CN101570636A - Liquid crystal aligning agent, liquid crystal display element, polyamic acid and imide amination polymer and compound thereof - Google Patents
Liquid crystal aligning agent, liquid crystal display element, polyamic acid and imide amination polymer and compound thereof Download PDFInfo
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- CN101570636A CN101570636A CNA2009101373751A CN200910137375A CN101570636A CN 101570636 A CN101570636 A CN 101570636A CN A2009101373751 A CNA2009101373751 A CN A2009101373751A CN 200910137375 A CN200910137375 A CN 200910137375A CN 101570636 A CN101570636 A CN 101570636A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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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
- G02F1/133703—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by introducing organic surfactant additives into the liquid crystal material
Abstract
The present invention relates to a liquid crystal aligning agent, a liquid crystal display element, a polyamic acid and an imide amination polymer and a compound thereof. Provided is a liquid crystal aligning agent with excellent printing property, capable of forming a liquid crystal aligning film without display spot having a high vertical aligning control force even though a VA type liquid crystal display element is produced by an ODF mode. The liquid crystal aligning agent contains at least one polymer selected from a group composed of the polyamic acid and the imide amination polymer thereof, and the polyamic acid is prepared by a reaction of tetracarboxylic acid di-anhydride and a diamin containing a special compound such as a typical compound represented by formula (1-2-1).
Description
Technical field
The present invention relates to liquid crystal aligning agent and liquid crystal display device.More particularly, even relate to when in the liquid crystal filling work procedure that liquid crystal display device is made, adopting under the liquid crystal drop mode (ODF mode), also can form the liquid crystal aligning agent that the liquid crystal orientation film of ODF spot can not occur, polyamic acid, its imide amination polymer, compound and by its liquid crystal display device that makes.
Background technology
At present, as liquid crystal display device, known TN type liquid crystal display device with so-called TN type (twisted-nematic) liquid crystal cell, it is being provided with the liquid crystal orientation film that formation is formed by polyamic acid, polyimide etc. on the substrate surface of nesa coating, substrate as used for liquid crystal display element, two these substrates are oppositely arranged, form nematic liquid crystal layer betwixt in the crack with positive dielectric anisotropy, constitute the box of sandwich structure, the major axis of liquid crystal molecule reverses 90 ° from a substrate continuously to another piece substrate.And, also developed and compared little IPS (switching face in) the type liquid crystal display device of STN (supertwist is to row) the type liquid crystal display device that can realize high-contrast and view angle dependency, VA (vertical orientated) type liquid crystal display device, optical compensation curved (OCB) type liquid crystal display device that video pictures high-speed response of little while of view angle dependency is good with TN type liquid crystal display device.
Material as the liquid crystal orientation film in these liquid crystal display device, known in the past polyimide, polymeric amide and polyester etc., polyimide particularly, because its thermotolerance, good with the affinity of liquid crystal, physical strength etc., and be used in most liquid crystal display device.
And in recent years, the manufacturing process of liquid crystal display device has obtained very big progress.Particularly with the maximization of substrate simultaneously, the technology such as (One Drop Fill mode abbreviate " ODF mode " as in this area) of mode under large substrate transportation techniques that is adopted and the liquid crystal drop is noticeable.This ODF mode, be at the liquid crystal that forms the necessary amounts of dripping on the substrate of liquid crystal orientation film, make its under vacuum with another piece baseplate-laminating after, the sealing agent of encapsulated liquid crystals is carried out UV curing, make all methods of filling liquid crystal of whole front panel, be to compare, can significantly shorten the technology of the engineering time of liquid crystal filling work procedure with the vacuum injection mode of implementing all the time.But, if adopt the ODF mode in the manufacturing processed of the VA type liquid crystal display device with polyimide liquid crystal orientation film, the trouble of the demonstration spot that is called " ODF spot " then can appear producing.This phenomenon is considered to cause inadequately owing to the vertical orientated control of liquid crystal orientation film.
In order to solve this problem of polyimide liquid crystal orientation film, occurred for example adopting by the method (referring to Patent Document 1 and 2) that contains the polyimide that diamines that ratio contains the diamines with hydrophobic functional groups such as chain alkyls makes with height.This technology is to confirm to have the excellent technique that improves vertical orientated control effect, yet the situation of the printing of infringement liquid crystal aligning agent occurred.
Therefore, need not damage required various of liquid crystal aligning agent must performance particularly printing, can form the liquid crystal aligning agent that can not produce the liquid crystal orientation film of above-mentioned ODF spot, and display quality liquid crystal display device with excellent.
[patent documentation 1] Japanese kokai publication hei 9-241646 communique
[patent documentation 2] TOHKEMY 2001-305549 communique
[patent documentation 3] Japanese kokai publication hei 9-278724 communique
No. 2684404 specification sheets of [patent documentation 4] Japanese Patent
[patent documentation 6] TOHKEMY 2002-327058 communique
Summary of the invention
The objective of the invention is, even provide when in the manufacturing processed of VA type liquid crystal display device, adopting the ODF mode, also can form and can not produce the liquid crystal orientation film that shows spot and show high vertical orientated control, and as the required various performances of liquid crystal aligning agent, the particularly good liquid crystal aligning agent of printing, and display quality liquid crystal display device with excellent.
The present invention is other purposes and advantage further, can be found out by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, first, reach by a kind of liquid crystal aligning agent, it comprises at least a polymkeric substance of selecting from the group of polyamic acid and imide amination polymer formation thereof, this polyamic acid is obtained with the diamine reactant of the compound that contains following formula (1) expression by the tetracarboxylic dianhydride
(in the formula (1), R is that the optional carbonatoms that is replaced by fluorine atom is 3～20 alkyl, and A is 1,4-cyclohexylidene or 1,4-phenylene, B
1For Sauerstoffatom or-OCO-
*(connecting key and (CH that wherein, have " * "
2)
bConnect), B
2For Sauerstoffatom or-COO-
*(connecting key that wherein, has " * " is connected with A), a is 0 or 1, and b is 2～10 integer, and c is 0 or 1).
Above-mentioned purpose of the present invention and advantage, the second, reach by liquid crystal display device with the liquid crystal orientation film that forms by above-mentioned liquid crystal aligning agent.
Embodiment
Liquid crystal aligning agent of the present invention comprises at least a polymkeric substance of selecting from the group of polyamic acid and imide amination polymer formation thereof, this polyamic acid is obtained with the diamine reactant of the compound that contains above-mentioned formula (1) expression by the tetracarboxylic dianhydride.
[polyamic acid]
The polyamic acid that can comprise in the liquid crystal aligning agent of the present invention can synthesize by making the tetracarboxylic dianhydride and the diamine reactant of the compound that contains above-mentioned formula (1) expression.
[tetracarboxylic dianhydride]
Used tetracarboxylic dianhydride in the polyamic acid that can comprise as liquid crystal aligning agent of the present invention synthetic can enumerate for example butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 3,5,6-three carboxyls norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2, the 5-dioxotetrahydrofuryl)-and 3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, following formula (T-I) and aliphatics or the ester ring type tetracarboxylic dianhydrides such as compound that (T-II) represent separately;
(in the above-mentioned formula, R
1And R
3Expression has the divalent organic group of aromatic nucleus, R separately
2And R
4Represent hydrogen atom or alkyl separately, a plurality of R of existence
2And R
4Separately can be identical, also can be different);
The pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dianhydride, to phenylene-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butyleneglycol-two (dehydration trimellitate), 1,6-hexylene glycol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), aromatic tetracarboxylic acid's dianhydrides such as compound that following formula (T-1)～(T-4) is represented separately.They can a kind ofly be used alone or in combination of two or more.
Used tetracarboxylic dianhydride in the polyamic acid that liquid crystal aligning agent of the present invention can comprise synthetic is from making the angle of the good liquid crystal aligning of its performance, preferably contain the butane tetracarboxylic acid dianhydride that is selected from the middle of above-mentioned, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5, the tetracarboxylic dianhydride of at least a (hereinafter referred to as " specific tetracarboxylic dianhydride (1) ") in the group that the compound of following formula (T-8) expression in the compound that the following formula (T-5)～(T-7) in the compound of 8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I) expression is represented separately and the compound of above-mentioned formula (T-II) expression constitutes.
As specific tetracarboxylic dianhydride (1), be preferably selected from 1,2 especially, 3,4-tetramethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, at least a in the group that the compound of 10-tetraketone, pyromellitic acid dianhydride and above-mentioned formula (T-5) expression constitutes.
In the polyamic acid that liquid crystal aligning agent of the present invention can comprise synthetic among the employed tetracarboxylic dianhydride, with respect to whole tetracarboxylic dianhydrides, preferably contain the above above-mentioned specific tetracarboxylic acid (1) of 20 moles of %, more preferably contain 50 moles more than the %, especially preferably contain 80 moles more than the %.
[diamines]
Used diamines in the polyamic acid that can contain in the liquid crystal aligning agent of the present invention synthetic is the diamines that contains the compound of above-mentioned formula (1) expression.
As the R in the above-mentioned formula (1), be preferably carbonatoms and be 3～10 alkyl, more preferably carbonatoms is 3～10 straight chained alkyl.B is preferably 2～6 integer.The diamino-phenyl in above-mentioned formula (1) left side is preferably 2,4-diamino-phenyl or 3,5-diamino-phenyl.
As the preferred example of the compound of above-mentioned formula (1) expression, can enumerate the compound that for example following formula (1-1)～(1-8) is represented separately,
(in the formula (1-1)～(1-8), b is identical with the definition in the above-mentioned formula (1), and d is 2～9 integer).
The compound of above-mentioned formula (1) expression, can by for example with the compound of following formula (2) expression as raw material,
Ordinary method in the organic chemistry is carried out suitable combination and synthesize.For example above-mentioned formula (1-2), (1-3) and the compound of (1-7) representing separately separately can be synthetic by arbitrary method of following synthetic route 1～3.
Synthetic route 1
Synthetic route 2
Synthetic route 3
(in the synthetic route 1～3, b and d respectively with above-mentioned formula (1-2), (1-3) or the definition (1-7) identical).The compound of above-mentioned formula (2) expression can be by adopting usually in liquid crystal compounds synthetic Grignard reaction, Knut Fridell-Kerafyrm thatch acylation reaction, triumphant cherish receive method such as (Kishner) reaction and synthesize.
Related other compounds in the above-mentioned formula (1) also can synthesize according to the method described above.
In the liquid crystal aligning agent of the present invention, because with following formula (2 ')
Contain-(CH in the structure of (in the formula (2 '), R is identical with the definition in the above-mentioned formula (1) separately with c) expression and the linking group that polymkeric substance is connected
2)
b-(wherein, b is identical with the definition in the above-mentioned formula (1).Together following), thereby can show high vertical orientated control.As the structure technology of employing with the similar of above-mentioned formula (2 '), the technology of record in known patent document 3 (Japanese kokai publication hei 9-278724 communique) and the patent documentation 4 (No. 2684404 Japanese patent specification), and the vertical orientated control of the liquid crystal orientation film that is formed by liquid crystal aligning agent of the present invention has surpassed these prior aries.This is because the structure of above-mentioned formula (2 ') has got involved the performance of vertical orientated control to a great extent by inference, its by by flexible big-(CH
2)
b-appear at the cause on the surface of liquid crystal orientation film.
Used diamines in the polyamic acid that can comprise in the liquid crystal aligning agent of the present invention synthetic can be the diamines that only contains the compound of above-mentioned formula (1) expression, perhaps also can be to remove the diamines that also contains other diamines the compound that above-mentioned formula (1) represents.
As operable other diamines here, can enumerate for example Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formylaniline, 4,4 '-diaminodiphenyl oxide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two (trifluoromethyl)-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diamino benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2,7 diamin of luorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene radical-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to the phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl;
1,1-m-xylene diamine, 1,3-propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamino heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0
2,7] 11 alkylidene group dimethyl diamines, 4,4 '-methylene radical two aliphatics or ester ring type diamines such as (hexahydroaniline);
2,3 diamino pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2,4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazines, 1,4-two (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazines, 2,4-diamino-6-methoxyl group-1,3, the 5-triazine, 2,4-diamino-6-phenyl-1,3, the 5-triazine, 2,4-diamino-6-methyl-s-triazine, 2, the 4-diaminostilbene, 3, the 5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3, the 5-diaminostilbene, 2, the 4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, 1,4-diamino piperazine, 3, the 6-proflavin, two (4-aminophenyl) phenyl amine, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl) p-diaminodiphenyl, the compound of following formula (D-I) expression
(in the formula (D-I), R
5The 1 valency organic group that expression has the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X
1The organic group of expression divalent, R
6The expression carbonatoms is 1～4 alkyl, and a1 represents 0～3 integer), have the diamines of the nitrogen-atoms beyond two primary aminos and this primary amino in the compound equimolecular of following formula (D-II) expression,
(in the formula (D-II), R
7The divalent organic group that expression has the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X
2The organic group of representing divalent separately, a plurality of X of existence
2Separately can be identical, also can be different, R
8Represent that separately carbonatoms is 1～4 alkyl, a2 represents 0～3 integer separately); Single-substituted two amines of following formula (D-III) expression,
(in the formula (D-III), R
9Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
10It is 6～30 alkyl that expression has 1 valency organic group of the group in the steroid backbone of being selected from, trifluoromethyl, Trifluoromethoxyphen-l and the fluoro phenyl or carbonatoms, R
11The expression carbonatoms is 1～4 alkyl, and a3 represents 0～3 integer); The diamino organo-siloxane of following formula (D-IV) expression,
(in the formula (D-IV), R
12Represent that separately carbonatoms is 1～12 alkyl, a plurality of R of existence
12Separately can be identical, also can be different, respectively do for oneself 1～3 integer of s, t is 1～20 integer); The compound that following formula (D-1)～(D-5) is represented separately etc.,
(y in the formula (D-4) is 2～12 integer, and the z in the formula (D-5) is 1～5 integer).
The phenyl ring of above-mentioned aromatic diamine, optional can be that 1～4 alkyl (preferable methyl) replaces by one or more carbonatoms.Above-mentioned formula (D-I), (D-II) and (D-III) in R
6, R
8And R
11Be preferably methyl separately, a1, a2 and a3 are preferably 0 or 1 separately, and more preferably 0.
During the polyamic acid that in liquid crystal aligning agent of the present invention, can comprise synthetic, other diamines with the compound coupling of above-mentioned formula (1) expression, preferably contain the Ursol D that is selected from the above-mentioned diamines, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, 1, the 4-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, the compound that above-mentioned formula (D-1)～(D-5) is represented separately, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl) p-diaminodiphenyl, the compound of following formula (D-6) expression in the compound of above-mentioned formula (D-I) expression, the compound of following formula (D-7) expression in the compound of above-mentioned formula (D-II) expression;
And the dodecyloxy-2 in the compound of above-mentioned formula (D-III) expression, 4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2, the diamines of at least a (hereinafter referred to as " other specific diamines ") in the group that the compound that 5-diaminobenzene and following formula (D-8)～(D-16) are represented separately constitutes.
Used diamines in the polyamic acid that can comprise in the liquid crystal aligning agent of the present invention synthetic, preferably with respect to whole diamines, contain the compound of above above-mentioned formula (1) expression of 1 mole of %, more preferably contain 5～50 moles of %, especially preferably contain 10～40 moles of %.
Used diamines in the polyamic acid that can comprise in the liquid crystal aligning agent of the present invention synthetic, preferably except that the compound of above-mentioned formula (1) expression, with respect to whole diamines, further contain 5～95 moles of aforesaid other specific diamines of %, more preferably contain 20～90 moles of %, especially preferably contain 50～90 moles of %.
Liquid crystal aligning agent of the present invention, since wherein in contained polymkeric substance synthetic in the used diamines above-mentioned formula (1) even the usage rate of the compound of expression is less, also can form liquid crystal orientation film, thereby the vertical orientated control of the printing of liquid crystal aligning agent and liquid crystal orientation film can two with good vertical orientation control force.In the present invention, above-mentioned formula (1) in the above-mentioned diamines is even the usage rate in the compound of expression is for example 40 moles below the %, even be 30 moles below the %, particularly 20 moles below the %, formed liquid crystal orientation film also can demonstrate good vertical orientated control.
[synthesizing of polyamic acid]
The polyamic acid that can comprise in the liquid crystal aligning agent of the present invention can make by making aforesaid tetracarboxylic dianhydride and diamine reactant.
Supply with the tetracarboxylic dianhydride of polyamic acid building-up reactions and the usage rate of diamine compound, preferably with respect to 1 contained in diamine compound equivalent amino, the anhydride group that makes the tetracarboxylic dianhydride is 0.2～2 normal ratio, more preferably is 0.3～1.2 normal ratio.
The building-up reactions of polyamic acid preferably in organic solvent, is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature condition.Reaction times is preferably 1～240 hour, more preferably 3～150 hours.Here, as organic solvent, so long as can dissolve the solvent of synthetic polyamic acid, then it is had no particular limits, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N, non-proton class polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; Between phenol solvent such as sylvan, xylenol, phenol, halogenated phenol.In addition, the consumption of organic solvent (a: wherein when organic solvent and following poor solvent coupling, be meant their total amount), being preferably the total amount (b) that makes tetracarboxylic dianhydride and diamine compound is the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction soln.
In the above-mentioned organic solvent, in the scope that the polyamic acid that does not make generation is separated out, the poor solvent alcohols of all right coupling polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, triglycol, ethylene glycol monomethyl ether, ethyl lactate, n-Butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, the ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF), methylene dichloride, 1, the 2-ethylene dichloride, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl oxide etc.
When polyamic acid synthetic, when with organic solvent and poor solvent coupling, the usage rate of poor solvent, total amount with respect to organic solvent and poor solvent, be preferably below the 80 weight %, more preferably below the 60 weight %, more preferably below the 50 weight %.
As mentioned above, obtained dissolving the reaction soln of polyamic acid.This reaction soln directly can be supplied with the preparation of liquid crystal aligning agent, also polyamic acid contained in the reaction soln can be separated the back and supply with the preparation of liquid crystal aligning agent, resupply the preparation of liquid crystal aligning agent after perhaps also isolated polyamic acid can being made with extra care.The separation of polyamic acid can obtain precipitate by above-mentioned reaction soln is put in a large amount of poor solvents, and the method for this precipitate of drying under reduced pressure is perhaps carried out reaction soln with vaporizer decompression distilled method again.In addition,, make its method of separating out with poor solvent then, or, can make with extra care polyamic acid with the operation of vaporizer underpressure distillation by carrying out that this polyamic acid is dissolved in the organic solvent once more.
[imide amination polymer]
The imide amination polymer that can comprise in the liquid crystal aligning agent of the present invention can be by making aforesaid polyamic acid dehydration closed-loop imidization.
As used tetracarboxylic dianhydride in imide amination polymer synthetic, the preferred use contained the tetracarboxylic dianhydride who is selected from least a (hereinafter referred to as " specific tetracarboxylic dianhydride (2) ") among the ester ring type tetracarboxylic dianhydride.As specific tetracarboxylic dianhydride (2), be preferably selected from 2,3 especially, 5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3,5:6-dianhydride and 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, at least a in the group that the 10-tetraketone constitutes.
Used tetracarboxylic dianhydride in the imide amination polymer that can comprise in the liquid crystal aligning agent of the present invention synthetic, preferably with respect to whole tetracarboxylic dianhydrides, contain the above aforesaid specific tetracarboxylic dianhydride (2) of 20 moles of %, more preferably contain 50 moles more than the %, especially preferably contain 80 moles more than the %.
As used diamines in above-mentioned imide amination polymer synthetic, can enumerate and the used identical diamines of diamines during above-mentioned polyamic acid is synthetic.
Above-mentioned imide amination polymer, can be the complete imidization thing of the amido acid structure fully dehydrating closed loop that had of raw material polyamic acid, also can be the only a part of dehydration closed-loop of amido acid structure, amido acid structure and imide ring structure and the part imidization thing deposited.
Contained imide amination polymer in the liquid crystal aligning agent of the present invention, its imidization rate is preferably more than 30%, is preferably 50% especially.
Above-mentioned imidization rate is meant the total quantity with respect to the amido acid structure number and the imide ring structure number of imide amination polymer, the value that the shared ratio of imide ring structure number is represented with percentage.At this moment, the part of imide ring can also be different imide ring.The imidization rate can be a primary standard with the tetramethylsilane by imide amination polymer being dissolved in the suitable deuterated solvent (for example deuterated dimethyl sulfoxide), at room temperature measures
1H-NMR, by measurement result according to the following equation (I) obtain.
Imidization rate (%)=(1-A
1/ A
2* α) * 100 (I)
(in the formula (I), A
1Be near the peak area that comes from NH matrix that occurs the chemical shift 10ppm, A
2For coming from the peak area of other protons, α is the proton with respect to 1 NH base in the imide amination polymer precursor (polyamic acid), the individual percentage of other protons).
Dehydration closed-loop for the polyamic acid of synthetic above-mentioned imide amination polymer, can (i) method by the heating polyamic acid, perhaps (ii) by polyamic acid is dissolved in the organic solvent, the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is carried out.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i) is preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer then can occur.Reaction times is preferably 0.5～24 hour, more preferably 2～12 hours.
In the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent, preferably 1 mole of repeating unit with respect to polyamic acid is 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, two picolins, triethylamine.But, be not limited to these.The dehydration closed-loop catalyst consumption with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.In addition, as used organic solvent in the dehydration closed-loop reaction, can enumerate as polyamic acid and synthesize middle solvent for use and illustrative organic solvent.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, and more preferably 10～150 ℃, the reaction times is preferably 0.5～24 hour, more preferably 2～8 hours.
The imide amination polymer that makes in the aforesaid method (i) can directly be supplied with it preparation of liquid crystal aligning agent, resupplies the preparation of liquid crystal aligning agent after perhaps also the imide amination polymer that makes can being made with extra care.In addition, aforesaid method (ii) in, obtain containing the reaction soln of imide amination polymer.This reaction soln, it directly can be supplied with the preparation of liquid crystal aligning agent, also can from reaction soln, remove dewatering agent and dehydration closed-loop catalyzer and supply with the preparation of liquid crystal aligning agent afterwards, imide amination polymer can also be separated the back and supply with the preparation of liquid crystal aligning agent, resupply the preparation of liquid crystal aligning agent after perhaps also isolating imide amination polymer can being made with extra care.From reaction soln, remove dewatering agent and dehydration closed-loop catalyzer, can adopt for example method such as solvent exchange.The separation of imide amination polymer, refining can be taked to carry out as the separating of polyamic acid, the described same operation of process for purification with above.
The polymkeric substance of-end modified type-
The polyamic acid that can comprise in the liquid crystal aligning agent of the present invention or its imide amination polymer can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using the polymkeric substance of end modified type, can under the prerequisite of not damaging effect of the present invention, further improve the coating performance of liquid crystal aligning agent etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds molecular weight regulator and carry out in polymerization reaction system.As molecular weight regulator, can enumerate single acid anhydride, monoamine compound, monoisocyanates compound etc.
As above-mentioned single acid anhydride, can enumerate for example maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.As above-mentioned monoamine compound, can enumerate for example aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane amine, n-hexadecane amine, n-heptadecane amine, Octadecane amine, NSC 62789 amine etc.As above-mentioned monoisocyanates compound, can enumerate for example phenylcarbimide, isocyanic acid naphthyl ester etc.
The usage rate of molecular weight regulator, the total amount of employed tetracarboxylic dianhydride and diamines is preferably below 5 weight parts, more preferably below 2 weight parts when synthetic with respect to the acid of 100 weight parts of polyamide.
-soltion viscosity-
Polyamic acid that as above makes or imide amination polymer preferably when being made into concentration when being the solution of 10 weight %, have the soltion viscosity of 20～800mPas, more preferably have the soltion viscosity of 30～500mPas.
The soltion viscosity of above-mentioned polymkeric substance (mPas) is the polymers soln of 10 weight % concentration that the good solvent (for example gamma-butyrolactone, N-N-methyl-2-2-pyrrolidone N-etc.) that adopts this polymkeric substance is made into, with E type rotational viscosimeter 25 ℃ of values of measuring down.
＜other additives 〉
Liquid crystal orientation film of the present invention comprises at least a polymkeric substance in the group that the imide amination polymer that is selected from aforesaid polyamic acid and dehydration closed-loop thereof and makes constitutes as essential composition, and can also contain other compositions as required.As this other compositions, can enumerate compound (hereinafter referred to as " epoxy compounds ") that intramolecularly for example has at least one epoxy group(ing), functional silanes compound etc.
As above-mentioned epoxy compounds, preferably can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl hexanaphthene etc.The mixture ratio of these epoxy compounds (is meant the total amount of polyamic acid contained in the liquid crystal aligning agent and imide amination polymer thereof with respect to the total amount of 100 parts by weight polymer.Be preferably below 40 weight parts, more preferably 0.1～30 weight part down together).
As above-mentioned functional silanes compound, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-3-aminopropyltriethoxywerene werene etc.
The mixture ratio of these functional silanes compounds with respect to 100 parts by weight polymer total amounts, is preferably below 40 weight parts.
＜liquid crystal aligning agent 〉
Liquid crystal aligning agent of the present invention is to be contained in the organic solvent and to constitute being selected from least a polymkeric substance in the group that aforesaid polyamic acid and imide amination polymer thereof constitute and optional as required other additive preferred dissolutions that cooperate.
As operable organic solvent in the liquid crystal aligning agent of the present invention, can enumerate as solvent used in the polyamic acid building-up reactions and illustrative solvent.In addition, but can also suitably select coupling as the building-up reactions of polyamic acid the time coupling and illustrative poor solvent.Preferred example as this organic solvent, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl oxide etc.They can use separately, perhaps also can two or more mixing use.
The solids content concn of liquid crystal aligning agent of the present invention (the total weight of the composition in the liquid crystal aligning agent except that organic solvent accounts for the ratio of liquid crystal aligning agent gross weight) is considered viscosity, volatility etc. and is suitably selected, and is preferably the scope of 1～10 weight %.That is to say that liquid crystal aligning agent of the present invention is coated on substrate surface with it, remove organic solvent, formation is filmed as liquid crystal orientation film, and is when solids content concn less than 1 weight %, too small and be difficult to obtain the situation of good liquid crystal orientation film with this thickness of filming occurring; On the other hand, when solids content concn surpassed 10 weight %, coating thickness was blocked up and be difficult to obtain the situation of good liquid crystal orientation film equally with occurring, and the viscosity that liquid crystal aligning agent can occur increases, and causes applying the situation of degradation.
Particularly preferred solids content concn scope, the method that is adopted when liquid crystal aligning agent is coated on substrate and difference.For example, when adopting spin-coating method, the scope of preferred especially 1.5～4.5 weight %.When adopting print process, especially preferably making solids content concn is the scope of 3～9 weight %, like this, can make soltion viscosity drop on the scope of 12～50mPas.When adopting ink jet method, especially preferably making solids content concn is the scope of 1～5 weight %, like this, can make soltion viscosity drop on the scope of 3～15mPas.
＜liquid crystal display device 〉
Liquid crystal display device of the present invention has the liquid crystal orientation film that is formed by aforesaid liquid crystal aligning agent of the present invention.Liquid crystal display device of the present invention is preferably the vertical alignment-type liquid crystal display device with vertical alignment-type liquid crystal box.
Liquid crystal display device of the present invention can be by for example following method manufacturing.
(1) adopts for example methods such as rolling method, spin-coating method, print process, ink jet method, liquid crystal aligning agent of the present invention is coated on the substrate one side that is provided with the nesa coating that forms pattern, then, film by the formation of heating applicator surface.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefine.Simultaneously go up the nesa coating that is provided with as substrate, can use stannic oxide (SnO
2) system NESA film (U.S. PPG register of company trade mark), Indium sesquioxide-stannic oxide (In
2O
3-SnO
2) the ITO film etc. of system.Making of the nesa coating of formation pattern, for example can adopt after forming patternless nesa coating on the substrate, form required method of patterning by photoengraving, when nesa coating forms, employing has the mask of required pattern, directly forms the method etc. of the nesa coating of pattern-like.When the coated with liquid crystal alignment agent,, can also on substrate, apply for example functional silanes compound, functionality titanium compound etc. in advance in order further to improve the adhesivity of formed liquid crystal orientation film and substrate surface.Behind the coated with liquid crystal alignment agent, the purpose for the sagging grade of alignment agent liquid that prevents to apply preferably preheats (prebake).The prebake temperature is preferably 30～200 ℃, and more preferably 40～150 ℃, preferred especially 40～100 ℃.The prebake time is preferably 0.5～10 minute, more preferably 1～5 minute.Then, in order to remove purpose such as desolvate fully, carry out roasting (afterwards curing) operation.This back stoving temperature is preferably 80～300 ℃, more preferably 120～250 ℃.After the time of curing be preferably 5～180 minutes, more preferably 10～120 minutes.
Liquid crystal aligning agent of the present invention forms filming as alignment films by removing organic solvent after applying, and be polyamic acid or have the imide ring structure simultaneously and during the imide amination polymer of amido acid structure when polymkeric substance contained in the liquid crystal aligning agent of the present invention, can also after filming, formation make it carry out the dehydration closed-loop reaction, to form filming of further imidization by further heating.
Here the thickness of filming of Xing Chenging is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) prefabricated two substrates that as above form liquid crystal orientation film by arrange liquid crystal between these two substrates, are made liquid crystal cell.The manufacturing of liquid crystal cell can be enumerated two kinds of for example following methods.
First method is previously known method.At first, by two substrates are oppositely arranged by gap (box gap), make separately liquid crystal orientation film relatively to, fitted with sealing agent in the peripheral position of two substrates, annotate the topping up crystalline substance in the box gap that is surrounded by substrate surface and sealing agent after, the sealing filling orifice can make liquid crystal cell.
Second method is the method that is called ODF (One Drop Fill) mode.Regulation position on the substrate in two substrates that form liquid crystal orientation film, apply for example ultra-violet solidified sealant material, again behind the liquid crystal that drips on the liquid crystal aligning face, another piece substrate of fitting, make the mutual subtend of liquid crystal orientation film, to whole irradiation ultraviolet radiation of substrate, make sealant cures then, can make liquid crystal cell.Liquid crystal aligning agent of the present invention owing to can form the good liquid crystal orientation film of vertical orientated property, even thereby when having the ODF of employing method and making VA type liquid crystal display device, also can make the advantage that can not produce the liquid crystal display device of ODF spot.
Adopting under the situation of arbitrary method, all needing to slowly cool to room temperature, the flow orientation when removing liquid crystal and filling by then liquid crystal cell being heated to after used liquid crystal is the temperature of isotropic phase.
Then, by the polaroid of on the outer surface of liquid crystal cell, fitting, can make liquid crystal display device of the present invention.
Here, as sealing agent, can use Resins, epoxy that for example contains as the alumina balls of solidifying agent and separator etc.
As liquid crystal, can enumerate nematic liquid crystal and dish shape type liquid crystal.The nematic liquid crystal that wherein preferably has negative dielectric anisotropic can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.And, can also further add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal or the chirality agent of selling with trade(brand)name " C-15 ", " CB-15 " (production of メ Le Network company) etc. and using.And, can also use oxygen base Ben Yajiaji-in the last of the ten Heavenly stems to ferroelectric liquid crystals such as amino-2-methyl butyl laurates.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol is extended that the polarizing coating that is referred to as " H film " that orientation absorbs the iodine gained simultaneously is clipped in the cellulose acetate protective membrane and the polaroid that polaroid of making or H film self are made.
[embodiment]
Synthesizing of the compound of＜above-mentioned formula (1) expression 〉
Embodiment 1 (synthesizing of compound (1-2-1))
According to following synthetic route 4, synthesized compound (1-2-1).
Synthetic route 4
Synthesizing of compound (1-2-1b)
In the 1L three-necked flask that agitator, nitrogen ingress pipe and thermometer are housed, add 66g compound (1-2-1a), 61g salt of wormwood, 27g ethylene iodohydrin and 300ml 1-Methyl-2-Pyrrolidone, under 100 ℃, carry out reaction in 5 hours.Reaction joins reaction mixture in the 1.5L water after finishing, and reclaims the precipitation that generates.This precipitation is dissolved in the vinyl acetic monomer, after gained solution with water washing 3 times,, removes again and desolvate, make 72g compound (1-2-1b) with dried over mgso, concentrated.
Synthesizing of compound (1-2-1c)
In the 1L three-necked flask that agitator, nitrogen ingress pipe and thermometer are housed, add 56g compound (1-2-1b), 17g potassium tert.-butoxide, 4.8g Tetrabutylammonium bromide and 400ml tetrahydrofuran (THF), with ice-cooled, stir 3 hours (with it as reaction solution A).
In addition, in the 1L three-necked flask that addition funnel, nitrogen ingress pipe and stirrer are housed, add 30g2,4-dinitrochlorobenzene and 30ml tetrahydrofuran (THF), it with ice-cooled, through slowly dripping above-mentioned reaction solution A more than 1 hour, is at room temperature carried out to former state reaction in 12 hours simultaneously.Reaction is injected into reaction mixture in the 1L water after finishing, and reclaims the precipitation that generates.This precipitation is dissolved in the ethyl acetate, and,, carries out recrystallization with ethanol again, obtain 65g compound (1-2-1c) with dried over mgso, concentrated with after the gained solution with water washing three times.
Synthesizing of compound (1-2-1)
In the 2L three-necked flask that reflux condensing tube, nitrogen ingress pipe and thermometer are housed, add 54g compound (1-2-1c), 226g tin chloride dihydrate and 1L ethyl acetate, under refluxing, reacted 4 hours.After reaction finishes, in reaction mixture, add potassium fluoride aqueous solution, remove by filter the precipitate of generation after, carry out separatory, and remove water layer, obtain organic layer.After this organic layer washed with potassium fluoride aqueous solution and water successively, with dried over mgso, concentrate, carry out recrystallization with ethanol again, obtain 36g compound (1-2-1).
Embodiment 2 (synthesizing of compound (1-7-1))
According to following synthetic route 5, synthesized compound (1-7-1).
Synthetic route 5
Synthesizing of compound (1-7-1b)
In the 1L three-necked flask that agitator, nitrogen ingress pipe and thermometer are housed, add 81g compound (1-7-1a), 60g succinyl oxide, 4.4g N, N-dimethyl aminopyridine, 36g triethylamine and 400ml ethyl acetate are carried out reaction in 8 hours under 90 ℃.After reaction finished, ethyl acetate was removed in distillation from reaction mixture, added the 2L chloroform in residue, obtained organic layer.With this organic layer successively with dilute hydrochloric acid washing three times, wash four times with water after, with dried over mgso, concentrate, leach and reclaim the precipitation of generation, be dried, obtain 97g compound (1-7-1b).
Synthesizing of compound (1-7-1c)
In the 5L three-necked flask that agitator, thermometer and nitrogen ingress pipe are housed, add 74g compound (1-7-1b), 43g 3,5-dinitrobenzene benzyl chloride, 83g salt of wormwood, 60g sodium iodide and 500ml N, dinethylformamide carries out reaction in 8 hours under 60 ℃.After reaction finishes, in reaction mixture, add the 3L chloroform, organic layer is washed with water three times.Then, to organic layer with dried over mgso after, concentrate, reclaim the solid of separating out, after washing with alcohol, ethanol is removed in decompression, obtains 88g compound (1-7-1c).
Synthesizing of compound (1-7-1)
In the 2L three-necked flask that agitator, thermometer and nitrogen ingress pipe are housed, add 82g compound (1-7-1c), 340g tin chloride dihydrate and 1L ethyl acetate, under refluxing, reacted 4 hours.After reaction finishes, in reaction mixture, add potassium fluoride aqueous solution, remove by filter the precipitate of generation after, carry out separatory, and remove water layer, obtain organic layer.After this organic layer washed with potassium fluoride aqueous solution and water successively, use dried over mgso, concentrate, carry out recrystallization with ethanol again, obtain 50g compound (1-7-1).
(synthesizing of imide amination polymer)
Embodiment 3
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 61g, as compound (1-2-1) 13g of diamines (with respect to 1 mole of TCA, be equivalent to 0.1 mole) and Ursol D 26g be dissolved in the 400g N-N-methyl-2-2-pyrrolidone N-, reacted 6 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 6000mPas.
Then, in the gained polyamic acid solution, append 1500g N-N-methyl-2-2-pyrrolidone N-, add 21g pyridine and 28g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction,, (, the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction are removed to system by the solvent in the system by this solvent exchange operation by being carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-.Down with), obtain containing the solution that 20 weight % imidization rates are about 50% imide amination polymer (A-1).This solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that imide amination polymer concentration is 6.0 weight %, and the soltion viscosity of mensuration is 25mPas.
Embodiment 4
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 61g, as compound (1-7-1) 13g of diamines (with respect to 1 mole of TCA, be equivalent to 0.1 mole) and Ursol D (PDA) 26g be dissolved in the 400g N-N-methyl-2-2-pyrrolidone N-, reacted 6 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 4800mPas.
Then, in the gained polyamic acid solution, append 1500g N-N-methyl-2-2-pyrrolidone N-, add 21g pyridine and 28g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction,, obtain containing the solution that 20 weight % imidization rates are about 50% imide amination polymer (A-2) by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-.This solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that imide amination polymer concentration is 6.0 weight %, and the soltion viscosity of mensuration is 22mPas.
Compare synthesis example 1
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 29g is as the following formula (R-1) of diamines
The compound 9.9g (with respect to 1 mole of TCA, being equivalent to 0.2 mole) and Ursol D (PDA) 11g of expression are dissolved in the 450g N-N-methyl-2-2-pyrrolidone N-, react 6 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 3500mPas.
Then, in the gained polyamic acid solution, append 500g N-N-methyl-2-2-pyrrolidone N-, add 10g pyridine and 13g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction,, obtain containing the solution that 20 weight % imidization rates are about 49% imide amination polymer (B-1) by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-.This solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that imide amination polymer concentration is 6.0 weight %, and the soltion viscosity of mensuration is 25mPas.
The preparation of＜liquid crystal aligning agent and evaluation 〉
Embodiment 5
[the printing evaluation preparation of liquid crystal aligning agent]
In the solution that contains imide amination polymer (A-1) that makes in the foregoing description 3, the imide amination polymer (A-1) with respect to contained in the above-mentioned solution of 100 weight parts adds the following formula of 20 weight parts (E-1)
The compound of expression is as epoxy compounds, add gamma-butyrolactone (BL), N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether (B C) again, being made into solvent composition is BL: NMP: BC=40: 30: 30 (weight ratio), solids content concn are the solution of 6.0 weight %.Is that the filter of 1 μ m filters with this solution with the aperture, prepare the liquid crystal aligning agent of printing evaluation usefulness.The soltion viscosity of under 25 ℃ this liquid crystal aligning agent being measured is 22mPas.
[evaluation of printing]
Printing evaluation liquid crystal aligning agent with above preparation, (Japan's description printing (strain) is made to adopt the liquid crystal orientation film printing press, オ Application グ ス ト ロ one マ one S40L-532) is coated on the transparency electrode face of the glass substrate that has ITO film system transparency electrode, heat 1 minute (prebake) down except that after desolvating at 80 ℃, heat 10 minutes (afterwards curing) down at 180 ℃ again, forming thickness is filming of 8000nm.This is filmed carry out visual observations, investigation has corrugationless and coating uneven, and do not observe printing inequality and pinprick this moment, and the printing of above-mentioned liquid crystal aligning agent is " well ".
[making the preparation of the liquid crystal aligning agent of used for liquid crystal display element]
In the solution that contains imide amination polymer (A-1) that in the foregoing description 3, makes, with respect to imide amination polymer (A-1) contained in the above-mentioned solution of 100 weight parts, the compound that adds the above-mentioned formula of 20 weight parts (E-1) expression is as epoxy compounds, add N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether (B C) again, being made into solvent composition is NMP: BC=50: 50 (weight ratios), solids content concn are the solution of 4 weight %.Is the filter filtration of 1 μ m with this solution with the aperture, and the liquid crystal aligning agent of used for liquid crystal display element is made in preparation.
[manufacturing of the liquid crystal display device of vertical orientated control evaluation usefulness]
Adopting spin coater that the liquid crystal aligning agent of the manufacturing used for liquid crystal display element of above preparation is coated in thickness is on the ITO film system nesa coating that is provided with on the one side of glass substrate of 1mm, heating 1 minute (prebake) down except that after desolvating in 80 ℃ on the hot-plate, heat 60 minutes (afterwards curing) down at 200 ℃ again, forming thickness is filming of 0.08 μ m.The sander of the roller that twines Artificial Fibers cloth is equipped with in employing, is that 400rpm, operator's console translational speed are 3cm/ second at the roller rotating speed, and fine hair is clamp-oned under the condition that length is 0.4mm, this is filmed carry out grinding process.Then, in ultrapure water,, then in 230 ℃ cleaning oven dry 25 minutes, make substrate with the liquid crystal orientation film that has carried out grinding process with ultrasonic washing after 1 minute.Repeat this operation, make the substrate that a pair of (two) have the liquid crystal orientation film that has carried out grinding process.
Then, on each outer rim with liquid crystal orientation film of above-mentioned a pair of substrate, coating overlaps and pressing liquid crystal aligning face antiparallel ground after having added the epoxy resin binder of alumina balls that diameter is 5.5 μ m, and tackiness agent is solidified.Then, (メ Le Network company produces to fill nematic liquid crystal by liquid crystal injecting port between a pair of substrate, MLC-6608) after, with the acrylic acid or the like Photocurable adhesive liquid crystal injecting port is sealed, the polaroid of fitting on the two sides, the outside of this liquid crystal cell again produces the liquid crystal display device of vertical orientated control evaluation usefulness.
[evaluation of vertical orientated control]
Liquid crystal display device to the vertical orientated control evaluation usefulness of above manufacturing, the tilt angle that adopts crystallization rotation horn cupping to measure is the situation more than 86 °, vertical orientated control is evaluated as " well ", less than 86 °, vertical orientated control is evaluated as " bad ", this liquid crystal display device shows 89 ° tilt angle, and vertical orientated control is " well ".
In addition, known grinding process of carrying out in above-mentioned [manufacturing of the liquid crystal display device of vertical orientated control evaluation usefulness] has the effect of subduing to the vertical orientated control of liquid crystal orientation film.Even so when carrying out the situation that grinding process also shows tilt angle more than 86 °, vertical orientated control be we can say extremely good, can produce this result's liquid crystal aligning agent, even use it for when making VA type liquid crystal display device, rule of thumb also can not know to produce the demonstration spot by the ODF mode.
[manufacturing of the liquid crystal display device of voltage retention evaluation usefulness]
In above-mentioned [manufacturing of the liquid crystal display device of vertical orientated control evaluation usefulness], except formed filming not carried out grinding process and subsequently the washing and drying treatment, similarly operate with above-mentioned [manufacturing of the liquid crystal display device of vertical orientated control evaluation usefulness], make the liquid crystal display device of voltage retention evaluation usefulness.
[evaluation of voltage retention]
Under 60 ℃, in the time span of 16.7 microseconds, the liquid crystal display device of the voltage retention evaluation usefulness of above manufacturing is applied the voltage of 5V, the voltage application time is 60 microseconds, measures then from voltage and removes voltage retention after 16.7 milliseconds.The voltage retention of this liquid crystal display device is 99%.
Embodiment 6 and comparative example 1
In the foregoing description 5, except use contains the solution of imide amination polymer shown in the table 1, operation similarly to Example 5, each prepares two kinds of liquid crystal aligning agent, and estimates.Evaluation result is listed in table 1 with the printing evaluation with the soltion viscosity of liquid crystal aligning agent.
Table 1
As finding out particularly by above embodiment, liquid crystal aligning agent of the present invention, owing to demonstrate superior printing characteristics, simultaneously, has good vertical orientated control by its liquid crystal orientation film that forms, even thereby have when adopting the ODF method to make VA type liquid crystal display device, also can make the advantage that can not produce the liquid crystal display device of ODF spot with high rate of finished products.
Claims (4)
1, a kind of liquid crystal aligning agent, it is characterized in that comprising at least a polymkeric substance of from the group of polyamic acid and imide amination polymer formation thereof, selecting, this polyamic acid is obtained with the diamine reactant of the compound that contains following formula (1) expression by the tetracarboxylic dianhydride
In the formula (1), R is that the optional carbonatoms that is replaced by fluorine atom is 3～20 alkyl, and A is 1,4-cyclohexylidene or 1,4-phenylene, B
1For Sauerstoffatom or-OCO-*, connecting key that wherein, has " * " and (CH
2)
bConnect B
2For Sauerstoffatom or-cOO-*, the connecting key that wherein, has " * " is connected with A, a is 0 or 1, b is 2～10 integer, c is 0 or 1.
2, a kind of liquid crystal display device is characterized in that having the liquid crystal orientation film that is formed by the described liquid crystal aligning agent of claim 1.
3, polyamic acid or its imide amination polymer, it is made with the diamine reactant of the compound that contains above-mentioned formula (1) expression by the tetracarboxylic dianhydride.
4, the compound of above-mentioned formula (1) expression.
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| JP2008118039A JP5282869B2 (en) | 2008-04-30 | 2008-04-30 | Liquid crystal aligning agent and liquid crystal display element |
| JP2008118039 | 2008-04-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103361081A (en) * | 2012-03-28 | 2013-10-23 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display component, polymer and compound |
| CN105037722A (en) * | 2011-04-28 | 2015-11-11 | 日产化学工业株式会社 | Polyimide precursor modified with dicarboxylic acid anhydride, imidized polyimide and liquid crystal aligning agent using it |
| CN111647412A (en) * | 2020-06-12 | 2020-09-11 | 江苏三月科技股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
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| KR102184058B1 (en) * | 2013-02-28 | 2020-11-27 | 닛산 가가쿠 가부시키가이샤 | Polymer, liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element |
| TWI482801B (en) * | 2013-09-18 | 2015-05-01 | Chi Mei Corp | Liquid crystal alignment composition, liquid crystal alignment film and liquid crystal display element having thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0848772A (en) * | 1994-08-03 | 1996-02-20 | Chisso Corp | Polyimide having liquid crystal group |
| JPH0873589A (en) * | 1994-09-02 | 1996-03-19 | Chisso Corp | Polyamide having side chain |
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| JP4788896B2 (en) * | 2006-02-22 | 2011-10-05 | Ｊｓｒ株式会社 | Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0848772A (en) * | 1994-08-03 | 1996-02-20 | Chisso Corp | Polyimide having liquid crystal group |
| JPH0873589A (en) * | 1994-09-02 | 1996-03-19 | Chisso Corp | Polyamide having side chain |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037722A (en) * | 2011-04-28 | 2015-11-11 | 日产化学工业株式会社 | Polyimide precursor modified with dicarboxylic acid anhydride, imidized polyimide and liquid crystal aligning agent using it |
| CN105037722B (en) * | 2011-04-28 | 2017-12-19 | 日产化学工业株式会社 | Polyimide precursor through dicarboxylic anhydride modification, polyimides obtained by imidizate and use its aligning agent for liquid crystal |
| CN103361081A (en) * | 2012-03-28 | 2013-10-23 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display component, polymer and compound |
| CN103361081B (en) * | 2012-03-28 | 2015-11-18 | Jsr株式会社 | Crystal aligning agent, liquid crystal orienting film, liquid crystal display device, polymkeric substance and compound |
| CN111647412A (en) * | 2020-06-12 | 2020-09-11 | 江苏三月科技股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
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| JP2009265539A (en) | 2009-11-12 |
| JP5282869B2 (en) | 2013-09-04 |
| TWI467290B (en) | 2015-01-01 |
| CN101570636B (en) | 2013-12-18 |
| KR101536007B1 (en) | 2015-07-10 |
| TW201003254A (en) | 2010-01-16 |
| KR20090115071A (en) | 2009-11-04 |
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