comprise high voltage holding ratio, quick mitigation to the residual charge that drives the inhibition of the ghost causing, less residual charge while applying DC voltage because exchanging and/or put aside because of DC voltage etc.
In order to meet above-mentioned requirements, the various schemes about polyimide liquid crystal orientation film are proposed.For example, as the ghost being caused by the DC voltage short liquid crystal orientation film of required time that disappears, propose to have used except polyamic acid or containing the liquid crystal orientation film (with reference to patent documentation 1) that also contains the aligning agent for liquid crystal of the tertiary amine of ad hoc structure the polyamic acid of imide, and having used the liquid crystal orientation film of the aligning agent for liquid crystal that contains soluble polyimide (imidizate condensate), this soluble polyimide uses the specific diamine compound of the divalent organic group that contains the nitrogen atoms such as pyridine skeleton as raw material (with reference to patent documentation 2).
Prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 9-316200 communique
Patent documentation 2: Japanese patent laid-open 10-104633 communique
Summary of the invention
Invent technical matters to be solved
Have in the liquid crystal display cells of the liquid crystal orientation film being obtained by the aligning agent for liquid crystal of above-mentioned patent documentation 1 and patent documentation 2, the mitigation of the residual charge of putting aside because of DC voltage is quick.But what present inventor discussed found that, the light transmission (below also referred to as transmissivity) of the liquid crystal orientation film that patent documentation 1 and patent documentation 2 obtain reduces.If the transmissivity of liquid crystal orientation film declines, during as liquid crystal display cells, the contrast of liquid crystal display cells also declines.Can make up by improving back light source brightness although contrast reduces, improve back light source brightness and will occur the power consumption quantitative change large new problem of backlight.
The object of the invention is to solve above-mentioned problem, provide and can obtain the quick and aligning agent for liquid crystal of the liquid crystal orientation film that transmissivity is high of the mitigation of the residual charge of putting aside because of DC voltage, liquid crystal orientation film and the liquid crystal display cells being obtained by this aligning agent for liquid crystal.
The technical scheme that technical solution problem adopts
Find according to present inventor's research, comprise and there is the poly amic acid ester that is selected from the represented repetitive of the formula (1) of amino, imino group and nitrogenous heterocyclic at least a kind of structure by use, the mitigation of the residual charge of putting aside because of DC voltage fast and transmissivity improve.
So, the present invention is the invention completing based on above-mentioned discovery, comprises following technology contents.
1. an aligning agent for liquid crystal, the poly amic acid ester and the organic solvent that contain the repetitive represented containing following formula (1).
[changing 1]
Figure BDA0000476593940000021
(in formula (1), X 14 valency organic groups, Y 1divalent organic group, X 1and Y 1middle at least one party is contained and is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure, R 1that carbon number is 1～5 alkyl, A 1and A 2respectively that maybe can to have substituent carbon number be 1～10 alkyl, alkenyl or alkynyl to hydrogen atom independently.）
2. the aligning agent for liquid crystal described in above-mentioned 1, wherein, the Y in formula (1) 1to contain the divalent organic group that is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure.
3. the aligning agent for liquid crystal described in above-mentioned 1 or 2, wherein, with respect to 1 mole of entire infrastructure unit, Y 1the ratio that is the represented repetitive of the above formula (1) that contains the divalent organic group that is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure is 40～100 % by mole.
4. the aligning agent for liquid crystal described in any one in above-mentioned 1～3, wherein, Y 1to be selected from least a kind of the represented divalent organic group that contains nitrogen-atoms of following formula (YD-1)～(YD-5).
[changing 2]
Figure BDA0000476593940000031
In formula (YD-1), A 11that carbon number is 3～15 3 valency nitrogen heterocyclic rings, Z 1that maybe can to have substituent carbon number be 1～20 1 valency alkyl to hydrogen atom.In formula (YD-2), W 1that carbon number is 1～10 3 valency alkyl, A 12that to contain nitrogenous heterocyclic carbon number be the disubstituted amido that aliphatic group that 3～15 1 valency organic group or 2 amino hydrogen are 1～6 by carbon number respectively independently replaces.In formula (YD-3), W 2that carbon number is 6～15 and the divalent organic group that contains 1 or 2 phenyl ring, W 3that carbon number is 2～5 alkylidene or biphenylene, Z 2be that hydrogen atom, carbon number are 1～5 alkyl or phenyl ring, a is 0 or 1.In formula (YD-4), A 13that carbon number is 3～15 divalent nitrogen heterocyclic ring.In formula (YD-5), A 14that carbon number is 3～15 divalent nitrogen heterocyclic ring, W 5that carbon number is 2～5 alkylidene.
5. the aligning agent for liquid crystal described in any one in above-mentioned 1～4, wherein, formula (YD-1), (YD-2), (YD-4) and (YD-5) described A 11, A 12, A 13and A 14the carbon number heterocycle that contains nitrogen-atoms that is 3～15 be selected from pyrrolidine, pyrroles, imidazoles, pyrazoles,
Figure BDA0000476593940000032
azoles, thiazole, piperidines, piperazine, pyridine, pyrazine, indoles, benzimidazole, quinoline, isoquinoline at least a kind.
6. the aligning agent for liquid crystal described in any one in above-mentioned 1～5, wherein, the Y in formula (1) 1to be selected from least a kind of the represented divalent organic group that contains nitrogen-atoms of following formula (YD-6)～(YD-23).
[changing 3]
Figure BDA0000476593940000041
(in formula (YD-14), respectively from 1 to 11 integer naturally of m, n, m+n is from 2 to 12 integer, in formula (YD-19), h is 1～3 integer, formula (YD-16) and (YD-23) in, j is from 0 to 3 integer.）
7. the aligning agent for liquid crystal described in any one in above-mentioned 1～6, wherein, in formula (1), X 1for selecting at least a kind of the represented structure of free following formula.
[changing 4]
8. a liquid crystal orientation film, is coated with and burns till and obtained by the aligning agent for liquid crystal described in any one in above-mentioned 1～7.
9. a liquid crystal display cells, has the liquid crystal orientation film described in above-mentioned 8.
The effect of invention
The transmissivity of the liquid crystal orientation film being obtained by aligning agent for liquid crystal of the present invention is high, and it is quick to have the mitigation of the residual charge of putting aside because of DC voltage of the liquid crystal display cells of this liquid crystal orientation film.
Embodiment
< poly amic acid ester >
The contained poly amic acid ester of aligning agent for liquid crystal of the present invention is the polyimide precursor that can obtain polyimide, for having the polymkeric substance that can carry out the position of following imidization reaction by heating.
[changing 5]
(R 1with the R in formula (1) 1identical.）
The poly amic acid ester that aligning agent for liquid crystal of the present invention contains the repetitive (structural unit) represented containing following formula (1).And the poly amic acid ester that contains the represented repetitive of this formula (1), can be R 1, A 1, A 2, X 1and Y 1being respectively a kind of poly amic acid ester that contains the represented repetitive of the formula (1) that only formed by same structure, can be also R 1, A 1, A 2, X 1and Y 1for the poly amic acid ester of the represented repetitive of the multiple multiple formula (1) that contains different structure.In addition, containing the poly amic acid ester of the represented repetitive of formula (1), can be also the poly amic acid ester that also contains the represented repetitive of formula (1) structure in addition.; it can be the poly amic acid ester that the represented repetitive of the formula (1) of same structure forms; also can be the poly amic acid ester that the represented repetitive of the formula (1) of different structure forms, can be also the represented repetitive of the formula (1) that contains same structure or different structure and the poly amic acid ester of the represented repetitive of formula (1) structure (repetitive that for example following formula (2) is represented) in addition in addition.
[changing 6]
Figure BDA0000476593940000061
In above-mentioned formula (1), R 1for carbon number is 1～5, preferably 1～2 alkyl, more preferably methyl.
In formula (1), A 1and A 2be 1～10 alkyl, alkenyl or alkynyl for hydrogen atom maybe can have substituent carbon number independently respectively.As the concrete example of abovementioned alkyl, can exemplified by methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, decyl, cyclopentyl, cyclohexyl, dicyclohexyl etc.As alkenyl, can exemplify 1 group that above CH-CH structure is replaced by C=C structure existing in abovementioned alkyl, more specifically, can exemplified by vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl group, 1,3-butadiene base, 2-pentenyl, 2-hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc.Can exemplify 1 the above CH existing in described alkyl as alkynyl 2-CH 2the group that structure is replaced by C ≡ C-structure, more specifically, can exemplify ethinyl, 1-propinyl, 2-propynyl etc.
It is 1～10 also can have substituting group that abovementioned alkyl, alkenyl, alkynyl need only overall carbon number, can also form ring structure by substituting group.In addition, forming ring structure by substituting group refers between substituting group or a part for substituting group and main body framework (forms A 1and A 2atom) be combined into as ring structure.
As this substituent example, can exemplify halogen group, hydroxyl, sulfydryl, nitro, aryl, organic oxygen base, organic sulfenyl, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide group, alkyl, alkenyl, alkynyl.
As substituent halogen group, can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom.
As substituent aryl, can exemplified by phenyl.This aryl can further be replaced by other above-mentioned substituting groups.
Can be represented by the represented structure of O-R as substituent organic oxygen base.This R can be identical or different, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.These R can also further be replaced by above-mentioned substituting group.As the concrete example of organic oxygen base, can exemplify methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy etc.
Can be represented by-represented the structure of S-R as substituent organic sulfenyl.As this R, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.These R can also further be replaced by above-mentioned substituting group.As the concrete example of organic sulfenyl, can exemplify methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, heptan sulfenyl, pungent sulfenyl etc.
Can be by-Si-(R) as substituent Organosilyl 3represented structure represents.This R can be identical or different, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.These R can also further be replaced by above-mentioned substituting group.As the concrete example of Organosilyl, can exemplify trimethyl silyl, triethylsilyl, tripropyl silicyl, tributyl silicyl, three amyl group silicyls, three hexyl silicyls, amyl group dimetylsilyl, hexyl dimetylsilyl etc.
Can be represented by-represented the structure of C (O)-R as substituent acyl group.As this R, can exemplify above-mentioned alkyl, alkenyl, aryl etc.These R can also further be replaced by above-mentioned substituting group.As the concrete example of acyl group, can exemplify formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc.
As substituent ester group can by-C (O) O-R or-the represented structure of OC (O)-R represents.As this R, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.These R can also further be replaced by above-mentioned substituting group.
As substituent thioester substrate can by-C (S) O-R or-the represented structure of OC (S)-R represents.As this R, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.These R can also further be replaced by above-mentioned substituting group.
As substituent phosphate-based can be by-OP (O)-(OR) 2represented structure represents.This R can be identical or different, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.These R can also further be replaced by above-mentioned substituting group.
Can be by-C (O) NH as substituent amide group 2, or-C (O) NHR ,-NHC (O) R ,-C (O) N (R) 2the represented structure of ,-NRC (O) R represents.This R can be identical or different, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.These R can also further be replaced by above-mentioned substituting group.As the substituting group of hydrogen atom that replaces R, can exemplify aryl.As this substituent aryl, can exemplify the group identical with above-mentioned aryl.This aryl can further be replaced by other above-mentioned substituting groups.
As substituent alkyl, can exemplify the group identical with above-mentioned alkyl.This alkyl can further be replaced by other above-mentioned substituting groups.
As substituent alkenyl, can exemplify the group identical with above-mentioned alkenyl.This alkenyl can further be replaced by other above-mentioned substituting groups.
As substituent alkynyl, can exemplify the group identical with above-mentioned alkynyl.This alkynyl can further be replaced by other above-mentioned substituting groups.
Conventionally,, if introduce bulky structure, reduce amino reactivity and the possibility of liquid crystal aligning owing to having, therefore as A 1and A 2, more preferably maybe can to have substituent carbon number be 1～5 alkyl to hydrogen atom, particularly preferably hydrogen atom, methyl or ethyl.
In formula (1), X 1the organic group of 4 valencys, Y 1the organic group of divalent, X 1and Y 1in at least one party contain and be selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure.The viewpoint of the simplicity of manufacturing from acquisition difficulty and the starting monomer of starting monomer (being diamine compound and tetracarboxylic acid derivatives etc.) is considered, Y 1preferably contain the divalent organic group that is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure.In addition, organic group refers to the alkyl for example can with N or O.
Y 1to contain in the situation of divalent organic group that is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure, Y 1if structure contain and be selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure, to its structure, there is no particular limitation.If enumerate concrete example, can exemplify following formula (YD-1)～(YD-5) represented contain the divalent organic group that is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure.
[changing 7]
Figure BDA0000476593940000091
In formula (YD-1), A 11that carbon number is 3～15 3 valency nitrogen heterocyclic rings, Z 1that maybe can to have substituent carbon number be 1～20 1 valency alkyl to hydrogen atom.
In formula (YD-2), W 1that carbon number is 1～10 3 valency alkyl, A 12that to contain nitrogenous heterocyclic carbon number be the disubstituted amido that aliphatic group that 3～15 1 valency organic group or 2 amino hydrogen are 1～6 by carbon number respectively independently replaces.
In formula (YD-3), W 2that carbon number is 6～15 and the divalent organic group that contains 1 or 2 phenyl ring, W 3that carbon number is 2～5 alkylidene or biphenylene, Z 2be that hydrogen atom, carbon number are 1～5 alkyl or phenyl ring, a is 0～1 integer.
In formula (YD-4), A 13that carbon number is 3～15 divalent nitrogen heterocyclic ring.
In formula (YD-5), A 14that carbon number is 3～15 divalent nitrogen heterocyclic ring, W 5that carbon number is 2～5 alkylidene.
As formula (YD-1), (YD-2), (YD-4) and A (YD-5) 11, A 12, A 13and A 14the carbon number nitrogen heterocyclic ring that is 3～15, if known structure, there is no particular limitation, can exemplify pyrrolidine, pyrroles, imidazoles, pyrazoles,
Figure BDA0000476593940000092
azoles, thiazole, piperidines, piperazine, pyridine, pyrazine, indoles, benzimidazole, quinoline, isoquinoline, more preferably piperazine, piperidines, indoles, benzimidazole, imidazoles, carbazole, pyridine.
In addition, be selected from the divalent organic group Y of amino, imino group and nitrogenous heterocyclic at least a kind of structure as containing in formula (1) 1concrete example, can exemplify the represented divalent organic group that contains nitrogen-atoms of following formula (YD-6)～(YD-23), when as liquid crystal display cells apply DC voltage time less residual charge and/or the viewpoint of the quick mitigation of the residual charge put aside because of DC voltage consider, particularly preferably formula (YD-16)～formula (YD-23).
[changing 8]
Figure BDA0000476593940000101
In formula (YD-14), respectively 1～11 integer naturally of m, n, m+n is 2～12 integer.In formula (YD-19), h is 1～3 integer, formula (YD-16) and (YD-23) in, j is 0～3 integer.
In the poly amic acid ester of the repetitive represented containing formula (1), Y 1for the ratio of the represented repetitive of the formula (1) that contains the divalent organic group that is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure is preferably 40～100 % by mole with respect to 1 mole of entire infrastructure unit, more preferably 60～100 % by mole, further preferably 80～100 % by mole.In addition, entire infrastructure unit refers to, form whole structural unit of the poly amic acid ester of the repetitive represented containing formula (1), particularly, the total amount (molar basis) of the represented repetitive of finger formula (1), or in the case of the structure containing beyond the represented repetitive of formula (1), refer to the total amount (molar basis) of the represented repetitive of repetitive that formula (1) is represented and formula (1) structure in addition.
In above formula (1), Y 1to contain in the situation of divalent organic group that is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure, X 1be 4 valency organic groups, to its structure, there is no particular limitation, also can two or more mix existence.If enumerate X 1concrete example, can exemplify X-1～X-46 shown below.Wherein, consider X from the difficulty that obtains of starting monomer 1difference is preferred X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X-21, X-25, X-26, X-27, X-28, X-32 or X-46 independently.In order to obtain the more liquid crystal orientation film of high-transmission rate, more preferably contain X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-25 or the X-46 of aliphatic structure, particularly preferably X-1 or X-2.On the other hand, in order to obtain the mitigation liquid crystal orientation film fast of the residual charge of putting aside because of DC voltage, more preferably contain X-26, X-27 or the X-28 of aromatic structure, particularly preferably X-26 or X-32.
[changing 9]
Figure BDA0000476593940000111
[changing 10]
[changing 11]
Figure BDA0000476593940000121
[changing 12]
Figure BDA0000476593940000122
In addition, the poly amic acid ester containing the represented repetitive of formula (1) that the present invention uses, not damaging in the scope of effect of the present invention, can contain the represented repetitive of formula (1) structure in addition.As the structure beyond the represented repetitive of formula (1), can exemplify the represented repetitive (structural unit) of following formula (2).
[changing 13]
Figure BDA0000476593940000123
In formula (2), A 1, A 2and R 1define identically with formula (1), X is the organic group of 4 valencys, and Y is the organic group of divalent.
X comprise its preference all with above-mentioned X 1define identical.
Y is divalent organic group, and to its structure, there is no particular limitation, also can two or more mix existence.If represent its concrete example, can exemplify following Y-1～Y-100.
Wherein, in order to obtain good liquid crystal aligning, preferably structure high linearity is introduced to poly amic acid ester, as Y, more preferably Y-7, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-43, Y-44, Y-45, Y-46, Y-48, Y-63, Y-71, Y-73, Y-74, Y-75, Y-98, Y-99, Y-100.In addition while wanting to improve tilt angle, be better that the structure of the structure on side chain with chain alkyl, aromatic ring, aliphatics ring, steroid skeleton or their combinations is introduced to poly amic acid ester, as Y, 1, more preferably Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97.Be 1～50 % by mole by making these structures with respect to the structure total amount of the diamine compound of the raw material from as poly amic acid ester, can show tilt angle arbitrarily.That is, be the diamines that contains these structures of 1～50 % by mole with respect to the total amount of the diamine compound of the raw material as poly amic acid ester by interpolation, can show tilt angle arbitrarily.
[changing 14]
Figure BDA0000476593940000131
[changing 15]
Figure BDA0000476593940000141
[changing 16]
Figure BDA0000476593940000142
[changing 17]
Figure BDA0000476593940000143
[changing 18]
Figure BDA0000476593940000144
[changing 19]
Figure BDA0000476593940000151
[changing 20]
Figure BDA0000476593940000152
[changing 21]
Figure BDA0000476593940000153
[changing 22]
Figure BDA0000476593940000161
[changing 23]
Figure BDA0000476593940000162
[changing 24]
Figure BDA0000476593940000163
[changing 25]
Figure BDA0000476593940000171
For the poly amic acid ester that contains the represented repetitive of formula (1) of the present invention, the ratio of the represented structural units of formula (2) is in entire infrastructure unit, with respect to forming containing 1 mole of the total amount of the entire infrastructure unit of the poly amic acid ester of the represented repetitive of formula (1), preferably 0～40 % by mole, more preferably 0～20 % by mole, further preferably 0～10 % by mole.
The manufacture method > of < poly amic acid ester
Poly amic acid ester can use tetracarboxylic acid derivatives and the diamine compounds (being designated hereinafter simply as diamines) such as tetracarboxylic dianhydride, tetrabasic carboxylic acid diester, dichloride tetrabasic carboxylic acid diester, synthetic by the method for (1) shown below～(3).As the diamine compound of the raw material using for the poly amic acid ester that obtains the repetitive represented containing formula (1), can exemplify following formula (a1).In addition, in order to obtain the poly amic acid ester of the repetitive represented containing formula (2), also can example as shown in the formula (a2) represented diamine compound as raw material.In addition, as the tetracarboxylic acid derivatives of the raw material using for the poly amic acid ester that obtains the repetitive represented containing formula (1), can exemplify following formula (b1)～(b3).And, in order to obtain the poly amic acid ester that contains the represented repetitive of formula (2), for example, also can use the X in following formula (b1)～(b3) 1the tetracarboxylic acid derivatives replacing with X is as raw material.
[changing 26]
Figure BDA0000476593940000172
(formula (a1) and (a2) in, A 1, A 2, Y 1and Y is identical with formula (2) with formula (1) respectively.）
[changing 27]
Figure BDA0000476593940000181
(in formula (b1)～(b3), R 1and X 1identical with formula (1) respectively.）
(1) carry out synthetic situation by polyamic acid
Poly amic acid ester can synthesize by the polyamic acid being obtained by tetracarboxylic dianhydride and diamines is carried out to esterification.
Particularly, can be by the polyamic acid that makes to be obtained by tetracarboxylic dianhydride and diamine reactant and esterifying agent under the existence of organic solvent, in-20～150 ℃, preferably react at 0～50 ℃ 30 minutes～24 hours, preferably within 1～4 hour, carry out synthesizing polyamides acid esters.
As esterifying agent, the esterifying agent of preferably easily removing by purifying, can exemplify N, dinethylformamide dimethylacetal, N, dinethylformamide diethyl acetal, N, dinethylformamide dipropyl acetal, N, dinethylformamide di neo-pentyl butyl acetal, N, dinethylformamide di-t-butyl acetal, 1-methyl-3-p-methylphenyl triazenes, 1-ethyl-3-p-methylphenyl triazenes, 1-propyl group-3-p-methylphenyl triazenes, 4-(4,6-dimethoxy)-1,3,5-triazine-2-yl)-4-methyl morpholine
Figure BDA0000476593940000182
hydrochloride etc.The repetitive of the polyamic acid that the tetracarboxylic dianhydride of the addition of esterifying agent with respect to 1 mole and diamine reactant obtain, preferably 2～6 molar equivalents.
Consider from the dissolubility of polymkeric substance (polyamic acid and poly amic acid ester), the preferred DMF of solvent, METHYLPYRROLIDONE or the gamma-butyrolacton that in above-mentioned reaction, use, these solvents can use a kind or two or more is mixed and is used.From being difficult for occurring the viewpoint consideration of separating out and easily obtain high molecular body of polymkeric substance, the concentration when synthetic is preferably 1～30 quality %, more preferably 5～20 quality %.
(2) carry out synthetic situation by the reaction of tetrabasic carboxylic acid diester diacid chloride and diamines
Poly amic acid ester can be synthetic by tetrabasic carboxylic acid diester diacid chloride and diamines.
Particularly, under the existence of alkali and organic solvent, in-20 ℃～150 ℃, at preferably 0 ℃～50 ℃, make tetrabasic carboxylic acid diester diacid chloride and diamine reactant 30 minutes～24 hours, preferably within 1～4 hour, synthesize.
Above-mentioned alkali can use pyridine, triethylamine, 4-dimethylaminopyridine etc., for reaction is leniently carried out, preferably uses pyridine.Consider from the amount of easily removing and the viewpoint that can easily obtain high molecular body, the addition of alkali is preferably 2～4 times moles with respect to tetrabasic carboxylic acid diester diacid chloride.
Consider from the dissolubility of starting monomer (tetracarboxylic acid derivatives and diamine compound) and polymkeric substance (polyamic acid and poly amic acid ester), the preferred METHYLPYRROLIDONE of solvent or the gamma-butyrolacton that in above-mentioned reaction, use, these solvents can use a kind or by two or more mix use.From being difficult for occurring the viewpoint consideration of separating out and easily obtain high molecular body of polymkeric substance, when synthetic, polymer concentration is preferably 1～30 quality %, more preferably 5～20 quality %.In addition, in order to prevent the hydrolysis of tetrabasic carboxylic acid diester diacid chloride, the preferably state of dehydration as far as possible of the solvent using in poly amic acid ester synthetic preferably carries out, to prevent sneaking into of extraneous gas body in nitrogen atmosphere.
(3) by tetrabasic carboxylic acid diester and the synthetic situation of diamines
Poly amic acid ester can be by synthesizing tetrabasic carboxylic acid diester and diamines polycondensation.
Particularly, under the existence of condensation agent, alkali and organic solvent, in 0 ℃～150 ℃, at preferably 0 ℃～100 ℃, make tetrabasic carboxylic acid diester and diamine reactant 30 minutes～24 hours, preferably within 3～15 hours, synthesize.
Above-mentioned condensation agent can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyl dimidazoles, dimethoxy-1,3,5-triazines methyl morpholine
Figure BDA0000476593940000191
, O-(benzotriazole-1-yl)-N, N, N', N'-tetramethylurea (TMU) tetrafluoro boric acid ester, O-(benzotriazole-1-yl)-N, N, N', N'-tetramethylurea (TMU) hexafluorophosphoric acid ester, (2,3-dihydroxy-2-sulfo--3-benzo
Figure BDA0000476593940000192
azoles base) phosphonic acid diphenyl ester etc.The addition of condensation agent is preferably 2～3 times moles with respect to tetrabasic carboxylic acid diester.
Above-mentioned alkali can use the tertiary amine such as pyridine, triethylamine.From the amount easily to remove and easily obtain high molecular body viewpoint consider, the addition of alkali is preferably 2～4 times moles with respect to diamine compound.
In addition, in above-mentioned reaction, add lewis acid can make reaction carry out efficiently as adjuvant.As lewis acid, the lithium halides such as preferred lithium chloride, lithium bromide.Lewis acidic addition is preferably 0～1.0 times mole with respect to diamine compound.
In the synthetic method of above-mentioned 3 kinds of poly amic acid esters, in order to obtain the poly amic acid ester of high molecular, the particularly preferably synthetic method of above-mentioned (1) or above-mentioned (2).
The solution of the poly amic acid ester making as mentioned above can be by separating out polymkeric substance (poly amic acid ester) at the well-beaten poor solvent that injects simultaneously.After carrying out that several is separated out and cleaning with poor solvent, at normal temperatures or heat drying, can obtain the powder of purified poly amic acid ester.Poor solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.
Containing the weight-average molecular weight of the poly amic acid ester of the represented repetitive of formula (1) preferably 5000～300000, more preferably 10000～200000.In addition, number-average molecular weight is preferably 2500～150000, and more preferably 5000～100000.
< aligning agent for liquid crystal >
Poly amic acid ester and organic solvent that aligning agent for liquid crystal of the present invention contains the repetitive represented containing above formula (1).So, the transmissivity of the liquid crystal orientation film being obtained by the aligning agent for liquid crystal of the poly amic acid ester that contains the repetitive represented containing formula (1) is high, and it is quick to have the mitigation of the residual charge of putting aside because of DC voltage of the liquid crystal display cells of this liquid crystal orientation film.
The aligning agent for liquid crystal that is still not clear the poly amic acid ester that why contains the repetitive represented containing formula (1) by use can solve technical matters of the present invention, but inventor thinks that reason is roughly as described below.
Generally speaking, because the acid imide rate of imidizate condensate (polyimide) is higher, absorbing wavelength is just longer, and therefore burning till the film (liquid crystal orientation film) that aligning agent for liquid crystal obtains can be painted.
On the other hand, the poly amic acid ester containing the represented repetitive of formula (1) contained in aligning agent for liquid crystal of the present invention is owing to being difficult for carrying out imidizate by heating (burning till), therefore the painted minimizing that imidizate causes can be inferred, the liquid crystal orientation film of high-transmission rate can be obtained.
In addition, known by present inventor's investigation, contain amino, imino group and nitrogenous heterocyclic compound, the nitrogen-atoms in this compound is subject to the impact of airborne oxygen and water oxidized, thereby painted.
And, the aligning agent for liquid crystal of the soluble polyimide that contains polyamic acid or a part of imidizate of polyamic acid is obtained, due to the carboxyl that contains high polarity in polymkeric substance (polyamic acid or polyimide), so strong with the interaction of water, can predict in polymkeric substance and will sneak into hydrone.Further, when above-mentioned polymkeric substance carries out imidizate by heating, using the water generating as leaving group.Inventor thinks that these water, by the oxidation that promotes to contain the contained nitrogen-atoms of amino, imino group and nitrogenous heterocyclic structure, can reduce the transmissivity of obtained film.
To this, contained containing the ester group in the poly amic acid ester of the represented repetitive of formula (1) in aligning agent for liquid crystal of the present invention, its polarity, lower than carboxyl, is the structure that is difficult for sneaking into hydrone.Further, poly amic acid ester is in the time carrying out imidizate by heating, using the alcohol generating as leaving group.Therefore, think and can reduce the facilitation of water for the oxidation that contains nitrogen-atoms contained in amino, imino group and nitrogenous heterocyclic structure, obtain the liquid crystal orientation film of high-transmission rate.
In addition, because aligning agent for liquid crystal of the present invention comprises the poly amic acid ester that possesses the represented repetitive of the formula (1) that contains amino, imino group and nitrogenous heterocyclic structure, therefore think that the mitigation of the residual charge of putting aside because of DC voltage of the liquid crystal display cells with the liquid crystal orientation film obtaining thus can be accelerated.
Thought by above-mentioned, the transmissivity of the liquid crystal orientation film being obtained by aligning agent for liquid crystal of the present invention is high, and it is quick to have the mitigation of the residual charge of putting aside because of DC voltage of the liquid crystal display cells of this liquid crystal orientation film.
In addition,, although recorded the aligning agent for liquid crystal containing containing the polyamic acid of imide in patent documentation 1, the polyamic acid containing imide of patent documentation 1 is not the Y of the represented repetitive of above formula (1) 1and X 1in containing the polyamic acid of imide, certainly, in documents 1 also completely not about the record of poly amic acid ester.In addition, although in patent documentation 2, recorded the aligning agent for liquid crystal of the imidizate condensate (, polyimide) that contains the structure with the divalent organic group that pyridine ring etc. contains nitrogen-atoms, in patent documentation 2 completely not about the record of poly amic acid ester.Thus, by the aligning agent for liquid crystal of patent documentation 1 and patent documentation 2, can not obtain transmissivity of the present invention high and there is the mitigation invention effect fast of the residual charge of putting aside because of DC voltage of the liquid crystal display cells of above-mentioned liquid crystal orientation film.
Aligning agent for liquid crystal of the present invention is for being dissolved in the state of the solution in organic solvent containing the poly amic acid ester of the represented repetitive of above formula (1).As long as there is described state, can be the reaction solution itself for example obtaining when synthesizing polyamides acid esters in organic solvent, or with the broad liquid of this reaction of suitable solvent dilution solution.In addition, when poly amic acid ester obtains as powder, can be dissolved in organic solvent and solution.
Poly amic acid ester in aligning agent for liquid crystal of the present invention is (following, also referred to as polymkeric substance) content (concentration), also can suitably change according to the setting of the thickness of the liquid crystal orientation film that will form, but consider from making its angle that forms even and flawless film, with respect to organic solvent, the content of component of polymer is preferably more than 0.5 quality %, considers from the angle of the storage stability of solution, more preferably below 15 quality %, particularly preferably 1～10 quality %.In addition, the highly concentrated solution that this situation can previously prepared polymkeric substance, dilutes while making aligning agent for liquid crystal by highly concentrated solution.The concentration of the highly concentrated solution of described component of polymer is 10～30 quality % preferably, more preferably 10～15 quality %.In addition, while the powder dissolution of component of polymer being prepared to solution at organic solvent, can heat.Preferably 20 ℃～150 ℃ of heating-up temperatures, particularly preferably 20 ℃～80 ℃.In addition, component of polymer refer to contain containing the poly amic acid ester of the represented repetitive of formula (1), as required not containing the polymkeric substance beyond poly amic acid ester, the poly amic acid ester of the represented repetitive of formula (1).
The contained above-mentioned organic solvent of aligning agent for liquid crystal of the present invention is not particularly limited as long as the solvent of component of polymer uniform dissolution.Its concrete example can exemplify N, dinethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-Pyrrolidone, NVP, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, 3-methoxyl-N, N-dimethyl propylene acid amides etc.These solvents can use a kind or by two or more mix use.In addition, even cannot be separately the solvent of dissolve polymer composition equably, as long as in the scope of not separating out at polymkeric substance, also can mix with above-mentioned organic solvent.
Aligning agent for liquid crystal of the present invention, except comprising the organic solvent take dissolve polymer composition as object, also can comprise to improve the solvent that painting film uniformity when aligning agent for liquid crystal is coated to substrate is object.This solvent uses the solvent of low surface tension compared with above-mentioned organic solvent conventionally.If lift its concrete example, can exemplify ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, ethyl carbitol acetic acid esters, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, single acetic acid propylene glycol ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, mono-ether-the 2-of propylene glycol-1-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.But two or more also uses these solvents.
In aligning agent for liquid crystal of the present invention, not damaging in the scope of effect of the present invention, can add other above-mentioned containing the polymkeric substance beyond the poly amic acid ester of the represented repetitive of formula (1), particularly, there is the not poly amic acid ester containing the represented repetitive of formula (1), polymkeric substance beyond poly amic acid ester, for reaching the specific inductive capacity that changes liquid crystal orientation film, the dielectric of the object of the electrical characteristics such as electric conductivity and conductive materials, be used for the silane coupling agent of the object that reaches the adaptation that improves liquid crystal orientation film and substrate, the hardness of film or the cross-linked compound of the object of density etc. while forming liquid crystal orientation film for improving.
< liquid crystal orientation film >
Liquid crystal orientation film of the present invention is that above-mentioned aligning agent for liquid crystal is coated to substrate, is dried as required film rear, that burn till gained.As the substrate of coating aligning agent for liquid crystal of the present invention, the substrate high as long as the transparency limits without special, can use the plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate, polycarbonate substrate etc., from the angle that production technology is simplified, preferably use and formed the ITO(Indium Tin Oxide that is useful on liquid crystal drive) substrate of electrode etc.In addition, in reflection type liquid crystal display element, if only limit to the substrate of a side, also can use the opaque materials such as silicon wafer, electrode now also can use the catoptrical materials such as aluminium.
As the coating process of aligning agent for liquid crystal of the present invention, can exemplify spin-coating method, print process, ink-jet method etc.Dry, the firing process that are coated with after aligning agent for liquid crystal of the present invention can be selected arbitrary temp and time.Conventionally, in order fully to remove the organic solvent containing, make its dry 1 minute～10 minutes in 50 ℃～120 ℃, burn till 5 minutes～120 minutes in 150 ℃～300 ℃ afterwards.In addition, also can not carry out drying process.Thickness to the film after burning till is not particularly limited, if but excessively thin, the reliability of liquid crystal display cells can reduce sometimes, therefore normally 5～300nm, preferably 10～200nm.
As the method for the liquid crystal orientation film of gained being carried out to orientation process, can exemplify rubbing manipulation, light orientation process method etc.In addition, in the present invention, also can not carry out orientation process.
As the concrete example of light orientation process method, can exemplify aforementioned film coated surface is irradiated towards the radioactive ray of certain orientation deflection, according to circumstances further at the temperature of 150～250 ℃, carry out heat treated, give the method for liquid crystal aligning ability with this.Can use ultraviolet ray and the visible ray of the wavelength with 100nm～800nm as radioactive ray.Wherein, preferably there is the ultraviolet ray of 100nm～400nm wavelength, particularly preferably there is the ultraviolet ray of 200nm～400nm wavelength.In addition, in order to improve liquid crystal aligning, when can being to heat film substrate at 50～250 ℃, irradiate radioactive ray.Preferably 1～10000mJ/cm of the exposure of aforementioned radioactive ray 2, particularly preferably 100～5000mJ/cm 2.The liquid crystal orientation film making as mentioned above can make liquid crystal molecule stably be orientated towards certain orientation.
< liquid crystal display cells >
Liquid crystal display cells of the present invention is to obtain the substrate with liquid crystal orientation film by said method by aligning agent for liquid crystal of the present invention, carries out as required after orientation process, manufactures by known method the liquid crystal display cells that liquid crystal structure cell is made.
Manufacture method to liquid crystal structure cell is not particularly limited, as enumerated an example, normally adopt using be formed with liquid crystal orientation film the 1 pair of substrate so that liquid crystal aligning face as inner side and be better clamping 1～30 μ m, after the mode that is more preferably the sept (Japanese: ス ペ ー サ ー) of 2～10 μ m arranges, around fixing with sealant, and inject the method that liquid crystal seals.Have no particular limits enclosing the method for liquid crystal, can exemplify after reducing pressure in the liquid crystal structure cell to making and inject the method etc. of dripping sealing after the vacuum method of liquid crystal, the liquid crystal that drips.
Embodiment
Below, the present invention will be described in more detail to exemplify embodiment, but the present invention is not limited thereto.The abbreviation using in the present embodiment and comparative example and the assay method of each characteristic are as described below.
DE-1: following formula (DE-1)
DE-2: following formula (DE-2)
DE-3: following formula (DE-3)
DA-1: following formula (DA-1)
DA-2: following formula (DA-2)
DA-3: following formula (DA-3)
NMP:N-N-methyl-2-2-pyrrolidone N-
BCS: butyl cellosolve
GBL: gamma-butyrolacton
[changing 28]
(in formula, Me represents methyl.）
[changing 29]
Figure BDA0000476593940000242
(in formula, Me represents methyl.）
[viscosity]
In synthesis example and comparison synthesis example, the viscosity of poly amic acid ester and polyamic acid solution is to utilize the E type viscosity meter TVE-22H((East Machine of Toki Sangyo Co., Ltd. industry society) system) at sample size 1.1mL, circular cone type rotor (コ ー ン ロ ー タ) TE-1(1 ° 34 ', R24), measure under the condition of 25 ℃ of temperature.
[molecular weight]
In addition, the molecular weight of poly amic acid ester adopts GPC(normal temperature gel permeation chromatography) device measures, and calculates number-average molecular weight (following, also referred to as Mn) and weight-average molecular weight (below, also referred to as Mw) with polyglycol, polyethylene oxide scaled value.
GPC device: Showa Denko K. K (Shodex society) system (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 ℃
Eluent: N, and N'-dimethyl formamide (as adjuvant, lithium bromide-hydrate (LiBrH 2o) be that 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) are that 30mmol/L, tetrahydrofuran (THF) are 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve making standard sample: Dong Cao company (East ソ ー society) TSK standard polyethylene oxide processed (weight-average molecular weight (Mw) approximately 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyglycol processed (peak molecular weight (Mp) approximately 12000,4000,1000).Overlap for fear of peak value, measured respectively 2 samples, mixed 900000,100000,12000,1000 these samples of 4 kinds and mixed 150000,30000,4000 these samples of 3 kinds.
(synthesis example 1)
In the 200ml four-hole boiling flask with stirring apparatus, add 3.39g(13.0mmol) DE-2,1.69g(5.99mmol) DE-3, add 84.69gNMP, stir and make its dissolving.Then, add 4.45g(44.0mmol) triethylamine, 3.99g(20.0mmol) 4,4'-diamino-diphenylamine, stirs and makes its dissolving.Stir this solution while add 16.87g(44.0mmol) (2,3-dihydroxy-2-sulfo--3-benzo
Figure BDA0000476593940000251
azoles base) phosphonic acid diphenyl ester, add again the NMP of 11.63g, under water-cooled, make its reaction 4 hours.The polyamic acid ester solution making is stirred while drop in the 2-propyl alcohol of 760g, and filter and take out the sediment of separating out, then obtain poly amic acid ester toner by 2-propyl alcohol washing 5 times, the drying of 253g.The molecular weight of this poly amic acid ester is Mn=13646, Mw=28242.
The poly amic acid ester toner that 1.78g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 16.02g, at room temperature stirs and within 24 hours, makes it dissolve, and obtains polyamic acid ester solution (PAE-1).
(synthesis example 2)
In the 200ml four-hole boiling flask with stirring apparatus, add 3.39g(13.0mmol) DE-2,1.69g(5.99mmol) DE-3, add 84.53gNMP, stir and make its dissolving.Then, add 4.45g(44.0mmol) triethylamine, 4.26g(20.0mmol) DA-1, stir and make its dissolving.Stir this solution while add 16.87g(44.0mmol) (2,3-dihydroxy-2-sulfo--3-benzo
Figure BDA0000476593940000261
azoles base) phosphonic acid diphenyl ester, add again the NMP of 12.02g, under water-cooled, make its reaction 4 hours.The polyamic acid ester solution making is stirred while drop in the 2-propyl alcohol of 781g, and filter and take out the sediment of separating out, then obtain poly amic acid ester toner by 2-propyl alcohol washing 5 times, the drying of 260g.The molecular weight of this poly amic acid ester is Mn=10326, Mw=21332.
The poly amic acid ester toner that 2.10g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 18.98g, at room temperature stirs and within 24 hours, makes it dissolve, and obtains polyamic acid ester solution (PAE-2).
(synthesis example 3)
In the 200ml four-hole boiling flask with stirring apparatus, add 1.69g(6.50mmol) DE-2,0.85g(3.00mmol) DE-3, add 61.89gNMP, stir and make its dissolving.Then, add 2.23g(22.0mmol) triethylamine, 3.92g(9.99mmol) DA-3, stir and make its dissolving.Stir this solution while add 8.43g(22.0mmol) (2,3-dihydroxy-2-sulfo--3-benzo
Figure BDA0000476593940000262
azoles base) phosphonic acid diphenyl ester, add again the NMP of 8.50g, under water-cooled, make its reaction 4 hours.The polyamic acid ester solution making is stirred while drop in the 2-propyl alcohol of 525g, and filter and take out the sediment of separating out, then obtain poly amic acid ester toner by 2-propyl alcohol washing 5 times, the drying of 175g.The molecular weight of this poly amic acid ester is Mn=22044, Mw=56569.
The poly amic acid ester toner that 2.11g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 18.99g, at room temperature stirs and within 24 hours, makes it dissolve, and obtains polyamic acid ester solution (PAE-3).
(synthesis example 4)
Making with the 300mL four-hole boiling flask of stirring apparatus is nitrogen atmosphere, adds 3.02g(11.3mmol) DA-2, add NMP and the 1.99g(25.2mmol of 108g) the pyridine as alkali, stir and make its dissolving.Then stir this two amine aqueous solution while add 3.42g(10.5mmol) DE-1, under water-cooled, make its reaction 4 hours.The polyamic acid ester solution making is stirred while drop in the 2-propyl alcohol of 468g, and filter and take out the sediment of separating out, then obtain poly amic acid ester toner by 2-propyl alcohol washing 5 times, the drying of 234g.The molecular weight of this poly amic acid ester is Mn=16548, Mw=37836.
The poly amic acid ester toner that 1.79g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 16.11g, at room temperature stirs and within 24 hours, makes it dissolve, and obtains polyamic acid ester solution (PAE-4).
(synthesis example 5)
Making with the 300mL four-hole boiling flask of stirring apparatus is nitrogen atmosphere, add 2.02g(10.1mmol) 4,4'-diamino-diphenylamine, 1.02g(6.70mmol) 3, NMP, the 2.99g(37.7mmol of 5-diaminobenzoic acid, 135g) the pyridine as alkali, stir and make its dissolving.Then stir this two amine aqueous solution while add 5.14g(15.8mmol) DE-1, under water-cooled, make its reaction 4 hours.The polyamic acid ester solution making is stirred while drop in the 2-propyl alcohol of 584g, and filter and take out the sediment of separating out, then obtain poly amic acid ester toner by 2-propyl alcohol washing 5 times, the drying of 292g.The molecular weight of this poly amic acid ester is Mn=9724, Mw=19380.
The poly amic acid ester toner that 3.56g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 32.09g, at room temperature stirs and within 24 hours, makes it dissolve, and obtains polyamic acid ester solution (PAE-5).
(relatively synthesis example 1)
Adding 3.99g(20.0mmol with the 100ml four-hole boiling flask of stirring apparatus and nitrogen ingress pipe) 4,4'-diamino-diphenylamine, adds the NMP of 63.9g, limit is supplied with nitrogen limit and is stirred and make its dissolving.Stir this two amine aqueous solution while add 2.63g(13.4mmol) 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1.30g(5.96mmol) pyromellitic acid anhydride, add again NMP to make solid component concentration reach 10 quality %, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-1).The viscosity of the polyamic acid solution making at 25 ℃ of temperature is 881mPas.In addition, the molecular weight of this polyamic acid is Mn=16766, Mw=59104.
(relatively synthesis example 2)
In the four-hole boiling flask of the 100ml with stirring apparatus and nitrogen ingress pipe, add 4.27g(20.00mmol) DA-1, add the NMP of 66.4g, limit is supplied with nitrogen limit and is stirred and make its dissolving.Stir this two amine aqueous solution while add 2.63g(13.4mmol) 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1.30g(5.96mmol) pyromellitic acid anhydride, add again NMP to make solid component concentration reach 10 quality %, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-2).The viscosity of the polyamic acid solution making at 25 ℃ of temperature is 153mPas.In addition, the molecular weight of this polyamic acid is Mn=13227, Mw=38432.
(relatively synthesis example 3)
In the 100ml four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, add 3.15g(8.02mmol) DA-3, add the NMP of 37.6g, limit is supplied with nitrogen limit and is stirred and make its dissolving.Stir this two amine aqueous solution while add 0.972g(4.96mmol) 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 0.526g(2.41mmol) pyromellitic acid anhydride, add again NMP to make solid component concentration reach 10 quality %, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-3).The viscosity of the polyamic acid solution making at 25 ℃ of temperature is 2045mPas.In addition, the molecular weight of this polyamic acid is Mn=16418, Mw=56595.
(embodiment 1)
In the Erlenmeyer flask of 50ml, put into stirrer, add the polyamic acid ester solution (PAE-1) obtaining in the synthesis example 1 of 5.52g, add 3.45gNMP, 2.22gBCS, use magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (A-1).
(embodiment 2)
In the Erlenmeyer flask of 50ml, put into stirrer, add the polyamic acid ester solution (PAE-2) obtaining in the synthesis example 2 of 5.12g, add 3.08gNMP, 2.07gBCS, use magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (A-2).
(embodiment 3)
In the Erlenmeyer flask of 50ml, put into stirrer, add the polyamic acid ester solution (PAE-3) obtaining in the synthesis example 3 of 4.04g, add 4.08gNMP, 2.03gBCS, use magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (A-3).
(embodiment 4)
In the Erlenmeyer flask of 50ml, put into stirrer, add the polyamic acid ester solution (PAE-4) obtaining in the synthesis example 4 of 4.99g, add 3.00gNMP, 2.02gBCS, use magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (A-4).
(embodiment 5)
In the Erlenmeyer flask of 50ml, put into stirrer, add the polyamic acid ester solution (PAE-5) obtaining in the synthesis example 5 of 5.33g, add 3.26gNMP, 2.30gBCS, use magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (A-5).
(comparative example 1)
In the Erlenmeyer flask of 50ml, put into stirrer, add the polyamic acid ester solution (PAA-1) obtaining in the comparison synthesis example 1 of 4.87g, add 2.97gNMP, 1.98gBCS, use magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (B-1).
(comparative example 2)
In the Erlenmeyer flask of 50ml, put into stirrer, add the polyamic acid ester solution (PAA-2) obtaining in the comparison synthesis example 2 of 5.22g, add 3.15gNMP, 2.18gBCS, use magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (B-2).
(comparative example 3)
In the Erlenmeyer flask of 50ml, put into stirrer, add the polyamic acid ester solution (PAA-3) obtaining in the comparison synthesis example 3 of 4.37g, add 4.38gNMP, 2.21gBCS, use magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (B-3).
(embodiment 6)
Filter after the aligning agent for liquid crystal (A-1) obtaining in embodiment 1 with the filtrator of 1.0 μ m, be spun on quartz base plate, dry after 5 minutes on the heating plate of 80 ℃ of temperature, burn till 1 hour the film of formation thickness 100nm with 230 ℃ of heated air circulation type stoves of temperature.The transmissivity of the film obtaining is used the (Island Jin System of Shimadzu Seisakusho Ltd. to do institute) ultraviolet-visible pectrophotometer (UV-3100PC) of system measures, and calculates to obtain the mean value of transmissivity of 360nm～800nm.The transmissivity of the film consequently, obtaining is 95.14%.Calculate transmissivity as shown in table 1.
(embodiment 7)
The aligning agent for liquid crystal (A-2) making, measured the transmissivity of film by method similarly to Example 6 in using embodiment 2.The transmissivity of the film consequently, obtaining is 93.35%.
(embodiment 8)
The aligning agent for liquid crystal (A-3) making, measured the transmissivity of film by method similarly to Example 6 in using embodiment 3.The transmissivity of the film consequently, obtaining is 92.74%.
(embodiment 9)
The aligning agent for liquid crystal (A-4) making, measured the transmissivity of film by method similarly to Example 6 in using embodiment 4.The transmissivity of the film consequently, obtaining is 96.17%.
(embodiment 10)
The aligning agent for liquid crystal (A-5) making, measured the transmissivity of film by method similarly to Example 6 in using embodiment 5.The transmissivity of the film consequently, obtaining is 95.35%.
(comparative example 4)
The aligning agent for liquid crystal (B-1) making, measured the transmissivity of film by method similarly to Example 6 in using comparative example 1.The transmissivity of the film consequently, obtaining is 89.58%.
(comparative example 5)
The aligning agent for liquid crystal (B-2) making, measured the transmissivity of film by method similarly to Example 6 in using comparative example 2.The transmissivity of the film consequently, obtaining is 91.35%.
(comparative example 6)
The aligning agent for liquid crystal (B-3) making, measured the transmissivity of film by method similarly to Example 6 in using comparative example 3.The transmissivity of the film consequently, obtaining is 88.56%.
[table 1]
? Aligning agent for liquid crystal Transmissivity
Embodiment 6 A-1 95.14％
Embodiment 7 A-2 93.35％
Embodiment 8 A-3 92.74％
Embodiment 9 A-4 96.17％
Embodiment 10 A-5 95.35％
Comparative example 4 B-1 89.58％
Comparative example 5 B-2 91.35％
Comparative example 6 B-3 88.56％
(embodiment 11)
After the aligning agent for liquid crystal (A-1) obtaining in filtrator filtration embodiment 1 with 1.0 μ m, be coated on and be formed with FFS(fringe field switching by spin coating, Off リ Application ジ フ ィ ー Le De ス ィ ッ チ Application グ, Fringe Field Switching) on the glass substrate of driving electrode, described FFS driving electrode is the ITO electrode with ground floor thickness 50nm, the second layer is as the silicon nitride of the thickness 500nm of dielectric film, ITO electrode (the electrode width: 3 μ m of the 3rd layer of comb teeth-shaped, electrode gap: 6 μ m, electrode height: 50nm) FFS driving electrode.On the heating plate of 80 ℃, make it be dried after 5 minutes, in the heated air circulation type stove of 230 ℃, burn till 30 minutes, the film that formation thickness is 100nm.On this coated surface, apply take roller revolution 1000rpm, platform (Japanese: ス テ ー ジ) translational speed 20mm/s, friction cloth and be pressed into the friction treatment of 0.4mm as condition, obtain the substrate with liquid crystal orientation film.In addition, on the glass substrate with the column spacer that is highly 4 μ m that is not formed with electrode as substrate in opposite directions, form too film, implementation orientation processing.
Using above-mentioned 2 plate bases as one group, printing and sealing agent on substrate, another 1 plate base of fitting, so that the relative orientation direction of liquid crystal orientation film is 0 °, then, makes sealant cures and makes negative crystal born of the same parents.In this negative crystal born of the same parents, inject liquid crystal MLC-2041(Merck & Co., Inc. system by decompression injection method), sealing inlet, obtains FFS and drives liquid crystal structure cell.This FFS is driven to liquid crystal structure cell, carry out the evaluation of electric charge relaxation properties with following method, consequently, exchanging Δ T while driving 0 minute is 47%, and exchanging Δ T while driving 5 minutes is 0%.
[electric charge relaxation properties]
Drive liquid crystal structure cell to be positioned on light source above-mentioned FFS, at the temperature of 45 ℃, measure after V-T characteristic (voltage-transmission characteristics), measured the transmissivity (Ta) of liquid crystal structure cell under the state of apply ± 1.5V/60Hz square wave.Then, the square wave of apply at the temperature of 45 ℃ ± 1.5V/60Hz, after 10 minutes, repeats to apply direct current 2V, makes it drive 120 minutes.Cut off DC voltage, the transmissivity (Tb) of the liquid crystal structure cell while only measuring again respectively with the rectangular wave drive of ± 1.5V/60Hz 0 minute and 5 minutes, is calculated transmissivity poor of the residual voltage generation in liquid crystal display cells by poor (the Δ T) of the transmissivity under each time (Tb) and initial transmission (Ta).
(embodiment 12)
Except the aligning agent for liquid crystal (A-2) that uses embodiment 2 to obtain, by method similarly to Example 11, to make FFS and drive liquid crystal structure cell, the result of evaluating its electric charge relaxation properties is, exchanging Δ T while driving 0 minute is 46%, and exchanging Δ T while driving 5 minutes is 0%.
(embodiment 13)
Except the aligning agent for liquid crystal (A-3) that uses embodiment 3 to obtain, by method similarly to Example 11, to make FFS and drive liquid crystal structure cell, the result of evaluating its electric charge relaxation properties is, exchanging Δ T while driving 0 minute is 46%, and exchanging Δ T while driving 5 minutes is 0%.
(embodiment 14)
Except the aligning agent for liquid crystal (A-4) that uses embodiment 4 to obtain, by method similarly to Example 11, to make FFS and drive liquid crystal structure cell, the result of evaluating its electric charge relaxation properties is, exchanging Δ T while driving 0 minute is 46%, and exchanging Δ T while driving 5 minutes is 0%.
(embodiment 15)
Except the aligning agent for liquid crystal (A-5) that uses embodiment 5 to obtain, by method similarly to Example 11, to make FFS and drive liquid crystal structure cell, the result of evaluating its electric charge relaxation properties is, exchanging Δ T while driving 0 minute is 46%, and exchanging Δ T while driving 5 minutes is 0%.
(comparative example 7)
The aligning agent for liquid crystal (B-1) obtaining in using comparative example 1, make FFS by method similarly to Example 11 and drive liquid crystal structure cell.This FFS drives liquid crystal structure cell to carry out the evaluation of electric charge relaxation properties with the method identical with embodiment 11, and consequently, exchanging Δ T while driving 0 minute is 46%, and exchanging Δ T while driving 5 minutes is 0%.
So, the liquid crystal orientation film of the embodiment 6～10 being obtained by the aligning agent for liquid crystal A-1～A-5 of the poly amic acid ester that contains the repetitive represented containing formula (1), with the liquid crystal orientation film comparison of comparative example 4～6, transmissivity is significantly higher.In addition, possesses the mitigation of the residual charge of putting aside because of DC voltage of the liquid crystal display cells of the liquid crystal orientation film being obtained by aligning agent for liquid crystal A-1～A-5 also quick.
The possibility of utilizing in industry
Aligning agent for liquid crystal of the present invention can obtain the less residual charge that has while applying DC voltage and/or characteristic and the high liquid crystal orientation film of transmissivity of the quick mitigation of the residual charge put aside because of DC voltage.Consequently, can be widely used in TN(twisted nematic, Twisted Nematic) element, STN(super-twist nematic, Super Twisted Nematic) element, TFT liquid crystal cell, and the liquid crystal display cells of vertical orientating type etc.

Claims (9)

1. an aligning agent for liquid crystal, is characterized in that, the poly amic acid ester and the organic solvent that contain the repetitive represented containing following formula (1),
[changing 1]
Figure FDA0000476593930000011
In formula (1), X 14 valency organic groups, Y 1divalent organic group, X 1and Y 1middle at least one party is contained and is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure, R 1that carbon number is 1～5 alkyl, A 1and A 2respectively that maybe can to have substituent carbon number be 1～10 alkyl, alkenyl or alkynyl to hydrogen atom independently.
2. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the Y in formula (1) 1to contain the divalent organic group that is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure.
3. aligning agent for liquid crystal as claimed in claim 1 or 2, is characterized in that, with respect to 1 mole of entire infrastructure unit, Y 1the ratio that is the represented repetitive of the above formula (1) that contains the divalent organic group that is selected from amino, imino group and nitrogenous heterocyclic at least a kind of structure is 40～100 % by mole.
4. the aligning agent for liquid crystal as described in any one in claim 1～3, is characterized in that, Y 1to be selected from least a kind of the represented divalent organic group that contains nitrogen-atoms of following formula (YD-1)～(YD-5),
[changing 2]
Figure FDA0000476593930000021
In formula (YD-1), A 11that carbon number is 3～15 3 valency nitrogen heterocyclic rings, Z 1that maybe can to have substituent carbon number be 1～20 1 valency alkyl to hydrogen atom; In formula (YD-2), W 1that carbon number is 1～10 3 valency alkyl, A 12that to contain nitrogenous heterocyclic carbon number be the disubstituted amido that aliphatic group that 3～15 1 valency organic group or 2 amino hydrogen are 1～6 by carbon number respectively independently replaces; In formula (YD-3), W 2that carbon number is 6～15 and the divalent organic group that contains 1 or 2 phenyl ring, W 3that carbon number is 2～5 alkylidene or biphenylene, Z 2be that hydrogen atom, carbon number are 1～5 alkyl or phenyl ring, a is 0～1 integer; In formula (YD-4), A 13that carbon number is 3～15 divalent nitrogen heterocyclic ring; In formula (YD-5), A 14that carbon number is 3～15 divalent nitrogen heterocyclic ring, W 5that carbon number is 2～5 alkylidene.
5. the aligning agent for liquid crystal as described in any one in claim 1～4, is characterized in that, formula (YD-1), (YD-2), (YD-4) and (YD-5) described A 11, A 12, A 13and A 14carbon number to be 3～15 contain nitrogen-atoms heterocycle is be selected from pyrrolidine, pyrroles, imidazoles, pyrazoles, at least a kind of ring of azoles, thiazole, piperidines, piperazine, pyridine, pyrazine, indoles, benzimidazole, quinoline, isoquinoline.
6. the aligning agent for liquid crystal as described in any one in claim 1～5, is characterized in that, the Y in formula (1) 1to be selected from least a kind of the represented divalent organic group that contains nitrogen-atoms of following formula (YD-6)～(YD-23),
[changing 3]
Figure FDA0000476593930000031
In formula (YD-14), respectively 1～11 integer naturally of m, n, m+n is 2～12 integer, in formula (YD-19), h is 1～3 integer, formula (YD-16) and (YD-23) in, j is 0～3 integer.
7. the aligning agent for liquid crystal as described in any one in claim 1～6, is characterized in that, in formula (1), and X 1for selecting at least a kind of the represented structure of free following formula,
[changing 4]
Figure FDA0000476593930000032
8. a liquid crystal orientation film, is characterized in that, is coated with and is fired into by the aligning agent for liquid crystal described in any one in claim 1～7.
9. a liquid crystal display cells, is characterized in that, has liquid crystal orientation film claimed in claim 8.
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