CN104718492A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- CN104718492A CN104718492A CN201380052996.4A CN201380052996A CN104718492A CN 104718492 A CN104718492 A CN 104718492A CN 201380052996 A CN201380052996 A CN 201380052996A CN 104718492 A CN104718492 A CN 104718492A
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- LUSRFRXLDMGHNU-UHFFFAOYSA-M Nc1cc(C(O[AlH2])=O)cc(N)c1 Chemical compound Nc1cc(C(O[AlH2])=O)cc(N)c1 LUSRFRXLDMGHNU-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- 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
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- 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
- C08G73/14—Polyamide-imides
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
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Abstract
Provided is a liquid crystal alignment agent comprising a solvent and a solvent-soluble polyimide obtained by imidizing a polyamic acid obtained by causing a polymerization reaction between a tetracarboxylic dianhydride that is represented by formula (1) and a diamine component. (In formula (1), W is the structure represented by the formula listed below) W: (In the formula, R1 is a hydrogen atom, -COOH, -N(CH2CH=CH2)2, or -(CH2)n1CH3. n1 is an integer between 0 and 20. R2 is -C(=O)-, -SO2-, -C(CH3)2-, -O-, -CH2-, -NH-, -C2H4-NH-CONH-C2H4-, or -O(CH2)m1O-. m1 is an integer between 1 and 5.)
Description
Technical field
The present invention relates to the aligning agent for liquid crystal, the liquid crystal orientation film using this aligning agent for liquid crystal and the liquid crystal display cells that use when making liquid crystal orientation film.
Background technology
The liquid crystal display cells used in LCD TV, liquid crystal display etc., as the display device realizing slim and light weight, is nowadays widely used.As the liquid crystal orientation film making liquid crystal aligning, the liquid crystal orientation film of the so-called polyimide of main use, this liquid crystal orientation film, by being coated with on glass substrate etc. using the solution of the polyimide precursors such as polyamic acid (also referred to as polyamic acid (polyamide acid)), poly amic acid ester or polyimide as the aligning agent for liquid crystal of major component, carries out burning till and obtaining.
In order to improve the display characteristic of this liquid crystal display cells, by changing the structure of polyamic acid, poly amic acid ester and polyimide, polyamic acid, poly amic acid ester and polyimide that blending rating is different, or add the method for adjuvant etc., carry out the improvement of liquid crystal aligning and electrical characteristics etc., the control of tilt angle etc. (with reference to patent documentation 1 etc.).
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2011-100099 publication
Summary of the invention
Invent technical matters to be solved
In above-mentioned aligning agent for liquid crystal, there is following problem in the aligning agent for liquid crystal containing polyimide: if it is first-class to be coated on substrate, then there is the phenomenon (also referred to as albefaction aggegation) of the agglutinator producing polymkeric substance (polyimide) in the end of coated surface, be difficult to obtain uniform film.
Problem of the present invention is the problem solving above-mentioned prior art, provides the aligning agent for liquid crystal of albefaction aggegation excellent, liquid crystal orientation film and liquid crystal display cells.
The technical scheme that technical solution problem adopts
Present inventor has performed and conscientiously study, found that to comprise and reaching in above-mentioned problem very effective with the aligning agent for liquid crystal of the tetracarboxylic dianhydride of the ad hoc structure solvent-soluble polyimide that is raw material and solvent, thus complete the present invention.
That is, the present invention has following main points.
1. an aligning agent for liquid crystal, is characterized in that, comprises the polyamic acid imidizate that the tetracarboxylic dianhydride that following formula (1) is represented and diamine component are carried out polyreaction and obtain and the solvent-soluble polyimide obtained and solvent.
[changing 1]
(in formula (1), W is the structure that following formula represents.)
[changing 2]
(in formula, R
1hydrogen atom ,-COOH ,-N (CH
2cH=CH
2)
2or-(CH
2)
n1cH
3; N1 is the integer of 0 ~ 20; R
2be-C (=O)-,-SO
2-,-C (CH
3)
2-,-O-,-CH
2-,-NH-,-C
2h
4-NH-CONH-C
2h
4-or-O (CH
2)
m1o-; M1 is the integer of 1 ~ 5.)
2. a liquid crystal orientation film, is characterized in that, uses the aligning agent for liquid crystal described in 1 and obtains.
3. a liquid crystal display cells, is characterized in that, possesses the liquid crystal orientation film described in 2.
The effect of invention
The albefaction aggegation excellent of aligning agent for liquid crystal of the present invention, even if the liquid crystal orientation film that therefore such as can obtain that the standing time after coating substrate etc. is long, homogeneity is also good.
Embodiment
Below, the present invention is described in detail.
Aligning agent for liquid crystal of the present invention comprises the polyamic acid imidizate that the tetracarboxylic dianhydride that above formula (1) is represented and diamine component are carried out polyreaction and obtain and the solvent-soluble polyimide obtained and solvent.Aligning agent for liquid crystal refers to the solution for making liquid crystal orientation film; Liquid crystal orientation film refers to for making liquid crystal along the film of the direction orientation of regulation.
As mentioned above, formula (1), W is the divalent group that following formula represents.In following formula, R
1hydrogen atom ,-COOH ,-N (CH
2cH=CH
2)
2or-(CH
2)
n1cH
3, preferred hydrogen atom ,-COOH or-N (CH
2cH=CH
2)
2.In addition, R
1binding site be not particularly limited, be better ortho position or contraposition relative to the-NH-be combined with phenyl ring.N1 is the integer of 0 ~ 20; R
2be-C (=O)-,-SO
2-,-C (CH
3)
2-,-O-,-CH
2-,-NH-,-C
2h
4-NH-CONH-C
2h
4-or-O (CH
2)
m1o-, preferably-SO
2-,-O-,-CH
2-,-NH-or-C
2h
4-NH-CONH-C
2h
4-.M1 is the integer of 1 ~ 5.
[changing 3]
In formula (1) ,-NH-be combined with the phenyl ring of W is present in contraposition or a position each other.
The tetracarboxylic dianhydride represented by making this formula (1) and diamine component carry out polyreaction, can obtain polyamic acid, by the polyamic acid imidizate by gained, can obtain polyimide.The polyimide of this gained is the polyimide of the solvent be dissolved in contained by aligning agent for liquid crystal of the present invention, i.e. solvent-soluble polyimide.
Aligning agent for liquid crystal of the present invention comprises the polyamic acid imidizate that the tetracarboxylic dianhydride that this formula (1) is represented and diamine component are carried out polyreaction and obtain and the solvent-soluble polyimide obtained and solvent.In addition, this solvent-soluble polyimide can be a kind of, also can be two or more.By making as mentioned above, to comprise the tetracarboxylic dianhydride represented with formula (1) be the solvent-soluble polyimide of raw material and the aligning agent for liquid crystal of solvent, as shown in following embodiment, and albefaction aggegation excellent.That is, aligning agent for liquid crystal of the present invention is coated on substrate etc. upper time, the phenomenon (also referred to as albefaction aggegation) of the agglutinator of the generation polymkeric substance (polyimide) occurred in the end of coated surface is inhibited, and therefore can obtain uniform film.Therefore, even if the liquid crystal orientation film that the standing time after coating substrate etc. is long, homogeneity is also good such as can be obtained.By making as mentioned above, to comprise the tetracarboxylic dianhydride represented with formula (1) be the solvent-soluble polyimide of raw material and the aligning agent for liquid crystal of solvent, not easily there is albefaction aggegation, the detailed reason that painting film uniformity is high is also unclear, but infer it is because under the impact of the amido link that the specific structure that has of the tetracarboxylic dianhydride represented in the formula (1) as raw material combines, improve with the intermiscibility of solvent.In addition, the tetracarboxylic dianhydride represented with formula (1) is that the dissolubility of solvent-soluble polyimide in the solvent for aligning agent for liquid crystal such as METHYLPYRROLIDONE or butoxy ethanol of raw material is high, also can not separate out even if placed for a long time by aligning agent for liquid crystal, storage stability is high.
In addition, the manufacture method of the tetracarboxylic dianhydride that formula (1) represents is not particularly limited, such as, by making 1,2,4-cyclohexanetricarboxylic acid-1,2-acid anhydride 4-acyl chlorides and H
2n-W-NH
2(W is identical with the W in formula (1)) reacts to manufacture.Specifically can exemplify the manufacture method recorded in Japanese Patent Laid-Open 2012-72121 publication.In addition, such as in manufacture, there is R
2for-C
2h
4-NH-CONH-C
2h
4-the formula (1) of W represent tetracarboxylic dianhydride time, such as, by making the diamine reactant recorded in 1,2,4-cyclohexanetricarboxylic acid-1,2-acid anhydride 4-acyl chlorides and WO2010/053128 text manufacture.
In addition, the tetracarboxylic dianhydride that the tetracarboxylic dianhydride's (being also denoted as other tetracarboxylic dianhydride below) beyond the tetracarboxylic dianhydride that formula (1) also can be made to represent and formula (1) represent reacts with diamine component together.Now, the tetracarboxylic dianhydride that formula (1) represents is better the amount use of 60 ~ 95 % by mole of the tetracarboxylic dianhydride's composition total amount to use in the synthesis of polyamic acid (and solvent-soluble polyimide), 70 ~ 90 % by mole that the are more preferably tetracarboxylic dianhydride's composition tetracarboxylic dianhydrides being formula (1) and representing.Tetracarboxylic dianhydride formula (1) represented and other tetracarboxylic dianhydride are also called tetracarboxylic dianhydride's composition.
As other tetracarboxylic dianhydride, the tetracarboxylic dianhydride that following formula (2) represents can be exemplified.
[changing 4]
(in formula (2), Z
14 valency organic groups of the carbon number 4 ~ 13 of the non-aromatic cyclic hydrocarbon base containing carbon number 4 ~ 6.)
In formula (2), as Z
1concrete example, the 4 valency organic groups that following formula (2a) ~ formula (2j) represents can be exemplified.
[changing 5]
(in formula (2a), Z
2~ Z
5be hydrogen atom, methyl, chlorine atom or phenyl ring, they can be the same or different each other; In formula (2g), Z
6and Z
7be hydrogen atom or methyl, they can be the same or different each other.)
In formula (2), from the viewpoint of the complexity of polymerisation reactivity and synthesis, Z
1particularly preferred structure be formula (2a), formula (2c), formula (2d), formula (2e), formula (2f) or formula (2g).Wherein, preferred formula (2a), formula (2e), formula (2f) or formula (2g).
In addition, the tetracarboxylic dianhydride that formula (2) represents is not particularly limited relative to the ratio of tetracarboxylic dianhydride's composition total amount, be better such as 5 ~ 40 % by mole of tetracarboxylic dianhydrides being above formula (2) and representing of tetracarboxylic dianhydride's composition total amount, be more preferably 10 ~ 30 % by mole.
As other tetracarboxylic dianhydride beyond the tetracarboxylic dianhydride that above formula (2) represents, Pyromellitic Acid can be exemplified, 2, 3, 6, 7-naphthalenetetracarbacidic acidic, 1, 2, 5, 6-naphthalenetetracarbacidic acidic, 1, 4, 5, 8-naphthalenetetracarbacidic acidic, 2, 3, 6, 7-anthracene tetracarboxylic acid, 1, 2, 5, 6-anthracene tetracarboxylic acid, 3, 3 ', 4, 4 '-bibenzene tetracarboxylic, 2, 3, 3 ', 4-bibenzene tetracarboxylic, two (3, 4-dicarboxyphenyi) ether, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic, two (3, 4-dicarboxyphenyi) sulfone, two (3, 4-dicarboxyphenyi) methane, 2, 2-two (3, 4-dicarboxyphenyi) propane, 1, 1, 1, 3, 3, 3-hexafluoro-2, 2-two (3, 4-dicarboxyphenyi) propane, two (3, 4-dicarboxyphenyi) dimethylsilane, two (3, 4-dicarboxyphenyi) diphenyl silane, 2, 3, 4, 5-pyridine tetracarboxylic acid, 2, 6-two (3, 4-dicarboxyphenyi) pyridine, 3, 3 ', 4, 4 '-diphenyl sulfone tetraformic acid, 3, 4, 9, 10-perylene tetracarboxylic acid or 1, 3-diphenyl-1, 2, 3, the dianhydride of 4-cyclobutanetetracarboxylic.
In addition, the tetracarboxylic dianhydride that the above formula (1) as the raw material of solvent-soluble polyimide represents, other tetracarboxylic dianhydride can be a kind of respectively, also can be two or more.
The diamine component that tetracarboxylic dianhydride's compositions such as the tetracarboxylic dianhydride represented with formula (1) react is not particularly limited, and can use diamines conventional in aligning agent for liquid crystal.As general diamines, general diamines can be exemplified, have and make the diamines of the side chain of liquid crystal vertical-tropism, make liquid crystal watch reveal the diamines of high tilt angle, have the diamines etc. of photoreactive group.
As general diamines, such as p-phenylenediamine (PPD) can be exemplified, 2,3,5,6-tetramethyl-para-phenylene diamine, 2,5-dimethyl-p-phenylenediamine, m-phenylene diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamido benzylalcohol, 2,4-diamido benzylalcohol, 4,6-diaminoresorcinol, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 2,2 '-diamino-diphenyl ether, 2,3 '-diamino-diphenyl ether, 4,4 '-sulfonyldianiline, 3,3 '-sulfonyldianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diaminodiphenyl sulfide, 4,4 '-diamino-diphenylamine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino-diphenylamine, 2,2 '-diamino-diphenylamine, 2,3 '-diamino-diphenylamine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diamido benzophenone, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2 '-diamido benzophenone, 2,3 '-diamido benzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalenes, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, two (3-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, Isosorbide-5-Nitrae-bis-(3-aminophenyl) butane, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminobenzene methyl) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 4,4 '-[1,3-phenylene two (methylene)] diphenylamine, 3,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 3,4 '-[1,3-phenylene two (methylene)] diphenylamine, 3,3 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 3,3 '-[1,3-phenylene two (methylene)] diphenylamine, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N '-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamide), N, N '-(1,3-phenylene) two (4-aminobenzamide), N, N '-(Isosorbide-5-Nitrae-phenylene) two (3-AB), N, N '-(1,3-phenylene) two (3-AB), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyl) terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, two (4-aminophenyl) anthracene of 9,10-, 4,4 '-bis-(4-amino-benzene oxygen) diphenylsulphone, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 2,2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, two (4-amino-benzene oxygen) propane of 1,3-, two (3-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (3-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (3-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, 1,7-(3-amino-benzene oxygen) heptane, two (4-amino-benzene oxygen) octane of 1,8-, two (3-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (3-amino-benzene oxygen) nonane of 1,9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) undecane, 1,11-(3-amino-benzene oxygen) undecane, 1,12-(4-amino-benzene oxygen) dodecane, the aromatic diamines such as 1,12-(3-amino-benzene oxygen) dodecane, two (4-aminocyclohexyl) methane, the alicyclic diamines such as two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-Diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1,11-diamino undecane, the aliphatic diamines such as 1,12-diamino dodecane.
This general diamines is better use with the amount of 50 ~ 95 of the diamine component used in the synthesis of polyamic acid (and solvent-soluble polyimide) % by mole, is more preferably 70 ~ 90 % by mole of diamine component.
As have the side chain making liquid crystal vertical-tropism diamines, make liquid crystal watch reveal the diamines of high tilt angle, can exemplify have chain alkyl, group at the midway circular structure of chain alkyl or branched structure, steroid radical, using the hydrogen moiety of these groups or the diamines of group as side chain being all substituted by fluorine atom.Specifically can exemplify the diamines that such as following formula (3), (4), (5), (6) represent, but be not limited to this.
[changing 6]
(in formula (3), l, m and n separately represent the integer of 0 or 1, R
3represent the alkylidene ether of the alkylidene of carbon number 2 ~ 6 ,-O-,-COO-,-OCO-,-NHCO-,-CONH-or carbon number 1 ~ 3, R
4, R
5and R
6separately represent phenylene or cycloalkylidene, R
7the alkyl representing hydrogen atom, carbon number 2 ~ 24 or the monovalence large ring-type replacement body containing fluoroalkyl, monovalence aromatic rings, univalent aliphatic series ring, monovalence heterocycle or be made up of them.)
In addition, from the viewpoint of the complexity of synthesis, the R in above formula (3)
3the preferably alkylidene ether of-O-,-COO-,-CONH-, carbon number 1 ~ 3.
In addition, from the viewpoint of complexity and the ability making liquid crystal vertical-tropism of synthesis, the R in formula (3)
4, R
5and R
6l, m, n, R shown in preferred following table 1
4, R
5and R
6combination.
[table 1]
| l | m | n | R 4 | R 5 | R 6 |
| 1 | 1 | 1 | Phenylene | Phenylene | Cyclohexylidene |
| 1 | 1 | 1 | Phenylene | Cyclohexylidene | Cyclohexylidene |
| 1 | 1 | 1 | Cyclohexylidene | Cyclohexylidene | Cyclohexylidene |
| 1 | 1 | 0 | Phenylene | Phenylene | － |
| 1 | 1 | 0 | Phenylene | Cyclohexylidene | － |
| 1 | 1 | 0 | Cyclohexylidene | Cyclohexylidene | － |
And, when at least one of l, m, n is 1, the R in formula (3)
7the alkyl of preferred hydrogen atom or carbon number 2 ~ 14 or containing fluoroalkyl, more preferably hydrogen atom or carbon number 2 ~ 12 alkyl or containing fluoroalkyl.In addition, when l, m, n are 0, R
7the alkyl of preferred carbon number 12 ~ 22 or replace body containing fluoroalkyl, monovalence aromatic rings, univalent aliphatic series ring, monovalence heterocycle, the large ring-type of monovalence that is made up of them, more preferably carbon number 12 ~ 20 alkyl or containing fluoroalkyl.
In addition, have and make the polymkeric substance of the side chain of liquid crystal vertical-tropism make the ability of liquid crystal vertical-tropism according to making the structure of the side chain of liquid crystal vertical-tropism and different, but in general, if make the amount of the side chain of liquid crystal vertical-tropism many, namely in diamine component, contained having makes the diamine contents of the side chain of liquid crystal vertical-tropism many, then make the ability of liquid crystal vertical-tropism improve, if above-mentioned amount is few, then aforementioned capabilities reduces.In addition, if having ring texture, then compared with not there is the situation of ring texture, exist and make the tendency that the ability of liquid crystal vertical-tropism is high.
[changing 7]
(in formula (4) and formula (5), A
10represent-COO-,-OCO-,-CONH-,-NHCO-,-CH
2-,-O-,-CO-or-NH-, A
11represent singly-bound or phenylene, a represents-R
3-(R
4)
l-(R
5)
m-(R
6)
n-R
7(R
3, R
4, R
5, R
6, R
7, l, m, n be identical with the definition in above formula (3)), a ' represents the divalent group of the structure remove the elements such as a hydrogen from the structure identical with above-mentioned a after.)
[changing 8]
(in formula (6), A
14the alkyl of the carbon number 3 ~ 20 that can be replaced by fluorine atoms, A
15isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, A
16that oxygen atom or-COO-* (, indicate key and the A of " * " here
15in conjunction with), A
17that oxygen atom or-COO-* (, indicate the key of " * " and (CH here
2) a
2in conjunction with).In addition, a
1be 0 or 1, a
2be the integer of 2 ~ 10, a
3be 0 or 1.)
To two amino (-NH in formula (3)
2) binding site do not limit.Specifically can exemplify: relative to side chain (-R
3-(R
4)
l-(R
5)
m-(R
6)
n-R
7), 2 on phenyl ring, 3,2,4,2,5,2,6,3,4,3,5.Wherein, consider from reactive viewpoint during synthesizing polyamides acid, preferably 2,4,2,5 or 3,5.If complexity when also considering synthesis diamines, then more preferably 2,4 or 3,5.
As the concrete structure of formula (3), the diamines that following formula [A-1] ~ formula [A-24] represents can be exemplified, but be not limited to this.
[changing 9]
(in formula [A-1] ~ formula [A-5], A
1be carbon number 2 ~ 24 alkyl or containing fluoroalkyl.)
[changing 10]
(in formula [A-6] and formula [A-7], A
2represent-O-,-OCH
2-,-CH
2o-,-COOCH
2-or-CH
2oCO-, A
3be the alkyl of carbon number 1 ~ 22, alkoxy, containing fluoroalkyl or fluoroalkoxy.)
[changing 11]
(in formula [A-8] ~ formula [A-10], A
4represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH
2-,-CH
2oCO-,-CH
2o-,-OCH
2-or-CH
2-, A
5be the alkyl of carbon number 1 ~ 22, alkoxy, containing fluoroalkyl or fluoroalkoxy.)
[changing 12]
(in formula [A-11] and formula [A-12], A
6represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH
2-,-CH
2oCO-,-CH
2o-,-OCH
2-,-CH
2-,-O-or-NH-, A
7fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl.)
[changing 13]
(in formula [A-13] and formula [A-14], A
8be the alkyl of carbon number 3 ~ 12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans-isomer.)
[changing 14]
(in formula [A-15] and formula [A-16], A
9be the alkyl of carbon number 3 ~ 12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans-isomer.)
[changing 15]
As the concrete example of the diamines that formula (4) represents, the diamines that following formula [A-25] ~ formula [A-30] represents can be exemplified, but be not limited to this.
[changing 16]
(in formula [A-25] ~ formula [A-30], A
12represent-COO-,-OCO-,-CONH-,-NHCO-,-CH
2-,-O-,-CO-or-NH-, A
13represent the alkyl of carbon number 1 ~ 22 or contain fluoroalkyl.)
As the concrete example of the diamines that formula (5) represents, the diamines that following formula [A-31] ~ formula [A-32] represents can be exemplified, but be not limited to this.
[changing 17]
Wherein, from the viewpoint of making the ability of liquid crystal vertical-tropism, the response speed of liquid crystal, the preferably diamines of [A-1], [A-2], [A-3], [A-4], [A-5], [A-25], [A-26], [A-27], [A-28], [A-29], [A-30].
This have make the diamines of the side chain of liquid crystal vertical-tropism and make diamines that liquid crystal watch reveals high tilt angle be better use with the amount of 0 ~ 50 of the diamine component used in the synthesis of polyamic acid (and solvent-soluble polyimide) % by mole, be more preferably 10 ~ 40 % by mole of diamine component.
As the diamines with photoreactive group; the diamines of the photoreactive group such as there is vinyl, acryloyl group, methacryl, allyl, styryl, cinnamoyl, chalcone base, cumarin base, dimaleoyl imino as side chain can be exemplified; the diamines that such as following general formula (7) represents, but be not limited to this.
[changing 18]
(in formula (7), R
8represent singly-bound or-CH
2-,-O-,-COO-,-OCO-,-NHCO-,-CONH-,-NH-,-CH
2o-,-N (CH
3)-,-CON (CH
3)-,-N (CH
3) any one in CO-, R
9represent singly-bound or the alkylidene of carbon number 1 ~ 20 that is non-substituted or that be replaced by fluorine atoms ,-the CH of alkylidene
2-can by-CF
2-or-CH=CH-at random replace, when any group below exemplified is not adjacent to each other, also can be replaced by these groups :-O-,-COO-,-OCO-,-NHCO-,-CONH-,-NH-, divalence carbocyclic ring, bivalent heterocyclic.R
10represent vinyl, acryloyl group, methacryl, allyl, styryl ,-N (CH
2cHCH
2)
2or the structure that following formula represents.)
[changing 19]
In addition, the R in above formula (7)
8although formed by the organic synthesis technology of routine, from the viewpoint of the complexity of synthesis, preferably-CH
2-,-O-,-COO-,-NHCO-,-NH-,-CH
2o-.
In addition, alternatively R
9arbitrary-CH
2-divalence carbocyclic ring or the carbocyclic ring of bivalent heterocyclic or heterocycle, specifically can exemplify following structure, but be not limited to this.
[changing 20]
Consider from photoreactive viewpoint, R
10preferred vinyl, acryloyl group, methacryl, allyl, styryl ,-N (CH
2cHCH
2)
2or the structure that following formula represents.
[changing 21]
In addition ,-the R of above formula (7)
8-R
9-R
10more preferably following structure.
[changing 22]
To two amino (-NH in formula (7)
2) binding site do not limit.Specifically can exemplify: relative to side chain (-R
8-R
9-R
10), 2 on phenyl ring, 3,2,4,2,5,2,6,3,4,3,5.Wherein, consider from reactive viewpoint during synthesizing polyamides acid, preferably 2,4,2,5 or 3,5.If complexity when also considering synthesis diamines, then more preferably 2,4 or 3,5.
As the diamines with photoreactive group, specifically can exemplify following compound, but be not limited to this.
[changing 23]
(in formula, X represents singly-bound or is selected from the conjugated group of-O-,-COO-,-NHCO-,-NH-, and Y represents singly-bound or the alkylidene of carbon number 1 ~ 20 that is non-substituted or that be replaced by fluorine atoms.)
In addition, this diamines with photoreactive group is better use with the amount of 0 ~ 70 of the diamine component used in the synthesis of polyamic acid (and solvent-soluble polyimide) % by mole, is more preferably 0 ~ 60 % by mole.
Above-mentioned diamines can according to liquid crystal aligning when making liquid crystal orientation film, tilt angle, voltage retention performance, accumulated charge, make liquid crystal display cells time the characteristic such as response speed of liquid crystal, be used alone, or mixing two or more.
The polyreaction of diamine component and tetracarboxylic dianhydride's composition is carried out usually in organic solvent.As the organic solvent now used, as long as the polyamic acid of generation can be dissolved, be not particularly limited.As concrete example, DMF can be exemplified, DMA, METHYLPYRROLIDONE, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, gamma-butyrolacton, isopropyl alcohol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, diox, normal hexane, normal heptane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether or 4-hydroxy-4-methyl-2-pentanone etc.These organic solvents can be used alone, also can be used in combination.Further, even the solvent of polyamic acid can not be dissolved, in the scope that the polyamic acid generated is not separated out, may be combined in above-mentioned solvent and use.In addition, the moisture in organic solvent hinders polyreaction, and the polyamic acid of generation can be made to be hydrolyzed, and therefore organic solvent preferably uses the organic solvent through dehydrating.
When diamine component and tetracarboxylic dianhydride's composition are reacted in organic solvent, following method can be exemplified: the solution that stirring makes diamine component be dispersed or dissolved in organic solvent and obtains, the method for then directly adding tetracarboxylic dianhydride's composition or adding again after making tetracarboxylic dianhydride's composition be dispersed or dissolved in organic solvent; The method of diamine component is added in the solution obtained making tetracarboxylic dianhydride's composition be dispersed or dissolved in organic solvent on the contrary; Alternately add the method etc. of tetracarboxylic dianhydride's composition and diamine component, any one method wherein can be used.In addition, when diamine component or tetracarboxylic dianhydride's composition use multiple reaction respectively, it can be made to react under the state be pre-mixed, it also can be made to react successively respectively, can also make to react respectively and the low-molecular weight hybrid reaction obtained.Polymerization temperature now can select the arbitrary temp of-20 DEG C ~ 150 DEG C, preferably the scope of-5 DEG C ~ 100 DEG C.In addition, reaction can be carried out with arbitrary concentration, if but concentration is too low, and be difficult to the polyamic acid (and solvent-soluble polyimide) obtaining high molecular, if excessive concentration, the viscosity of reactant liquor is too high, is difficult to stir uniformly.Therefore, the concentration of the total amount of diamine component and tetracarboxylic dianhydride's composition is preferably 1 ~ 50 quality %, more preferably 5 ~ 30 quality % in reactant liquor.Can carry out with high concentration in initial reaction stage, and then additional organic solvent.
In the polyreaction of polyamic acid, the total mole number of diamine component is preferably 0.8 ~ 1.2 with the ratio of the total mole number of tetracarboxylic dianhydride's composition.Identical with common polycondensation reaction, this mol ratio is more close to 1.0, and the molecular weight of the polyamic acid of generation is larger.
Being polymerized thus and the polyamic acid obtained, such as, is the polymkeric substance with the repetitive that following formula [a] represents.
[changing 24]
(in formula [a], R
11the 4 valency organic groups deriving from tetracarboxylic dianhydride's compositions such as tetracarboxylic dianhydride that the above formula (1) as raw material represents, R
12derive from the diamine component H as raw material
2n-R
12-NH
2divalent organic group, j represents positive integer.)
Above formula [a] can be R
11and R
12be respectively a kind of, there is the polymkeric substance of same repetitive, or also can be R
11or R
12for the polymkeric substance of multiple, that there is different structure repetitive.
Then, by making such polyamic acid dehydration closed-loop, solvent-soluble polyimide can be obtained.
As the method making polyamic acid imidizate, the hot-imide of the solution of directly heating polyamic acid can be exemplified or in the solution of polyamic acid, add the catalysis imidizate of catalyzer.
Make temperature during polyamic acid hot-imide be 100 ~ 400 DEG C in the solution, preferably 120 ~ 250 DEG C, preferably adopt the method for carrying out imidizate while being expelled to outside system by the water generated by imidization reaction.
The catalysis imidizate of polyamic acid by adding base catalyst and acid anhydrides in polyamic acid solution, at-20 ~ 250 DEG C, preferably can stir and carrying out at 0 ~ 180 DEG C.The amount of base catalyst is 0.5 ~ 30 mole times of acid amides acidic group, and be better 2 ~ 20 moles times, acid anhydrides amount is 1 ~ 50 mole times of acid amides acidic group, is better 3 ~ 30 moles times.As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine or trioctylamine etc. can be exemplified, wherein pyridine have for make reaction carry out for appropriateness alkalescence, therefore preferably.As acid anhydrides, acetic anhydride, trimellitic anhydride or pyromellitic dianhydride etc. can be exemplified, wherein, use during acetic anhydride and be easy to carry out reacting the purifying after terminating, therefore preferably.Acid imide rate based on catalysis imidizate can control by regulating catalytic amount and temperature of reaction, reaction time.
When reclaiming polymkeric substance (solvent-soluble polyimide or the polyamic acid) of generation from the reaction solution of polymkeric substance (solvent-soluble polyimide or polyamic acid), reaction solution is put in solvent and make it precipitate.As the solvent for precipitating, methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene or water etc. can be exemplified.The polymkeric substance putting into precipitation in solvent after filtered and recycled, can carry out drying under normal or reduced pressure, under normal temperature or heating.In addition, if the polymkeric substance repeating to make precipitation reclaim 2 ~ 10 times is dissolved in organic solvent and precipitate the operation of recovery more again, then the impurity in polymkeric substance can be reduced.As solvent now, can exemplify such as alcohols, ketone or hydro carbons etc., if use the solvent being selected from more than 3 kinds of above-mentioned solvent, then purification efficiency improves further, therefore preferably.
The dehydration closed-loop rate (acid imide rate) of the acid amides acidic group of the solvent-soluble polyimide contained by aligning agent for liquid crystal of the present invention need not be 100%, can select arbitrarily according to purposes and object in the scope of 0% to 100%, preferably 50% ~ 90%, more preferably 82% ~ 86%.
In addition, for the molecular weight of polyamic acid or solvent-soluble polyimide, consider the homogeneity of the operability when intensity of the polymkeric substance tunicle (liquid crystal orientation film) of gained, polymkeric substance tunicle are formed, polymkeric substance tunicle, 5000 ~ 1000000 are preferably, more preferably 10000 ~ 150000 with the Weight-average molecular gauge utilizing GPC (gel permeation chromatography) method to record.
< solvent >
In addition, as long as the solvent contained by aligning agent for liquid crystal of the present invention can dissolve above-mentioned solvent-soluble polyimide, be not particularly limited, N can be exemplified, dinethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl-2-pyrrolidone, NVP, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 1, 3-dimethyl-2-imidazolidinone, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, the organic solvents such as diethylene glycol dimethyl ether and 4-hydroxy-4-methyl-2-pentanone.These organic solvents can be used alone, also can be used in combination.
For the solvent in aligning agent for liquid crystal of the present invention, form uniform polymkeric substance tunicle from the viewpoint of by coating, the content of solvent is preferably 70 ~ 99 quality %.Its content suitably can change according to the thickness of Object LC alignment films.
The composition > of other aligning agent for liquid crystal of <
Component of polymer contained by aligning agent for liquid crystal of the present invention can be only the polyamic acid imidizate that the tetracarboxylic dianhydride that above formula (1) is represented and diamine component are carried out polyreaction and obtain and the solvent-soluble polyimide obtained, the polyamic acid imidizate that also tetracarboxylic dianhydride that above formula (1) is represented and diamine component can be carried out polyreaction and obtain and the solvent-soluble polyimide that obtains and other polymer mixed in addition.Now, the total amount of the solvent-soluble polyimide obtained relative to the polyamic acid imidizate that the tetracarboxylic dianhydride making above formula (1) represent and diamine component are carried out polyreaction and obtain, the content of other polymkeric substance is in addition 0.5 ~ 90 quality %, preferably 1.0 ~ 80 quality %.As other polymkeric substance in addition, except the polyamic acid that the tetracarboxylic dianhydride represented except making above formula (1) and diamine component carry out polyreaction and obtain, also can exemplify by not comprising tetracarboxylic dianhydride's composition of the tetracarboxylic dianhydride that above formula (1) represents and diamine component and the polyamic acid obtained or solvent-soluble polyimide.Further, as the polymkeric substance beyond polyamic acid and solvent-soluble polyimide, specifically, poly amic acid ester, acrylate copolymer, methacrylate polymer, polystyrene or polyamide etc. can be exemplified.
In aligning agent for liquid crystal of the present invention, in the scope not damaging effect of the present invention, can containing the film thickness uniformity of polymkeric substance tunicle when can improve coating of liquid crystalline alignment agent further and the organic solvent (also referred to as poor solvent) of surface smoothness or compound.The compound etc. of the adaptation that can improve liquid crystal orientation film and substrate can also be contained.
As the concrete example of poor solvent improving film thickness uniformity and surface smoothness, such as isopropyl alcohol can be exemplified, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, normal hexane, n-pentane, normal octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 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, propylene glycol-1-single ethylether-2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate or isoamyl lactate etc. have the organic solvent etc. of low surface tension.
These poor solvents can use one, also can be multiple used in combination.When using poor solvent as above, be better 5 ~ 80 quality % accounting for organic solvent total amount contained in aligning agent for liquid crystal, be more preferably 20 ~ 60 quality %.
As the compound improving film thickness uniformity and surface smoothness further, fluorine class surfactant, siloxane type surfactants, non-ionics etc. can be exemplified.More specifically, such as エ Off ト ッ プ EF301 can be exemplified, EF303, EF352 (illuminating product Co., Ltd. (ト ー ケ system プ ロ ダ クツ society) system), メ ガ Off ァ ッ Network F171, F173, R-30 (large Japanese ink Co., Ltd. (large Japanese イ Application キ society) system), Off ロ ラ ー De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ ー エ system society) system), ア サ ヒ ガ ー De AG710, サ ー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc.The usage ratio of these surfactants relative to component of polymer 100 mass parts contained in aligning agent for liquid crystal, preferably 0.01 ~ 2 mass parts, more preferably 0.01 ~ 1 mass parts.
As the compound of adaptation improving liquid crystal orientation film and substrate, can exemplify containing functional silanes compound or contain the compound of epoxy radicals, such as 3-TSL 8330 can be exemplified, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTES of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) cyclohexane of 1,3-, N, N, N ', N ' ,-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
During the compound using these to improve with the adaptation of substrate, relative to component of polymer 100 mass parts contained in aligning agent for liquid crystal, its content is better 0.1 ~ 30 mass parts, is more preferably 1 ~ 20 mass parts.If less than 0.1 mass parts, then cannot expect the effect that adaptation improves, if more than 30 mass parts, then the orientation of liquid crystal is deteriorated sometimes.
In aligning agent for liquid crystal of the present invention except above-mentioned poor solvent and compound, as long as in the scope not damaging effect of the present invention, then can add dielectric and the conductive materials of the object for reaching the electrical characteristics such as specific inductive capacity, electric conductivity changing liquid crystal orientation film.
< liquid crystal orientation film liquid crystal display cells >
Aligning agent for liquid crystal of the present invention to be coated on substrate and after burning till, the orientation process such as can carry out that friction treatment or illumination are penetrated, thus is used as liquid crystal orientation film.In addition, during for vertical orientated purposes etc., even if do not carry out orientation process can be used as liquid crystal orientation film yet.As substrate now used, as long as the substrate that the transparency is high, be not particularly limited, except glass substrate, also can use the plastic bases etc. such as acrylic acid substrate and polycarbonate substrate.Simplify from the viewpoint of technique, preferably use is formed with the substrate of ITO (tin indium oxide (Indium Tin the Oxide)) electrode etc. for liquid crystal drive.In addition, in reflection type liquid crystal display element, also can use the opaque substrates such as silicon wafer, but be only limitted to one-sided substrate, electrode now also can use the material of the reflected light such as aluminium.
Be not particularly limited the coating process of aligning agent for liquid crystal, the method be coated with is carried out in industrial usual employing by serigraphy, hectographic printing, flexographic printing or ink-jet method etc.As other coating process, there are infusion process, rolling method, slot coated method, spin-coating method or spraying process etc., these methods can be used according to object.The albefaction aggegation excellent of above-mentioned aligning agent for liquid crystal of the present invention, so the agglutinator of solvent-soluble polyimide that the end of the coated surface producing coating of liquid crystalline alignment agent on substrate hardly and formed easily produces, therefore, it is possible to the liquid crystal orientation film of obtained homogeneity and transparency excellence.
Although it is not required for aligning agent for liquid crystal being coated the drying process after on substrate, when not burning till immediately to unfixing for each block substrate during this period of time or coating of burning till after coating, preferably comprise drying process.As long as the degree that solvent removing can not be out of shape because of reasons such as the transports of substrate to film shape by this drying, this drying means is not particularly limited.Such as, dry 0.5 ~ 30 minute can be exemplified on the heating plate of temperature 40 DEG C ~ 150 DEG C, preferably 60 DEG C ~ 100 DEG C, the preferred method of 1 ~ 5 minute.
By burning till the film formed with said method coating of liquid crystalline alignment agent, can be made into liquid crystal orientation film (polymkeric substance tunicle).Now, firing temperature can be the arbitrary temp of 100 DEG C ~ 350 DEG C, preferably 140 DEG C ~ 300 DEG C, more preferably 150 DEG C ~ 230 DEG C, is more preferably 160 DEG C ~ 220 DEG C.As firing time, it can be the random time of 5 minutes ~ 240 minutes.Preferably 10 ~ 90 minutes, more preferably 20 ~ 80 minutes.Heating can adopt conventional known method, such as heating plate, heat-circulation type stove or IR (infrared ray) type stove, band oven etc.If the thickness of the liquid crystal orientation film after burning till is blocked up, then unfavorable in the power consumption of liquid crystal display cells, if excessively thin, then the reliability of liquid crystal display cells reduces sometimes, therefore preferably 5 ~ 300nm, more preferably 10 ~ 100nm.When making liquid crystal horizontal alignment or tilted alignment, by rub or polarized UV rays irradiation etc., process is implemented to the liquid crystal orientation film after burning till.
Liquid crystal display cells of the present invention, after being with the substrate of liquid crystal orientation film by said method by aligning agent for liquid crystal acquisition of the present invention, is manufactured the liquid crystal display cells of liquid crystal cell by known method.To enumerate an example, then liquid crystal display cells of the present invention is the liquid crystal display cells possessing following liquid crystal cell, this liquid crystal cell comprise configure in opposite directions two pieces of substrates, be arranged on the liquid crystal layer between substrate and be arranged on the above-mentioned liquid crystal orientation film formed by aligning agent for liquid crystal of the present invention between substrate and liquid crystal layer.As such liquid crystal display cells of the present invention, the various liquid crystal display cells such as twisted-nematic (TN:TwistedNematic) mode, vertical orientated (VA:Vertical Alignment) mode, horizontal alignment (IPS:In-Plane Switching) mode, OCB orientation (OCB:Optically CompensatedBend) can be exemplified.
As the manufacture method of liquid crystal cell, following method can be illustrated: a pair substrate preparing to be formed with above-mentioned liquid crystal orientation film, the liquid crystal orientation film of one piece of substrate scatters sept, be in the mode of inner side by another block baseplate-laminating with liquid crystal aligning face, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with sept after, baseplate-laminating is carried out the method etc. sealed.
In addition, manufacture in the liquid crystal display cells of the mode (vertical orientation mode) that the liquid crystal molecule vertical orientated relative to substrate is responded under the effect of electric field, when PSA (Polymer Sustained Alignment) the type liquid crystal display of adding photopolymerizable compound in advance in liquid-crystal composition or the SC-PVA type liquid crystal display of adding photopolymerizable compound in liquid crystal orientation film (aligning agent for liquid crystal), liquid crystal etc. can be injected and after sealing being formed with between a pair substrate of above-mentioned liquid crystal orientation film, while to liquid crystal orientation film and liquid crystal applied voltages irradiation ultraviolet radiation on one side, thus polymerizable compound is polymerized.
As liquid crystal, the positive type liquid crystal with positive dielectric constant anisotropy or the negative type liquid crystal with negative dielectric constant anisotropy can be used, specifically, MLC-2003, MLC-6608, MLC-6609 etc. that Merck & Co., Inc. (メ ルク society) makes can such as be used.
As mentioned above, the liquid crystal display cells made with aligning agent for liquid crystal of the present invention is owing to having uniform liquid crystal orientation film, therefore excellent in reliability.
[embodiment]
Below, exemplify embodiment and more specific description is carried out to the present invention.In addition, the present invention should not be construed as limited to this.The abbreviation used in embodiment and comparative example is as described below.
< tetracarboxylic dianhydride >
PPHT: the N that following formula represents, N '-bis-(1,2-cyclohexane dicarboxylic acid acid anhydride-4-base) carbonyl-Isosorbide-5-Nitrae-phenylenediamine
PSHT: the N that following formula represents, N '-bis-(1,2-cyclohexane dicarboxylic acid acid anhydride-4-base) carbonyl-3,3 '-diamino-diphenyl sulfone
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
TDA:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride
[changing 25]
< diamines >
Two (4-aminophenethyl) urea of BAPU:1,3-
DADA:N, N-diallyl-2,4-diamido aniline
APC16:1,3-diamido-4-hexadecane oxygen base benzene
APC18:1,3-diamido-4-octadecane oxygen base benzene
P-PDA: p-phenylenediamine (PPD)
< organic solvent >
NMP:N-N-methyl-2-2-pyrrolidone N-
BCS:2-butyl cellosolve
The assay method implemented in the present embodiment is below shown.
The mensuration > of < molecular weight
The molecular weight of polyamic acid and polyimide measures this polyamic acid or polyimide by GPC (normal temperature gel permeation chromatography) device, calculates number-average molecular weight and weight-average molecular weight as polyglycol, polyethylene oxide scaled value.
GPC device: Shodex (Showa Denko K. K) Inc. (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 DEG C
Eluent: N, N'-dimethyl formamide (as adjuvant, lithium bromide-hydrate (LiBrH
2o) be 30 mMs/L, phosphoric acid anhydrous crystal (o-phosphoric acid) is 30 mMs/L, tetrahydrofuran (THF) is 10mL/L)
Flow velocity: 1.0ml/ minute
Calibration curve making standard sample: (East ソ ー society of TOSOH Co., Ltd) polyglycol (molecular weight about 12000,4000,1000) made of TSK standard polyethylene oxide processed (molecular weight about 900000,150000,100000,30000) and Polymer Laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society).
The mensuration > of < acid imide rate
The acid imide rate of polyimide measures as follows.
The polyimide powder of 20mg is joined NMR stopple coupon, adds deuterated dimethyl sulfoxide (DMSO-d
6, 0.05%TMS (tetramethylsilane) potpourri) 0.53ml, make it dissolve completely.For this solution, determine the proton N MR of 500MHz with the NMR analyzer (JNM-ECA500) that NEC data Co., Ltd. (Japanese Electricity デ ー タ system society) makes.Acid imide rate is tried to achieve as follows: the proton coming from unconverted structure before and after imidizate is decided to be standard proton, uses the peak integrated value of this proton and the proton peak integrated value of the NH base from polyamic acid that occurs near 9.5ppm ~ 10.0ppm to be tried to achieve by following formula.
Acid imide rate (%)=(1-α x/y) × 100
In above formula, x is the proton peak integrated value of the NH base from polyamic acid, and y is the peak integrated value of standard proton, the number ratio of the reference proton of NH matrix relative to polyamic acid when α is polyamic acid (acid imide rate is 0%).
(synthesis example 1)
Use the PPHT of 1.33g as tetracarboxylic dianhydride's composition, use the p-PDA of 0.32g as diamine component, react 18 hours in the NMP of 14.93g, at room temperature, obtain the solution of the solid component concentration 10wt% of polyamic acid (PAA-1).
(synthesis example 2 ~ 8)
Except adopting the composition shown in table 2, the method same with above-mentioned synthesis example 1 is adopted to obtain the solution of the polyamic acid (PAA-2 ~ PAA-8) of synthesis example 2 ~ 8.
[table 2]
(synthesis example 9)
The NMP adding 12.59g in the solution 15.1g of the polyamic acid (PAA-1) obtained in synthesis example 1 dilutes, and is modulated into the polyamic acid solution of solid component concentration 6wt%.In this polyamic acid solution, add acetic anhydride 2.95g and pyridine 1.37g, react 3 hours at 50 DEG C, carry out imidizate.After the polyimide solution obtained is cooled to room temperature, be fed in 150g methyl alcohol, reclaim the solid matter of precipitation.Further, after this solid matter of washed with methanol 2 times, in 100 DEG C of drying under reduced pressure, the khaki powder of polyimide (SPI-1) is obtained.Measure the acid imide rate of polyimide (SPI-1), result is 79%.
(synthesis example 10 ~ 16)
Except adopting the composition shown in table 3, the method same with above-mentioned synthesis example 9 is adopted to obtain the powder of the polyimide (SPI-2 ~ SPI-8) of synthesis example 10 ~ 16.
[table 3]
(embodiment 1)
Add the NMP of 7.53g in polymkeric substance (polyimide SPI-1) 0.50g obtained in above-mentioned synthesis example 9, at room temperature stir 3 hours.At the end of stirring, polyimide dissolves completely.In this solution, add the BCS of 2.01g further, at room temperature stir 1 hour, obtain the polymer solution (A1) that solid component concentration is 5.0wt%.Using this polymer solution directly as the aligning agent for liquid crystal for the formation of liquid crystal orientation film.
(embodiment 2 ~ 7, comparative example 1)
Except adopting the composition shown in table 4, method is similarly to Example 1 adopted to obtain the polymer solution (A2 ~ A7) of embodiment 2 ~ 7 and the polymer solution (B1) of comparative example 1.In addition, also all similarly to Example 1, at the end of stirring, polyimide dissolves each embodiment 2 ~ 7 completely.
[table 4]
[making of liquid crystal cell]
By the polymer solution (A1), the i.e. aligning agent for liquid crystal (A1) that obtain in embodiment 1 with after 1.0 μm of frit, be spun on the glass substrate of band transparency electrode, on the heating plate of 80 DEG C after dry 80 seconds, burn till 10 minutes in 230 DEG C, obtain the film (polyimide film) of thickness 100nm.Rub after (roller footpath 120mm, rotating speed 1000rpm, translational speed 50mm/sec, intrusion 0.3mm) with rayon cloth to this polyimide film, the ultrasonic irradiation of 1 minute is carried out in pure water, in 80 DEG C of dryings 10 minutes, form liquid crystal orientation film.Prepare two pieces of substrates with above-mentioned liquid crystal orientation film, after the liquid crystal aligning face of one piece of substrate arranges the sept of 6 μm, with the orthogonal condition of the frictional direction of two pieces of substrates by two pieces of substrate in combination, by environmental seal, but leave liquid crystal injecting port, make the negative crystal born of the same parents that structure cell interval (cell gap) is 6 μm.In this structure cell, under normal temperature, vacuum injects liquid crystal (MLC-2003 (C080), Merck Japanese firm (メ Le Network ジ ャ パ Application society) makes), and sealing inlet, obtains the liquid crystal cell of liquid crystal torsion 90 degree of orientations.
In addition, about the aligning agent for liquid crystal (B1) obtained in the aligning agent for liquid crystal obtained in embodiment 2 ~ 7 (A2 ~ A7) and comparative example 1, the method same with the aligning agent for liquid crystal (A1) obtained in embodiment 1 is also adopted to manufacture liquid crystal cell.
[evaluation of tilt angle]
After 1 hour is heated at 120 DEG C to the liquid crystal cell of gained, carry out the mensuration of tilt angle." the Axo Scan " of tilt angle Axo Metrix company adopts Muller matrix method to measure.Result is shown in table 5.
[evaluation of albefaction aggegation characteristic]
Cr substrate drips each aligning agent for liquid crystal (polymer solution) respectively that obtain in the embodiment 1 ~ 7 of about 0.1ml and comparative example 1, places under the environment of temperature 23 DEG C, humidity 55%.Near the every 10 minutes ends with this drop of microscopic examination.In addition, observe and carry out with the multiplying power of 100 times.Produce time of agglutinator being evaluated as below 10 minutes ×, be evaluated as △ more than 10 minutes and less than 1 hour, be evaluated as zero more than 1 hour and less than 3 hours, more than 3 hours, be evaluated as ◎.Evaluation result is shown in table 5.
[table 5]
As shown in table 5, the known tetracarboxylic dianhydride containing representing with formula (1) is that the aligning agent for liquid crystal (polymer solution) of the embodiment 1 ~ 7 of the polyimide of raw material is in the evaluation of albefaction aggegation characteristic, even if place and also do not produce agglutinator completely in more than 3 hours, there is excellent albefaction aggegation characteristic.On the other hand, comparative example 1 produced agglutinator within 10 minutes, and albefaction aggegation characteristic is poor.In addition, also confirm that the aligning agent for liquid crystal of embodiment 1 ~ 7 achieves the good orientation (tilt angle) of liquid crystal by orientation process.
Claims (3)
1. an aligning agent for liquid crystal, is characterized in that, comprises the polyamic acid imidizate that the tetracarboxylic dianhydride that following formula (1) is represented and diamine component are carried out polyreaction and obtain and the solvent-soluble polyimide obtained and solvent;
In formula (1), W is the structure that following formula represents;
In formula, R
1hydrogen atom ,-COOH ,-N (CH
2cH=CH
2)
2or-(CH
2)
n1cH
3; N1 is the integer of 0 ~ 20; R
2be-C (=O)-,-SO
2-,-C (CH
3)
2-,-O-,-CH
2-,-NH-,-C
2h
4-NH-CONH-C
2h
4-or-O (CH
2)
m1o-; M1 is the integer of 1 ~ 5.
2. a liquid crystal orientation film, is characterized in that, uses the aligning agent for liquid crystal described in claim 1 and obtains.
3. a liquid crystal display cells, is characterized in that, possesses liquid crystal orientation film according to claim 2.
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| JP2012178940 | 2012-08-10 | ||
| JP2012-178940 | 2012-08-10 | ||
| PCT/JP2013/071283 WO2014024893A1 (en) | 2012-08-10 | 2013-08-06 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
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| JP (1) | JP6217937B2 (en) |
| KR (1) | KR102146140B1 (en) |
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| JP6394045B2 (en) * | 2014-04-25 | 2018-09-26 | 日本ゼオン株式会社 | Polyimide, laminated film, retardation film, and laminated film manufacturing method |
| JP6394046B2 (en) * | 2014-04-25 | 2018-09-26 | 日本ゼオン株式会社 | Varnish, laminate, and method for producing laminate |
| JP2016124956A (en) * | 2014-12-26 | 2016-07-11 | 富士ゼロックス株式会社 | Polyamideimide precursor composition, polyamideimide molded article, and method for preparing polyamideimide molded article |
| JP6551040B2 (en) * | 2015-08-18 | 2019-07-31 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
| JP7139956B2 (en) * | 2018-10-04 | 2022-09-21 | Jnc株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, tetracarboxylic dianhydride, polyamic acid and its derivatives |
| JP7120032B2 (en) * | 2019-01-10 | 2022-08-17 | Jnc株式会社 | Liquid crystal aligning agent for photo-alignment, liquid crystal alignment film, and liquid crystal display element |
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| JPH0820637B2 (en) * | 1988-05-10 | 1996-03-04 | 日立化成工業株式会社 | Liquid crystal alignment film and liquid crystal display device |
| TWI427121B (en) * | 2006-09-01 | 2014-02-21 | Jnc Corp | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP5407394B2 (en) | 2008-03-21 | 2014-02-05 | Ｊｎｃ株式会社 | Photo-alignment agent, alignment film, and liquid crystal display device using the same |
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| JP5783023B2 (en) * | 2011-12-07 | 2015-09-24 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
-
2013
- 2013-08-06 WO PCT/JP2013/071283 patent/WO2014024893A1/en active Application Filing
- 2013-08-06 KR KR1020157005589A patent/KR102146140B1/en active IP Right Grant
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- 2013-08-06 JP JP2014529519A patent/JP6217937B2/en active Active
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| CN1085890A (en) * | 1987-10-08 | 1994-04-27 | 日立化成工业株式会社 | Dicyclohexyl-3,4,3 ', 4 '-tetracarboxylic acid or its dianhydride and the polymeric amide-acid and the polyimide of gained thus |
| WO2006129771A1 (en) * | 2005-06-01 | 2006-12-07 | Mitsubishi Chemical Corporation | Tetracarboxylic acid or polyesterimide thereof, and process for production of the same |
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| CN104718492B (en) | 2018-09-18 |
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| KR20150043360A (en) | 2015-04-22 |
| JPWO2014024893A1 (en) | 2016-07-25 |
| JP6217937B2 (en) | 2017-10-25 |
| TW201422677A (en) | 2014-06-16 |
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