CN101570636B - 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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- CN101570636B CN101570636B CN2009101373751A CN200910137375A CN101570636B CN 101570636 B CN101570636 B CN 101570636B CN 2009101373751 A CN2009101373751 A CN 2009101373751A CN 200910137375 A CN200910137375 A CN 200910137375A CN 101570636 B CN101570636 B CN 101570636B
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- 0 CC(CC1)CCC1C1CCC(*)CC1 Chemical compound CC(CC1)CCC1C1CCC(*)CC1 0.000 description 2
- BAHPQISAXRFLCL-UHFFFAOYSA-N COc(ccc(N)c1)c1N Chemical compound COc(ccc(N)c1)c1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 1
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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 while adopting under liquid crystal drop mode (ODF mode) in the liquid crystal filling work procedure that liquid crystal display device is manufactured, also can form liquid crystal aligning agent, polyamic acid, its imide amination polymer, the compound of the liquid crystal orientation film that not there will be the ODF spot and the liquid crystal display device made by it.
Background technology
At present, as liquid crystal display device, the 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 on the substrate surface of nesa coating, formation is formed by polyamic acid, polyimide etc., substrate as used for liquid crystal display element, two these substrates are oppositely arranged, form betwixt the nematic liquid crystal layer with positive dielectric anisotropy in gap, form 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 the STN that can realize high-contrast (supertwist is to row) type liquid crystal display device and little IPS (switching in face) the type liquid crystal display device of 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 polyimide, polymeric amide and polyester etc. in the past, polyimide particularly, due to 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 large progress.Particularly with the maximization of substrate simultaneously, the technology such as mode under the large substrate transportation techniques adopted and liquid crystal drop (One Drop Fill mode, in this area referred to as " ODF mode ") are noticeable.This ODF mode, at the liquid crystal that forms on the substrate of liquid crystal orientation film the necessary amounts of dripping, make its under vacuum with another piece baseplate-laminating after, the sealing agent of encapsulated liquid crystals is carried out to UV to be solidified, make all methods of filling liquid crystal of whole panel, be to compare with the vacuum injection mode of implementing all the time, can significantly shorten the technology of the engineering time of liquid crystal filling work procedure.But, if adopt the ODF mode in the manufacturing processed of the VA type liquid crystal display device with polyimide liquid crystal orientation film, there will be the trouble that produces the demonstration spot that is called " ODF spot ".This phenomenon is considered to cause not due to the vertical orientated control of liquid crystal orientation film.
In order to solve this problem of polyimide liquid crystal orientation film, occurred such as 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 to 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 the good liquid crystal display device of display quality.
[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 while 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 the required various performances as liquid crystal aligning agent, the good liquid crystal display device of the particularly good liquid crystal aligning agent of printing, and display quality.
The present invention is other purposes and advantage further, can be found out by the following description.
According to the present invention, above object and advantages of the present invention, first, by a kind of liquid crystal aligning agent that is used to form the liquid crystal orientation film of vertical alignment-type liquid crystal display device, reached, it comprises at least one 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 formula (1), the alkyl that R is 3～20 for the carbonatoms that optionally replaced by fluorine atom, A is Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, B
1for Sauerstoffatom or-OCO-* is (wherein, with the connecting key of " * " and (CH
2)
bconnect), B
2for Sauerstoffatom or-COO-* (wherein, being connected with A with the connecting key of " * "), a is 0 or 1, the b integer that is 2～10, c is 0 or 1, the following formula in its Chinese style (1)
The unit meaned is following formula
Any one in the unit meaned, in above-mentioned formula, with connecting key and the B of "+"
2connect).
Above object and advantages of the present invention, the second, by the vertical alignment-type liquid crystal display device with the liquid crystal orientation film formed by above-mentioned liquid crystal aligning agent, reached.
Embodiment
Liquid crystal aligning agent of the present invention comprises at least one polymkeric substance of selecting from the group of polyamic acid and imide amination polymer formation thereof, and 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 liquid crystal aligning agent of the present invention, can synthesize by making tetracarboxylic dianhydride and the diamine reactant of the compound that contains above-mentioned formula (1) expression.
[tetracarboxylic dianhydride]
Tetracarboxylic dianhydride used 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-bis-is 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-, tri-carboxyl norbornanes-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-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 5-(2,5-dioxotetrahydrofuryl)-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-, tri-carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-dioxa, three ring [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) mean separately,
(in above-mentioned formula, R
1and R
3mean to have separately the divalent organic group of aromatic nucleus, R
2and R
4mean separately hydrogen atom or alkyl, 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, Isosorbide-5-Nitrae, 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 '-bis-(3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-bis-(3,4-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-bis-(triphenyl phthalic acid) dianhydride, metaphenylene-bis-(triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol-bis-(dehydration trimellitate), propylene glycol-bis-(dehydration trimellitate), BDO-bis-(dehydration trimellitate), 1,6-hexylene glycol-bis-(dehydration trimellitate), 1,8-ethohexadiol-bis-(dehydration trimellitate), 2,2-bis-(4-hydroxyphenyl) propane-bis-(dehydration trimellitate), aromatic tetracarboxylic acid's dianhydrides such as compound that following formula (T-1)～(T-4) means separately.They can a kind ofly be used alone or in combination of two or more.
Tetracarboxylic dianhydride used in the polyamic acid that liquid crystal aligning agent of the present invention can comprise synthetic, from making its angle that shows good liquid crystal aligning, preferably contain to be selected from the butane tetracarboxylic acid dianhydride in 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-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-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-, tri-carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-dioxa, three ring [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, the tetracarboxylic dianhydride of at least one (hereinafter referred to as " specific tetracarboxylic dianhydride (1) ") in the group that the compound that the following formula (T-8) in the compound that the compound that the following formula (T-5)～(T-7) in the compound that 4,5,8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I) mean means separately and above-mentioned formula (T-II) mean means forms.
As specific tetracarboxylic dianhydride (1), particularly preferably be selected from 1, 2, 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)-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-tri-carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0
2,6] undecane-3,5,8, at least one in the group that the compound that 10-tetraketone, pyromellitic acid dianhydride and above-mentioned formula (T-5) mean forms.
In the tetracarboxylic dianhydride who uses in the polyamic acid that liquid crystal aligning agent of the present invention can comprise synthetic, with respect to whole tetracarboxylic dianhydrides, preferably contain the above-mentioned specific tetracarboxylic acid (1) more than 20 % by mole, more preferably contain more than 50 % by mole, particularly preferably contain more than 80 % by mole.
[diamines]
Diamines used in the polyamic acid that can contain in liquid crystal aligning agent of the present invention synthetic is the diamines that contains the compound that above-mentioned formula (1) means.
R as in above-mentioned formula (1), be preferably the alkyl that carbonatoms is 3～10, the straight chained alkyl that more preferably carbonatoms is 3～10.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.
The preferred example of the compound meaned as above-mentioned formula (1), can enumerate formula (1-2), (1-3), (1-6) in the compound that for example following formula (1-1)～(1-8) means separately and the compound (1-7) meaned separately
(in formula (1-1)～(1-8), b is identical with the definition in above-mentioned formula (1), the integer that d is 2～9).
The compound that above-mentioned formula (1) means, can be by for example usining compound that following formula (2) means as raw material,
Ordinary method in organic chemistry is carried out to suitable combination and synthesize.For example above-mentioned formula (1-2), (1-3) and the compound that (1-7) means separately, can synthesize by the either method of following synthetic route 1～3 separately.
(in synthetic route 1～3, b and d respectively with above-mentioned formula (1-2), (1-3) or the definition (1-7) identical).The compound that above-mentioned formula (2) means can be by usually adopting in liquid crystal compounds synthetic Grignard reaction, Knut Fridell-Kerafyrm thatch acylation reaction, triumphant cherish receive the method such as (Kishner) reaction and synthesize.
Related other compounds in above-mentioned formula (1), also can synthesize according to the method described above.
In liquid crystal aligning agent of the present invention, due to by following formula (2 ')
Contain-(CH in the linking group that the structure that (in formula (2 '), R is identical with the definition in above-mentioned formula (1) separately with c) means is connected with polymkeric substance
2)
b-(wherein, b is identical with the definition in above-mentioned formula (1).Lower same), thereby can show high vertical orientated control.Structure technology as 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 patent documentation 4 (No. 2684404 Japanese patent specification), and the vertical orientated control of the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention has surpassed these prior aries.This is to have got involved to a great extent the performance of vertical orientated control due to the structure of above-mentioned formula (2 ') by inference, its by by flexible large-(CH
2)
b-appear at the cause on the surface of liquid crystal orientation film.
Diamines used in the polyamic acid that can comprise in liquid crystal aligning agent of the present invention synthetic, can be the diamines that only contains the compound of above-mentioned formula (1) expression, or can be still to contain the diamines of other diamines except the compound that above-mentioned formula (1) means.
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, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 3,3 '-bis-(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-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-[4-(4-amino-benzene oxygen) phenyl] sulfone, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(3-amino-benzene oxygen) benzene, 9,9-bis-(4-aminophenyl)-10-hydrogen anthracene, 2,7 diamin of luorene, 9,9-dimethyl-2,7 diamin of luorene, 9,9-bis-(4-aminophenyl) fluorenes, 4,4 '-methylene radical-bis-(2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-bis-is 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 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 4,4 '-bis-[(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, aliphatics or the ester ring type diamines such as 4 '-methylene radical two (hexahydroaniline);
2,3 diamino pyridine, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2, the 4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazines, Isosorbide-5-Nitrae-bis-(3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazines, 2,4-diamino-6-methoxyl group-1,3,5-triazines, 2,4-diamino-6-phenyl-1,3,5-triazines, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazines, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2,6-diaminopurine, 5,6-diaminostilbene, the 3-dimethyl uracil, 3,5-diaminostilbene, 2,4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, Isosorbide-5-Nitrae-diamino piperazine, 3,6-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 '-bis-(4-aminophenyl) p-diaminodiphenyl, the compound that following formula (D-I) means,
(in formula (D-I), R
5mean the 1 valency organic group with the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X
1the organic group that means divalent, R
6mean the alkyl that carbonatoms is 1～4, a1 means 0～3 integer), there is the diamines of the nitrogen-atoms beyond two primary aminos and this primary amino in the compound equimolecular that means of following formula (D-II),
(in formula (D-II), R
7mean the divalent organic group with the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X
2the organic group that means separately divalent, a plurality of X of existence
2separately can be identical, also can be different, R
8mean separately the alkyl that carbonatoms is 1～4, a2 means 0～3 integer separately); The single-substituted Diamines that following formula (D-III) means,
(in formula (D-III), R
9mean be selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
10mean to have 1 valency organic group of the group in the steroid backbone of being selected from, trifluoromethyl, Trifluoromethoxyphen-l and difluorophenyl or the alkyl that carbonatoms is 6～30, R
11mean the alkyl that carbonatoms is 1～4, a3 means 0～3 integer); The diamino organo-siloxane that following formula (D-IV) means,
(in formula (D-IV), R
12mean separately the alkyl that carbonatoms is 1～12, a plurality of R of existence
12separately can be identical, also can be different, respectively do for oneself 1～3 integer of s, the integer that t is 1～20); The compound that following formula (D-1)～(D-5) means separately etc.,
(integer that the y in formula (D-4) is 2～12, the integer that the z in formula (D-5) is 1～5).
The alkyl (preferable methyl) that the phenyl ring of above-mentioned aromatic diamine can be optionally 1～4 by one or more carbonatoms replaces.Above-mentioned formula (D-I), (D-II) and (D-III) in R
6, R
8and R
11be preferably separately methyl, a 1, a2 and a3 are preferably 0 or 1 separately, and more preferably 0.
During the polyamic acid that can comprise in liquid crystal aligning agent of the present invention synthetic, other diamines of coupling, preferably contain the Ursol D be selected from above-mentioned diamines together with the compound meaned with above-mentioned formula (1), 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, Isosorbide-5-Nitrae-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline), Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, the compound that above-mentioned formula (D-1)～(D-5) means separately, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-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 '-bis-(4-aminophenyl) p-diaminodiphenyl, the compound that following formula (D-6) in the compound that above-mentioned formula (D-I) means means, the compound that following formula (D-7) in the compound that above-mentioned formula (D-II) means means,
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 one (hereinafter referred to as " other specific diamines ") in the group that the compound that 5-diaminobenzene and following formula (D-8)～(D-16) mean separately forms.
Diamines used in the polyamic acid that can comprise in liquid crystal aligning agent of the present invention synthetic, preferably with respect to whole diamines, contain the compound that more than 1 % by mole, above-mentioned formula (1) means, more preferably contain 5～50 % by mole, particularly preferably contain 10～40 % by mole.
Diamines used in the polyamic acid that can comprise in liquid crystal aligning agent of the present invention synthetic, preferably except the compound that above-mentioned formula (1) means, with respect to whole diamines, further contain 5～95 % by mole of other specific diamines as above, more preferably contain 20～90 % by mole, particularly preferably contain 50～90 % by mole.
Liquid crystal aligning agent of the present invention, due to above-mentioned formula (1) in diamines used in wherein contained polymkeric substance synthetic even the usage rate of the compound meaned is less, also can form the liquid crystal orientation film with good vertical orientation control force, thereby the vertical orientated control of the printing of liquid crystal aligning agent and liquid crystal orientation film can two.In the present invention, above-mentioned formula (1) in above-mentioned diamines though the usage rate in the compound meaned for for example below 40 % by mole, be even below 30 % by mole, particularly, below 20 % by mole, formed liquid crystal orientation film also can demonstrate good vertical orientated control.
[synthesizing of polyamic acid]
The polyamic acid that can comprise in liquid crystal aligning agent of the present invention, can make by making tetracarboxylic dianhydride as above 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 equivalent amino contained in diamine compound, the ratio that the anhydride group that makes the tetracarboxylic dianhydride is 0.2～2 equivalent, more preferably be the ratio of 0.3～1.2 equivalent.
The building-up reactions of polyamic acid, preferably, in organic solvent, be preferable over-20～150 ℃, more preferably carry out under the temperature condition of 0～100 ℃.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, it is had no particular limits, can enumerate for example METHYLPYRROLIDONE, N, the non-proton class polar solvents such as N-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; Between the 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, refer to their total amount), be preferably the amount that the total amount (b) that makes tetracarboxylic dianhydride and diamine compound is 0.1～30 % by weight with respect to the total amount (a+b) of reaction soln.
In above-mentioned organic solvent, in the scope of separating out at the polyamic acid that does not make to generate, the poor solvent alcohols of all right coupling polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.As the object lesson of this poor solvent, can enumerate for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, 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, methoxy methyl propionate, 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, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl oxide etc.
When polyamic acid synthetic, when by 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 80 % by weight, more preferably below 60 % by weight, more preferably below 50 % by weight.
As mentioned above, obtained dissolving the reaction soln of polyamic acid.This reaction soln directly can be supplied with to the preparation of liquid crystal aligning agent, also polyamic acid contained in reaction soln can be separated to the preparation of rear supply liquid crystal aligning agent, or resupply the preparation of liquid crystal aligning agent after 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, then the method for this precipitate of drying under reduced pressure, or the method that reaction soln is distillated with the vaporizer decompression is carried out.In addition, by carrying out once or several times making this polyamic acid again be dissolved in organic solvent, then with poor solvent, make its method of separating out, or, by the operation of vaporizer underpressure distillation, can make with extra care polyamic acid.
[imide amination polymer]
The imide amination polymer that can comprise in liquid crystal aligning agent of the present invention, can be by making polyamic acid dehydration closed-loop imidization as above.
As tetracarboxylic dianhydride used in imide amination polymer synthetic, preferably use the tetracarboxylic dianhydride of containing at least one (hereinafter referred to as " specific tetracarboxylic dianhydride (2) ") that are selected from the ester ring type tetracarboxylic dianhydride.As specific tetracarboxylic dianhydride (2), particularly preferably be selected from 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, 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-tri-carboxyls-2-carboxyl norbornane-2:3, 5:6-dianhydride and 4, 9-dioxa three ring [5.3.1.0
2,6] undecane-3,5,8, at least one in the group that the 10-tetraketone forms.
Tetracarboxylic dianhydride used in the imide amination polymer that can comprise in liquid crystal aligning agent of the present invention synthetic, preferably with respect to whole tetracarboxylic dianhydrides, contain specific tetracarboxylic dianhydride as above (2) more than 20 % by mole, more preferably contain more than 50 % by mole, particularly preferably contain more than 80 % by mole.
As diamines used in above-mentioned imide amination polymer synthetic, can enumerate the diamines identical with diamines used during above-mentioned polyamic acid is synthetic.
Above-mentioned imide amination polymer, can be the complete imide compound of the amido acid structure fully dehydrating closed loop that has of raw material polyamic acid, can be also only a part of dehydration closed-loop, amido acid structure and imide ring structure the part imide compound of depositing of amido acid structure.
Contained imide amination polymer in liquid crystal aligning agent of the present invention, its imide rate is preferably more than 30%, is particularly preferably 50%.
Above-mentioned imide rate, refer to the total quantity with respect to 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 means with percentage.Now, the part of imide ring can also be different imide ring.The imide rate can for example, be take tetramethylsilane as primary standard by imide amination polymer being dissolved in suitable deuterated solvent (deuterated dimethyl sulfoxide), at room temperature measures
1h-NMR, by measurement result according to the following equation (I) obtain.
Imide rate (%)=(1-A
1/ A
2* α) * 100 (I)
(in formula (I), A
1for near the peak area that comes from NH matrix occurred chemical shift 10ppm, A
2for coming from the peak area of other protons, α is the proton with respect to 1 NH base in 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) by the method for heating polyamic acid, perhaps (ii), by polyamic acid is dissolved in organic solvent, adds the method for dewatering agent and dehydration closed-loop catalyzer heating as required to carry out in this solution.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i), be preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, there will be the situation of the molecular weight and molecular weight of gained imide amination polymer.Reaction times is preferably 0.5～24 hour, more preferably 2～12 hours.
In the method for adding dewatering agent and dehydration closed-loop catalyzer in polyamic acid solution of above-mentioned (ii), as dewatering agent, can use acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride.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 tertiary amines such as pyridine, collidine, two picolins, triethylamine.But, be not limited to these.The consumption of dehydration closed-loop catalyzer, with respect to 1 mole of dewatering agent used, be preferably 0.01～10 mole.In addition, as organic solvent used in the dehydration closed-loop reaction, can enumerate as the synthetic middle solvent for use of polyamic acid and illustrative organic solvent.And the temperature of reaction of dehydration closed-loop reaction, be preferably 0～180 ℃, more preferably 10～150 ℃, the reaction times is preferably 0.5～24 hour, more preferably 2～8 hours.
The imide amination polymer made in aforesaid method (i), can directly supply with the preparation of liquid crystal aligning agent by it, or resupply the preparation of liquid crystal aligning agent after also the imide amination polymer made can being made with extra care.In addition, in aforesaid method (ii), obtain the reaction soln that contains imide amination polymer.This reaction soln, it directly can be supplied with to 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 to the preparation of rear supply liquid crystal aligning agent, or resupply the preparation of liquid crystal aligning agent after also the imide amination polymer of separation can being made with extra care.Remove dewatering agent and dehydration closed-loop catalyzer from reaction soln, can adopt such as methods such as solvent exchanges.The separation of imide amination polymer, refining, can take 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 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 property of liquid crystal aligning agent etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, to adding molecular weight regulator in polymerization reaction system, carries out.As molecular weight regulator, can enumerate single acid anhydride, monoamine compound, monoisocyanates compound etc.
As above-mentioned single acid anhydride, can enumerate such as 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 such as 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 such as phenylcarbimide, isocyanic acid naphthyl ester etc.
The usage rate of molecular weight regulator, the tetracarboxylic dianhydride who uses while synthesizing with respect to 100 weight parts of polyamide acid and the total amount of diamines, be preferably below 5 weight parts, more preferably below 2 weight parts.
-soltion viscosity-
The polyamic acid as above made or imide amination polymer, preferably, when being made into the solution that concentration is 10 % by weight, have the soltion viscosity of 20～800mPas, more preferably has the soltion viscosity of 30～500mPas.
The soltion viscosity of above-mentioned polymkeric substance (mPas), the polymers soln of the 10 % by weight concentration that are made into of the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) to adopting this polymkeric substance, the value of measuring under 25 ℃ with E type rotational viscosimeter.
<other additives >
Liquid crystal orientation film of the present invention comprises at least one polymkeric substance in the group that the imide amination polymer that is selected from polyamic acid as above and dehydration closed-loop thereof and makes forms as essential composition, and can also contain other compositions as required.As this other compositions, can enumerate such as the compound that there is at least one epoxy group(ing) in molecule (hereinafter referred to as " epoxy compounds "), 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-bis-(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, (refer to the total amount of polyamic acid and imide amination polymer thereof contained in liquid crystal aligning agent with respect to the total amount of 100 parts by weight polymer.Lower same), be preferably below 40 weight parts, more preferably 0.1～30 weight part.
As above-mentioned functional silanes compound, can enumerate for example 3-TSL 8330, APTES, 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-APTES, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilicane alkyl-Isosorbide-5-Nitrae, 7-tri-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-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, N-bis-(oxyethylene group)-3-TSL 8330, N-bis-(oxyethylene group)-APTES etc.
The mixture ratio of these functional silanes compounds, with respect to 100 parts by weight polymer total amounts, be preferably below 40 weight parts.
<liquid crystal aligning agent >
Liquid crystal aligning agent of the present invention be by be selected from least one polymkeric substance in the group that polyamic acid as above and imide amination polymer thereof form and as required optional other additive preferred dissolutions that coordinate be contained in organic solvent and form.
As operable organic solvent in 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 in the time of can also suitably selecting coupling as the building-up reactions of polyamic acid coupling and illustrative poor solvent.Preferred example as this organic solvent, can enumerate for example METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, the 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methoxy methyl propionate, 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, or 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 liquid crystal aligning agent except 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 % by weight.That is to say, liquid crystal aligning agent of the present invention, be coated on substrate surface by it, remove organic solvent, formation is filmed as liquid crystal orientation film, when solids content concn less than 1 % by weight, will occur that this thickness of filming is too small and be difficult to obtain the situation of good liquid crystal orientation film; On the other hand, when solids content concn surpasses 10 % by weight, will occur that coating thickness is blocked up and be difficult to equally obtain the situation of good liquid crystal orientation film, and, there will be the viscosity of liquid crystal aligning agent to increase, cause the situation of coating property variation.
Particularly preferred solids content concn scope, the method adopted when liquid crystal aligning agent is coated on to substrate and difference.For example, when adopting spin-coating method, the scope of 1.5～4.5 % by weight particularly preferably.When adopting print process, particularly preferably make the scope that solids content concn is 3～9 % by weight, like this, can make soltion viscosity drop on the scope of 12～50mPas.When adopting ink jet method, particularly preferably make the scope that solids content concn is 1～5 % by 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 formed by liquid crystal aligning agent of the present invention as above.Liquid crystal display device of the present invention is 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 manufacture.
(1) adopt methods such as rolling method, spin-coating method, print process, ink jet method, liquid crystal aligning agent of the present invention is coated on to the substrate that is provided with the nesa coating that forms pattern and simultaneously goes up, then, by the heating applicator surface, form and film.Here, as substrate, can use glass such as float glass, soda-lime glass; The plastics transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefine.The nesa coating simultaneously above arranged as substrate, can be used 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 and after the patternless nesa coating of formation, form the method for required pattern by photoengraving, when nesa coating forms on substrate, 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, in order further to improve the adhesivity of formed liquid crystal orientation film and substrate surface, can also on substrate, apply in advance such as functional silanes compound, functionality titanium compound etc.After the coated with liquid crystal alignment agent, in order to prevent the purpose of the sagging grade of alignment agent liquid of coating, preferably preheated (prebake).The prebake temperature is preferably 30～200 ℃, and more preferably 40～150 ℃, particularly preferably 40～100 ℃.The prebake time is preferably 0.5～10 minute, more preferably 1～5 minute.Then, except purposes such as desolventizings, carry out roasting (curing afterwards) operation for fully.Should be preferably 80～300 ℃, more preferably 120～250 ℃ by rear stoving temperature.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 after applying, removing organic solvent, and contained polymkeric substance is polyamic acid or has the imide ring structure and during the imide amination polymer of amido acid structure simultaneously in liquid crystal aligning agent of the present invention, can also after filming, formation make it carry out the dehydration closed-loop reaction by further heating, to form filming of further imidization.
Here the thickness of filming formed, be 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 between these two substrates, arranging liquid crystal, manufacture liquid crystal cell.The manufacture of liquid crystal cell, can enumerate 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 liquid crystal orientation film separately relatively to, fitted with sealing agent in the peripheral position of two substrates, after annotating the topping up crystalline substance in the box gap surrounded by substrate surface and sealing agent, 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 a substrate in two substrates that form liquid crystal orientation film, coating is ultra-violet solidified sealant material for example, on the liquid crystal aligning face, drip again after liquid crystal, another piece substrate of fitting, make the mutual subtend of liquid crystal orientation film, then to whole irradiation ultraviolet radiation of substrate, make sealant cures, can make liquid crystal cell.Liquid crystal aligning agent of the present invention, owing to can forming the good liquid crystal orientation film of vertical orientated property, even thereby have while adopting the ODF method to manufacture VA type liquid crystal display device, also can make the advantage that can not produce the liquid crystal display device of ODF spot.
In the situation that adopt either method, all need, by after then liquid crystal cell being heated to temperature that liquid crystal used is isotropic phase, to slowly cool to room temperature the flow orientation when removing liquid crystal and filling.
Then, by the polaroid of fitting, can make liquid crystal display device of the present invention on the outer surface of liquid crystal cell.
Here, as sealing agent, can use such as the epoxy resin containing as the alumina balls of solidifying agent and separator etc.
As liquid crystal, can enumerate nematic liquid crystal and dish shape type liquid crystal.Wherein preferably there is the nematic liquid crystal of negative dielectric anisotropic, can use such as 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, cubane-like liquid crystal etc.And, can also further add cholesteryl liquid crystals such as 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 being used.And, can also use oxygen base α-tolylene-to ferroelectric liquid crystals such as amino-2-methyl butyl laurates in the last of the ten Heavenly stems.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol is extended to 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 the polaroid of making or H film self are made.
[embodiment]
Synthesizing of the compound that<above-mentioned formula (1) means >
Embodiment 1 (synthesizing of compound (1-2-1))
According to following synthetic route 4, synthesized compound (1-2-1).
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, carry out reaction in 5 hours under 100 ℃.Reaction joins reaction mixture in 1.5L water after finishing, and reclaims the precipitation generated.This precipitation is dissolved in vinyl acetic monomer, by after gained solution with water washing 3 times, by dried over mgso, concentrated, then, except desolventizing, makes 72g compound (1-2-1b).
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 (using 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 to reaction in 12 hours simultaneously.Reaction is injected into reaction mixture in 1L water after finishing, and reclaims the precipitation generated.This precipitation is dissolved in ethyl acetate, and, by after gained solution with water washing three times, by dried over mgso, concentrated, then carries out recrystallization with ethanol, obtain 65g compound (1-2-1c).
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.Reaction adds potassium fluoride aqueous solution after finishing in reaction mixture, after removing by filter the precipitate of generation, carries out separatory, and removes water layer, obtains organic layer.After this organic layer is washed with potassium fluoride aqueous solution and water successively, by dried over mgso, concentrated, then carry out recrystallization with ethanol, 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).
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 finishes, from reaction mixture, ethyl acetate is removed in distillation, in residue, adds the 2L chloroform, obtains organic layer.This organic layer, successively with dilute hydrochloric acid washing three times, after washing four times with water, by dried over mgso, concentrated, is leached 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 DMF carry out reaction in 8 hours under 60 ℃.Reaction adds the 3L chloroform after finishing in reaction mixture, and organic layer is washed with water three times.Then, with after dried over mgso, concentrated to organic layer, reclaim the solid of separating out, with 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.Reaction adds potassium fluoride aqueous solution after finishing in reaction mixture, after removing by filter the precipitate of generation, carries out separatory, and removes water layer, obtains organic layer.After this organic layer is washed with potassium fluoride aqueous solution and water successively, use dried over mgso, concentrated, then carry out recrystallization with ethanol, 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 METHYLPYRROLIDONE, under 60 ℃, reaction is 6 hours, obtains the solution containing 20 % by weight polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 6000mPas.
Then, in the gained polyamic acid solution, append the 1500g METHYLPYRROLIDONE, then add 21g pyridine and 28g acetic anhydride, carry out dehydration closed-loop reaction in 4 hours under 110 ℃.After the dehydration closed-loop reaction, carry out solvent exchange by the solvent by system with new METHYLPYRROLIDONE and (by this solvent exchange operation, the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction are removed to system.Lower with), obtain containing the solution that 20 % by weight imide rates are about 50% imide amination polymer (A-1).This solution that takes a morsel, add METHYLPYRROLIDONE, is made into the solution that imide amination polymer concentration is 6.0 % by 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 METHYLPYRROLIDONE, under 60 ℃, reaction is 6 hours, obtains the solution containing 20 % by weight polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 4800mPas.
Then, in the gained polyamic acid solution, append the 1500g METHYLPYRROLIDONE, then add 21g pyridine and 28g acetic anhydride, carry out dehydration closed-loop reaction in 4 hours under 110 ℃.After dehydration closed-loop reaction, by the solvent by system, with new METHYLPYRROLIDONE, carry out solvent exchange, obtain containing the solution that 20 % by weight imide rates are about 50% imide amination polymer (A-2).This solution that takes a morsel, add METHYLPYRROLIDONE, is made into the solution that imide amination polymer concentration is 6.0 % by 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, 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 that mean are dissolved in the 450g METHYLPYRROLIDONE, and under 60 ℃, reaction is 6 hours, obtains the solution containing 20 % by weight polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 3500mPas.
Then, in the gained polyamic acid solution, append the 500g METHYLPYRROLIDONE, then add 10g pyridine and 13g acetic anhydride, carry out dehydration closed-loop reaction in 4 hours under 110 ℃.After dehydration closed-loop reaction, by the solvent by system, with new METHYLPYRROLIDONE, carry out solvent exchange, obtain containing the solution that 20 % by weight imide rates are about 49% imide amination polymer (B-1).This solution that takes a morsel, add METHYLPYRROLIDONE, is made into the solution that imide amination polymer concentration is 6.0 % by weight, and the soltion viscosity of mensuration is 25mPas.
The preparation of<liquid crystal aligning agent and evaluation >
Embodiment 5
[preparation of liquid crystal aligning agent for the printing evaluation]
To make in above-described embodiment 3 containing in the solution of imide amination polymer (A-1), the imide amination polymer (A-1) with respect to contained in the above-mentioned solution of 100 weight part, add the following formula of 20 weight part (E-1)
The compound meaned is as epoxy compounds, add gamma-butyrolactone (BL), METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (BC), being made into solvent composition is the solution that BL:NMP:BC=40:30:30 (weight ratio), solids content concn are 6.0 % by weight again.The filter that is 1 μ m with aperture by this solution filters, and prepares to obtain the liquid crystal aligning agent of printing evaluation use.The soltion viscosity of under 25 ℃, this liquid crystal aligning agent being measured is 22mPas.
[evaluation of printing]
Printing evaluation liquid crystal aligning agent by above preparation, (Japan's description printing (strain) is manufactured to adopt the liquid crystal orientation film printing press, オ Application グ ス ト ロ mono-マ mono-S40L-532) be coated on the transparent electrical pole-face with the glass substrate of ITO film transparency electrode processed, under 80 ℃, heating 1 minute (prebake) is except after desolventizing, heat 10 minutes (curing afterwards) under 180 ℃, what the formation thickness was 8000nm films again.This is filmed and carries out visual observations, and investigation has corrugationless and coating inequality, does not now observe printing inequality and pinprick, and the printing of above-mentioned liquid crystal aligning agent is " well ".
[manufacturing the preparation of the liquid crystal aligning agent of used for liquid crystal display element]
To make in above-described embodiment 3 containing in the solution of imide amination polymer (A-1), with respect to imide amination polymer (A-1) contained in the above-mentioned solution of 100 weight part, the compound that adds the above-mentioned formula of 20 weight part (E-1) to mean is as epoxy compounds, add METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (BC), being made into solvent composition is the solution that NMP:BC=50:50 (weight ratio), solids content concn are 4 % by weight again.The filter that is 1 μ m with aperture by this solution filters, and the liquid crystal aligning agent of used for liquid crystal display element is manufactured in preparation.
[manufacture of the liquid crystal display device of vertical orientated control evaluation use]
Adopt spin coater the liquid crystal aligning agent of the manufacture used for liquid crystal display element of above preparation to be coated on the ITO film nesa coating processed arranged on the one side of the glass substrate that thickness is 1mm, after on hot-plate, under 80 ℃, heating 1 minute (prebake) removes desolventizing, heat 60 minutes (curing afterwards) under 200 ℃, forming thickness is filming of 0.08 μ m again.The sander of the roller that is wound around Artificial Fibers cloth is equipped with in employing, at the roller rotating speed, is that 400rpm, operator's console translational speed are 3cm/ second, and fine hair is clamp-oned under the condition that length is 0.4mm, and this is filmed and carries out grinding process.Then, with ultrasonic washing after 1 minute, then in the cleaning oven of 230 ℃ dry 25 minutes, make the substrate with the liquid crystal orientation film that has carried out grinding process in ultrapure water.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, after coating has added the epoxy resin binder of the alumina balls that diameter is 5.5 μ m, liquid crystal aligning face antiparallel ground is overlapped and pressing, then tackiness agent is solidified.Then, by liquid crystal injecting port, to filling nematic liquid crystal between a pair of substrate, (メ Le Network company produces, 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, produce the liquid crystal display device of vertical orientated control evaluation use.
[evaluation of vertical orientated control]
Liquid crystal display device to the vertical orientated control evaluation use of above manufacture, 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 the tilt angle of 89 °, and vertical orientated control is " well ".
In addition, known grinding process of carrying out in above-mentioned [manufacture of the liquid crystal display device of vertical orientated control evaluation use], have to the vertical orientated control of liquid crystal orientation film the effect of subduing.Even so when carrying out the situation that grinding process also shows tilt angle more than 86 °, vertical orientated control can be said extremely good, can produce the liquid crystal aligning agent of this result, even use it for while by the ODF mode, manufacturing VA type liquid crystal display device, rule of thumb also can not know and can produce the demonstration spot.
[manufacture of the liquid crystal display device of voltage retention evaluation use]
In above-mentioned [manufacture of the liquid crystal display device of vertical orientated control evaluation use], except formed filming not carried out grinding process and washing and drying treatment subsequently, similarly operate with above-mentioned [manufacture of the liquid crystal display device of vertical orientated control evaluation use], manufacture the liquid crystal display device of voltage retention evaluation use.
[evaluation of voltage retention]
Under 60 ℃, in the time span of 16.7 microseconds, the liquid crystal display device of the voltage retention evaluation use of above manufacture is applied to the voltage of 5V, the voltage application time is 60 microseconds, then measures from voltage and removes to the voltage retention 16.7 milliseconds.The voltage retention of this liquid crystal display device is 99%.
Embodiment 6 and comparative example 1
In above-described embodiment 5, except the solution that use contains imide amination polymer shown in table 1, operation similarly to Example 5, each prepares two kinds of liquid crystal aligning agent, and is estimated.Evaluation result is listed in table 1 with the printing evaluation together with the soltion viscosity of liquid crystal aligning agent.
Table 1
As being found out particularly by above embodiment, liquid crystal aligning agent of the present invention, owing to demonstrating good printing, simultaneously, the liquid crystal orientation film formed by it has good vertical orientated control, even thereby have while adopting the ODF method to manufacture 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 (3)
1. a liquid crystal aligning agent that is used to form the liquid crystal orientation film of vertical alignment-type liquid crystal display device, it is characterized in that the imide amination polymer that comprises polyamic acid, this polyamic acid is obtained with the diamine reactant of the compound that contains following formula (1) expression by the tetracarboxylic dianhydride
In formula (1), the alkyl that R is 3～20 for the carbonatoms that optionally replaced by fluorine atom, A is Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, B
1for Sauerstoffatom or-OCO-*, wherein, with the connecting key of " * " and (CH
2)
bconnect B
2for Sauerstoffatom or-COO-*, wherein, with the connecting key of " * ", with A, be connected, a is 0 or 1, the b integer that is 2～10, c is 0 or 1, the following formula in its Chinese style (1)
The unit meaned is following formula
Any one in the unit meaned, in above-mentioned formula, with connecting key and the B of "+"
2connect;
Wherein said tetracarboxylic dianhydride comprises the ester ring type tetracarboxylic dianhydride.
2. a vertical alignment-type liquid crystal display device, is characterized in that having the liquid crystal orientation film formed by liquid crystal aligning agent claimed in claim 1.
3. an imide amination polymer, it is by the polyamic acid imidization is obtained, and this polyamic acid is made with the diamine reactant that contains the compound that following formula (1) means by the tetracarboxylic dianhydride who comprises the ester ring type tetracarboxylic dianhydride,
In formula (1), the alkyl that R is 3～20 for the carbonatoms that optionally replaced by fluorine atom, A is Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, B
1for Sauerstoffatom or-OCO-*, wherein, with the connecting key of " * " and (CH
2)
bconnect B
2for Sauerstoffatom or-COO-*, wherein, with the connecting key of " * ", with A, be connected, a is 0 or 1, the b integer that is 2～10, c is 0 or 1, the following formula in its Chinese style (1)
Any one in the unit meaned, in above-mentioned formula, with connecting key and the B of "+"
2connect.
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| JP6079210B2 (en) * | 2012-03-28 | 2017-02-15 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, polymer and compound |
| 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 |
| 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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