CN103797408B - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element - Google Patents

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element Download PDF

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CN103797408B
CN103797408B CN201280043903.7A CN201280043903A CN103797408B CN 103797408 B CN103797408 B CN 103797408B CN 201280043903 A CN201280043903 A CN 201280043903A CN 103797408 B CN103797408 B CN 103797408B
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liquid crystal
formula
particular polymers
dianhydride
aligning agent
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CN103797408A (en
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新津新平
小野豪
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Nissan Chemical Corp
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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
    • C08G73/02—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
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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

Abstract

Aligning agent for liquid crystal of the invention contains following particular polymers (A) and particular polymers (B).Particular polymers (A): make containing two rings [3,3,0] octane -2,4,6, tetracarboxylic dianhydride's ingredient of 8- tetracarboxylic dianhydride and containing using 4,4 '-diamino-diphenylamines, 3,6- diaminocarbazole be at least one of the diamine compound of representative diamine component react obtained by polyamic acid.Particular polymers (B): the polyimide precursor with the structural unit that following formula (7) indicate.In formula (7), R indicates hydrogen atom or alkyl, Y indicates 4 valence organic groups, and X indicates divalent organic group, and 10~100 moles of % of X are that have the divalent organic group of any one of formula (8)~(10) in structure or to phenylene.In formula (8), m1For 2~18 integer.In formula (9), the one or more of the arbitrary hydrogen atom on phenyl ring can be replaced by 1 valence organic group other than primary amino group, m2For 1~8 integer.In formula (10), the one or more of the arbitrary hydrogen atom on phenyl ring can be replaced by 1 valence organic group other than primary amino group, m3For 1~4 integer.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element
Technical field
The present invention relates to the aligning agent for liquid crystal used when forming liquid crystal orientation film, liquid crystal orientation film and utilize its liquid crystal Display element.
Background technique
Now, liquid crystal display element is widely used as display device.Component parts as liquid crystal display element Liquid crystal orientation film is the film for keeping liquid crystal evenly distributed, in the case that liquid crystal aligning is insufficient, easily causes and referred to as shows not And the display of afterimage is bad.Show that undesirable generation is sometimes related with the ionic impurity in liquid crystal, as the reduction impurity Method, propose the scheme such as patent document 1.
In addition, usually implementing to use cloth to wipe with and wiping the orientation process for being known as friction on polymeric membrane surface in liquid crystal orientation film. But if the rub resistance of liquid crystal orientation film is not enough, causes film to be scratched and generate scar and dust or film itself are shelled From reducing the display quality of liquid crystal display element.It is therefore desirable to which liquid crystal orientation film rub resistance with higher, proposes The technical solution as shown in patent document 2~5.
In addition, in order to obtain the liquid crystal display element of high display quality, exhibit high brilliance is also critically important.Therefore, it also requires Liquid crystal orientation film has high-transmission rate.
On the other hand, it if the volume resistivity of liquid crystal orientation film is high, there are accumulated charge is difficult to decay, afterimage disappears It deflorates the problems such as time-consuming.As the method for shortening the afterimage cancellation time, use volume electricity as described in Patent Document 6 is proposed The method of the low alignment films of resistance rate.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2002-323701 bulletin
Patent document 2: Japanese Patent Laid-Open 7-120769 bulletin
Patent document 3: Japanese Patent Laid-Open 9-146100 bulletin
Patent document 4: Japanese Patent Laid-Open 2008-90297 bulletin
Patent document 5: Japanese Patent Laid-Open 9-258229 bulletin
Patent document 6: International Publication No. 2004/053583
Summary of the invention
The technical problems to be solved by the invention
But in recent years, in the development process of the high-quality of liquid crystal display element, have using powerful backlight Tendency.Therefore, not only the low this point of the volume resistivity of liquid crystal orientation film is critically important, but also will not cause volume electric because of light The resistance rate this point that changes is also critically important.For example, in liquid crystal orientation film in liquid crystal display element, due to wiring and black matrix etc. Presence, sometimes exist compared with other parts light be more difficult to the part being irradiated to.If the volume electricity of liquid crystal orientation film Resistance rate changes because of light, then element can not integrally show uniform after image characteristic, and people is caused to observe referred to as The display of afterimage and display unevenness is bad.
The present invention be in view of the above fact and complete invention, provide it is a kind of can obtain liquid crystal aligning, rub resistance, Voltage retention performance and charge accumulation excellent, ionic impurity amount is few, transmissivity is high and the volume resistivity as caused by light The aligning agent for liquid crystal of the small liquid crystal orientation film of variation, liquid crystal orientation film and being not susceptible to show bad, contrast reduction, The liquid crystal display element of the burn-in of display etc..
Technical scheme applied to solve the technical problem
The present inventor is conscientiously studied in order to achieve the above object, as a result, it has been found that, using contain particular polymers (A) With the aligning agent for liquid crystal of particular polymers (B), above-mentioned purpose can be reached.
In conclusion the present invention is using following the description as technology contents.
1. a kind of aligning agent for liquid crystal contains following particular polymers (A) and particular polymers (B)；
Particular polymers (A): polyamic acid obtained by reacting tetracarboxylic dianhydride's ingredient and diamine component, the tetrabasic carboxylic acid Two anhydride components contain the dianhydride of the tetrabasic carboxylic acid of following formula (1) expression, the diamines that the diamine component contains following formula (5) and (6) indicate At least one of compound；
[changing 1]
[changing 2]
(in formula (5) and (6), the one or more of the arbitrary hydrogen atom on phenyl ring can be had by 1 valence other than primary amino group Machine group replaces.)
Particular polymers (B): the polyimide precursor with the structural unit that following formula (7) indicate；
[changing 3]
(in formula (7), R indicates that hydrogen atom or alkyl, Y indicate that 4 valence organic groups, X indicate divalent organic group, and the 10 of X ~100 moles of % are that have the divalent organic group of any one of following formula (8)~(10) in structure or to phenylene.)
[changing 4]
(in formula (8), m1For 2~18 integer.)
[changing 5]
(in formula (9), the one or more of arbitrary hydrogen atom on phenyl ring can be by 1 valence organic group other than primary amino group Group replaces, m2For 1~8 integer.)
[changing 6]
(in formula (10), the one or more of arbitrary hydrogen atom on phenyl ring can be by 1 valence organic group other than primary amino group Group replaces, m3For 1~4 integer.)
Aligning agent for liquid crystal described in 2.1, wherein tetracarboxylic dianhydride's ingredient in particular polymers (A) is indicated by following formula (1) Tetrabasic carboxylic acid dianhydride and selected from following formula (2)~(4) indicate tetrabasic carboxylic acid at least one compound dianhydride constitute；
[changing 7]
(in formula (3), R1、R2、R3、R4Separately indicate the alkyl of hydrogen atom or carbon number 1~3.)
Aligning agent for liquid crystal described in 3.2, wherein tetracarboxylic dianhydride's ingredient in particular polymers (A) is rubbed by 10~100 The tetrabasic carboxylic acid of the dianhydride for the tetrabasic carboxylic acid that the formula (1) of your % indicates and 0~90 mole of % indicated selected from formula (2)~(4) is at least A kind of dianhydride composition of compound.
Aligning agent for liquid crystal described in 4.3, wherein tetracarboxylic dianhydride's ingredient in particular polymers (A) is rubbed by 10~100 The dianhydride for the tetrabasic carboxylic acid that the dianhydride for the tetrabasic carboxylic acid that the formula (1) of your % indicates and the formula (3) of 0~90 mole of % indicate is constituted.
Aligning agent for liquid crystal described in any one of 5.1~4, wherein 20~100 moles of % of the Y of formula (7) are that have fragrance 4 valence organic groups of race's structure.
6. a kind of liquid crystal orientation film is obtained by using aligning agent for liquid crystal described in any one of 1~5.
7. a kind of liquid crystal display element, with liquid crystal orientation film described in 1~6.
The effect of invention
By using aligning agent for liquid crystal of the invention, liquid crystal aligning, rub resistance, voltage retention performance and electricity can be obtained The liquid crystal that lotus Accumulation is excellent, ionic impurity amount is few, transmissivity is high and the variation of the volume resistivity as caused by light is small takes To film, it is possible to provide the liquid crystal display element of high-quality.
Specific embodiment
Hereinafter, the present invention is described in detail.
Aligning agent for liquid crystal of the invention is the composition for being used to form liquid crystal orientation film, characterized in that containing making tetrabasic carboxylic acid Two anhydride components and diamine component reaction obtained by polyamic acid (hereinafter also referred to as particular polymers (A)) and have general formula (7) table The polyimide precursor (hereinafter also referred to as particular polymers (B)) of the structural unit shown, under tetracarboxylic dianhydride's ingredient contains The dianhydride for the tetrabasic carboxylic acid that formula (1) indicates, the diamine component contain in following formula (5) and the diamine compound of (6) expression at least It is a kind of.
[changing 8]
[changing 9]
(in formula (5) and (6), the one or more of the arbitrary hydrogen atom on phenyl ring can be had by 1 valence other than primary amino group Machine group replaces.)
[changing 10]
(in general formula (7), R indicates that hydrogen atom or alkyl, Y indicate 4 valence organic groups, X expression divalent organic group, and X 10~100 moles of % are that have the divalent organic group of any one of following formula (8)~(10) in structure or to phenylene.)
[changing 11]
(in formula (8), m1For 2~18 integer.)
[changing 12]
(in formula (9), the one or more of arbitrary hydrogen atom on phenyl ring can be by 1 valence organic group other than primary amino group Group replaces, m2For 1~8 integer.)
[changing 13]
(in formula (10), the one or more of arbitrary hydrogen atom on phenyl ring can be by 1 valence organic group other than primary amino group Group replaces, m3For 1~4 integer.)
About the ratio of particular polymers (A) and particular polymers (B), relative to particular polymers (A) and specific aggregation The total amount of object (B), particular polymers (A) preferably 10~95 weight %, more preferably 60~90 weight %.Particular polymers (A) If very few, the charge accumulation characteristic and rub resistance of liquid crystal orientation film deteriorate sometimes, and particular polymers (B) are if mistake Few, then liquid crystal aligning deteriorates sometimes.Particular polymers contained in aligning agent for liquid crystal of the invention (A) and specific aggregation Object (B) both can be respectively one kind, or two or more.
<particular polymers (A)>
Tetracarboxylic dianhydride's ingredient used in the manufacture of particular polymers (A) contains the two of the tetrabasic carboxylic acid of following formula (1) expression Acid anhydride.
[changing 14]
Specifically, the tetrabasic carboxylic acid that tetracarboxylic dianhydride's ingredient preferably in particular polymers (A) is indicated by following formula (1) The dianhydride of at least one compound of dianhydride and the tetrabasic carboxylic acid selected from following formula (2)~(4) expression is constituted.
[changing 15]
(in formula (3), R1、R2、R3、R4Separately indicate the alkyl of hydrogen atom or carbon number 1~3.)
As the ratio of components of preferred tetracarboxylic dianhydride's ingredient in particular polymers (A), tetrabasic carboxylic acid that formula (1) indicates Dianhydride is 10~100 moles of % of tetracarboxylic dianhydride's ingredient entirety, at least one of the tetrabasic carboxylic acid indicated selected from formula (2)~(4) The dianhydride of compound is 0~90 mole of % of tetracarboxylic dianhydride's ingredient entirety.The dianhydride of tetrabasic carboxylic acid that preferably formula (1) indicates is 10~90 moles of % of tetracarboxylic dianhydride's ingredient entirety, at least one compound of the tetrabasic carboxylic acid indicated selected from formula (2)~(4) Dianhydride is 10~90 moles of % of tetracarboxylic dianhydride's ingredient entirety.The dianhydride of the more preferably tetrabasic carboxylic acid of formula (1) expression is tetrabasic carboxylic acid 20~80 moles of % of two anhydride components entirety, the dianhydride for being selected from at least one compound for the tetrabasic carboxylic acid that formula (2)~(4) indicate are 20~80 moles of % of tetracarboxylic dianhydride's ingredient entirety.The dianhydride for the tetrabasic carboxylic acid that particularly preferably formula (1) indicates is tetracarboxylic dianhydride The dianhydride of 25~75 moles of % of ingredient entirety, at least one compound of the tetrabasic carboxylic acid indicated selected from formula (2)~(4) are tetracarboxylic acids 25~75 moles of % of acid dianhydride component entirety.
From the angle of liquid crystal aligning, the combination of preferred tetracarboxylic dianhydride's ingredient is the tetrabasic carboxylic acid that formula (1) indicates Dianhydride and formula (3) indicate tetrabasic carboxylic acid dianhydride.
Diamine component used in the manufacture of particular polymers (A) contains the diamine compound and following formula of following formula (5) expression (6) at least one of the diamine compound indicated.
[changing 16]
(in formula (5) and (6), the one or more of the arbitrary hydrogen atom on phenyl ring can be had by 1 valence other than primary amino group Machine group replaces.)
From the angle of liquid crystal aligning, formula (5) is preferably the diamines of the hexichol amido with 4,4 ' bondings, from liquid crystal The angle of orientation is set out, and formula (6) is preferably the diamines of the carbazyl with 3,6 bondings.
In above formula (5) or (6), the one or more of arbitrary hydrogen atom on phenyl ring can be by 1 valence other than primary amino group Organic group replaces.As the 1 valence organic group, can enumerate the alkyl of carbon number 1~20, the alkenyl of carbon number 2~20, carbon number 1~ 20 alkoxy, carbon number 1~20 containing fluoroalkyl, the fluorine-containing alkenyl of carbon number 2~20, the fluoroalkoxy of carbon number 1~20, hexamethylene Base, phenyl, fluorine atom and the group being made of their combination etc., from the angle of liquid crystal aligning, are preferably selected from The alkyl of carbon number 1~4, the alkenyl of carbon number 2~4, the alkoxy of carbon number 1~4, carbon number 1~4 containing fluoroalkyl, carbon number 2~4 1 valence organic group of the fluoroalkoxy of fluorine-containing alkenyl, carbon number 1~4.The structure of formula (5) and (6) more preferably, is benzene The unsubstituted structure of hydrogen atom on ring.
In particular polymers (A), the total amount phase for the diamine compound that the diamine compound and formula (6) that formula (5) indicates indicate For ratio preferably 10~100 moles of %, more preferably 60~100 moles of % of whole diamine components.It is indicated by formula (5) Diamine compound and formula (6) indicate diamine compound total amount be 10 moles of % or more, volume resistance can be effectively reduced Rate is easy to get the polyamic acid that volume resistivity is low and the variation of the volume resistivity as caused by light is small, and voltage is kept Characteristic is good, and is easy to assign liquid crystal orientation film with excellent charge accumulation characteristic and rub resistance.
In the diamine compound that formula (5) or formula (6) indicate, from the reactivity with tetracarboxylic dianhydride and liquid crystal aligning is made The angle of liquid crystal aligning when film is set out, particularly preferably 4,4 '-diamino-diphenylamines, 3,6- diaminocarbazole.
It is of the invention not damaging other than the diamine compound that formula (5) or formula (6) indicate in particular polymers (A) Other diamine compounds in the range of effect, other than the diamine compound that can also be indicated containing formula (5) or formula (6).As Other diamine compounds can enumerate the diamine compound of following formula (15) expression.Its concrete example is as follows, and but not limited thereto.
[changing 17]
H2N-A-NH2(15)
As the diamine compound that there is A the formula (15) of nitrogen-atoms to indicate, 2,3- diamino-pyridine, 2,6- diamino can be enumerated Yl pyridines, 3,4- diamino-pyridine, 2,4- di-amino-pyrimidine, 2,4- diamino -6- hydroxy pyrimidine, 2,4- diaminostilbene, 3,5- Triazine, 2,4- diaminostilbene, 3,5- triazine, 2,4- diamino -6- isopropoxy -1,3,5- triazine, 2,4- diamino -6- methoxy Base -1,3,5- triazine, 2,4- diamino -6- phenyl -1,3,5- triazine, 2,6-diaminopurine, 1,4- bis- (3- aminopropyls) Piperazine, 2,4- diamino -5- phenyl thiazole, 3,5- diaminostilbene, 2,4- triazole, 3,6- proflavin, rivanol, 2,5- are bis- (4- aminophenyl) -1,3,4-Diazole, diethylenetriamines, trien, 3,3 '-diamino-di-n-propylamine, five sub- second Base hexamine, N, bis- (3- aminopropyl) methylamines of N-, 4,4 '-diaminobenzene formailides, 2,6- diamino -4- nitrotoleune, N, N '-bis- (4- aminophenyl)-N- aniline, N, bis- (4- the aminophenyl)-N- methylamines of N '-, 4,4 '-diamino-diphenyl ureas etc..
As the example for the diamine compound that aliphatic diamine, i.e. formula (15) indicate, diaminomethane, 1,2- bis- can be enumerated Aminoethane, 1,3- diaminopropanes, 1,4- diaminobutane, 1,6- diamino hexane, 1,7- diaminoheptane, 1,8- diamino Base octane, 1,9- diamino nonane, 1,10- diamino decane, 1,3- diamino -2,2- dimethylpropane, diamino -2 1,4-, 2- dimethylbutane, 1,6- diamino -2,5- dimethylhexane, 1,7- diamino -2,5- dimethyl heptane, 1,7- diamino - 4,4- dimethyl heptane, 1,7- diamino -3- methyl heptane, 1,9- diamino -5- methylnonane, 2,11- diamino dodecane, Bis- (3- amino propoxyl group) ethane of 1,12- diamino octadecane, 1,2- etc..
As alicyclic diamine, i.e. formula (15) indicate diamine compound example, can enumerate Isosorbide-5-Nitrae-diaminocyclohexane, 1,3- diaminocyclohexane, 4,4 '-diamino-dicyclohexyl methanes, 4,4 '-diamino -3,3 '-dimethyidicyclohexyl-methane With isophorone diamine etc..
As carbon-ring type aromatic diamine, i.e. formula (15) indicate diamine compound example, can enumerate o-phenylenediamine, Phenylenediamine, p-phenylenediamine, diaminotoluene class (such as 2,4 di amino toluene), 1,4- diamino -2- methoxybenzene, 2,5- bis- Amino-xylene class, 1,3- diamino -4- chlorobenzene, 1,4- diamino -2,5- dichloro-benzenes, 1,4- diamino -4- cumene, 4, 4 '-diamino-diphenyls -2,2 '-propane, 4,4 '-diaminodiphenyl-methanes, 2,2 '-diamino Stilbene, 4,4 '-diamino Stilbene, 4,4 '-diaminodiphenyl ethers, 4,4 '-diphenyl sulfides, 4,4 '-diaminodiphenylsulfones, 3,3 '-diaminodiphenylsulfones, 4,4 '-diaminos Yl benzoic acid phenyl ester, 2,2 '-diamino benzophenone, 4,4 '-diamino benzils, bis- (4- aminophenyl) phosphine oxides, bis- (3- ammonia Base phenyl) methyl sulfonium hydroxide, bis- (4- aminophenyl) phenyl phosphine oxides, the oxidation of bis- (4- aminophenyl) cyclohexyl Phosphine, 1,8- diaminonaphthalene, 1,5- diaminonaphthalene, 1,5- diamino-anthraquinone, diamino-fluorene, bis- (4- aminophenyl) diethyl silicon Alkane, bis- (4- aminophenyl) dimethylsilanes, bis- (4- aminophenyl) tetramethyl disiloxanes, 3,4 '-diaminodiphenyl ethers, connection Bis- [4- (4- amino-benzene oxygen) phenyl] propane of aniline, 2,2 '-dimethylbenzidines, 2,2-, bis- [4- (4- amino-benzene oxygen) benzene Base] sulfone, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-, 1,4- be bis- Bis- (4- amino-benzene oxygen) benzene of (4- amino-benzene oxygen) benzene, 1,3- etc..
As the diamine compound that there is A the formula (15) of the characteristic for the pre-tilt angle for improving liquid crystal to indicate, 1- 12 can be enumerated Alkoxy -2,4- diaminobenzene, 1- hexadecane epoxide -2,4- diaminobenzene, 1- octadecane epoxide -2,4- diaminobenzene, 1,1- Bis- (4- aminophenyl) hexamethylenes, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] octanes, 4,4 '-diamino -3- dodecyls Diphenyl ether, 4- (4- trans--n-heptyl cyclohexyl benzene oxygroup) -1,3- diaminobenzene, 4- (4- is trans--pentyl cyclohexyl benzene oxygen Base) -1,3- diaminobenzene, 4- be trans--n-pentyl dicyclohexyl -3,5- diaminobenzoic acid ester etc..
<particular polymers (B)>
Particular polymers (B) are the polyimide precursors for the structural unit (repetitive unit) that there are following formula (7) to indicate.Polyamides Imines precursor refers to polyamic acid or poly amic acid ester.
[changing 18]
Particular polymers (B) are either be respectively that formula (7) that is a kind of, being only made of same structure indicates with R, X and Y Structural unit polyimide precursor, or being also possible to have R, X or Y is a variety of formulas (7) table that is a variety of, being different structure The polyimide precursor of the structural unit shown.In addition, particular polymers (B) can be the structural unit also indicated with formula (7) The polyimide precursor of structure in addition.That is, particular polymers (B) are either the structure indicated by the formula (7) of same structure The polyimide precursor that unit is constituted is also possible to the polyimides being made of the structural unit that the formula (7) of different structure indicates Furthermore precursor can also be the structural unit that the formula (7) with same structure or different structure indicates and the structure that formula (7) indicates The polyimide precursor of structure other than unit.
In formula (7), R is hydrogen atom or alkyl.As alkyl, the alkyl of carbon number 1~6 can be enumerated.
In formula (7), X is divalent organic group, as described above, two or more can also be mixed either a kind of, But at least one X must have any divalent organic group of following formula (8)~(10) in structure or to phenylene.
[changing 19]
[changing 20]
[changing 21]
In the X of formula (7), there is the divalent organic group of any one of these formula (8)~(10) or to phenylene in structure The ratio of (being also denoted as " specific structure " below) is 10~100 moles of %, preferably 50~100 moles of %.If the ratio mistake Few, then liquid crystal aligning deteriorates sometimes.Divalent organic group in structure with any one of these formula (8)~(10) or The structure of X other than phenylene is not particularly limited, such as in order to improve the pre-tilt angle of liquid crystal, can enumerate with chain alkyl, The divalent organic group of the substituent group of the effect at inclination angle is improved known to perfluoroalkyl, steroid skeleton group etc..
In formula (8), m1For 2~18 integer, from the angle of liquid crystal aligning and heat resistance, preferably 3~12, more It is well 4~8.Divalent organic group in structure with formula (8) preferably also includes aromatic rings, as in structure with formula (8) The concrete example of divalent organic group can enumerate following formula (11)~(14), and but not limited thereto.
[changing 22]
In formula (11)~(14), m1For 2~18 integer, preferably 3~12, more preferably 4~8.
In formula (9), m2For 1~8 integer, from the angle of voltage retention performance, preferably 1~3, more preferably 1 or 2。
In formula (10), m3For 1~4 integer, from the angle of the stability of polyamic acid solution, preferably 1 or 2.
Formula (9), (10), (11)~(14) and in phenylene, the one or more of the arbitrary hydrogen atom on phenyl ring can To be replaced by 1 valence organic group other than primary amino group.As 1 valence organic group other than the primary amino group, carbon number 1~20 can be enumerated Alkyl, the alkenyl of carbon number 2~20, the alkoxy of carbon number 1~20, carbon number 1~20 containing fluoroalkyl, carbon number 2~20 it is fluorine-containing Alkenyl, the fluoroalkoxy of carbon number 1~20, cyclohexyl, phenyl, fluorine atom and the group being made of their combination etc., from The angle of liquid crystal aligning is set out, and the alcoxyl of the alkyl of carbon number 1~4, the alkenyl of carbon number 2~4, carbon number 1~4 is preferably selected from 1 valence organic group of the fluoroalkoxy containing fluoroalkyl, the fluorine-containing alkenyl of carbon number 2~4, carbon number 1~4 of base, carbon number 1~4.Make It is the unsubstituted structure of hydrogen atom on phenyl ring for preferred structure.
The Y of formula (7) is 4 valence organic groups, as described above, either one kind, two or more can also be mixed.Y Structure be not particularly limited, from the angle for further increasing liquid crystal aligning, preferably at least a kind of Y is with aromatic series 4 valence organic groups of structure (i.e. aromatic group).At this point, in the Y of formula (7), the 4 valence organic groups with aromatic structure It is preferably in a proportion of 20~100 moles of %, more preferably 50~100 moles of %.As the 4 valence organic groups with aromatic structure, Preferably from Pyromellitic Acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, bis- (3,4- dicarboxyls Phenyl) structure obtained by 4 carboxyls is removed in the tetrabasic carboxylic acids such as ether, bis- (3,4- dicarboxyphenyi) sulfones, 2,3,6,7- naphthalene tetracarboxylic acid.
The Y of formula (7) be from 1,2,3,4- cyclobutane tetrabasic carboxylic acid, 2,3,5- tricarboxylic cyclopentyl acetic acid, dicarboxyl -1 3,4-, 4 carboxyls are removed in the tetrabasic carboxylic acids such as 2,3,4- tetrahydro -1- naphthalene succinic, two rings [3,3,0] octane -2,4,6,8- tetrabasic carboxylic acid and are obtained Structure in the case where, although have the tendency that reduce liquid crystal aligning, be improved the effect of voltage retention performance.Therefore, weight It is preferably only the poly- of the structural unit of formula (7) expression of these 4 valence organic groups with Y in the case where depending on voltage retention Imide precursor, or the structural unit with formula (7) expression that Y is these 4 valence organic groups and Y are that these 4 valences are organic The polyimide precursor for the structural unit that the formula (7) of 4 valence organic groups other than group indicates.
The method for obtaining the polyimide precursor for the structural unit that there are formula (7) to indicate is not particularly limited.Can usually it pass through Tetracarboxylic dianhydride's ingredient of tetracarboxylic dianhydride containing the Y for constitutional formula (7) and the diamines for containing the X for constitutional formula (7) Diamine component reaction and obtain.
In the case where obtaining the polyimide precursor that a variety of Y are mixed at a specific ratio, or to obtain a variety of X In the case where the polyimide precursor being mixed at a specific ratio, if according to respective target mix ratio example come using with In the tetracarboxylic dianhydride of composition Y or the diamines for constituting X and react its.For example, in order to make in polyimide precursor The ratio of X with specific structure reaches 10 moles of %, as long as keeping diamine component used in the synthesis of polyimide precursor total The ratio of the diamines for constituting the X with specific structure in amount reaches 10 moles of %.Similarly, in order to keep polyamides sub- The ratio of Y in amine precursor with aromatic structure reaches 20 moles of %, as long as making used in the synthesis of polyimide precursor The ratio of the tetracarboxylic dianhydride for constituting the Y with aromatic structure in tetracarboxylic dianhydride's ingredient total amount reaches 20 moles of % ?.
The concrete example of the diamines of X for constitutional formula (7) is as follows, and but not limited thereto.
As the diamines for constituting the X in structure with formula (8), 1,3- diaminopropanes, Isosorbide-5-Nitrae-diamino can be enumerated Butane, 1,5- 1,5-DAP, 1,6- diamino hexane, 1,7- diaminoheptane, 1,8- diamino-octane, 1,9- diamino nonyl Alkane, 1,10- diamino decane etc..In addition, as the diamines for constituting the X with formula (8) and aromatic ring in structure, it can example Diamines corresponding with formula (11) is lifted, i.e. bis- (4- aminophenyl) propane of 1,3-, bis- (4- aminophenyl) butane of Isosorbide-5-Nitrae-, 1,5- are bis- Bis- (4- aminophenyl) hexanes of (4- aminophenyl) pentane, 1,6-, bis- (4- aminophenyl) heptane of 1,7-, bis- (the 4- amino of 1,8- Phenyl) octane, bis- (4- aminophenyl) nonanes of 1,9-, bis- (4- aminophenyl) decane of 1,10- etc..Similarly, it can enumerate and formula (12) bis- (4- amino-benzene oxygen) propane of corresponding diamines, i.e. 1,3-, bis- (4- amino-benzene oxygen) butane of Isosorbide-5-Nitrae-, the bis- (4- of 1,5- Amino-benzene oxygen) pentane, bis- (4- amino-benzene oxygen) hexanes of 1,6-, bis- (4- amino-benzene oxygen) heptane of 1,7-, bis- (the 4- ammonia of 1,8- Phenoxyl) octane, bis- (4- amino-benzene oxygen) nonanes of 1,9-, bis- (4- amino-benzene oxygen) decane of 1,10- etc..Similarly, make For diamines corresponding with formula (13), two (4- aminophenyl) propane -1,3-, bis- acid esters, two (4- aminophenyl) butane-can be enumerated Bis- acid esters of 1,4-, two (4- aminophenyl) pentane -1,5-, two acid esters, two (4- aminophenyl) hexane -1,6-, two acid esters, two (4- Aminophenyl) two acid esters of heptane -1,7-, two (4- aminophenyl) octane -1,8-, two acid esters, two (4- aminophenyl) nonanes -1, Bis- acid esters of 9-, two (4- aminophenyl) decane -1,10-, two acid esters etc..It similarly, can example as diamines corresponding with formula (14) Lift bis- (4- (4- amino-benzene oxygen) phenoxy group) propane of 1,3-, 1,4- bis- (4- (4- amino-benzene oxygen) phenoxy group) butane, 1,5- Bis- (4- (4- amino-benzene oxygen) phenoxy group) pentanes, 1,6- bis- (4- (4- amino-benzene oxygen) phenoxy group) hexanes, the bis- (4- of 1,7- (4- amino-benzene oxygen) phenoxy group) heptane, bis- (4- (4- amino-benzene oxygen) phenoxy group) octanes of 1,8-, bis- (4- (the 4- amino of 1,9- Phenoxy group) phenoxy group) nonane, bis- (4- (4- amino-benzene oxygen) phenoxy group) decane of 1,10- etc..
As the diamines for constituting the X in structure with formula (9), 1,3- bis- (4- amino-benzene oxygen) benzene, 1 can be enumerated, Bis- (4- (4- amino-benzene oxygen) phenoxy group) benzene of bis- (4- amino-benzene oxygen) benzene of 4-, 1,3-, the bis- (4- (4- amino-benzene oxygen) of 1,4- Phenoxy group) benzene etc..
As the diamines for constituting the X in structure with formula (10), 4,4 '-diaminobenzidines, 4,4 '-two can be enumerated Amino-p-terphenyl etc..
It is that Isosorbide-5-Nitrae-diaminobenzene can be enumerated to the diamines of phenylene as X.
The diamines enumerated in above-mentioned concrete example is preferably, with tetracarboxylic acid as the raw material for synthesizing particular polymers (B) , it is preferable to use 10~100 moles of %, more preferably rubbing using 50~100 in diamine component used in the reaction of acid dianhydride component These diamines of your %, the polyimide precursor of the structural unit indicated with formula (7) thus synthesized is as particular polymers It (B) is preferred.
In addition to this, there is the divalent organic group of any one of formula (8)~(10) or to sub- benzene for constituting in structure The concrete example of the diamines of X other than base is as follows, and but not limited thereto.
As the example of alicyclic diamine, Isosorbide-5-Nitrae-diaminocyclohexane, 1,3- diaminocyclohexane, 4 can be enumerated, 4 '-two Amino bicyclic hexyl methane, 4,4 '-diamino -3,3 '-dimethyidicyclohexyl amine and isophorone diamine etc..
As the example of carbon-ring type aromatic diamine, o-phenylenediamine, m-phenylene diamine (MPD), 2,4- diaminotoluene, 1 can be enumerated, 3- diamino -4- chlorobenzene, 4,4 '-diamino-diphenyls -2,2 '-propane, 4,4 '-diaminodiphenyl-methanes, 2,2 '-diamino Stilbene, 4,4 '-diamino Stilbene, 4,4 '-diaminodiphenyl ethers, 4,4 '-diphenylsulfides, 4,4 '-diaminodiphenylsulfones, 3,3 '-two Aminodiphenyl sulfone, 4,4 '-diaminobenzoic acid phenyl esters, 2,2 '-diamino benzophenone, 4,4 '-diamino benzils, bis- (4- ammonia Base phenyl) phosphine oxide, bis- (3- aminophenyl) methyl sulfonium hydroxides, bis- (4- aminophenyl) phenyl phosphine oxides, bis- (4- Aminophenyl) cyclohexyl phosphine oxide, 1,8- diaminonaphthalene, 1,5- diaminonaphthalene, 1,5- diamino-anthraquinone, diamino-fluorene, bis- (4- Aminophenyl) diethylsilane, bis- (4- aminophenyl) dimethylsilanes, bis- (4- aminophenyl) tetramethyl disiloxanes, 3, Bis- [4- (4- amino-benzene oxygen) phenyl] propane of 4 '-diaminodiphenyl ethers, 2,2-, bis- [4- (4- amino-benzene oxygen) phenyl] sulfones, Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-, bis- (4- amino-benzene oxygen) benzene of 1,4-, bis- (the 4- aminobenzene oxygen of 1,3- Base) benzene etc..
As the example for the diamines for other than 2 amino also including nitrogen-atoms, 2,4- diamino-diphenylamine, 2 can be enumerated, 4- diamino-pyridine, 2,4- diamino-s- triazine, 2,7 diaminodibenz of uran, 3,7- diaminophenothiazine, 2,5- diamino Base -1,3,4- thiadiazoles, 2,4- diamino -6- phenyl-s- triazine, N, N '-bis- (4- aminophenyl)-N- phenyl amines, N, N '-are bis- (4- aminophenyl)-N- methyl amine, 4,4 '-diamino-diphenyl ureas etc..
As the diamines of the pre-tilt angle for improving liquid crystal, 1- dodecyloxy -2,4- diaminobenzene, 1- 16 can be enumerated Bis- (4- aminophenyl) hexamethylenes of alkoxy -2,4- diaminobenzene, 1- octadecane epoxide -2,4- diaminobenzene, 1,1-, 2,2- are bis- [4- (4- amino-benzene oxygen) phenyl] octane, 4,4 '-diamino -3- dodecyl diphenyl oxides, 4- (4- is trans--n-heptyl hexamethylene Phenoxyl) -1,3- diaminobenzene, 4- (4- trans--pentyl cyclohexyl phenoxy group) -1,3- diaminobenzene, 4- trans--positive penta Base dicyclohexyl -3,5- diaminobenzoic acid ester etc..
In the case that R in general formula (7) is alkyl, the pure and mild tetrabasic carboxylic acids such as methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol can be made Two anhydride reactants and become after tetracarboxylic acid acid diesters with diamines dehydrating condensation and obtain, or make alcohol and polyamic acid dehydrating condensation and obtain ?.
<synthesis of polyamic acid or poly amic acid ester>
Particular polymers (A) or specific poly- are obtained by the reaction of tetracarboxylic dianhydride's ingredient and diamine component as described above In the case where closing object (B), easy be tetracarboxylic dianhydride's ingredient and diamine component are mixed in organic solvent make its react and The method for obtaining polyamic acid.In addition, can get poly amic acid ester by the method by the converting carboxylate groups of polyamic acid at ester.
As long as the organic solvent used when above-mentioned reaction can dissolve the solvent of the polyamic acid or poly amic acid ester that generate It is just not particularly limited, to enumerate its concrete example, then can enumerate n,N-Dimethylformamide, n,N-dimethylacetamide, N- N-methyl-2-2-pyrrolidone N, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, γ-Ding Nei Ester etc..These solvents can be used alone, and can also be used in mixed way.Even in addition, insoluble polyamic acid or polyamic acid The solvent of ester, as long as in the range of the polyamic acid of generation or poly amic acid ester will not be precipitated, it can also be with above-mentioned solvent It is used in mixed way.In addition, the moisture in organic solvent hinders polymerization reaction, and the polyamic acid or poly amic acid ester that generate can be made Hydrolysis, therefore it is preferable to use have been subjected to the organic solvent farthest dehydrated for organic solvent.
The method for mixing tetracarboxylic dianhydride's ingredient and diamine component in organic solvent enumerate stirring make diamines at It is dispersed or dissolved in solution obtained by organic solvent, directly add tetracarboxylic dianhydride's ingredient wherein or makes tetracarboxylic dianhydride Ingredient is dispersed or dissolved in the method added again after organic solvent；Have on the contrary tetracarboxylic dianhydride's ingredient to be dispersed or dissolved in The method of diamine component is added in solution obtained by solvent；Alternately add the method for tetracarboxylic dianhydride's ingredient and diamine component Deng, the present invention in can be any one of them method.In addition, tetracarboxylic dianhydride's ingredient or diamine component are made of multiple compounds When, the state that Multiple components can be pre-mixed is reacted, and can also successively be reacted respectively.
Temperature when tetracarboxylic dianhydride's ingredient and diamine component react in organic solvent is usually 0~150 DEG C, compared with It is well 5~100 DEG C, more preferably 10~80 DEG C.The faster completion of the higher polymerization reaction of temperature is unable to get sometimes but if excessively high The polymer (polyamic acid or polyester-imides) of high molecular weight.In addition, reaction can be carried out with arbitrary concentration, but if concentration It is too low, then it is difficult to obtain the polymer of high molecular weight, the viscosity of reaction solution is excessively high if excessive concentration, it is difficult to carry out uniform Stirring, therefore preferably 1~50 weight %, preferably 5~30 weight %.It can be carried out in initial reaction stage with high concentration, Then organic solvent is added again.
The ratio of tetracarboxylic dianhydride ingredient and diamine component used in the polymerization reaction of polyamic acid or poly amic acid ester It is preferably 1:0.8~1.2 with molar ratio computing.In addition, making polyamic acid obtained by diamine component excess or poly amic acid ester sometimes The coloring of solution can become larger, therefore while taking notice of the coloring of solution can be 1:0.8~1.Identical as common polycondensation reaction, this rubs You are than closer to 1:1, the molecular weight of resulting polyamic acid or poly amic acid ester is bigger.If polyamic acid or polyamic acid The molecular weight of ester is too small, then thus obtained painting film strength may be insufficient, on the contrary, if polyamic acid or polyamic acid The molecular weight of ester is excessive, then the viscosity of the aligning agent for liquid crystal thus manufactured may be excessively high, the operability and painting when film is formed The uniformity of film is poor.Therefore, polyamic acid or poly amic acid ester used in aligning agent for liquid crystal of the invention are (dense with reduced viscosity 30 DEG C are spent in 0.5dl/g, NMP) meter preferably 0.1~2.0, more preferably 0.2~1.5.
It is used molten when not wanting to make the polymerization containing polyamic acid or poly amic acid ester in aligning agent for liquid crystal of the invention There are when unreacted monomer component and impurity, carry out precipitating recycling and purifying when agent or in reaction solution.This method is preferable It is to put into the solution of polyamic acid or poly amic acid ester in the Weak solvent in stirring, carries out precipitating recycling.Polyamic acid or Poly amic acid ester precipitating recycling used in Weak solvent be not particularly limited, can enumerate methanol, acetone, hexane, butyl cellosolve, Heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene etc..The polyamide precipitated and putting into Weak solvent Acid or poly amic acid ester can carry out room temperature or heat drying after filtering, cleaning and recycling under normal pressure or reduced pressure, from And powder is made.If the operation that the powder is re-dissolved in good solvent and reprecipitation for repeating 2~10 times, can also Purify polyamic acid or poly amic acid ester.When can not thoroughly remove impurity by primary sedimentation reclaimer operation, preferably it is somebody's turn to do Purification procedures.As poor solvent at this time, if using 3 kinds of such as alcohols, ketone, hydro carbons etc. or more of poor solvent, Purification efficiency further increases, therefore preferably.
<aligning agent for liquid crystal>
Aligning agent for liquid crystal of the invention is as described above, contain above-mentioned particular polymers (A) and particular polymers (B).Pass through The aligning agent for liquid crystal for containing particular polymers (A) and particular polymers (B) as described above is made, liquid crystal aligning, resistance to can be obtained Frictional property, voltage retention performance and charge accumulation excellent, ionic impurity amount is few, transmissivity is high and the body as caused by light The small liquid crystal orientation film of the variation of product resistivity.
For why can generate said effect by composition of the invention and do not know, but think reason approximately as institute It states.Polyamic acid obtained by the dianhydride of the tetrabasic carboxylic acid indicated using formula (1) is difficult to carry out imidizate under the action of heat.Therefore Think, be coated with, be burnt into it is residual in liquid crystal orientation film prepared by the aligning agent for liquid crystal of the invention containing particular polymers (A) ingredient Deposit a large amount of carboxyls.Think that the carboxyl and the nitrogen-atoms of the diamine compound indicated from formula (5) or formula (6) interact, To which the migration of the unpaired electron on the nitrogen-atoms as caused by light is suppressed, as a result, liquid crystal orientation film by light guide The variation of the volume resistivity of cause is suppressed.Furthermore it is also believed that passing through the interaction of the carboxyl and nitrogen-atoms, volume resistance Rate itself can also reduce.
In turn, there is formula containing such particular polymers (A) and liquid crystal aligning excellent conduct simultaneously by being made (7) indicate structural unit polyimide precursor particular polymers (B) aligning agent for liquid crystal, can obtain liquid crystal aligning, Rub resistance, voltage retention performance and charge accumulation excellent, ionic impurity amount is few, transmissivity is high and as caused by light The small liquid crystal orientation film of the variation of volume resistivity.
The form of the aligning agent for liquid crystal of invention described below is containing particular polymers (A) and particular polymers (B) Coating fluid, but as long as uniform film can be formed on substrate, then aligning agent for liquid crystal of the invention is also possible to other forms.
The coating fluid containing particular polymers (A) and particular polymers (B) is made, it both can be by polyamic acid or polyamides The reaction solution of amino acid ester directly mixes, after the polyamic acid of solid content or poly amic acid ester can also being dissolved in organic solvent It is mixed.
As the organic solvent, as long as the solvent of contained polymer (polyamic acid or polyester-imides) can be dissolved It is just not particularly limited, to enumerate its concrete example, then can enumerate n,N-Dimethylformamide, n,N-dimethylacetamide, N- N-methyl-2-2-pyrrolidone N, N- methyl caprolactam, 2-Pyrrolidone, N- ethyl pyrrolidone, n-vinyl pyrrolidone, two First sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton etc., these solvents can be used it is a kind of can also be more Kind is used in mixed way.
In addition, even if the solvent of polymer can not be dissolved when being single use, as long as the range that will not be precipitated in polymer It is interior, then it can be mixed with aligning agent for liquid crystal of the invention.It is especially known by moderately mixing ethyl cellosolve, the molten fibre of butyl Agent, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1- methoxy-2-propanol, 1- ethyoxyl -2- Propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- Monomethyl ether -2- acetic acid esters, propylene glycol -1- list ethylether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygroup) propyl alcohol, Methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc. have the solvent of low surface tension, can make Painting film uniformity when being coated on substrate improves, therefore these solvents can be also suitably used for aligning agent for liquid crystal of the invention.
Aligning agent for liquid crystal of the invention can according to liquid crystal orientation film to be formed thickness setting and suitably change Solid component concentration, solid component concentration are preferably 1~10 weight %.If being difficult to form uniform and nothing less than 1 weight % The film of defect, if being higher than 10 weight %, the storage stability of solution is deteriorated sometimes.
In addition to this, in order to improve the adaptation of film and substrate, silicon can also be added in aligning agent for liquid crystal of the invention The additives such as alkane coupling agent, or other polymer other than particular polymers (A) and particular polymers (B) can be added.
The aligning agent for liquid crystal of the invention obtained as described above can be coated on substrate after filtering as needed, dry, Be burnt into and film be made, by the coated surface carry out friction or light irradiation etc. orientation process, can be used as liquid crystal orientation film, or It can be used as liquid crystal orientation film without orientation process.
At this moment, as long as the transparent high substrate of substrate used is then limited without special, glass substrate, third can be used Plastic bases such as olefin(e) acid substrate or polycarbonate substrate etc., from the angle for simplifying production technology, it is preferable to use being formed with The substrate of ITO (tin indium oxide (Indeium Tin Oxide)) electrode for liquid crystal drive etc..In addition, reflective liquid crystal is aobvious Show in element, the opaque substance such as silicon wafer can be used, but be only limitted to the substrate of side, electrode at this time also can be used The reflectorized materials such as aluminium.
As the coating method of aligning agent for liquid crystal, spin-coating method, print process, ink-jet method etc. can be enumerated, but in terms of productivity Consider, hectographic printing method is industrially widely used, this method can be also suitably used for aligning agent for liquid crystal of the invention.
Drying process after coating of liquid crystalline alignment agent is not required, but arrives the time before firing after coating to each piece In the case where not being burnt into immediately after being all not fixed or be coated with for substrate, drying process is preferably included.As long as the drying makes Solvent evaporation reaches the degree that film shape will not be deformed by reasons such as the carryings of substrate, to its drying means without special It limits.The following method can specifically be enumerated, make its dry 0.5 in 50~150 DEG C, more preferably 80~120 DEG C of heating plate~ 30 minutes, more preferably 1~5 minute.
Firing after being coated with aligning agent for liquid crystal and drying as needed can be under the arbitrary temp in 100~350 DEG C It carries out, but preferably 150~300 DEG C, more preferably 200 DEG C~250 DEG C.When in aligning agent for liquid crystal including polyamic acid, by polyamides Amino acid changes to the conversion ratio of polyimide conversion with the firing temperature, but aligning agent for liquid crystal of the invention is not necessarily to 100% acyl Imidization.Preferably with high 10 DEG C of heat treatment temperature or more than sealant cures necessary in liquid crystal cell manufacturing process etc. Temperature be burnt into.
It is unfavorable in the consumption concerned power of liquid crystal display element if the thickness of the film after firing is blocked up, if mistake Thin, then the reliability of liquid crystal display element reduces sometimes, therefore is 5~300nm, preferably 10~100nm.
There is excellent characteristic by the liquid crystal orientation film that aligning agent for liquid crystal of the invention obtains as described above, therefore can be used as TN (twisted nematic (Twisted Nematic)), STN (super twisted nematic (Super Twisted Nematic)), The liquid crystal display element and ferroelectricity of TFT, horizontal electric field type etc. and the liquid crystal aligning used for liquid crystal display element of anti-ferroelectricity Film.It is especially suitable as being easy to happen the used for liquid crystal display element of the horizontal electric field type of the burn-in as caused by liquid crystal aligning Liquid crystal orientation film.
<liquid crystal display element>
Liquid crystal display element of the invention is to obtain band liquid crystal aligning by aligning agent for liquid crystal of the invention by the above method After the substrate of film, the liquid crystal display element that liquid crystal cell is formed is manufactured by well known method.If lifting a manufacture liquid If the example of Jingjing born of the same parents, following method is usually used: a pair of of the substrate for being formed with liquid crystal orientation film is pressed from both sides across 1~30 μm, preferably 2~10 μm of spacer, according to frictional direction is arranged at the requirement at any angle in 0~270 °, with sealing Agent is fixed by periphery, seals after injecting liquid crystal.The method of enclosed liquid crystal is not particularly limited, can be enumerated to liquid obtained Jingjing is intracellular depressurized after inject the dropping method etc. being sealed after the vacuum method of liquid crystal, the liquid crystal that drips.
The liquid crystal aligning of the liquid crystal display element made from aligning agent for liquid crystal of the invention is excellent as described above, and has Excellent electrical characteristics, therefore can be made into the liquid crystal display device of the reduction and burn-in that are not susceptible to contrast, suitable for TN, Liquid crystal display element of STN, TFT, horizontal electric field type etc. etc. uses the liquid crystal display element of the various modes of nematic crystal.This Outside, by selecting used liquid crystal, it can also be used to the liquid crystal display element of ferroelectricity and anti-ferroelectricity.These liquid crystal displays member In part, particularly preferred for the liquid crystal display element for the horizontal electric field type for being easy to happen the burn-in as caused by liquid crystal aligning.
Embodiment
Hereinafter, enumerating embodiment, the present invention will be described in more detail, but the present invention is not limited to this.Following implementations Abbreviation used in example and comparative example is as described below.
DA-1:4,4'- diamino-diphenylamine
DA-2:4,4'- diaminodiphenyl-methane
Bis- (4- amino-benzene oxygen) pentanes of DA-3:1,5-
CA-1:1,2,3,4- cyclobutane tetracarboxylic dianhydride
CA-2: two rings [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride
CA-3: pyromellitic acid anhydride
CA-4:3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride
[synthesis example 1]
In the 200ml four-hole boiling flask with agitating device and nitrogen ingress pipe be added 7.97g (40.0mmol) DA-1 and The DA-2 of 1.98g (10.0mmol), adds the n-methyl-2-pyrrolidone of 72.34g, and stirring while supplying nitrogen makes It is dissolved.The CA-1 that 6.86g (35.0mmol) is added while stirring the diamine solution is stirred 30 minutes under water temperature.So Afterwards, the CA-2 that 3.13g (12.5mmol) is added while agitating solution adds n-methyl-2-pyrrolidone so that solid Constituent concentration reaches 20 mass %, is stirred 3 hours at 50 DEG C with oil bath in a nitrogen atmosphere.Then, N- methyl -2- is added Pyrrolidones stir at 50 DEG C with oil bath one late so that solid component concentration reaches 11 mass % in a nitrogen atmosphere, is obtained The solution of polyamic acid.The polyamic acid solution is confirmed with E type viscosimeter (Toki Sangyo Co., Ltd. (Dong Ji industry society) system) Viscosity at 25 DEG C is 191mPas.
The addition that the n-methyl-2-pyrrolidone, 2.20g of 5.3g are added in the polyamic acid solution of 20.0g has 1.0 The n-methyl-2-pyrrolidone solution of the 3-aminopropyltriethoxysilane of weight % and the butyl cellosolve of 9.17g, obtain The polyamic acid solution (A1) for being 6.0 mass % to solid component concentration.
[synthesis example 2]
In the 300ml four-hole boiling flask with agitating device and nitrogen ingress pipe be added 7.49g (37.6mmol) DA-1 and The DA-2 of 1.86g (9.4mmol), adds the n-methyl-2-pyrrolidone of 72.08g, and stirring while supplying nitrogen makes it Dissolution.The CA-1 that 2.12g (10.8mmol) is added while stirring the diamine solution is stirred 30 minutes under water temperature.Then, The CA-2 that 8.82g (35.3mmol) is added while agitating solution adds n-methyl-2-pyrrolidone so that solid component Concentration reaches 20 mass %, is stirred 3 hours at 50 DEG C with oil bath in a nitrogen atmosphere.Then, N- methyl -2- pyrroles is added Alkanone stir at 50 DEG C with oil bath one late so that solid component concentration reaches 11 mass % in a nitrogen atmosphere, obtains polyamides The solution of amino acid.Confirm that viscosity of the polyamic acid solution at 25 DEG C is with E type viscosimeter (Toki Sangyo Co., Ltd.'s system) 207mPa·s。
The addition that the n-methyl-2-pyrrolidone, 2.20g of 6.25g are added in the polyamic acid solution of 20.0g has The n-methyl-2-pyrrolidone solution of the 3-aminopropyltriethoxysilane of 1.0 weight % and the butyl cellosolve of 9.48g, Obtain the polyamic acid solution (A2) that solid component concentration is 5.8 mass %.
[synthesis example 3]
In the 300ml four-hole boiling flask with agitating device and nitrogen ingress pipe be added 8.93g (44.8mmol) DA-1 and The DA-2 of 2.22g (11.2mmol), adds the n-methyl-2-pyrrolidone of 108.54g, and stirring while supplying nitrogen makes It is dissolved.The CA-2 that 13.52g (54.0mmol) is added while stirring the diamine solution adds N- methyl -2- pyrrolidines Ketone stir at 50 DEG C with oil bath one late so that solid component concentration reaches 12 mass % in a nitrogen atmosphere, obtains polyamide The solution of acid.Confirm that viscosity of the polyamic acid solution at 25 DEG C is with E type viscosimeter (Toki Sangyo Co., Ltd.'s system) 153mPa·s。
The addition that the n-methyl-2-pyrrolidone, 2.32g of 10.92g are added in the polyamic acid solution of 16.8g has The molten fibre of butyl of the n-methyl-2-pyrrolidone solution and 10.01g of the 3-aminopropyltriethoxysilane of 1.0 weight % Agent obtains the polyamic acid solution (A3) that solid component concentration is 5.8 mass %.
[synthesis example 4]
The n-methyl-2-pyrrolidone of 80.0g is added in the 100ml four-hole boiling flask with agitating device and nitrogen ingress pipe With the DA-1 of 3.83g (28mmol), stirred to dissolve while supplying nitrogen.It is added while stirring the diamine solution The CA-1 of 3.30g (17mmol) is stirred 2.5 hours at 10~15 DEG C.Then, the DA-2 for adding 0.95g (4.8mmol), in After being stirred 0.5 hour at 10~15 DEG C, the CA-4 of 1.44g (4.8mmol) is added, stirs 5 hours, is gathered at 20~25 DEG C The solution of amic acid.Viscosity of the polyamic acid solution at 25 DEG C is confirmed with E type viscosimeter (Toki Sangyo Co., Ltd.'s system) For 168mPas.
The addition that the n-methyl-2-pyrrolidone, 5.0g of 1.66g are added in the polyamic acid solution of 50.0g has 1.0 The addition of the n-methyl-2-pyrrolidone solution, 10g of the 3-aminopropyltriethoxysilane of weight % has 5.0 weight %'s The n-methyl-2-pyrrolidone solution of 3- phenyl amino propyl trimethoxy silane and the butyl cellosolve of 16.67g, consolidate Body constituent concentration is the polyamic acid solution (A4) of 6.0 mass %.
[synthesis example 5]
In the 100ml four-hole boiling flask with agitating device and nitrogen ingress pipe be added 6.87g (24mmol) DA-3 and The n-methyl-2-pyrrolidone of 80.0g stirs to dissolve while supplying nitrogen.. while stirring the diamine solution The CA-3 for adding 5.03g (23mmol), adds n-methyl-2-pyrrolidone so that solid component concentration reaches 12 mass %, An evening is stirred at 50 DEG C with oil bath, obtains the solution of polyamic acid.Confirmed with E type viscosimeter (Toki Sangyo Co., Ltd.'s system) Viscosity of the polyamic acid solution at 25 DEG C is 525mPas.
The addition that the n-methyl-2-pyrrolidone, 12g of 18g are added in the polyamic acid solution of 50g has 5.0 weights The n-methyl-2-pyrrolidone solution of the 3- phenyl amino propyl trimethoxy silane of % and the butyl cellosolve of 20g are measured, is obtained The polyamic acid solution (B1) for being 6.0 mass % to solid component concentration.
[embodiment 1]
By polyamic acid solution obtained in synthesis example (A1) and polyamic acid solution (B1) with weight ratio (A1)/(B1)= 80/20 condition mixing, obtains aligning agent for liquid crystal of the invention (C1).
[embodiment 2]
By polyamic acid solution obtained in synthesis example (A2) and polyamic acid solution (B1) with weight ratio (A2)/(B1)= 80/20 condition mixing, obtains aligning agent for liquid crystal of the invention (C2).
[embodiment 3]
By polyamic acid solution obtained in synthesis example (A3) and polyamic acid solution (B1) with weight ratio (A3)/(B1)= 80/20 condition mixing, obtains aligning agent for liquid crystal of the invention (C3).
[comparative example 1]
By polyamic acid solution obtained in synthesis example (A4) and polyamic acid solution (B1) with weight ratio (A4)/(B1)= 80/20 condition mixing, obtains aligning agent for liquid crystal of the invention (C4).
Using aligning agent for liquid crystal obtained in embodiment 1, embodiment 2, embodiment 3, comparative example 1, pass through following methods point Sample, measurement liquid crystal aligning, volume resistivity, voltage retention, ion concentration and transmissivity Zhi Zao not evaluated.Acquired results Shown in table 1~3.
<manufacture of liquid crystal cell>
It is spun on the glass substrate with transparent electrode after resulting aligning agent for liquid crystal is filtered with 1.0 μm of filters, 70 DEG C heating plate on after dry 2 minutes, be burnt into 15 minutes in 230 DEG C, obtain the film of film thickness 100nm.With rayon cloth to this Polyimide film is rubbed after (roller diameter 120mm, revolving speed 1000rpm, movement speed 20mm/sec, intrusion 0.4mm), pure The ultrasonic irradiation that 1 minute is carried out in water, it is 10 minutes dry in 80 DEG C.In Examples 1 to 3 and comparative example 1, in the friction treatment In do not generate scar or dust because film is scratched, and also the removing of film, rub resistance be not excellent.Prepare 2 pieces to have The substrate of above-mentioned liquid crystal orientation film is arranged after 4 μm of spacer, with 2 pieces of substrates in the liquid crystal alignment film surface of one piece of substrate The antiparallel condition of frictional direction by 2 pieces of substrate in combination, surrounding is sealed, but leave liquid crystal injecting port, is made between structure cell The negative crystal born of the same parents for being 4 μm every (cell gap).Vacuum injection liquid crystal (MLC-2041, the Merck & Co., Inc. into the structure cell at normal temperature System), inlet is sealed, antiparallel type liquid crystal cell is made.
<liquid crystal aligning>
No orientation defect is denoted as " good ", will had by the state of orientation that the liquid crystal cell is observed with polarizing microscope Orientation defect is denoted as " bad ".
<measurement of volume resistivity>
It is spun on the glass substrate with ito transparent electrode after resulting aligning agent for liquid crystal is filtered with 0.2 μm of filter, It is dry in 80 DEG C of heating plate to be burnt into 20 minutes in 220 DEG C after five minutes, form the film (liquid crystal orientation film) of film thickness 220nm. Across mask in the film coated surface AM aluminum metallization, the upper electrode (aluminium electrode) of 1.0mm φ is formed, measures and uses as volume resistivity Sample.The voltage for applying 10V between the ITO electrode and aluminium electrode of the sample, measures the electricity from applying voltage after 180 seconds Flow valuve calculates volume resistivity according to the measured value of the value and electrode area, film thickness.In addition, in advance under sample substrate Side's setting LED backlight, is measured in the case where turning on light and under turning off the light respectively, measures the variation of the volume resistivity as caused by light. Value when value when LED is turned off the light is turned on light divided by LED, acquired results are denoted as " ◎ " if it is 1.0~2.0, if it is 2.0~ 3.0 are denoted as "○", in addition to this be denoted as "×".
<measurement of voltage retention>
Using liquid crystal cell obtained in the same manner as above-mentioned<manufacture of liquid crystal cell>, Toyo Corp. is used The 6254 type liquid crystal evaluation of physical property devices of (Dongyang テ Network ニ カ society) system are measured.With 60 μ sec. of application time, interval After the condition of 100msec. applies the voltage of 1V, measures the voltage retention from applying and releasing after 100msec. and (apply solution certainly Except rise 100msec. after voltage/application it is rigid after voltage × 100%).When measurement, the temperature of liquid crystal cell is set as 23 DEG C and 100 DEG C be measured.
<measurement of ion concentration>
Using liquid crystal cell obtained in the same manner as above-mentioned<manufacture of liquid crystal cell>, Toyo Corp. is used The 6254 type liquid crystal evaluation of physical property devices of (Dongyang テ Network ニ カ society) system are measured.When measurement, apply the three of 10V, 0.01Hz Angle wave, calculate gained waveform with the comparable area of ion concentration, as ion concentration.When measurement, by liquid crystal cell Temperature is set as 23 DEG C and 60 DEG C and is measured.
<measurement of transmissivity>
It is spun on quartz base plate after aligning agent for liquid crystal is filtered with 1.0 μm of filters, it is 2 points dry in 70 DEG C of heating plate Zhong Hou is burnt into 15 minutes in 230 DEG C, obtains the film of film thickness 100nm.Using the sample, with Shimadzu Seisakusho Ltd., (Shimadzu is made Institute) system UV-3100PC self-recording spectrophotometer be measured.
[table 1]
[table 2]
[table 3]
By these results it has been confirmed that by using aligning agent for liquid crystal of the invention, liquid crystal aligning, rub resistance can be obtained Property excellent, voltage retention performance is high, charge accumulation is reduced, ion concentration is low, transmissivity is high and the volume resistivity as caused by light The small liquid crystal orientation film of variation.In addition, having the liquid crystal display of the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention The liquid crystal aligning of element is excellent, and has excellent electrical characteristics, therefore can be made into and be not susceptible to show bad, contrast drop Low and burn-in liquid crystal display device.

Claims (6)

1. aligning agent for liquid crystal contains following particular polymers (A) and particular polymers (B)；
Particular polymers (A): polyamic acid obtained by reacting tetracarboxylic dianhydride's ingredient and diamine component, the tetracarboxylic dianhydride The dianhydride of the compound for the tetrabasic carboxylic acid that the dianhydride and formula (3) for the tetrabasic carboxylic acid that ingredient is indicated by following formula (1) indicate is constituted, the diamines At least one of the diamine compound that ingredient contains following formula (5) and (6) indicate；
[changing 1]
In formula (3), R1、R2、R3、R4Separately indicate the alkyl of hydrogen atom or carbon number 1~3；
[changing 2]
In formula (5) and (6), the one or more of arbitrary hydrogen atom on phenyl ring can be by 1 valence organic group other than primary amino group Group replaces；
Particular polymers (B): the polyimide precursor with the structural unit that following formula (7) indicate；
[changing 3]
In formula (7), R indicates that hydrogen atom or alkyl, Y indicate that 4 valence organic groups, X indicate divalent organic group, and the 10~100 of X Mole % is divalent organic group with any one of following formula (8)~(10) in structure or to phenylene；
[changing 4]
In formula (8), m1For 2~18 integer；
[changing 5]
In formula (9), the one or more of the arbitrary hydrogen atom on phenyl ring can be taken by 1 valence organic group other than primary amino group Generation, m2For 1~8 integer；
[changing 6]
In formula (10), the one or more of the arbitrary hydrogen atom on phenyl ring can be taken by 1 valence organic group other than primary amino group Generation, m3For 1~4 integer.
2. aligning agent for liquid crystal as described in claim 1, which is characterized in that tetracarboxylic dianhydride's ingredient in particular polymers (A) The change for the tetrabasic carboxylic acid that the dianhydride of the tetrabasic carboxylic acid indicated by the formula (1) of 10~100 moles of % and the formula (3) of 0~90 mole of % indicate The dianhydride for closing object is constituted.
3. aligning agent for liquid crystal as claimed in claim 2, which is characterized in that tetracarboxylic dianhydride's ingredient in particular polymers (A) The tetrabasic carboxylic acid for being selected from formula (3) and indicating of the dianhydride of the tetrabasic carboxylic acid indicated by the formula (1) of 10~90 moles of % and 10~90 moles of % At least one compound dianhydride constitute.
4. aligning agent for liquid crystal as described in claim 1, which is characterized in that 20~100 moles of % of the Y of formula (7) are that have virtue 4 valence organic groups of fragrant race's structure.
5. liquid crystal orientation film, which is characterized in that obtained by using aligning agent for liquid crystal according to any one of claims 1 to 4.
6. liquid crystal display element, which is characterized in that have liquid crystal orientation film described in claim 5.
CN201280043903.7A 2011-07-12 2012-07-10 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element Active CN103797408B (en)

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