CN1710467A - Vertical liquid crystal orientating agent and vertical liquid crystal display element - Google Patents

Vertical liquid crystal orientating agent and vertical liquid crystal display element Download PDF

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CN1710467A
CN1710467A CNA2005100772243A CN200510077224A CN1710467A CN 1710467 A CN1710467 A CN 1710467A CN A2005100772243 A CNA2005100772243 A CN A2005100772243A CN 200510077224 A CN200510077224 A CN 200510077224A CN 1710467 A CN1710467 A CN 1710467A
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liquid crystal
organic solvent
ether
vertical liquid
crystal orientating
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CN100549784C (en
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六鹿泰显
丸谷英三
栗山敬祐
西川通则
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JSR Corp
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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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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Abstract

The invention provides a vertical orientation agent with which a vertical liquid crystal orientation film having superior coating properties and free of a defect such as coating unevenness can stably be obtained. Disclosed are a mixed solvent consisting of a 1st organic solvent which has surface tension of >=39 dyne/cm and contains a nitrogen atom in a molecule, a 2nd organic solvent which has surface tension of >=39 dyne/cm and does not contain a nitrogen atom in a molecule, and a 3rd organic solvent which has surface tension of <=32 dyne/cm and the vertical liquid crystal orientation agent which contains a partially imidized polymer of polyamic acid and/or polyimide dissolved in the mixed solvent.

Description

Vertical liquid crystal orientating agent and vertical liquid crystal display element
Technical field
The present invention relates to vertical liquid crystal orientating agent and vertical liquid crystal display element.More particularly, relate to stably to form for the liquid crystal display cells of making of large substrate and do not have the coating not vertical liquid crystal orientating agent of the vertical liquid crystal oriented film of defective such as gentle aperture and liquid crystal display cells with the vertical liquid crystal oriented film that makes by this liquid crystal orientating agent.
Background technology
At present, known having has the TN type liquid crystal display cells of so-called TN type (twisted nematic) liquid crystal cell as liquid crystal display cells, this element is at the substrate of the liquid crystal orientating membrane that formations such as forming polyamic acid, polyimide on the substrate surface of nesa coating is set as liquid crystal display cells, 2 these substrates are oppositely arranged, form nematic crystal layer betwixt in the crack with positive dielectric anisotropy, constitute the box of sandwich construction, the major axis of liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.
And, developed and compared with TN type liquid crystal display cells that contrast is higher, its view angle dependency STN (STN Super TN) type liquid crystal display cells still less.This STN type liquid crystal display cells fusion optically active substance chiral reagent in nematic crystal uses as liquid crystal, utilizes by the major axis that makes liquid crystal molecule and is in the birefringence effect of turning round turnback between substrate continuously or producing with the state of upper span.
In addition, known lateral electric field type liquid crystal display element in addition, its 2 electrodes that drive liquid crystal are provided with the broach shape on a side chassis, produce the electric field parallel with real estate, the control liquid crystal molecule.The directed of liquid crystal manifested by the liquid crystal orientating membrane of implementing grinding process usually in these liquid crystal display cells.
As the liquid crystal display cells beyond above-mentioned, known having has the liquid crystal display cells of vertical orientation (Vertical Alignment) type liquid crystal cell, has liquid crystal molecule vertical orientation on substrate of negative dielectric anisotropic in this liquid crystal cell.In this liquid crystal display cells, the control of the orientation of liquid crystal is undertaken by the liquid crystal orientating membrane that is formed by the liquid crystal orientating agent that contains polymkeric substance such as polyamic acid, polyimide usually.
Liquid crystal orientating membrane has formed on color filter or the semi-conductive substrate that has an electrode by adopting roll coater method or methods such as spin coater method, print process that liquid crystal orientating agent is coated on, and makes solvent evaporation and forms through baking.But when the coating performance of used liquid crystal orientating agent is good inadequately, defectives such as coating injustice that the membrane thickness unevenness owing to liquid crystal orientating membrane produces or aperture can appear.Because this defective can produce very big influence to liquid crystal aligning, the situation of graceful graph picture can appear obtaining in the liquid crystal display cells that contains the liquid crystal orientating membrane with defective.
So, in order to obtain the good liquid crystal orientating agent of coating performance, carried out using as disclosed technology in patent documentation 1, patent documentation 2 and the patent documentation 3 to improve the uneven research of coating, in liquid crystal display cells manufacturing process in the past, brought into play extraordinary effect, but this is because the less result who also makes contributions of size of liquid crystal display cells at that time.
The common application of liquid crystal display cells will form a pair of parent baseplate-laminating of oriented film and form box, inject the polylith preparation method that cuts out behind the liquid crystal.
In the past, because the size of the liquid crystal display cells of making is very little with respect to substrate, can obtain several to tens liquid crystal display cells by a pair of parent substrate, even the oriented film on the parent substrate partly has the unequal defective of coating, owing to obtain most liquid crystal display cells that do not contain this part, thereby can realize very high manufacturing efficient.
But in recent years, liquid crystal display cells has the trend of maximization, has produced recently to reach 40 inches other liquid crystal display cells of level.
Maximize on the other hand at liquid crystal display cells, because the restriction of being made and carrying, the maximization degree of parent substrate is confined very little, the quantity of the liquid crystal display cells that a pair of parent substrate can the obtain situation that reduction also occurs compared with the past.
Therefore, when having defective on the liquid crystal orientating membrane that forms on the parent substrate, also enlarge markedly the influence of making the efficient generation is compared with the past, therefore, press for the liquid crystal orientating agent that a kind of coating performance compared with the past significantly improves, can stably make flawless liquid crystal orientating membrane.
Patent documentation 1: Japanese kokai publication hei 11-264643 communique
Patent documentation 2: TOHKEMY 2001-265048 communique
Patent documentation 3: TOHKEMY 2002-95499 communique
Summary of the invention
The object of the invention provides the vertical liquid crystal orientating agent that a kind of coating performance is good, can stably make the vertical liquid crystal oriented film that does not have the unequal defective of coating.
Another object of the present invention provides a kind of vertical liquid crystal display element with the vertical liquid crystal oriented film that is made by liquid crystal orientating agent of the present invention.
Other purpose of the present invention and advantage can be clear that from the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, first, realize that by a kind of vertical liquid crystal orientating agent it is characterized in that comprising by surface tension is that the 1st organic solvent, the surface tension that have nitrogen-atoms in 39 dyne/cm or above, the molecule is that the 2nd organic solvent of nonnitrogenous atom in 39 dyne/cm or above, the molecule and surface tension are the mixed solvent formed of 32 dyne/cm or the 3rd following organic solvent and part imide amination polymer and/or the polyimide that is dissolved in the polyamic acid in this mixed solvent.
According to the present invention, above-mentioned purpose of the present invention and advantage, the second, realize by a kind of vertical liquid crystal display element, it is characterized in that having the liquid crystal orientating membrane that forms by vertical liquid crystal orientating agent of the present invention.
Even when using large substrate, also can stably make the vertical liquid crystal oriented film that does not have the unequal defective of coating by liquid crystal orientating agent of the present invention, can be suitable for making super-huge liquid crystal display cells.
Liquid crystal display cells of the present invention can be used for various devices effectively, for example is applicable to display device such as desk-top computer, wrist-watch, table clock, mobile phone, counting display screen, word processor, personal computer, liquid crystal TV set.
Embodiment
Liquid crystal orientating agent of the present invention, as mentioned above, by the part imide amination polymer of polyamic acid and/or polyimide being dissolved in the mixed solvent that the 1st organic solvent, the 2nd organic solvent and the 3rd organic solvent form and the solution composition that obtains.
Above-mentioned polyimide makes by the polyamic acid dehydration closed-loop with tetracarboxylic dianhydride and diamine compound open loop addition polymerization gained usually.The part imide amination polymer usually can be by making the method for polyamic acid partial dehydration closed loop, or make amic acid give the method that polymers and acid imide give polymers bonding synthetic segmented copolymer to make.
＜polyamic acid 〉
[tetracarboxylic dianhydride]
As the tetracarboxylic dianhydride, can enumerate for example butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane 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 tetracarboxylic 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-5-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-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-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)-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-8-ethyl-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, 5-(2,5-dioxo tetrahydrofuran methylene)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid dianhydride, dicyclo [2,2,2]-and Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), following formula (I) and aliphatics and the alicyclic ring shape tetracarboxylic dianhydrides such as compound that (II) represent
Figure A20051007722400072
(in the formula, R 1And R 3Expression has the divalent organic group of aromatic rings, R 2And R 4Expression hydrogen atom or alkyl, the R of a plurality of existence 2And R 4Separately can be identical, also can be different);
Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone 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 dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dicarboxylic anhydride, 3,3 ', 4,4 '-all fluorine isopropylidene two phthalandione dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalandione) phosphniline oxide dicarboxylic anhydride, right-phenylene-two (triphenyl phthalandione) dianhydride, between-phenylene-two (triphenyl phthalandione) dianhydride, two (triphenyl phthalandiones)-4,4 '-diphenyl ether dianhydride, two (triphenyl phthalandiones)-4,4 '-diphenyl methane dianhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butylene glycol-two (dehydration trimellitate), 1,6-hexanediol-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 of following formula (1)～(4) representative.They can a kind of independent or 2 kinds or above being used in combination.
Figure A20051007722400081
Wherein, from showing the angle of good liquid crystal aligning, preferred butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic 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)-and naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2,2,2]-and Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, the compound of following formula (8) representative in the compound of following formula (5)～(7) representative in the compound of following formula (I) representative and the compound of following formula (II) representative, as particularly preferred, can enumerate 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane 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-2 ', 5 '-diketone), the compound of pyromellitic acid dianhydride and following formula (5) representative.
Especially, when the repetitive (acid imide unit) of the repetitive (amic acid unit) of (I-1) representative and above-mentioned formula (I-2) representative when existing simultaneously, (I-1) middle P 14 valency organic groups of representative and the middle P of the repetitive (acid imide unit) of (I-2) representative 24 valency organic groups of representative separately can be identical, also can be different, and as P 1Preferred group, can enumerate the (ii) group of representative separately of following formula (i) and formula (i ') and formula.As P 2Preferred group can be enumerated the group with alicyclic ring skeleton, especially preferably enumerates following formula (ii) and (ii ') group of representative separately.
Figure A20051007722400102
(in the formula, P 1And P 2Be the organic group of 4 valencys independently of each other, Q 1And Q 2Be the organic group of divalent independently of each other, R is halogen atom, methyl or ethyl, and a is 0 or 1 integer, and b is 0～5 integer, and c and d are 0～4 integer).
As the object lesson of preferred tetracarboxylic dianhydride in each repetitive, the tetracarboxylic dianhydride who constitutes the amic acid unit for example can enumerate 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 2,3, the compound of 5-tricarboxylic basic ring amyl group acetic acid dianhydride, pyromellitic acid dianhydride, formula (5) representative etc.In addition, constitute the preferred alicyclic ring shape of the tetracarboxylic dianhydride tetracarboxylic dianhydride of acid imide unit, can enumerate 2 especially, 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-1,3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1,3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone) etc.
[diamine compound]
The synthetic middle diamine compound that uses as above-mentioned polyamic acid, can enumerate for example p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diamido diphenylethane, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl) 1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido 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-two (4-aminophenyl) fluorenes, 4,4 '-methylene-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 1,4,4 '-(right-the phenylene isopropylidene) two (aniline), 4,4 '-(-the phenylene isopropylidene) two (aniline), 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, 4-(4-n-heptyl cyclohexyl)-phenoxy group-2, aromatic diamines such as 4-diaminobenzene;
1, xylyene diamine, 1 between 1-, 3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4, the inferior indanyl dimethylene of 7-methylene diamines, three ring [6.2.1.0 2,7]-undecylene two methanediamines, 4,4 '-methylene two aliphatics and alicyclic ring shape diamines such as (cyclohexylamine);
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2,4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3, the 5-triazine, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3, the 5-triazine, 2,4-diamido-6-methyl-s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3,5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, the diamines that has 2 primary amino radicals and this primary amino radical nitrogen-atoms in addition in the compound equimolecular of two (4-aminophenyl) phenyl amine and following formula (III)～(IV) representative
Figure A20051007722400131
(in the formula, R 5Expression is selected from 1 valency organic group of the ring texture with nitrogen atom of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic group),
(in the formula, X represents to be selected from the divalent organic group of the ring texture with nitrogen atom of pyridine, pyrimidine, triazine, piperidines and piperazine, R 6Expression divalent organic group, the X of a plurality of existence can be the same or different);
Single-substituted two amines of following formula (V) representative; The diamido organosiloxane of following formula (VI) representative;
(in the formula, R 7Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R 8It is 6～30 alkyl that expression has the 1 valency organic group of group of the steroid backbone of being selected from, trifluoromethyl and fluorine or carbon number),
(in the formula, R 9The expression carbon number is 1～12 alkyl, the R of a plurality of existence 9Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer);
Can enumerate the compound of following formula (9)～(13) representative etc.These diamine compounds can be separately or 2 kinds or above being used in combination.
(in the formula, y is 2～12 integer, and z is 1～5 integer).
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl 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 '-(right-the phenylene diisopropylidene) two (aniline), 4,4 '-(-the phenylene diisopropylidene) two (aniline), 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, the compound of above-mentioned formula (9)～(13) representative, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, the compound of following formula (14) representative in the compound of above-mentioned formula (III) representative, the compound of following formula (16)～(21) representative in the compound of following formula (15) representative in the compound of above-mentioned formula (IV) representative and the compound of above-mentioned formula (V) representative.
Figure A20051007722400161
[synthesizing of polyamic acid]
Supply with the tetracarboxylic dianhydride of polyamic acid synthetic reaction and the usage rate of diamine compound, preferably with respect to contained amino in the 1 equivalent diamine compound, the anhydride group that makes the tetracarboxylic dianhydride is the ratio of 0.2～2 equivalent, more preferably the ratio of 0.3～1.2 equivalent.
The synthetic reaction of polyamic acid is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature conditions in organic solvent.Here, as organic solvent,, it is had no particular limits as long as can dissolve synthetic polyamic acid.Can illustration for example N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, N, aprotic polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, hexamethyl tricresyl phosphite acid amides; Between phenol solvent such as sylvan, xylenols, phenol, halogenated phenol.In addition, to be preferably the total amount (b) that makes tetracarboxylic dianhydride and diamine compound be the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction solution to the consumption of organic solvent (a).
[poor solvent]
In addition, in the scope that the polyamic acid that does not make generation is separated out, can also unite in the above-mentioned organic solvent and use polyamic acid poor solvent alcohols, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, glycol monoethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, diethy-aceto oxalate, 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, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.Then, this reaction solution is put in a large amount of poor solvents, obtained precipitate.Can get polyamic acid by this precipitate of drying under reduced pressure.And, once more this polyamic acid is dissolved in the organic solvent, separate out with poor solvent then, by carrying out once or this operation several times, can make with extra care polyamic acid.
＜polyimide 〉
The polyimide that constitutes liquid crystal orientating agent of the present invention can be by preparing above-mentioned polyamic acid dehydration closed-loop.The dehydration closed-loop of polyamic acid perhaps (ii) is dissolved in polyamic acid in the organic solvent by for example method of (i) heating polyamic acid, add dewatering agent and dehydration closed-loop catalyzer in this solution, and the method for heating is as required carried out successfully.
Temperature of reaction is preferably 50～200 ℃, more preferably 60～170 ℃ in the method for above-mentioned (i) heating polyamic acid.When 50 ℃ of temperature of reaction less thaies, the dehydration closed-loop reaction is difficult to carry out fully, if temperature of reaction surpasses 200 ℃, the situation that the molecular weight of gained imide amination polymer reduces can occur.
On the other hand, (ii) in polyamic acid solution, in the method for adding dewatering agent and dehydration closed-loop catalyzer,, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride above-mentioned as dewatering agent.The consumption of dewatering agent with respect to 1 mole of polyamic acid repetitive, is preferably 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidines, 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 the organic solvent that uses in the dehydration closed-loop reaction, can enumerate the identical organic solvent of illustrative organic solvent with synthesize middle solvent for use as polyamic acid.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.In addition, by the reaction solution that so obtains is carried out the operation same with the polyamic acid process for purification, can make with extra care polyimide.
＜part imide amination polymer 〉
Used part imide amination polymer has the structure that above-mentioned polyamic acid part imidizate is obtained among the present invention.Among the present invention in the used part imide amination polymer imidizate rate be preferably 10～90%, more preferably 30～70%.Here, " imidizate rate " is meant the sum with respect to repetitive in the polymkeric substance, the value that the ratio of the number of repeat unit of formation imide ring is represented with %.At this moment, the part of imide ring can also be different acid imide (ィ ソ ィ ミ De) ring.
Method as the composite part imide polymer, for example can use (i) by heating above-mentioned polyamic acid partly the method for dehydration closed-loop, (ii) by above-mentioned polyamic acid is dissolved in the organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer and heating as required, carry out partly dehydration closed-loop and synthetic method, perhaps (iii) by tetracarboxylic dianhydride, diamine compound and diisocyanate cpd are mixed, heating is carried out condensation and synthetic method as required.
In the method for above-mentioned (i), temperature of reaction is preferably 300 ℃ or following, more preferably 100～250 ℃.If temperature of reaction surpasses 300 ℃, the situation of the molecular weight reduction of gained part imide amination polymer can appear.
On the other hand, as used dewatering agent in above-mentioned method (ii), can enumerate for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.The consumption of dewatering agent with respect to 1 mole of polyamic acid repetitive, is preferably 0.2～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidines, triethylamine.But, be not limited to these.And the consumption of imidization catalyst with respect to 1 mole of used dewatering agent, is preferably 0.1～10 mole.In addition, as the organic solvent that uses in the dehydration closed-loop reaction, can enumerate the identical organic solvent of illustrative organic solvent with synthesize middle solvent for use as polyamic acid.And the temperature of reaction of dehydration closed-loop is preferably 0～180 ℃, more preferably 60～150 ℃.In addition, by the reaction solution that so obtains is carried out the operation same with the polyamic acid process for purification, can the FF imide amination polymer.
As the object lesson of diisocyanate cpd used in the above-mentioned reaction (iii), can enumerate aliphatic diisocyanates such as hexamethylene diisocyanate; Cyclohexane-1,2-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1,2-two ' methylcyclohexane-ω, ω '-diisocyanate, 1,4-two ' methylcyclohexane-ω, ω '-diisocyanate, isophorone diisocyanate, 1,3,5-trimethyl-2-propyl cyclohexane-1 ω, 2 ω-diisocyanate, dicyclohexyl methyl hydride-4, alicyclic ring shape diisocyanate such as 4 '-diisocyanate; Diphenyl methane-4,4 '-diisocyanate, 1,3-phenylene vulcabond, 1,4-phenylene vulcabond, 1-methyl-2,4-phenylene vulcabond, 1-methyl-2, the aromatic diisocyanates such as diisocyanate of 6-phenylene vulcabond, following formula (22)～(26) representative.
Figure A20051007722400201
Wherein, as preferably enumerating dicyclohexyl methyl hydride-4,4 '-diisocyanate, diphenyl methane-4,4 '-diisocyanate, 1-methyl-2,4-phenylene vulcabond, 1-methyl-2,6-phenylene vulcabond.They can be separately or 2 kinds or above being used in combination.In addition, the unessential especially catalyzer of above-mentioned reaction (iii), temperature of reaction is preferably 50～200 ℃, more preferably 100～160 ℃.
[end modified]
＜end modified type polymkeric substance 〉
Above-mentioned polyamic acid and part imide amination polymer can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using this end modified type polymkeric substance, can under the prerequisite of not damaging effect of the present invention, improve the coating characteristics of liquid crystal orientating agent etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, for example adds monoester anhydride, monoamine compound, monoisocyanates compound etc. and synthesize in reaction system.Here, as monoester anhydride, can enumerate for example maleic anhydride, anhydride phthalic acid, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.In addition, as monoamine compound, can enumerate for example aniline, cyclo-hexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane amine, n-hexadecane amine, n-heptadecane amine, n-octadecane amine, n-eicosane amine etc.In addition, as the monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
[logarithm viscosity]
The logarithm viscosity of＜polymkeric substance 〉
As above the logarithm viscosity of gained polyamic acid and part imide amination polymer (η ln) value is preferably 0.05～10dl/g, more preferably 0.05～5dl/g.
Logarithm viscosity of the present invention (η ln) value is by using the N-N-methyl-2-2-pyrrolidone N-as solvent, is that the solution of 0.5g/100ml carries out viscosimetric analysis to concentration under 30 ℃, the value of being tried to achieve by following formula (A).
Figure A20051007722400221
[liquid crystal orientating agent]
Liquid crystal orientating agent of the present invention constitutes by polyimide and/or part imide amination polymer are dissolved in the organic solvent.
As the organic solvent that constitutes liquid crystal orientating agent of the present invention, using by surface tension is that the 1st organic solvent, the surface tension that have nitrogen-atoms in 39 dyne/cm or above, the molecule is that the 2nd organic solvent and the surface tension of nonnitrogenous atom in 39 dyne/cm or above, the molecule is the mixed solvent that 32 dyne/cm or the 3rd following organic solvent are formed.
The mixture ratio of the 1st organic solvent, the 2nd organic solvent and the 3rd organic solvent preferably satisfies following formula
(A×B×C)×10 -3≥12，
More preferably 14 or more than, here, it is the weight % of the 1st organic solvent of benchmark, the weight % of the 2nd organic solvent and the weight % of the 3rd organic solvent that A, B and C are respectively with the total weight of the 1st organic solvent, the 2nd organic solvent and the 3rd organic solvent.
As the object lesson of the 1st organic solvent, can enumerate for example N-N-methyl-2-2-pyrrolidone N-and N, N-dimethyl-2-imidazolidinone etc.The content of this solvent, the angle from the solubleness of polymkeric substance is preferably 5～75 weight %, more preferably 15～70 weight %.
As the object lesson of the 2nd organic solvent, can enumerate for example gamma-butyrolacton or carbonic allyl ester etc.The content of this solvent from the hygroscopic angle of directing agent, is preferably 5～75 weight %, more preferably 10～65 weight %.
As the 3rd organic solvent, can enumerate for example ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, dipropylene glycol dimethyl ether and 4-hydroxy-4-methyl-2 pentanone etc.The content of this solvent, the angle of homogeneity (レ ベ リ Application グ) is preferably 5～70 weight %, more preferably 15～60 weight % during from printing.
Solid component concentration is considered viscosity, volatility and is selected in the liquid crystal orientating agent of the present invention, is preferably 1～10 weight %.Liquid crystal orientating agent of the present invention is coated substrate surface, formation is filmed as liquid crystal orientating membrane, when solid component concentration less than 1 weight %, the thickness that causes this to film is too small, is difficult to obtain good liquid crystal orientating membrane, when solid component concentration surpasses 10 weight %, cause coating thickness blocked up, be difficult to obtain good liquid crystal orientating membrane, and, the viscosity of liquid crystal orientating agent increases, the easy variation of coating characteristics.Temperature when in addition, preparing liquid crystal orientating agent of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
Liquid crystal orientating agent of the present invention in order to improve the toughness of oriented film, can contain the compound that has epoxy radicals in the molecule as required.
As this compound that contains epoxy radicals, 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 diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N '-four glycidyl group-m-benzene dimethylamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
In addition, liquid crystal orientating agent of the present invention as required, in order to improve the cohesive of oriented film and substrate, is chosen wantonly and can be contained the compound with functionality silicon.As this compound with functionality silicon, 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-carbethoxyl group-3-TSL 8330, N-carbethoxyl group-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 acid esters, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (hydroxyethyl)-3-TSL 8330, N-two (hydroxyethyl)-3-aminopropyltriethoxywerene werene etc.
＜liquid crystal display cells 〉
With the liquid crystal display cells that liquid crystal orientating agent of the present invention makes, can be by for example following method manufacturing.
(1) by for example methods such as roll coater method, spin coater method, print process, ink-jet method, liquid crystal orientating agent of the present invention is coated on the substrate one side that is provided with the nesa coating that forms pattern, then,, coated face films by being added thermosetting.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutyleneterephthalate, polyethersulfone, polycarbonate.Simultaneously go up set nesa coating as substrate, can use tin oxide (SnO 2) system NESA film (U.S. PPG register of company trade mark), indium oxide-tin oxide (In 2O 3-SnO 2) the ITO film etc. of system.The formation of these electrically conducting transparent film figures is adopted photoetch method and is used the method for mask in advance.Can use metals such as Al or Ag in the reflecting electrode, perhaps contain the alloy of these metals etc.As long as have enough reflectivity, it had no particular limits.When the coating of liquid crystal orientating agent, for the cohesive of further improving substrate surface and nesa coating or reflecting electrode and filming, can also be on the surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Heating-up temperature behind the coating of liquid crystalline directing agent is preferably 80～300 ℃, more preferably 120～250 ℃.The liquid crystal orientating agent of the present invention that contains polyamic acid, by removing organic solvent after the coating, formation is filmed as oriented film, or carries out dehydration closed-loop by further heating, can form filming of further imidizate.The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) with the film coated surface that forms shown in the open 2002-327058 communique of Jap.P., on substrate, form structure with the photosensitivity resin, on it, form the vertical liquid crystal oriented film.
(3) make 2 substrates that as above form the vertical liquid crystal oriented film, make 2 substrates staggered relatively, fitted with sealant in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealant, inject filling liquid crystal by gap (box gap), the sealing filling orifice constitutes liquid crystal cell.Then, at the outside surface of liquid crystal cell, transparency carrier one side that promptly constitutes liquid crystal cell is provided with polaroid, makes liquid crystal display cells.
Here, as sealant, for example can use epoxy resin as the salic ball of hardening agent and separator etc.
As liquid crystal, can enumerate nematic crystal and dish shape type liquid crystal, wherein preferred nematic crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, phenylcyclohexane class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl thiacyclohexane class liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, also can add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chiral reagent (カ ィ ラ Le drug) sold with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use the strong dielectricity liquid crystal of oxygen base benzylidene-p-amino-2-methyl butyl cinnamic acid etc. in the last of the ten Heavenly stems.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate will make polyvinyl alcohol (PVA) extend directedly, the polarizing coating that is referred to as the H film that absorbs iodine simultaneously is clipped in the acetate fiber diaphragm and the polaroid that polaroid of making or H film make self.
By the following examples the present invention is carried out more specific description, but the present invention is not limited to these embodiment.Printing performance, vertical orientation are estimated by the following method in embodiment and the comparative example.
[the printing performance test of liquid crystal orientating agent]
Liquid crystal orientating agent of the present invention is coated the glass substrate that has ITO film system transparency electrode (on the transparency electrode face of 300mm * 400mm * 0.7mm) with liquid crystal orientating membrane printing machine (Japanese photographic printer (strain) system), behind baking formation liquid crystal orientating membrane, the peripheral position of this liquid crystal orientating membrane, the microscope that the central part multiplying power is 20 times are observed, do not have the uneven situation of coating and be judged to be " well ", have the uneven situation of coating to be judged to be " bad ".
[vertical orientation]
At off voltage and apply under the situation of 12V alternating voltage (peak-peak), observe liquid crystal display cells by cross Nicol prism (Network ロ ス ニ コ Le), under polarizing microscope, observe and have or not abnormal area, the situation in no abnormal zone is judged to be " well ", and be judged to be " bad " of abnormal area arranged.
Synthesis example 1
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224.17g (1.0 moles), be dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-as the p-phenylenediamine 68.13g (0.63 mole) of diamine compound, the diamine compound 193.44g (0.37 mole) of above-mentioned formula (16) representative, reacted 6 hours down at 60 ℃.Then, reaction solution is injected in the big excessive methyl alcohol, makes the reaction product precipitation, then, use methanol wash, in 40 ℃ of dryings 15 hours, obtaining 520g logarithm viscosity was the polyamic acid of 0.57dl/g by under reduced pressure.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours, carry out above-mentioned same precipitation, washing, decompression, obtain the polyimide that 19.0g logarithm viscosity is 0.50dl/g (it is called as " polyimide (PI-1) ").
Synthesis example 2
In synthesis example 1 except the diamine compound that uses 77.86g (0.72 mole) p-phenylenediamine, 146.38g (0.28 mole) above-mentioned formula (16) representative as diamine compound, similarly operate with synthesis example 1, obtaining 390g logarithm viscosity is the polyamic acid of 0.45dl/g.Except using 30g gained polyamic acid, similarly carry out imidizate with synthesis example 1, obtain the polyimide that 18.9g logarithm viscosity is 0.56dl/g (it is called as " polyimide (PI-2) ").
Synthesis example 3
In synthesis example 2 except the diamine compound that uses 95.16g (0.88 mole) p-phenylenediamine, 62.74g (0.12 mole) above-mentioned formula (16) representative as diamine compound, similarly operate with synthesis example 2, obtaining 450g logarithm viscosity is the polyamic acid of 0.38dl/g.Then, except using 4.8g pyridine and 6.1g acetic anhydride, similarly operate, obtain the polyimide that 20.3g logarithm viscosity is 0.40dl/g (it is called as " polyimide (PI-3) ") with synthesis example 2.
Synthesis example 4
In synthesis example 3 except using 97.33g (0.88 mole) p-phenylenediamine, 37.66g (0.1 mole) 2,4-diaminostilbene-octadecane oxygen base benzene is as beyond the diamine compound, similarly operate with synthesis example 1, obtain the polyimide that 24.3g logarithm viscosity is 0.42dl/g (it is called as " polyimide (PI-4) ").
Synthesis example 5
In synthesis example 1, except using 64.88g (0.88 mole) p-phenylenediamine, 36.65g (0.1 mole) 4-(4-n-heptyl cyclohexyl) phenoxy group-2, the 4-diaminobenzene is as beyond the diamine compound, similarly operate with synthesis example 1, obtain the polyimide that 24.3g logarithm viscosity is 0.49dl/g (it is called as " polyimide (PI-5) ").
Synthesis example 6
In synthesis example 1, except the diamine compound that uses 86.51g (0.80 mole) p-phenylenediamine, 104.56g (0.20 mole) above-mentioned formula (16) representative as the diamine compound, similarly operate with synthesis example 1, obtain the polyimide that 18.0g logarithm viscosity is 0.42dl/g (it is called as " polyimide (PI-6) ").
Synthesis example 7
In synthesis example 1, except the diamine compound that uses 75.70g (0.70 mole) p-phenylenediamine, 39.65g (0.20 mole) diaminodiphenyl-methane, 52.28g (0.10 mole) above-mentioned formula (16) representative as the diamine compound, similarly operate with synthesis example 1, obtain the polyimide that 17.5g logarithm viscosity is 0.50dl/g (it is called as " polyimide (PI-7) ").
Embodiment 1
(printing performance test)
The part imide amination polymer (PI-1) that makes in the synthesis example 1 is dissolved in N-N-methyl-2-2-pyrrolidone N-/gamma-butyrolacton/ethylene glycol monobutyl ether mixed solvent (weight ratio 70/10/20), make the solution that solid component concentration is 5 weight %, after fully stirring, is the filter filtration of 1 μ m with this solution with the aperture, prepares liquid crystal orientating agent of the present invention.Use liquid crystal orientating membrane printing machine (Japanese photographic printer (strain) system) above-mentioned liquid crystal orientating agent to be coated on the ITO film system nesa coating that is arranged on the glass substrate one side, at the preliminarily dried that under 80 ℃, carries out 1 minute on the heating plate, then in clean baking oven in 200 ℃ dry 1 hour down, form liquid crystal orientating membrane.It is uneven that this liquid crystal orientating membrane is not observed coating, and therefore, the printing performance of the liquid crystal orientating agent of preparation is judged as " well " among the embodiment 1.
(vertical orientation test)
The part imide amination polymer (PI-1) that makes in the synthesis example 1 is dissolved in N-N-methyl-2-2-pyrrolidone N-/gamma-butyrolacton/ethylene glycol monobutyl ether mixed solvent (weight ratio 70/10/20), make the solution that solid component concentration is 3.5 weight %, after fully stirring, with this solution is the filter filtration of 1 μ m with the aperture, the use spin coater is coated on the ITO film system nesa coating that is arranged on the glass substrate one side, at the preliminarily dried that under 80 ℃, carries out 1 minute on the heating plate, then in clean baking oven in 200 ℃ dry 1 hour down, make transparent electrode substrate with liquid crystal orientating membrane.Then, on each outer rim with the above-mentioned coating of liquid crystalline oriented film substrate of a pair of transparency electrode/transparent electrode substrate with liquid crystal orientating membrane, it is the epoxy adhesive of the alumina balls of 3.5 μ m that coating adds diameter, then, the liquid crystal aligning face is relatively overlapped and carry out pressing, bonding agent is solidified.Then, (メ Le Network society system MLC-6608), is sealed liquid crystal injecting port with the acrylic compounds Photocurable adhesive then, and the polaroid of fitting on the two sides in the substrate outside is made liquid crystal display cells to fill negative type liquid crystal by liquid crystal injecting port between substrate.When the vertical orientation of gained liquid crystal display cells is estimated, do not produce abnormal area, be judged as " well ".The results are shown in table 2.
Embodiment 2～18
Except according to the prescription shown in the following table 1, be dissolved in the part imide amination polymer (PI-2)～(PI-5) of gained in the synthesis example 2～5 in the mixed solvent beyond, liquid crystal orientating agent of the present invention is prepared in operation similarly to Example 1.Adopt so liquid crystal orientating agent of preparation respectively, operation is estimated printing performance, vertical orientation similarly to Example 1.The results are shown in table 1.
Comparative example 1～3
According to the prescription shown in the following table 1, similarly prepare liquid crystal orientating agent with embodiment.And printing performance and vertical orientation are estimated.The results are shown in table 2.
Table 1
Polymkeric substance Solvent composition (A×B×C)÷1000
The 1st organic solvent The 2nd organic solvent The 3rd organic solvent
Embodiment 1 ????PI-1 ????A-1(70) ????B-1(10) ????C-1(20) ???????14
Embodiment 2 ????PI-1 ????A-1(20) ????B-1(20) ????C-1(60) ???????24
Embodiment 3 ????PI-1 ????A-1(30) ????B-1(50) ????C-1(20) ???????30
Embodiment 4 ????PI-1 ????A-1(30) ????B-1(40) ????C-1(30) ???????36
Embodiment 5 ????PI-1 ????A-1(40) ????B-1(45) ????C-1(15) ???????27
Embodiment 6 ????PI-1 ????A-1(20) ????B-1(60) ????C-1(20) ???????24
Embodiment 7 ????PI-1 ????A-1(20) ????B-1(65) ????C-1(15) ???????20
Embodiment 8 ????PI-1 ????A-2(20) ????B-1(60) ????C-1(20) ???????24
Embodiment 9 ????PI-1 ????A-1(50) ????B-2(10) ????C-1(40) ???????20
Embodiment 10 ????PI-1 ????A-1(40) ????B-1(45) ????C-2(15) ???????27
Embodiment 11 ????PI-1 ????A-1(40) ????B-1(45) ????C-3(15) ???????27
Embodiment 12 ????PI-1 ????A-1(40) ????B-1(45) ????C-4(15) ???????27
Embodiment 13 ????PI-2 ????A-1(70) ????B-1(10) ????C-1(20) ???????14
Embodiment 14 ????PI-3 ????A-1(70) ????B-1(10) ????C-1(20) ???????14
Embodiment 15 ????PI-4 ????A-1(70) ????B-1(10) ????C-1(20) ???????14
Embodiment 16 ????PI-5 ????A-1(70) ????B-1(10) ????C-1(20) ???????14
Embodiment 17 ????PI-6 ????A-1(50) ????B-2(10) ????C-1(40) ???????20
Embodiment 18 ????PI-7 ????A-1(50) ????B-2(10) ????C-1(40) ???????20
Comparative example 1 ????PI-1 ????A-1(100) ??????-- ???????-- ???????0
Comparative example 2 ????PI-1 ??????-- ????B-1(100) ???????-- ???????0
Comparative example 3 ????PI-1 ????A-1(95) ??????-- ????C-1(5) ???????0
Table 1 is annotated: in each solvent species, bracket inner digital is represented content ratio.The symbol implication is as follows:
Solvent
The A-1:N-N-methyl-2-2-pyrrolidone N-
A-2:N, N '-dimethyl-1-imidazolidinone
B-1: gamma-butyrolacton
B-2: carbonic allyl ester
C-1: glycol monoethyl ether
C-2: diethylene glycol monomethyl ether
C-3: dipropylene glycol monomethyl ether
C-4:4-hydroxy-4-methyl-2 pentanone
Table 2
Printing performance Vertical orientation
Central part The periphery position
Embodiment 1 Well Well Well
Embodiment 2 Well Well Well
Embodiment 3 Well Well Well
Embodiment 4 Well Well Well
Embodiment 5 Well Well Well
Embodiment 6 Well Well Well
Embodiment 7 Well Well Well
Embodiment 8 Well Well Well
Embodiment 9 Well Well Well
Embodiment 10 Well Well Well
Embodiment 11 Well Well Well
Embodiment 12 Well Well Well
Embodiment 13 Well Well Well
Embodiment 14 Well Well Well
Embodiment 15 Well Well Well
Embodiment 16 Well Well Well
Embodiment 17 Well Well Well
Embodiment 18 Well Well Well
Comparative example 1 Bad Bad Well
Comparative example 2 Bad Bad Well
Comparative example 3 Bad Bad Well

Claims (6)

1, a kind of vertical liquid crystal orientating agent, it is characterized in that comprising by surface tension is that the 1st organic solvent, the surface tension that have nitrogen-atoms in 39 dyne/cm or above, the molecule is that the 2nd organic solvent of nonnitrogenous atom in 39 dyne/cm or above, the molecule and surface tension are the mixed solvent formed of 32 dyne/cm or the 3rd following organic solvent and part imide amination polymer and/or the polyimide that is dissolved in the polyamic acid in this mixed solvent.
2, vertical liquid crystal orientating agent as claimed in claim 1, wherein the mixture ratio of the 1st organic solvent, the 2nd organic solvent and the 3rd organic solvent satisfies following formula
(A×B×C)×10 -3≥12，
Here, to be respectively with the total weight of the 1st organic solvent, the 2nd organic solvent and the 3rd organic solvent be the weight % of the 1st organic solvent of benchmark, the weight % of the 2nd organic solvent and the weight % of the 3rd organic solvent for A, B and C.
3, vertical liquid crystal orientating agent as claimed in claim 1, wherein the 1st organic solvent is for being selected from N-N-methyl-2-2-pyrrolidone N-and N, N-dimethyl-2-imidazolidinone at least a.
4, vertical liquid crystal orientating agent as claimed in claim 1, wherein the 2nd organic solvent is be selected from gamma-butyrolacton and carbonic allyl ester at least a.
5, vertical liquid crystal orientating agent as claimed in claim 1, wherein the 3rd organic solvent is for being selected from 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, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, dipropylene glycol dimethyl ether and 4-hydroxy-4-methyl-2 pentanone at least a.
6, a kind of vertical liquid crystal display element is characterized in that having by any liquid crystal orientating membrane that described vertical liquid crystal orientating agent forms of claim 1～5.
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TWI359858B (en) 2012-03-11

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