CN103797408A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

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

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CN103797408A
CN103797408A CN201280043903.7A CN201280043903A CN103797408A CN 103797408 A CN103797408 A CN 103797408A CN 201280043903 A CN201280043903 A CN 201280043903A CN 103797408 A CN103797408 A CN 103797408A
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liquid crystal
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dianhydride
aligning agent
particular polymers
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CN103797408B (en
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新津新平
小野豪
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Nissan Chemical Corp
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    • 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
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    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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Abstract

A liquid crystal aligning agent which contains a specific polymer (A) and a specific polymer (B) described below. Specific polymer (A): a polyamic acid which is obtained by reacting a tetracarboxylic acid dianhydride component that contains bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid dianhydride with a diamine component that contains at least one diamine compound as typified by 4,4'-diaminodiphenyl amine and 3,6-diaminocarbazole. Specific polymer (B): a polyimide precursor which has a structural unit represented by formula (7). (In formula (7), R represents a hydrogen atom or an alkyl group; Y represents a tetravalent organic group; and X represents a divalent organic group, with 10-100% by mole of X being a divalent organic group having one of the moieties represented by formulae (8)-(10) in the structure or a paraphenylene group.) (In formula (8), m1 represents an integer of 2-18.) (In formula (9), one or more arbitrary hydrogen atoms on the benzene rings may be substituted by monovalent organic groups other than primary amino groups; and m2 represents an integer of 1-8.) (In formula (10), one or more arbitrary hydrogen atoms on the benzene rings may be substituted by monovalent organic groups other than primary amino groups; and m3 represents an integer of 1-4.)

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
Technical field
Aligning agent for liquid crystal, the liquid crystal orientation film using while the present invention relates to form liquid crystal orientation film and the liquid crystal display cells that utilizes it.
Background technology
Now, liquid crystal display cells is widely used as display device.Liquid crystal orientation film as the component parts of liquid crystal display cells is the film that makes liquid crystal evenly distributed, in the inadequate situation of liquid crystal aligning, easily causes to be called as to show that the demonstration of inequality and after image is bad.Show that bad generation is sometimes relevant with the ionic impurity in liquid crystal, as the method that reduces this impurity, proposed as the scheme of patent documentation 1.
In addition,, in liquid crystal orientation film, conventionally implement to use cloth to wipe with to wipe the orientation process that is called friction on polymeric membrane surface.But, if the rub resistance of liquid crystal orientation film is not enough, causes film to be scratched and produce scar and dust, or film itself peels off, the display quality of liquid crystal display cells is reduced.Therefore, require liquid crystal orientation film to there is higher rub resistance, proposed the technical scheme as shown in patent documentation 2～5.
Further, in order to obtain the liquid crystal display cells of high display quality, exhibit high brilliance is also very important.Therefore, also require liquid crystal orientation film to there is high-transmission rate.
On the other hand, if the specific insulation of liquid crystal orientation film is high, there is the problem such as cancellation spended time that electric charge is difficult to decay, after image of accumulating.As shortening the method for after image cancellation time, the method for the alignment films that use specific insulation as patent documentation 6 is low is proposed.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2002-323701 communique
Patent documentation 2: Japanese patent laid-open 7-120769 communique
Patent documentation 3: Japanese patent laid-open 9-146100 communique
Patent documentation 4: Japanese Patent Laid-Open 2008-90297 communique
Patent documentation 5: Japanese patent laid-open 9-258229 communique
Patent documentation 6: No. 2004/053583rd, International Publication
Summary of the invention
Invent technical matters to be solved
But, in recent years, in the evolution of the high-quality of liquid crystal display cells, have the tendency that uses powerful backlight.Therefore, not only the low this point of the specific insulation of liquid crystal orientation film is very important, and can not cause because of light the specific insulation this point that changes also very important.For example, in the liquid crystal orientation film in liquid crystal display cells, due to the existence of wiring and black matrix etc., exist sometimes light compared with other parts to be more difficult to the part being irradiated to.If the specific insulation of liquid crystal orientation film changes because of light, element entirety cannot demonstrate uniform after image characteristic, causes people to observe and is called as after image and shows that uneven demonstration is bad.
The present invention is the invention completing in view of the above fact, and it provides a kind of can obtain liquid crystal aligning, rub resistance, voltage retention performance and electric charge Accumulation excellence, ionic impurity amount is few, transmissivity is high and the liquid crystal display cells of reduction, the burning screen of demonstration etc. of bad, contrast occurs to show for the aligning agent for liquid crystal of the liquid crystal orientation film that the variation of the specific insulation that caused by photoconduction is little, liquid crystal orientation film and being difficult for.
The technical scheme that technical solution problem adopts
The inventor has carried out conscientiously research in order to achieve the above object, found that, utilizes the aligning agent for liquid crystal that contains particular polymers (A) and particular polymers (B), can achieve the above object.
In sum, the present invention is using following content as technology contents.
1. an aligning agent for liquid crystal, it contains following particular polymers (A) and particular polymers (B);
Particular polymers (A): make the reaction of tetracarboxylic dianhydride's composition and two amine components and polyamic acid, the dianhydride of the tetrabasic carboxylic acid that described tetracarboxylic dianhydride's composition contains following formula (1) expression, at least one in the diamine compound that described two amine components contain following formula (5) and (6) expression;
[changing 1]
Figure BDA0000474775050000021
[changing 2]
(in formula (5) and (6), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical.)
Particular polymers (B): the polyimide precursor with the structural unit of following formula (7) expression;
[changing 3]
Figure BDA0000474775050000032
(in formula (7), R represents hydrogen atom or alkyl, Y represents 4 valency organic groups, and X represents divalent organic group, and 10～100 % by mole of X be in structure, have in following formula (8)～(10) any divalent organic group or to phenylene.)
[changing 4]
Figure BDA0000474775050000033
(in formula (8), m 1it is 2～18 integer.)
[changing 5]
Figure BDA0000474775050000034
(in formula (9), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical, m 2it is 1～8 integer.)
[changing 6]
Figure BDA0000474775050000035
(in formula (10), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical, m 3it is 1～4 integer.)
Aligning agent for liquid crystal described in 2.1, wherein, the tetracarboxylic dianhydride's composition in particular polymers (A) by following formula (1) represent tetrabasic carboxylic acid dianhydride and be selected from following formula (2)～(4) represent tetrabasic carboxylic acid at least one compound dianhydride form;
[changing 7]
Figure BDA0000474775050000041
(in formula (3), R 1, R 2, R 3, R 4represent independently respectively the alkyl of hydrogen atom or carbon number 1～3.)
Aligning agent for liquid crystal described in 3.2, the dianhydride of at least one compound of the tetrabasic carboxylic acid that the dianhydride of the tetrabasic carboxylic acid that wherein, the tetracarboxylic dianhydride's composition in particular polymers (A) is represented by the formula (1) of 10～100 % by mole and the formula that is selected from (2)～(4) of 0～90 % by mole represent forms.
Aligning agent for liquid crystal described in 4.3, the dianhydride of the tetrabasic carboxylic acid that the dianhydride of the tetrabasic carboxylic acid that wherein, the tetracarboxylic dianhydride's composition in particular polymers (A) is represented by the formula (1) of 10～100 % by mole and the formula (3) of 0～90 % by mole represent forms.
Aligning agent for liquid crystal in 5.1～4 described in any one, wherein, 20～100 % by mole of the Y of formula (7) is the 4 valency organic groups with aromatic structure.
6. a liquid crystal orientation film, it is by using the aligning agent for liquid crystal described in any one in 1～5 to obtain.
7. a liquid crystal display cells, it has the liquid crystal orientation film described in 1～6.
The effect of invention
The aligning agent for liquid crystal of the application of the invention, can obtain liquid crystal aligning, rub resistance, voltage retention performance and electric charge Accumulation excellence, ionic impurity amount is few, transmissivity is high and the little liquid crystal orientation film of variation of the specific insulation that caused by photoconduction, and the liquid crystal display cells of high-quality can be provided.
Embodiment
Below, the present invention is described in detail.
Aligning agent for liquid crystal of the present invention is the composition that is used to form liquid crystal orientation film, it is characterized in that, contain tetracarboxylic dianhydride's composition and two amine components are reacted and the polyamic acid (below also referred to as particular polymers (A)) obtaining and the polyimide precursor (below also referred to as particular polymers (B)) with the structural unit of general formula (7) expression, the dianhydride of the tetrabasic carboxylic acid that described tetracarboxylic dianhydride's composition contains following formula (1) expression, at least one in the diamine compound that described two amine components contain following formula (5) and (6) expression.
[changing 8]
Figure BDA0000474775050000051
(in formula (5) and (6), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical.)
[changing 10]
Figure BDA0000474775050000052
(in general formula (7), R represents hydrogen atom or alkyl, Y represents 4 valency organic groups, and X represents divalent organic group, and 10～100 % by mole of X be in structure, have in following formula (8)～(10) any divalent organic group or to phenylene.)
[changing 11]
(in formula (8), m 1it is 2～18 integer.)
[changing 12]
Figure BDA0000474775050000054
(in formula (9), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical, m 2it is 1～8 integer.)
[changing 13]
(in formula (10), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical, m 3it is 1～4 integer.)
About the ratio of particular polymers (A) and particular polymers (B), with respect to the total amount of particular polymers (A) and particular polymers (B), preferably 10～95 % by weight of particular polymers (A), more preferably 60～90 % by weight.Particular polymers (A) is if very few, and the electric charge Accumulation of liquid crystal orientation film and rub resistance are deteriorated sometimes, and particular polymers (B) is if very few, and liquid crystal aligning is deteriorated sometimes.Particular polymers (A) and particular polymers (B) contained in aligning agent for liquid crystal of the present invention both can be respectively a kind of, can be also two or more.
< particular polymers (A) >
The dianhydride of the tetrabasic carboxylic acid that the tetracarboxylic dianhydride's composition using in the manufacture of particular polymers (A) contains following formula (1) expression.
[changing 14]
Figure BDA0000474775050000062
Particularly, be better that the dianhydride of the tetrabasic carboxylic acid that represented by following formula (1) of tetracarboxylic dianhydride's composition in particular polymers (A) and the dianhydride that is selected from least one compound of the tetrabasic carboxylic acid that following formula (2)～(4) represent form.
[changing 15]
Figure BDA0000474775050000063
(in formula (2), R 1, R 2, R 3, R 4represent independently respectively the alkyl of hydrogen atom or carbon number 1～3.)
As the ratio of components of the preferred tetracarboxylic dianhydride's composition in particular polymers (A), the dianhydride of the tetrabasic carboxylic acid that formula (1) represents is 10～100 % by mole of tetracarboxylic dianhydride's composition entirety, and the dianhydride that is selected from least one compound of the tetrabasic carboxylic acid of formula (2)～(4) expression is 0～90 % by mole of tetracarboxylic dianhydride's composition entirety.The dianhydride that is better the tetrabasic carboxylic acid of formula (1) expression is 10～90 % by mole of tetracarboxylic dianhydride's composition entirety, and the dianhydride that is selected from least one compound of the tetrabasic carboxylic acid of formula (2)～(4) expression is 10～90 % by mole of tetracarboxylic dianhydride's composition entirety.The dianhydride that is more preferably the tetrabasic carboxylic acid of formula (1) expression is 20～80 % by mole of tetracarboxylic dianhydride's composition entirety, and the dianhydride that is selected from least one compound of the tetrabasic carboxylic acid of formula (2)～(4) expression is 20～80 % by mole of tetracarboxylic dianhydride's composition entirety.The dianhydride of the tetrabasic carboxylic acid that particularly preferably formula (1) represents is 25～75 % by mole of tetracarboxylic dianhydride's composition entirety, and the dianhydride that is selected from least one compound of the tetrabasic carboxylic acid of formula (2)～(4) expression is 25～75 % by mole of tetracarboxylic dianhydride's composition entirety.
From the angle of liquid crystal aligning, the combination of preferred tetracarboxylic dianhydride's composition is the dianhydride of tetrabasic carboxylic acid and the dianhydride of the tetrabasic carboxylic acid that formula (3) represents that formula (1) represents.
At least one in the diamine compound that the diamine compound that two amine components that use in the manufacture of particular polymers (A) contain following formula (5) expression and following formula (6) represent.
[changing 16]
(in formula (5) and (6), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical.)
From the angle of liquid crystal aligning, formula (5) is better the diamines with the hexichol amido of 4,4 ' bonding, and from the angle of liquid crystal aligning, formula (6) is better the diamines with the carbazyl of 3,6 bondings.
In above formula (5) or (6), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical.As this 1 valency organic group, can exemplify the alkyl of carbon number 1～20, the thiazolinyl of carbon number 2～20, the alkoxy of carbon number 1～20, carbon number 1～20 containing fluoroalkyl, the fluorine-containing thiazolinyl of carbon number 2～20, the fluoroalkoxy of carbon number 1～20, cyclohexyl, phenyl, fluorine atom and by their group constituting etc., from the angle of liquid crystal aligning, it is better the alkyl that is selected from carbon number 1～4, the thiazolinyl of carbon number 2～4, the alkoxy of carbon number 1～4, carbon number 1～4 containing fluoroalkyl, the fluorine-containing thiazolinyl of carbon number 2～4, 1 valency organic group of the fluoroalkoxy of carbon number 1～4.As the structure of preferred formula (5) and (6), be that hydrogen atom on phenyl ring is without the structure replacing.
In particular polymers (A), the total amount of the diamine compound that the diamine compound that formula (5) represents and formula (6) represent is with respect to preferably 10～100 % by mole of the ratios of whole two amine components, more preferably 60～100 % by mole.Be more than 10 % by mole by making the diamine compound of formula (5) expression and the total amount of the diamine compound that formula (6) represents, can effectively reduce specific insulation, easily obtain the little polyamic acid of variation of the low and specific insulation that caused by photoconduction of specific insulation, and voltage retention performance is good, and easily give liquid crystal orientation film with excellent electric charge Accumulation and rub resistance.
In the diamine compound that formula (5) or formula (6) represent, from the angle of the liquid crystal aligning with the reactive of tetracarboxylic dianhydride and while making liquid crystal orientation film, particularly preferably 4,4 '-diamino-diphenylamine, 3,6-diamido carbazole.
In particular polymers (A), except the diamine compound of formula (5) or formula (6) expression, not damaging in the scope of effect of the present invention, also can contain other diamine compound beyond the diamine compound that formula (5) or formula (6) represent.As other diamine compound, can exemplify the diamine compound that following formula (15) represents.Its concrete example is as follows, but is not limited to this.
[changing 17]
H 2N-A-NH 2 (15)
There is the diamine compound of formula (15) expression of nitrogen-atoms as A, can exemplify 2, 3-diamino-pyridine, 2, 6-diamino-pyridine, 3, 4-diamino-pyridine, 2, 4-di-amino-pyrimidine, 2, 4-diamido-6-hydroxy pyrimidine, 2, 4-diaminostilbene, 3, 5-triazine, 2, 4-diaminostilbene, 3, 5-triazine, 2, 4-diamido-6-isopropoxy-1, 3, 5-triazine, 2, 4-diamido-6-methoxyl-1, 3, 5-triazine, 2, 4-diamido-6-phenyl-1, 3, 5-triazine, 2, 6-diaminopurine, 1, two (3-aminopropyl) piperazines of 4-, 2, 4-diamido-5-phenyl thiazole, 3, 5-diaminostilbene, 2, 4-triazole, 3, 6-proflavin, rivanol, 2, two (the 4-aminophenyls)-1 of 5-, 3, 4-
Figure BDA0000474775050000081
diazole, diethylene triamine, trien, 3,3 '-diamido-di-n-propylamine, penten, N, two (3-aminopropyl) methylamines, 4 of N-, 4 '-diaminobenzene formailide, 2,6-diamido-4-nitrotoluene, N, N '-bis-(4-aminophenyl)-N-aniline, N, N '-bis-(4-aminophenyl)-N-methylamine, 4,4 '-diamino-diphenyl urea etc.
As aliphatic diamine, it is the example of the diamine compound of formula (15) expression, can exemplify diamido methane, 1, 2-diaminoethanes, 1, 3-diaminopropanes, 1, 4-diaminobutane, 1, 6-diamino hexane, 1, 7-diamido heptane, 1, 8-diamino-octane, 1, 9-diamido nonane, 1, 10-diamino decane, 1, 3-diamido-2, 2-dimethylpropane, 1, 4-diamido-2, 2-dimethylbutane, 1, 6-diamido-2, 5-dimethylhexane, 1, 7-diamido-2, 5-dimethyl heptane, 1, 7-diamido-4, 4-dimethyl heptane, 1, 7-diamido-3-methylheptane, 1, 9-diamido-5-methylnonane, 2, 11-diamido dodecane, 1, 12-diamido octadecane, 1, 2-two (the amino propoxyl group of 3-) ethane etc.
As alicyclic diamine, the example of diamine compound that formula (15) represents, can exemplify Isosorbide-5-Nitrae-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamido-3,3 '-dimethyl dicyclohexyl methyl hydride and isophorone diamine etc.
As carbon-ring type aromatic diamine, be the example of the diamine compound of formula (15) expression, can exemplify o-phenylenediamine, m-phenylene diamine, p-phenylenediamine (PPD), diaminotoluene class (for example 2,4-diaminotoluene), Isosorbide-5-Nitrae-diamido-2-methoxybenzene, 2,5-diamido xylene, 1,3-diamido-4-chlorobenzene, Isosorbide-5-Nitrae-diamido-2,5-dichloro-benzenes, Isosorbide-5-Nitrae-diamido-4-cumene, 4,4 '-diamino-diphenyl-2,2 '-propane, 4,4 '-diaminodiphenyl-methane, 2,2 '-diamido Stilbene, 4,4 '-diamido Stilbene, 4,4 '-diaminodiphenyl ether, 4,4 '-diphenyl sulfide, DDS, 3,3 '-diamino-diphenyl sulfone, 4,4 '-diaminobenzoic acid phenyl ester, 2,2 '-diamido benzophenone, 4,4 '-diamido benzil, two (4-aminophenyl) phosphine oxide, two (3-aminophenyl) methyl sulfonium hydroxide, two (4-aminophenyl) phenyl phosphine oxide, two (4-aminophenyl) cyclohexyl phosphine oxide, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diamino-anthraquinone, diamino-fluorene, two (4-aminophenyl) diethylsilane, two (4-aminophenyl) dimethylsilane, two (4-aminophenyl) tetramethyl disiloxane, 3,4 '-diaminodiphenyl ether, biphenylamine, 2,2 '-dimethylbenzidine, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-etc.
There is the diamine compound of formula (15) expression of the characteristic of the tilt angle that improves liquid crystal as A, can exemplify 1-dodecyloxy-2, 4-diaminobenzene, 1-hexadecane oxygen base-2, 4-diaminobenzene, 1-octadecane oxygen base-2, 4-diaminobenzene, 1, two (4-aminophenyl) cyclohexanes of 1-, 2, two [4-(4-amino-benzene oxygen) phenyl] octanes of 2-, 4, 4 '-diamido-3-dodecyl diphenyl oxide, 4-(4-trans-n-heptyl cyclohexyl phenoxy group)-1, 3-diaminobenzene, 4-(4-trans-n-pentyl cyclohexyl phenoxy group)-1, 3-diaminobenzene, 4-is trans-n-pentyl dicyclohexyl-3, 5-diaminobenzoic acid ester etc.
< particular polymers (B) >
Particular polymers (B) is the polyimide precursor with the structural unit (repetitive) of following formula (7) expression.Polyimide precursor refers to polyamic acid or poly amic acid ester.
[changing 18]
Figure BDA0000474775050000101
Particular polymers (B) can be both to have R, X and Y to be respectively the polyimide precursor of the structural unit that formula a kind of, that be only made up of same structure (7) represents, or can be also that to have R, X or Y be polyimide precursor multiple, structural unit that represent for the multiple formula (7) of different structure.In addition, particular polymers (B) can be the polyimide precursor of structure also having beyond the structural unit that formula (7) represents.; particular polymers (B) can be both the polyimide precursor being made up of the structural unit of formula (7) expression of same structure; also can be the polyimide precursor that the structural unit that represented by the formula (7) of different structure forms, can be the polyimide precursor of the structure beyond the structural unit that represents of the structural unit that represents of the formula (7) with same structure or different structure and formula (7) in addition.
In formula (7), R is hydrogen atom or alkyl.As alkyl, can exemplify the alkyl of carbon number 1～6.
In formula (7), X is divalent organic group, as mentioned above, can be both a kind of, also can be two or more mixing exist, but at least one X must be in structure, have following formula (8)～(10) any divalent organic group or to phenylene.
[changing 19]
[changing 20]
Figure BDA0000474775050000103
[changing 21]
Figure BDA0000474775050000104
In the X of formula (7), in structure, have in these formulas (8)～(10) any divalent organic group or be 10～100 % by mole to the ratio of phenylene (being also denoted as " ad hoc structure " below), preferably 50～100 % by mole.If this ratio is very few, liquid crystal aligning is deteriorated sometimes.In structure, have in these formulas (8)～(10) any divalent organic group or the structure of the X beyond phenylene is not particularly limited, for example, in order to improve the tilt angle of liquid crystal, can exemplify the substituent divalent organic group of the known effects that is improved inclination angle such as thering is chain alkyl, perfluoroalkyl, steroid skeleton group.
In formula (8), m 1be 2～18 integer, from liquid crystal aligning and stable on heating angle, preferably 3～12, more preferably 4～8.The divalent organic group in structure with formula (8) is better also to comprise aromatic rings, as the concrete example of divalent organic group in structure with formula (8), can exemplify following formula (11)～(14), but be not limited to this.
[changing 22]
In formula (11)～(14), m 1be 2～18 integer, preferably 3～12, more preferably 4～8.
In formula (9), m 2be 1～8 integer, from the angle of voltage retention performance, preferably 1～3, more preferably 1 or 2.
In formula (10), m 3be 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 hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical.As 1 valency organic group beyond this primary amino radical, can exemplify the alkyl of carbon number 1～20, the thiazolinyl of carbon number 2～20, the alkoxy of carbon number 1～20, carbon number 1～20 containing fluoroalkyl, the fluorine-containing thiazolinyl of carbon number 2～20, the fluoroalkoxy of carbon number 1～20, cyclohexyl, phenyl, fluorine atom and by their group constituting etc., from the angle of liquid crystal aligning, it is better the alkyl that is selected from carbon number 1～4, the thiazolinyl of carbon number 2～4, the alkoxy of carbon number 1～4, carbon number 1～4 containing fluoroalkyl, the fluorine-containing thiazolinyl of carbon number 2～4, 1 valency organic group of the fluoroalkoxy of carbon number 1～4.As preferred structure, be that hydrogen atom on phenyl ring is without the structure replacing.
The Y of formula (7) is 4 valency organic groups, as mentioned above, can be both a kind of, also can two or more mixing exist.The structure of Y is not particularly limited, and from the angle of further raising liquid crystal aligning, is better that at least one Y is the 4 valency organic groups with aromatic structure (being aromatic group).Now, in the Y of formula (7), the preferred proportion with 4 valency organic groups of aromatic structure is 20～100 % by mole, more preferably 50～100 % by mole.As the 4 valency organic groups with aromatic structure, be better from Pyromellitic Acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, two (3,4-dicarboxyl phenyl) ether, two (3,4-dicarboxyl phenyl) sulfone, 2,3, the structure of removing 4 carboxyls in the tetrabasic carboxylic acids such as 6,7-naphthalene tetracarboxylic acid and obtain.
The Y of formula (7) is from 1,2,3,4-cyclo-butane tetrabasic carboxylic acid, 2,3,5-tricarboxylic base 2-Cyclopentylacetic acid, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic, two ring [3,3,0] octane-2, in the situation of the structure of removing 4 carboxyls in the tetrabasic carboxylic acids such as 4,6,8-tetrabasic carboxylic acid and obtain, although have the tendency that reduces liquid crystal aligning, be improved the effect of voltage retention performance.Therefore, pay attention in the situation of voltage retention, be better the polyimide precursor with the structural unit that Y only represents for the formula (7) of these 4 valency organic groups, or to have Y be that the structural unit that represents of the formula (7) of these 4 valency organic groups and Y are the polyimide precursor of the structural unit that represents of the formula (7) of 4 valency organic groups beyond these 4 valency organic groups.
The method that acquisition has the polyimide precursor of the structural unit of formula (7) expression is not particularly limited.Conventionally can by containing be useful on constitutional formula (7) Y tetracarboxylic dianhydride tetracarboxylic dianhydride's composition and obtain containing the reaction of two amine components of diamines of the X that is useful on constitutional formula (7).
Obtaining multiple Y mixes with specific ratio in the situation of the polyimide precursor existing, or will obtain multiple X mixes with specific ratio in the situation of the polyimide precursor existing, as long as use tetracarboxylic dianhydride for forming Y or for forming the diamines of X and making its reaction according to target blending ratio separately.For example, in order to make the ratio in polyimide precursor with the X of ad hoc structure reach 10 % by mole, as long as the ratio for the diamines that forms the X with ad hoc structure in the two amine component total amounts that make to use in polyimide precursor synthetic reaches 10 % by mole.Similarly, in order to make the ratio in polyimide precursor with the Y of aromatic structure reach 20 % by mole, as long as the ratio for the tetracarboxylic dianhydride that forms the Y with aromatic structure in the tetracarboxylic dianhydride's composition total amount that makes to use in polyimide precursor synthetic reaches 20 % by mole.
Concrete example for the diamines of the X of constitutional formula (7) is as follows, but is not limited to this.
As the diamines for forming structure with the X of formula (8), can exemplify 1,3-diaminopropanes, 1,4-diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diamido heptane, 1,8-diamino-octane, 1,9-diamido nonane, 1,10-diamino decane etc.Also have, as the diamines for forming structure with the X of formula (8) and aromatic ring, can exemplify the diamines corresponding with formula (11), 1, two (4-aminophenyl) propane, 1 of 3-, two (4-aminophenyl) butane, 1 of 4-, two (4-aminophenyl) pentanes, 1 of 5-, two (4-aminophenyl) hexanes, 1 of 6-, two (4-aminophenyl) heptane, 1 of 7-, two (4-aminophenyl) octanes, 1 of 8-, two (4-aminophenyl) nonanes, 1 of 9-, two (4-aminophenyl) decane of 10-etc.Similarly, can exemplify the diamines corresponding with formula (12), 1, two (4-amino-benzene oxygen) propane, 1 of 3-, two (4-amino-benzene oxygen) butane, 1 of 4-, two (4-amino-benzene oxygen) pentanes, 1 of 5-, two (4-amino-benzene oxygen) hexanes, 1 of 6-, two (4-amino-benzene oxygen) heptane, 1 of 7-, two (4-amino-benzene oxygen) octanes, 1 of 8-, two (4-amino-benzene oxygen) nonanes, 1 of 9-, two (4-amino-benzene oxygen) decane of 10-etc.Similarly, as the diamines corresponding with formula (13), can exemplify two (4-aminophenyl) propane-1,3-bis-acid esters, two (4-aminophenyl) butane-1,4-bis-acid esters, two (4-aminophenyl) pentane-1,5-bis-acid esters, two (4-aminophenyl) hexane-1,6-bis-acid esters, two (4-aminophenyl) heptane-1,7-bis-acid esters, two (4-aminophenyl) octane-1,8-bis-acid esters, two (4-aminophenyl) nonane-1,9-bis-acid esters, two (4-aminophenyl) decane-1,10-bis-acid esters etc.Similarly, as the diamines corresponding with formula (14), can exemplify 1, two (4-(4-amino-benzene oxygen) phenoxy group) propane of 3-, 1, two (4-(4-amino-benzene oxygen) phenoxy group) butane of 4-, 1, two (4-(4-amino-benzene oxygen) phenoxy group) pentanes of 5-, 1, two (4-(4-amino-benzene oxygen) phenoxy group) hexanes of 6-, 1, two (4-(4-amino-benzene oxygen) phenoxy group) heptane of 7-, 1, two (4-(4-amino-benzene oxygen) phenoxy group) octanes of 8-, 1, two (4-(4-amino-benzene oxygen) phenoxy group) nonanes of 9-, 1, two (4-(4-amino-benzene oxygen) phenoxy group) decane of 10-etc.
As the diamines for forming structure with the X of formula (9), can exemplify 1, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (4-amino-benzene oxygen) benzene, 1 of 4-, two (4-(4-amino-benzene oxygen) phenoxy group) benzene of 3-, Isosorbide-5-Nitrae-bis-(4-(4-amino-benzene oxygen) phenoxy group) benzene etc.
As the diamines for forming structure with the X of formula (10), can exemplify 4,4 '-diaminobenzidine, 4,4 '-diamido-p-terphenyl etc.
Be the diamines to phenylene as X, can exemplify Isosorbide-5-Nitrae-diaminobenzene.
The diamines of enumerating in above-mentioned concrete example is as being preferred for the synthesis of the raw material of particular polymers (B), in two amine components that use in the reacting of tetracarboxylic dianhydride's composition, preferably use 10～100 % by mole, more preferably use these diamines of 50～100 % by mole, the synthetic polyimide precursor with the structural unit that formula (7) represents is preferred as particular polymers (B) thus.
In addition, for forming structure, to have any divalent organic group or concrete example of diamines to the X beyond phenylene in formula (8)～(10) as follows, but be not limited to this.
As the example of alicyclic diamine, can exemplify Isosorbide-5-Nitrae-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamido-3,3 '-dimethyl dicyclohexyl amine and isophorone diamine etc.
As the example of carbon-ring type aromatic diamine, can exemplify o-phenylenediamine, m-phenylene diamine, 2,4-diaminotoluene, 1,3-diamido-4-chlorobenzene, 4,4 '-diamino-diphenyl-2,2 '-propane, 4,4 '-diaminodiphenyl-methane, 2,2 '-diamido Stilbene, 4,4 '-diamido Stilbene, 4,4 '-diaminodiphenyl ether, 4,4 '-diphenylsulfide, DDS, 3,3 '-diamino-diphenyl sulfone, 4,4 '-diaminobenzoic acid phenyl ester, 2,2 '-diamido benzophenone, 4,4 '-diamido benzil, two (4-aminophenyl) phosphine oxide, two (3-aminophenyl) methyl sulfonium hydroxide, two (4-aminophenyl) phenyl phosphine oxide, two (4-aminophenyl) cyclohexyl phosphine oxide, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diamino-anthraquinone, diamino-fluorene, two (4-aminophenyl) diethylsilane, two (4-aminophenyl) dimethylsilane, two (4-aminophenyl) tetramethyl disiloxane, 3,4 '-diaminodiphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-etc.
As the example that also comprises the diamines of nitrogen-atoms except 2 amino, can exemplify 2,4-diamino-diphenylamine, 2,4-diamino-pyridine, 2,4-diamido-s-triazine, 2,7-diamido dibenzofurans, 3,7-diaminophenothiazine, 2,5-diaminostilbene, 3,4-thiadiazoles, 2,4-diamido-6-phenyl-s-triazine, N, N '-bis-(4-aminophenyl)-N-phenyl amine, N, N '-bis-(4-aminophenyl)-N-methyl amine, 4,4 '-diamino-diphenyl urea etc.
As the diamines of the tilt angle for improving liquid crystal, can exemplify 1-dodecyloxy-2, 4-diaminobenzene, 1-hexadecane oxygen base-2, 4-diaminobenzene, 1-octadecane oxygen base-2, 4-diaminobenzene, 1, two (4-aminophenyl) cyclohexanes of 1-, 2, two [4-(4-amino-benzene oxygen) phenyl] octanes of 2-, 4, 4 '-diamido-3-dodecyl diphenyl oxide, 4-(4-trans-n-heptyl cyclohexyl phenoxy group)-1, 3-diaminobenzene, 4-(4-trans-n-pentyl cyclohexyl phenoxy group)-1, 3-diaminobenzene, 4-is trans-n-pentyl dicyclohexyl-3, 5-diaminobenzoic acid ester etc.
In the situation that R in general formula (7) is alkyl, can make the alcohol such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol and tetracarboxylic dianhydride reaction and obtain with diamines dehydrating condensation after becoming tetrabasic carboxylic acid diester, or making alcohol and polyamic acid dehydrating condensation and obtain.
The synthetic > of < polyamic acid or poly amic acid ester
Obtain in the situation of particular polymers (A) or particular polymers (B) by the reaction of tetracarboxylic dianhydride's composition and two amine components as mentioned above, easy is, in organic solvent, tetracarboxylic dianhydride's composition and two amine components are mixed to the method that makes its reaction and obtain polyamic acid.Further, by the carboxyl of polyamic acid being changed into the method for ester, can obtain poly amic acid ester.
The organic solvent using when above-mentioned reaction is just not particularly limited as long as dissolving the polyamic acid of generation or the solvent of poly amic acid ester, if enumerate its concrete example, can exemplify N, dinethylformamide, DMA, METHYLPYRROLIDONE, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton etc.These solvents can be used alone, but also also mix together.Further, even the solvent of insoluble solution polyamic acid or poly amic acid ester, in the scope that can not separate out at polyamic acid or the poly amic acid ester of generation, also can use with above-mentioned solvent.In addition, the moisture in organic solvent hinders polyreaction, and can make the polyamic acid or the poly amic acid ester hydrolysis that generate, and therefore organic solvent preferably uses the organic solvent through farthest dehydrating.
The method that tetracarboxylic dianhydride's composition and two amine components are mixed in organic solvent can exemplify and stir the solution that makes two amine components be dispersed or dissolved in organic solvent and to obtain, and directly adds therein tetracarboxylic dianhydride's composition or makes tetracarboxylic dianhydride's composition be dispersed or dissolved in the method for adding again after organic solvent; The method of adding two amine components in the solution obtaining tetracarboxylic dianhydride's composition is dispersed or dissolved in to organic solvent on the contrary; Alternately adding the method for tetracarboxylic dianhydride's composition and two amine components etc., can be any method wherein in the present invention.In addition, when tetracarboxylic dianhydride's composition or two amine components are made up of multiple compounds, the state that Multiple components can be pre-mixed reacts, and also can react successively respectively.
Temperature when tetracarboxylic dianhydride's composition and two amine components react in organic solvent is generally 0～150 ℃, and preferably 5～100 ℃, more preferably 10～80 ℃.The higher polyreaction of temperature completes sooner, if but too high, sometimes cannot obtain the polymkeric substance (polyamic acid or polyester-imides) of high molecular.In addition, reaction can be carried out with concentration arbitrarily, if but concentration is too low, be difficult to obtain the polymkeric substance of high molecular, if excessive concentration, the viscosity of reactant liquor is too high, is difficult to stir uniformly, therefore be preferably 1～50 % by weight, be more preferably 5～30 % by weight.Can carry out with high concentration in initial reaction stage, and then append organic solvent.
The tetracarboxylic dianhydride's composition using in the polyreaction of polyamic acid or poly amic acid ester and the ratio of two amine components are better 1:0.8～1.2 with molar ratio computing.In addition, make two amine components excessive and polyamic acid or poly amic acid ester sometimes the painted of solution can become large, while therefore taking notice of solution painted, can be 1:0.8～1.Identical with common polycondensation reaction, this mol ratio is more close to 1:1, and the polyamic acid of gained or the molecular weight of poly amic acid ester are larger.If the molecular weight of polyamic acid or poly amic acid ester is too small, the painting film strength obtaining thus may be not enough, on the contrary, if the molecular weight of polyamic acid or poly amic acid ester is excessive, the viscosity of the aligning agent for liquid crystal of manufacturing thus may be too high, operability when film forms and the lack of homogeneity of film.Therefore, the polyamic acid using in aligning agent for liquid crystal of the present invention or poly amic acid ester be in reduced viscosity (in concentration 0.5dl/g, NMP 30 ℃) preferably 0.1～2.0, and more preferably 0.2～1.5.
In not wanting to make aligning agent for liquid crystal of the present invention, contain polyamic acid or poly amic acid ester polymerization time when solvent used, or while there is unreacted monomer component and impurity in reaction solution, precipitate and reclaim and purifying.The method is better that the solution of polyamic acid or poly amic acid ester is put in the Weak solvent in stirring, precipitates recovery.During the precipitation of polyamic acid or poly amic acid ester reclaims, Weak solvent used is not particularly limited, and can exemplify methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc.Can after filtering, cleaning and reclaim, under normal pressure or reduced pressure, carry out normal temperature or heat drying by putting into the polyamic acid or the poly amic acid ester that precipitate in Weak solvent, thereby make powder.If repeat 2～10 times this powder is dissolved in again to good solvent reppd operation, also can purifying polyamic acid or poly amic acid ester.Cannot thoroughly remove impurity by primary sedimentation reclaimer operation time, be better to carry out this purification procedures.As poor solvent now, if use such as 3 kinds of above poor solvents such as alcohols, ketone, hydro carbons, purification efficiency further improves, therefore preferred.
< aligning agent for liquid crystal >
Aligning agent for liquid crystal of the present invention is described above, contains above-mentioned particular polymers (A) and particular polymers (B).By making the aligning agent for liquid crystal that contains as mentioned above particular polymers (A) and particular polymers (B), can obtain liquid crystal aligning, rub resistance, voltage retention performance and electric charge Accumulation excellence, ionic impurity amount is few, transmissivity is high and the little liquid crystal orientation film of variation of the specific insulation that caused by photoconduction.
For why producing above-mentioned effect unclear by formation of the present invention, but think that reason is roughly as described below.Use formula (1) represent tetrabasic carboxylic acid dianhydride and polyamic acid be difficult to carry out imidizate under hot effect.Therefore think, be coated with, burn till the aligning agent for liquid crystal of the present invention that contains particular polymers (A) composition and remaining a large amount of carboxyls in the liquid crystal orientation film making.Think that this carboxyl and the nitrogen-atoms of the diamine compound that derives from formula (5) or formula (6) expression interact, thereby the migration of the unpaired electron on the nitrogen-atoms being caused by photoconduction is suppressed, consequently, the variation of the specific insulation being caused by photoconduction of liquid crystal orientation film is suppressed.Think in addition, by the interaction of this carboxyl and nitrogen-atoms, specific insulation itself also can reduce.
And then, the conduct that simultaneously contains such particular polymers (A) and liquid crystal aligning excellence by making has the aligning agent for liquid crystal of the particular polymers (B) of the polyimide precursor of the structural unit that formula (7) represents, can obtain liquid crystal aligning, rub resistance, voltage retention performance and electric charge Accumulation excellence, ionic impurity amount is few, transmissivity is high and the little liquid crystal orientation film of variation of the specific insulation that caused by photoconduction.
Below the form of the aligning agent for liquid crystal of the present invention of explanation is the coating fluid that contains particular polymers (A) and particular polymers (B), if but can on substrate, form uniform film, aligning agent for liquid crystal of the present invention can be also other form.
Make the coating fluid that contains particular polymers (A) and particular polymers (B), both the reaction solution of polyamic acid or poly amic acid ester directly can be mixed, also the polyamic acid of solid content or poly amic acid ester can be dissolved in after organic solvent its mixing.
As this organic solvent, as long as the solvent that can dissolve contained polymkeric substance (polyamic acid or polyester-imides) is just not particularly limited, if enumerate its concrete example, can exemplify N, dinethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton etc., these solvents can use one also can multiple mixing to use.
In addition, even solvent that cannot dissolve polymer while use separately, as long as in the scope that can not separate out at polymkeric substance, can mix with aligning agent for liquid crystal of the present invention.Particularly known to moderately mixing ethyl cellosolve, butyl cellosolve, 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, propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, mono-ethylether-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 lactates etc. have the solvent of low surface tension, painting film uniformity can make to coat substrate time improves, therefore these solvents are also suitable for aligning agent for liquid crystal of the present invention.
Aligning agent for liquid crystal of the present invention can be according to the setting of the thickness of the liquid crystal orientation film that will form and appropriate change solid component concentration, and solid component concentration is better 1～10 % by weight.If less than 1 % by weight, is difficult to form even and flawless film, if higher than 10 % by weight, the storage stability variation of solution sometimes.
In addition, in order to improve the adaptation of film and substrate, in aligning agent for liquid crystal of the present invention, the adjuvants such as silane coupling agent can also be added, or particular polymers (A) and particular polymers (B) other polymkeric substance in addition can be added.
The aligning agent for liquid crystal of the present invention obtaining is as mentioned above after filtering as required, can coat substrate, be dried, burn till and make film, by this coated surface being rubbed or the orientation process such as irradiation, can be used as liquid crystal orientation film, or do not carry out orientation process and can be used as liquid crystal orientation film.
At this moment, substrate used limits without special as long as the high substrate of the transparency, can use the plastic bases such as glass substrate, acrylic acid substrate or polycarbonate substrate etc., from the angle that production technology is simplified, preferably use the substrate that is formed with ITO (tin indium oxide (Indeium Tin the Oxide)) electrode for liquid crystal drive etc.In addition, in reflection type liquid crystal display element, can use the opaque materials such as silicon wafer, but only limit to the substrate of a side, electrode now also can use the reflectorized materials such as aluminium.
As the coating process of aligning agent for liquid crystal, can exemplify spin-coating method, print process, ink-jet method etc., but from the viewpoint of productivity, the industrial hectographic printing method that is widely used, the method is also suitable for aligning agent for liquid crystal of the present invention.
Drying process after coating of liquid crystalline alignment agent is optional, but in the case of coating is not burnt till after fixing or coating each piece substrate immediately to the time before burning till afterwards, preferably includes drying process.Described dry can, because the carrying of substrate etc. is former thereby the degree of distortion, its drying means be not particularly limited as long as making solvent evaporation reach film shape.Specifically can exemplify following method, make it at 50～150 ℃, more preferably on the heating plate of 80～120 ℃ dry 0.5～30 minute, more preferably 1～5 minute.
Be coated with aligning agent for liquid crystal and as required dried burning till can under the arbitrary temp in 100～350 ℃, carry out, but be better 150～300 ℃, be more preferably 200 ℃～250 ℃.While comprising polyamic acid in aligning agent for liquid crystal, the conversion ratio being transformed to polyimide by polyamic acid changes with this firing temperature, but aligning agent for liquid crystal of the present invention is without 100% imidizate.Better to burn till than high 10 ℃ of above temperature such as the heat treatment temperature of necessary sealant cures in liquid crystal structure cell manufacture process etc.
If the thickness of the film after burning till is blocked up, unfavorable aspect the power consumption of liquid crystal display cells, if excessively thin, the reliability of liquid crystal display cells reduces sometimes, is therefore 5～300nm, preferably 10～100nm.
The liquid crystal orientation film being obtained by aligning agent for liquid crystal of the present invention as mentioned above has excellent characteristic, therefore can be used as the liquid crystal display cells of TN (twisted nematic (Twisted Nematic)), STN (super twisted nematic type (Super Twisted Nematic)), TFT, horizontal electric field type etc. and the liquid crystal orientation film used for liquid crystal display element of ferroelectricity and anti-ferroelectricity.Particularly be suitable as the liquid crystal orientation film used for liquid crystal display element of the horizontal electric field type of the burning screen that easy generation causes by liquid crystal aligning.
< liquid crystal display cells >
Liquid crystal display cells of the present invention is to be obtained after the substrate with liquid crystal orientation film by aligning agent for liquid crystal of the present invention by said method, manufactures by known method the liquid crystal display cells that liquid crystal structure cell forms.If for words of manufacturing the example of liquid crystal structure cell, generally to adopt following method: by a pair of substrate folder that is formed with liquid crystal orientation film across 1～30 μ m, be preferably the sept of 2～10 μ m, according to making frictional direction become the setting of requirement at any angle in 0～270 °, with sealant, periphery is fixed, after injection liquid crystal, sealed.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.
The liquid crystal aligning excellence of the liquid crystal display cells making with aligning agent for liquid crystal of the present invention as mentioned above, and there are excellent electrical characteristics, therefore can be made into the liquid crystal display device that is difficult for that the reduction of contrast occurs and burns screen, the liquid crystal display cells etc. that is suitable for TN, STN, TFT, horizontal electric field type etc. uses the liquid crystal display cells of the variety of way of nematic crystal.In addition,, by the liquid crystal of selecting to use, also can be used for the liquid crystal display cells of ferroelectricity and anti-ferroelectricity.In these liquid crystal display cells, be particularly preferred for the liquid crystal display cells of the horizontal electric field type that the burning screen being caused by liquid crystal aligning easily occurs.
Embodiment
Below, the present invention will be described in more detail to exemplify embodiment, but the present invention is not limited thereto.Abbreviation used in following embodiment and comparative example is as described below.
DA-1:4,4'-diamino-diphenylamine
DA-2:4,4'-diaminodiphenyl-methane
DA-3:1, two (4-amino-benzene oxygen) pentanes of 5-
CA-1:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
CA-2: two ring [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
CA-3: pyromellitic acid anhydride
CA-4:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride
[synthesis example 1]
In the 200ml four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, add the DA-1 of 7.97g (40.0mmol) and the DA-2 of 1.98g (10.0mmol), add the METHYLPYRROLIDONE of 72.34g, supplying nitrogen stirs and makes its dissolving on one side on one side again.Stir this two amine aqueous solution while add the CA-1 of 6.86g (35.0mmol), under water temperature, stir 30 minutes.Then, agitating solution adds the CA-2 of 3.13g (12.5mmol) on one side on one side, then adds METHYLPYRROLIDONE so that solid component concentration reaches 20 quality %, under nitrogen atmosphere, stirs 3 hours with oil bath at 50 ℃.Then, then add METHYLPYRROLIDONE so that solid component concentration reaches 11 quality %, under nitrogen atmosphere, stir an evening at 50 ℃ with oil bath, obtain the solution of polyamic acid.By E type viscosity meter ((East Machine industry society of Toki Sangyo Co., Ltd.) system) confirm that the viscosity of this polyamic acid solution at 25 ℃ is 191mPas.
In this polyamic acid solution of 20.0g, add the METHYLPYRROLIDONE of 5.3g, the METHYLPYRROLIDONE solution that adds the APTES that has 1.0 % by weight of 2.20g and the butyl cellosolve of 9.17g, obtain the polyamic acid solution that solid component concentration is 6.0 quality % (A1).
[synthesis example 2]
In the 300ml four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, add the DA-1 of 7.49g (37.6mmol) and the DA-2 of 1.86g (9.4mmol), add the METHYLPYRROLIDONE of 72.08g, supplying nitrogen stirs and makes its dissolving on one side on one side again.Stir this two amine aqueous solution while add the CA-1 of 2.12g (10.8mmol), under water temperature, stir 30 minutes.Then, agitating solution adds the CA-2 of 8.82g (35.3mmol) on one side on one side, then adds METHYLPYRROLIDONE so that solid component concentration reaches 20 quality %, under nitrogen atmosphere, stirs 3 hours with oil bath at 50 ℃.Then, then add METHYLPYRROLIDONE so that solid component concentration reaches 11 quality %, under nitrogen atmosphere, stir an evening at 50 ℃ with oil bath, obtain the solution of polyamic acid.Confirm that with E type viscosity meter (Toki Sangyo Co., Ltd.'s system) viscosity of this polyamic acid solution at 25 ℃ is 207mPas.
In this polyamic acid solution of 20.0g, add the METHYLPYRROLIDONE of 6.25g, the METHYLPYRROLIDONE solution that adds the APTES that has 1.0 % by weight of 2.20g and the butyl cellosolve of 9.48g, obtain the polyamic acid solution that solid component concentration is 5.8 quality % (A2).
[synthesis example 3]
In the 300ml four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, add the DA-1 of 8.93g (44.8mmol) and the DA-2 of 2.22g (11.2mmol), add the METHYLPYRROLIDONE of 108.54g, supplying nitrogen stirs and makes its dissolving on one side on one side again.Stir this two amine aqueous solution while add the CA-2 of 13.52g (54.0mmol), add METHYLPYRROLIDONE again so that solid component concentration reaches 12 quality %, under nitrogen atmosphere, stir an evening at 50 ℃ with oil bath, obtain the solution of polyamic acid.Confirm that with E type viscosity meter (Toki Sangyo Co., Ltd.'s system) viscosity of this polyamic acid solution at 25 ℃ is 153mPas.
In this polyamic acid solution of 16.8g, add the METHYLPYRROLIDONE of 10.92g, the METHYLPYRROLIDONE solution that adds the APTES that has 1.0 % by weight of 2.32g and the butyl cellosolve of 10.01g, obtain the polyamic acid solution that solid component concentration is 5.8 quality % (A3).
[synthesis example 4]
In the 100ml four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, add the METHYLPYRROLIDONE of 80.0g and the DA-1 of 3.83g (28mmol), supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the CA-1 of 3.30g (17mmol), at 10～15 ℃, stir 2.5 hours.Then, add the DA-2 of 0.95g (4.8mmol), at 10～15 ℃, stir after 0.5 hour, add the CA-4 of 1.44g (4.8mmol), at 20～25 ℃, stir 5 hours, obtain the solution of polyamic acid.Confirm that with E type viscosity meter (Toki Sangyo Co., Ltd.'s system) viscosity of this polyamic acid solution at 25 ℃ is 168mPas.
In this polyamic acid solution of 50.0g, add METHYLPYRROLIDONE, the METHYLPYRROLIDONE solution that adds the APTES that has 1.0 % by weight of 5.0g, the adding of 10g of 1.66g to have the METHYLPYRROLIDONE solution of the 3-of 5.0 % by weight phenyl amino propyl trimethoxy silicane and the butyl cellosolve of 16.67g, obtain the polyamic acid solution that solid component concentration is 6.0 quality % (A4).
[synthesis example 5]
In the 100ml four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, add the DA-3 of 6.87g (24mmol) and the METHYLPYRROLIDONE of 80.0g, supplying nitrogen stirs and makes its dissolving on one side on one side.Stir this two amine aqueous solution while add the CA-3 of 5.03g (23mmol), then add METHYLPYRROLIDONE so that solid component concentration reaches 12 quality %, stir an evening at 50 ℃ with oil bath, obtain the solution of polyamic acid.Confirm that with E type viscosity meter (Toki Sangyo Co., Ltd.'s system) viscosity of this polyamic acid solution at 25 ℃ is 525mPas.
In this polyamic acid solution of 50g, add METHYLPYRROLIDONE, the adding of 12g of 18g to have the METHYLPYRROLIDONE solution of the 3-of 5.0 % by weight phenyl amino propyl trimethoxy silicane and the butyl cellosolve of 20g, obtain the polyamic acid solution that solid component concentration is 6.0 quality % (B1).
[embodiment 1]
The polyamic acid solution obtaining in synthesis example (A1) and polyamic acid solution (B1) are mixed with the condition of weight ratio (A1)/(B1)=80/20, obtain aligning agent for liquid crystal of the present invention (C1).
[embodiment 2]
The polyamic acid solution obtaining in synthesis example (A2) and polyamic acid solution (B1) are mixed with the condition of weight ratio (A2)/(B1)=80/20, obtain aligning agent for liquid crystal of the present invention (C2).
[embodiment 3]
The polyamic acid solution obtaining in synthesis example (A3) and polyamic acid solution (B1) are mixed with the condition of weight ratio (A3)/(B1)=80/20, obtain aligning agent for liquid crystal of the present invention (C3).
[comparative example 1]
The polyamic acid solution obtaining in synthesis example (A4) and polyamic acid solution (B1) are mixed with the condition of weight ratio (A4)/(B1)=80/20, obtain aligning agent for liquid crystal of the present invention (C4).
Use the aligning agent for liquid crystal obtaining in embodiment 1, embodiment 2, embodiment 3, comparative example 1, manufacture respectively evaluation sample by following method, measure liquid crystal aligning, specific insulation, voltage retention, ion concentration and transmissivity.Acquired results is shown in table 1～3.
The manufacture > of < liquid crystal structure cell
After being filtered with 1.0 μ m filters, the aligning agent for liquid crystal of gained is spun on the glass substrate with transparency electrode, and dry after 2 minutes on the heating plate of 70 ℃, burn till 15 minutes in 230 ℃, obtain the film of thickness 100nm.This polyimide film is rubbed after (roller footpath 120mm, rotating speed 1000rpm, translational speed 20mm/sec, the amount of being pressed into 0.4mm) with rayon cloth, in pure water, carries out the ultrasonic irradiation of 1 minute, in 80 ℃ dry 10 minutes.In embodiment 1～3 and comparative example 1, in this friction treatment, all do not produce scar or dust because film is scratched, and also there is no peeling off of film, rub resistance excellence.Prepare 2 substrates with above-mentioned liquid crystal orientation film, after the sept of 4 μ m being set on the liquid crystal aligning face of a substrate, with the antiparallel condition of frictional direction of 2 substrates by 2 substrate in combination, sealing around, but leave liquid crystal injecting port, making structure cell interval (cell gap) is the negative crystal born of the same parents of 4 μ m.Inject liquid crystal (MLC-2041, Merck & Co., Inc.'s system) to vacuum in this structure cell at normal temperatures, by inlet sealing, make antiparallel type liquid crystal structure cell.
< liquid crystal aligning >
Observe the state of orientation of this liquid crystal structure cell with polarizing microscope, will not be orientated be denoted as " well " of defect, will have be denoted as " bad " of orientation defect.
The mensuration > of < specific insulation
After being filtered with 0.2 μ m filter, the aligning agent for liquid crystal of gained is spun on the glass substrate with ito transparent electrode, and dry after 5 minutes on the heating plate of 80 ℃, burn till 20 minutes in 220 ℃, form the film (liquid crystal orientation film) of thickness 220nm.In this film coated surface AM aluminum metallization, form the upper electrode (aluminium electrode) of 1.0mm φ across mask, measure the sample of use as specific insulation.Between the ITO of this sample electrode and aluminium electrode, apply the voltage of 10V, measure the current value after 180 seconds from applying voltage, calculate specific insulation according to the measured value of this value and electrode area, thickness.In addition, LED-backlit source is set below sample substrate in advance, under turning on light and under turning off the light, measures respectively, measure the variation of the specific insulation being caused by light.Value when value when LED is turned off the light is turned on light divided by LED, acquired results if 1.0～2.0 be denoted as " ◎ ", 2.0～3.0 are denoted as "○" if, in addition be denoted as "×".
The mensuration > of < voltage retention
Using the liquid crystal structure cell similarly making with the manufacture > of above-mentioned < liquid crystal structure cell, with the (East Yang テ of Toyo Corp. Network ニ カ society) the 6254 type liquid crystal evaluation of physical property devices made measure.Condition with application time 60 μ sec., interval 100msec. applies after the voltage of 1V, measure from apply remove voltage retention after 100msec. (from apply remove voltage after 100msec./apply voltage × 100% after just finishing).When mensuration, the temperature of liquid crystal structure cell is made as to 23 ℃ and 100 ℃ and measures.
The mensuration > of < ion concentration
Using the liquid crystal structure cell similarly making with the manufacture > of above-mentioned < liquid crystal structure cell, with the (East Yang テ of Toyo Corp. Network ニ カ society) the 6254 type liquid crystal evaluation of physical property devices made measure.When mensuration, apply the triangular wave of 10V, 0.01Hz, calculate the area suitable with ion concentration of gained waveform, set it as ion concentration.When mensuration, the temperature of liquid crystal structure cell is made as to 23 ℃ and 60 ℃ and measures.
The mensuration > of < transmissivity
After being filtered with 1.0 μ m filters, aligning agent for liquid crystal is spun on quartz base plate, and dry after 2 minutes on the heating plate of 70 ℃, burn till 15 minutes in 230 ℃, obtain the film of thickness 100nm.Using this sample, do institute with the (Island Jin System of Shimadzu Seisakusho Ltd.) the UV-3100PC self-recording spectrophotometer of system measures.
[table 1]
Figure BDA0000474775050000241
[table 2]
[table 3]
Can be confirmed by these results, the aligning agent for liquid crystal of the application of the invention, can obtain liquid crystal aligning, rub resistance excellence, voltage retention performance is high, electric charge is accumulated minimizing, ion concentration is low, transmissivity is high and the little liquid crystal orientation film of variation of the specific insulation that caused by photoconduction.In addition, there is the liquid crystal aligning excellence of the liquid crystal display cells of the liquid crystal orientation film being obtained by aligning agent for liquid crystal of the present invention, and there are excellent electrical characteristics, therefore can be made into and be difficult for the liquid crystal display device that occurs to show the reduction of bad, contrast and burn screen.

Claims (7)

1. aligning agent for liquid crystal, it contains following particular polymers (A) and particular polymers (B);
Particular polymers (A): make the reaction of tetracarboxylic dianhydride's composition and two amine components and polyamic acid, the dianhydride of the tetrabasic carboxylic acid that described tetracarboxylic dianhydride's composition contains following formula (1) expression, at least one in the diamine compound that described two amine components contain following formula (5) and (6) expression;
[changing 1]
Figure FDA0000474775040000011
In formula (5) and (6), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical;
Particular polymers (B): the polyimide precursor with the structural unit of following formula (7) expression;
[changing 3]
In formula (7), R represents hydrogen atom or alkyl, Y represents 4 valency organic groups, and X represents divalent organic group, and 10～100 % by mole of X be in structure, have in following formula (8)～(10) any divalent organic group or to phenylene;
[changing 4]
Figure FDA0000474775040000013
In formula (8), m 1it is 2～18 integer;
[changing 5]
Figure FDA0000474775040000021
In formula (9), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical, m 2it is 1～8 integer;
[changing 6]
Figure FDA0000474775040000022
In formula (10), the one or more of the hydrogen atom arbitrarily on phenyl ring can be replaced by 1 valency organic group beyond primary amino radical, m 3it is 1～4 integer.
2. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, the tetracarboxylic dianhydride's composition in particular polymers (A) by following formula (1) represent tetrabasic carboxylic acid dianhydride and be selected from following formula (2)～(4) represent tetrabasic carboxylic acid at least one compound dianhydride form;
[changing 7]
In formula (3), R 1, R 2, R 3, R 4represent independently respectively the alkyl of hydrogen atom or carbon number 1～3.
3. aligning agent for liquid crystal as claimed in claim 2, it is characterized in that, the dianhydride of at least one compound of the tetrabasic carboxylic acid that the dianhydride of the tetrabasic carboxylic acid that the tetracarboxylic dianhydride's composition in particular polymers (A) is represented by the formula (1) of 10～100 % by mole and the formula that is selected from (2)～(4) of 0～90 % by mole represent forms.
4. aligning agent for liquid crystal as claimed in claim 3, it is characterized in that, the dianhydride of at least one compound of the tetrabasic carboxylic acid that the dianhydride of the tetrabasic carboxylic acid that the tetracarboxylic dianhydride's composition in particular polymers (A) is represented by the formula (1) of 10～100 % by mole and the formula that is selected from (3) of 0～90 % by mole represent forms.
5. the aligning agent for liquid crystal as described in any one in claim 1～4, is characterized in that, 20～100 % by mole of the Y of formula (7) is the 4 valency organic groups with aromatic structure.
6. liquid crystal orientation film, is characterized in that, requires the aligning agent for liquid crystal described in any one in 1～5 to obtain by right to use.
7. liquid crystal display cells, is characterized in that, has liquid crystal orientation film claimed in claim 6.
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