CN101747907B - Liquid crystal alignment agent, liquid crystal display element, polyamic acid and imidization polymer thereof - Google Patents

Liquid crystal alignment agent, liquid crystal display element, polyamic acid and imidization polymer thereof Download PDF

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CN101747907B
CN101747907B CN2009102243577A CN200910224357A CN101747907B CN 101747907 B CN101747907 B CN 101747907B CN 2009102243577 A CN2009102243577 A CN 2009102243577A CN 200910224357 A CN200910224357 A CN 200910224357A CN 101747907 B CN101747907 B CN 101747907B
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liquid crystal
polyamic acid
compound
dianhydride
aligning agent
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CN101747907A (en
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秋池利之
高桥良彰
内山克博
谏山纯
河口和雄
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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

Abstract

The present invention relates to a liquid crystal alignment agent, a liquid crystal display element, a polyamic acid and an imidization polymer. The invention provides a liquid crystal alignment agent which can form the liquid crystal alignment film that has little electric performance reduction and excellent printing performance when the printing is performed with small amount of liquid, and a liquid crystal display element which has no reduced display quality when continuous driving is performed for a long time. The liquid crystal alignment agent comprises at least one polymer selected froma group which is composed of a polyamic acid and an imidization polymer thereof, wherein the polyamic acid is prepared by a reaction between tetracarboxylic dianhydride which comprises 2,3,5-tricarboxylic cyclopentyl acetic dianhydride and a dianhydride that comprises a specific dianhydride with alkyl dicyclohexyl. The liquid crystal display element is provided with the liquid crystal alignment film formed by the liquid crystal alignment agent.

Description

Liquid crystal aligning agent, liquid crystal display device, polyamic acid and imide amination polymer thereof
Technical field
The present invention relates to liquid crystal aligning agent, liquid crystal display device, polyamic acid and imide amination polymer thereof.More particularly, relate to and to form electric property descend less liquid crystal orientation film and the good liquid crystal aligning agent of printing, even and carry out long-time continuous and drive the liquid crystal display device that display quality also can not descend.
Background technology
At present, as liquid crystal display device, known TN type liquid crystal display device with so-called TN type (twisted-nematic) liquid crystal cell, it forms liquid crystal orientation film at the substrate surface that is provided with nesa coating, as the substrate of used for liquid crystal display element, two this substrate subtend ground are arranged, form the nematic liquid crystal layer with positive dielectric anisotropy betwixt in the crack, constitute the box of sandwich structure, the major axis of liquid crystal molecule reverses 90 ° (patent documentations 1) continuously from a substrate to another piece substrate.In addition, also developed to compare with TN type liquid crystal display device and can realize that good optical compensation curved of IPS (switching in the face) type liquid crystal display device, video pictures high-speed response of little while of view angle dependency that more the STN of high-contrast (supertwist is to row) type liquid crystal display device and view angle dependency are little (the type liquid crystal display device of optical compensation birefringence=OCB), adopt (patent documentations 2～5) such as vertical orientated (VA=Vertical Alignment) type liquid crystal display device of the nematic liquid crystal with negative dielectric anisotropic.
Material as the liquid crystal orientation film in these liquid crystal display device, known polyimide, polymeric amide and polyester etc. so far, polyimide particularly, its thermotolerance, good with the affinity of liquid crystal, physical strength etc. is so be used (patent documentation 1～6) in the liquid crystal display device mostly.
In recent years, liquid crystal display device develops to the televisor purposes seeking.In the liquid crystal display device of televisor purposes, in order to tackle becoming more meticulous and the development of animation technique for fixing of height of demonstration, use be the rapid response type liquid crystal.Adopt response fast to drive in the long-time continuous of lighting down backlight with the liquid crystal display device of liquid crystal if make, then have the tendency of image quality variation, thereby expectation solves by liquid crystal orientation film.
In addition, in order to effectively utilize liquid crystal aligning agent, the existing amount of liquid of just attempting reducing employed liquid crystal aligning agent when printing is even so need few amount of liquid also to show the liquid crystal aligning agent of superior printing characteristics.
Prior art
[patent documentation]
[patent documentation 1] Japanese kokai publication hei 4-153622 communique
[patent documentation 2] Japanese kokai publication sho 60-107020 communique
[patent documentation 3] Japanese kokai publication sho 56-91277 communique
No. 5928733 specification sheets of [patent documentation 4] United States Patent (USP)
[patent documentation 5] Japanese kokai publication hei 11-258605 communique
[patent documentation 6] Japanese kokai publication sho 62-165628 communique
Summary of the invention
The present invention In view of the foregoing makes, even its objective is to provide to form electric property descend less liquid crystal orientation film and also good liquid crystal aligning agent of printing when printing with a spot of amount of liquid, even and carry out long-time continuous and drive the liquid crystal display device that display quality also can not descend.
Other purposes of the present invention and advantage can be learned by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, first, reached by a kind of liquid crystal aligning agent, it contains at least a polymkeric substance in the group that is selected from polyamic acid and imide amination polymer formation thereof, and this polyamic acid is to contain 2,3 by making, the tetracarboxylic dianhydride of 5-tricarboxylic basic ring amyl group acetic acid dianhydride makes with the diamine reactant of the compound that contains following formula (1) expression
Figure G2009102243577D00031
(in the formula (1), R IFor the optional carbonatoms that can be replaced by fluorine atom is 3～20 alkyl, R IIFor-O-* ,-COO-* or-OCO-* (wherein, the connecting key of band " * " links to each other with phenyl ring)).
Above-mentioned purpose of the present invention and advantage, the second, reached by the liquid crystal display device with the liquid crystal orientation film that is formed by above-mentioned liquid crystal aligning agent.
Liquid crystal aligning agent of the present invention, even when printing with less amount of liquid, printing is also good, can form to show filming of height homogeneity.By the electricity excellent property of filming that liquid crystal aligning agent of the present invention forms, with its liquid crystal orientation film as liquid crystal display device, even drive backlight the supply for a long time down of lighting, electric property can variation yet.Therefore, have the liquid crystal display device of the present invention of this liquid crystal orientation film, even carry out long continuous drive, display quality can not descend yet, and therefore, the display element that can be suitable as various display unit uses.
Liquid crystal display device of the present invention is applicable to for example display unit of clock and watch, portable game machine, word processor, subnotebook PC, automobile navigation instrument, pick up camera, portable data assistance, digital camera, mobile telephone, various watch-dog, liquid crystal TV set etc.
Embodiment
Liquid crystal aligning agent of the present invention contains at least a polymkeric substance in the group that is selected from polyamic acid and imide amination polymer formation thereof, this polyamic acid is to contain 2 by making, the tetracarboxylic dianhydride of 3,5-tricarboxylic basic ring amyl group acetic acid dianhydride makes with the diamine reactant of the compound that contains above-mentioned formula (1) expression.
＜polyamic acid 〉
The polyamic acid that can contain in the liquid crystal aligning agent of the present invention can react by the diamines that makes the tetracarboxylic dianhydride of containing 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride and the compound that contains above-mentioned formula (1) expression and synthesize.
[tetracarboxylic dianhydride]
For the synthesis of the tetracarboxylic dianhydride of the polyamic acid among the present invention, be the tetracarboxylic dianhydride of containing 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride.As above-mentioned tetracarboxylic dianhydride, can only use 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, perhaps also 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride and other tetracarboxylic dianhydrides can be carried out coupling.
As operable other tetracarboxylic dianhydrides here, can enumerate for example butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-, two chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,3 ', 4,4 ', the dicyclohexyl tetracarboxylic dianhydride, 3,5,6-, three carboxyls norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-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)-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-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-, two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone, following formula (T-I) and the aliphatics tetracarboxylic dianhydrides and 2,3 such as compound that (T-II) represent separately, the ester ring type tetracarboxylic dianhydride beyond the 5-tricarboxylic basic ring amyl group acetic acid dianhydride,
Figure G2009102243577D00051
(in the above-mentioned formula, R 1And R 3The divalent organic group of respectively doing for oneself and having aromatic nucleus, R 2And R 4Respectively do for oneself hydrogen atom or alkyl, a plurality of R 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 '-sulfobenzide tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dianhydride, to phenylene-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butyleneglycol-two (dehydration trimellitate), 1,6-hexylene glycol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), following formula (T-1)～(T-4)
Figure G2009102243577D00071
Biao Shi aromatic tetracarboxylic acid's dianhydrides such as compound separately.They can a kind ofly be used alone or in combination of two or more.
As operable other tetracarboxylic dianhydrides among the present invention, from can making its angle that shows good liquid crystal aligning, be preferably in the middle of above-mentioned and be selected from the butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene 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-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-, three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-, two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1, at least a (hereinafter referred to as " other specific tetracarboxylic dianhydrides (1) ") in the group that the compound of following formula (T-8) expression in the compound of the compound that the following formula (T-5)～(T-7) in the compound of 4,5,8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I) expression is represented separately and above-mentioned formula (T-II) expression constitutes.
Figure G2009102243577D00091
As other specific tetracarboxylic dianhydrides (1), be preferably especially and be selected from 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-, three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-, two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8, at least a in the group that the compound of 10-tetraketone, pyromellitic acid dianhydride and above-mentioned formula (T-5) expression constitutes.
For the synthesis of the tetracarboxylic dianhydride of the polyamic acid among the present invention, preferably with respect to whole tetracarboxylic dianhydrides, contain above 2,3, the 5-tricarboxylic basic ring amyl group acetic acid dianhydride of 20 moles of %, more preferably contain 50 moles more than the %, especially preferably contain 80 moles more than the %.
[diamines]
For the synthesis of the diamines of the polyamic acid among the present invention, it is the diamines that contains the compound of above-mentioned formula (1) expression.
R in the above-mentioned formula (1) IIt is 3～20 alkyl for the optional carbonatoms that can be replaced by fluorine atom.As R IPreferred carbonatoms is 3～20 straight chained alkyl, as its concrete example, can enumerate for example normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.; Particularly preferred R IIt is 4～12 straight chained alkyl for carbonatoms.
As R II, preferred-O-* or-OC O-* (wherein, the connecting key of band " * " links to each other with phenyl ring).
Work as R IIFor-O-* is when (wherein, the connecting key of band " * " links to each other with phenyl ring), and two amino are with respect to R IIBe positioned at 2 and 4;
Work as R IIFor-OCO-* is when (wherein, the connecting key of band " * " links to each other with phenyl ring), and two amino are with respect to R IIBe positioned at 3 and 5;
That is to say, the compound of above-mentioned formula (1) expression, preferably following formula (1-1) and the compound (1-2) represented separately,
Figure G2009102243577D00101
(in the following formula, R IIdentical with the definition in the above-mentioned formula (1) respectively).
The compound of above-mentioned formula (1-1) expression, for example, shown in following synthetic route 1-1, can by with the alcohol of formula (2) expression after making alkoxide in the presence of the suitable alkali such as potassium tert.-butoxide, make itself and 2, the 4-DNCB reaction obtains the midbody compound of formula (1-1A) expression, and the suitable reduction system that then it adopted palladium carbon and hydrazine etc. reduces and synthesizes.
Synthetic route 1
(in synthetic route 1-1, R IIdentical with the definition in the above-mentioned formula (1)).
The compound of above-mentioned formula (1-2) expression, for example, shown in following synthetic route 1-2, alcohol that can be by making formula (2) expression in the presence of suitable alkali such as pyridine with 3, the reaction of 5-dinitrobenzoyl chloride, after obtaining the midbody compound of formula (1-2A) expression, the reduction system that it is suitable that it adopts palladium carbon and hydrazine etc. is reduced and synthesize
Figure G2009102243577D00121
Synthetic route 1-2
(in synthetic route 1-2, R IIdentical with the definition in the above-mentioned formula (1)).
The alcohol of formula (2) expression can adopt in liquid crystal compounds synthetic appropriate means such as normally used grignard reaction, Fu-Ke acylation reaction, Kishner reaction to synthesize.
The compound of representing with compound and the above-mentioned formula (1-2) of above-mentioned formula (1-1) expression is the compound of the above-mentioned formula of representative (1) expression, owing to have the bicyclohexane unit, so have the advantage that can form the liquid crystal orientation film that can show high vertical orientated property, and, the compound of above-mentioned formula (1) expression has the advantage that raw material used in synthesizing obtains easily.
For the synthesis of the diamines of the polyamic acid among the present invention, can be the diamines of only being formed by the compound of above-mentioned formula (1) expression, perhaps also can except the compound of above-mentioned formula (1) expression, also contain other diamines.
As operable other diamines here, can enumerate for example Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formylaniline, 4,4 '-diaminodiphenyl oxide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two (trifluoromethyl)-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diamino benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2, the 7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene radical-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to the phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, the aromatic diamines such as compound that following formula (D-1)～(D-5) is represented separately
Figure G2009102243577D00141
(y in the formula (D-4) is 2～12 integer, and the z in the formula (D-5) is 1～5 integer.)
1,1-m-xylene diamine, 1,3-propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0 2,7] 11 alkylidene group dimethyl diamines, 4,4 '-methylene radical two aliphatie diamine or ester ring type diamines such as (hexahydroaniline);
2,3 diamino pyridine, 2,6-diamino-pyridine, 3, the 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, 1,4-two (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazines, 2,4-diamino-6-methoxyl group-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3, the 5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3,5-diaminostilbene, 2, the 4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, 1,4-diamino piperazine, 3, the 6-proflavin, two (4-aminophenyl) aniline, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl) p-diaminodiphenyl, the compound of following formula (D-I) expression
(in the formula (D-I), R 5For having 1 valency organic group of the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X 1Be the organic group of divalent, R 6For carbonatoms is 1～4 alkyl, a1 is 0～3 integer), have the diamines of the nitrogen-atoms beyond 2 primary aminos and this primary amino in the compound equimolecular of following formula (D-II) expression,
(in the formula (D-II), R 7For having the divalent organic group of the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X 2Respectively the do for oneself organic group of divalent, a plurality of X of existence 2Separately can be identical, also can be different, R 8The carbonatoms of respectively doing for oneself is 1～4 alkyl, respectively do for oneself 0～3 integer of a2);
The single-substituted diamines such as compound of following formula (D-III) expression,
Figure G2009102243577D00162
(in the formula (D-III), R 9For-O-,-COO-* ,-OCO-* ,-NHCO-* ,-CONH-* (connecting key and the R that wherein, more than have " * " 10Connect) or-CO-, R 10For having skeleton in the steroid backbone of being selected from, trifluoromethyl, Trifluoromethoxyphen-l and the fluoro phenyl or 1 valency organic group of group, perhaps carbonatoms is 6～30 alkyl, R 11For carbonatoms is 1～4 alkyl, a3 is 0～3 integer);
The diamino organo-siloxanes such as compound of following formula (D-IV) expression etc.,
Figure G2009102243577D00163
(in the formula (D-IV), R 12The carbonatoms of respectively doing for oneself is 1～12 alkyl, a plurality of R of existence 12Separately can be identical, also can be different, respectively do for oneself 1～3 integer of p, q is 1～20 integer).These diamines can be used alone or in combination of two or more.
The phenyl ring of above-mentioned aromatic diamine can also be that 1～4 alkyl (preferable methyl) replaces by one or more carbonatoms.Above-mentioned formula (D-I), (D-II) and (D-III) in R 6, R 8And R 11Be preferably methyl separately, a1, a2 and a3 are preferably 0 or 1 separately, and more preferably 0.
As having R in the above-mentioned formula (D-III) 10The R of steroid backbone 101 valency organic group, preferred carbonatoms is 17～51 group, more preferably carbonatoms is 17～30 group.As the R with steroid backbone 10Object lesson, can enumerate for example cholestane-3-base, courage steroid-5-alkene-3-base, courage steroid-24-alkene-3-base, courage steroid-5,24-diene-3-base, lanostane-3-base etc.
During polyamic acid in synthetic the present invention, other diamines with the compound coupling of above-mentioned formula (1) expression, preferably contain and be selected from Ursol D in the middle of above-mentioned, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino-diphenyl thioether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, 1, the 4-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, the compound that above-mentioned formula (D-1)～(D-5) is represented separately, 2, the 6-diamino-pyridine, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl) p-diaminodiphenyl, the compound of following formula (D-6) expression in the compound of above-mentioned formula (D-I) expression, the compound of following formula (D-7) expression in the compound of above-mentioned formula (D-II) expression;
And the dodecyloxy-2 in the compound of above-mentioned formula (D-III) expression, 4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2, the diamines of at least a (hereinafter referred to as " other specific diamines ") in the group that the compound that 5-diaminobenzene and following formula (D-8)～(D-16) are represented separately constitutes.
Figure G2009102243577D00191
Figure G2009102243577D00201
Figure G2009102243577D00211
Particularly preferred other specific diamines are for being selected from Ursol D, 4,4 '-diaminodiphenylmethane, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-(to the phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, 1,4-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline), 1, at least a in the group that 4-two (4-amino-benzene oxygen) benzene and 4,4 '-two (4-amino-benzene oxygen) biphenyl constitute.
For the synthesis of the diamines of the polyamic acid among the present invention, preferably with respect to whole diamines, contain the compound of above above-mentioned formula (1) expression of 1 mole of %, more preferably contain 5～50 moles of %, especially preferably contain 10～40 moles of %.
Diamines for the synthesis of the polyamic acid that can contain in the liquid crystal aligning agent of the present invention, preferably except the compound of above-mentioned formula (1) expression, further contain 5～99 moles of aforesaid other specific diamines of % with respect to whole diamines, more preferably contain 50～95 moles of %, especially preferably contain 60～90 moles of %.
[synthesizing of polyamic acid]
Polyamic acid among the present invention can make by making aforesaid tetracarboxylic dianhydride and diamine reactant.
Supply with the tetracarboxylic dianhydride of polyamic acid building-up reactions and the usage rate of diamine compound, preferably with respect to 1 contained in diamine compound equivalent amino, the anhydride group that makes the tetracarboxylic dianhydride is the ratio of 0.2～2 equivalent, more preferably is the ratio of 0.3～1.2 equivalent.
The building-up reactions of polyamic acid preferably in organic solvent, is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature condition.Reaction times is preferably 1～240 hour, more preferably 3～150 hours.Here, as organic solvent, so long as can dissolve the solvent of synthetic polyamic acid, then have no particular limits, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N, non-proton property polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; Between phenol solvent such as sylvan, xylenol, phenol, halogenated phenol etc.In addition, the consumption of organic solvent (a: wherein when organic solvent and following poor solvent coupling, refer to their total amount), being preferably the total amount (b) that makes tetracarboxylic dianhydride and diamine compound is the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction soln.
In the above-mentioned organic solvent, in the scope that the polyamic acid that does not make generation is separated out, can also coupling be commonly referred to be alcohols, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons of the poor solvent of polyamic acid etc.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, triglycol, ethylene glycol monomethyl ether, ethyl lactate, n-Butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, the ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF), methylene dichloride, 1, the 2-ethylene dichloride, 1,4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.
When synthesizing polyamides acid, when with organic solvent and aforesaid poor solvent coupling, the usage rate of poor solvent, total amount with respect to organic solvent and poor solvent, be preferably below the 80 weight %, more preferably below the 60 weight %, more preferably below the 50 weight %.
As mentioned above, obtained dissolving the reaction soln of polyamic acid.This reaction soln, it directly can be supplied with the modulation of liquid crystal aligning agent, also polyamic acid contained in the reaction soln can be separated the back and supply with the modulation of liquid crystal aligning agent, resupply the modulation of liquid crystal aligning agent after perhaps also isolated polyamic acid can being made with extra care.The separation of polyamic acid can obtain precipitate by above-mentioned reaction soln is put in a large amount of poor solvents, and the method for this precipitate of drying under reduced pressure perhaps distillates the method for reaction soln with the vaporizer decompression and carries out.In addition, be dissolved in again in the organic solvent by making this polyamic acid, make its method of separating out with poor solvent then, perhaps carry out once or the method for the operation that distillates with vaporizer decompression several times, can make with extra care polyamic acid.
[imide amination polymer]
Imide amination polymer among the present invention can make by aforesaid polyamic acid is carried out the dehydration closed-loop imidization.
As used tetracarboxylic dianhydride in imide amination polymer synthetic, be to contain 2, the tetracarboxylic dianhydride of 3,5-tricarboxylic basic ring amyl group acetic acid dianhydride is as used tetracarboxylic dianhydride in imide amination polymer synthetic, can only use 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride perhaps also can be with 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride and other tetracarboxylic dianhydride's coupling.As operable other tetracarboxylic dianhydrides here, can enumerate the same compound that above conduct can be described for the synthesis of other tetracarboxylic dianhydrides of polyamic acid.
As other used tetracarboxylic dianhydrides in imide amination polymer synthetic, the preferred use is selected from 2, at least a (hereinafter referred to as " other specific tetracarboxylic dianhydrides (2) ") in the group that ester ring type tetracarboxylic dianhydride beyond 3, the 5-tricarboxylic basic ring amyl group acetic acid dianhydride constitutes.As other specific tetracarboxylic dianhydrides (2), be preferably selected from 1,3 especially, 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)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3,5:6-dianhydride and 4,9-, two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8, at least a in the group that the 10-tetraketone constitutes.
Used tetracarboxylic dianhydride in the imide amination polymer that can contain in the liquid crystal aligning agent of the present invention synthetic, preferably with respect to whole tetracarboxylic dianhydrides, contain 20 moles of % above 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, more preferably contain 50 moles more than the %, especially preferably contain 80 moles more than the %.
As used diamines in above-mentioned imide amination polymer synthetic, identical with diamines used during above-mentioned polyamic acid is synthetic.
Above-mentioned imide amination polymer, can be the complete imidization thing of the amido acid structure fully dehydrating closed loop that has of its precursor polyamic acid, also can be a part of dehydration closed-loop, amido acid structure and the imide ring structure of only amido acid structure and the part imidization thing of depositing.
Contained imide amination polymer in the liquid crystal aligning agent of the present invention, its imidization rate is preferably more than 40%, and more preferably 60%, more preferably 60～85%.By using the imide amination polymer of this scope imidization rate, can obtain the liquid crystal aligning agent that printing is good, can form the better liquid crystal orientation film of electric property.
Above-mentioned imidization rate refers 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 is represented with percentage.At this moment, the part of imide ring can also be different imide ring.The imidization rate can be primary standard with the tetramethylsilane by imide amination polymer being dissolved in the suitable deuterated solvent (for example deuterated dimethyl sulfoxide), at room temperature measures 1H-NMR, by measurement result according to the following equation (I) obtain.
Imidization rate (%)=(1-A 1/ A 2* α) * 100 (I)
(in the formula (I), A 1Be near the peak area that comes from NH matrix that occurs the chemical shift 10ppm, A 2For come from other protons peak area, α is the proton with respect to 1 NH base in the imide amination polymer precursor (polyamic acid), the individual percentage of other protons).
Dehydration closed-loop for the polyamic acid of synthetic above-mentioned imide amination polymer, can (i) method by the heating polyamic acid, perhaps (ii) by polyamic acid is dissolved in the organic solvent, the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is carried out.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i) is preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer then can occur.Reaction times is preferably 0.5～24 hour, more preferably 2～12 hours.
In the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii), as dewatering agent, can use for example 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 for example tertiary amines such as pyridine, collidine, two picolins, triethylamine.But, be not limited to these.The usage rate of dehydration closed-loop catalyzer with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.In addition, as used organic solvent in the dehydration closed-loop reaction, can enumerate synthetic as polyamic acid in used solvent and illustrative organic solvent.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, and more preferably 10～150 ℃, the reaction times is preferably 0.5～24 hour, more preferably 2～8 hours.
The imide amination polymer that makes in the aforesaid method (i) can directly be supplied with it modulation of liquid crystal aligning agent, resupplies the modulation of liquid crystal aligning agent after perhaps also the imide amination polymer that makes can being made with extra care.In addition, aforesaid method (ii) in, obtain containing the reaction soln of imide amination polymer.This reaction soln, it directly can be supplied with the modulation of liquid crystal aligning agent, also can from reaction soln, remove dewatering agent and dehydration closed-loop catalyzer and supply with the modulation of liquid crystal aligning agent afterwards, imide amination polymer can also be separated the back and supply with the modulation of liquid crystal aligning agent, resupply the modulation of liquid crystal aligning agent after perhaps also the imide amination polymer that separates can being made with extra care.From reaction soln, remove dewatering agent and dehydration closed-loop catalyzer, can adopt for example method such as solvent exchange.The separation of imide amination polymer, refining can be taked to carry out as the separating of polyamic acid, the described same operation of process for purification with above.
The polymkeric substance of-end modified type-
The polyamic acid that can contain in the liquid crystal aligning agent of the present invention and imide amination polymer thereof can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting separately.By using the polymkeric substance of end modified type, can under the prerequisite of not damaging effect of the present invention, further improve the coating performance of liquid crystal aligning agent etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds molecular weight regulator in the polymerization reaction system and carry out.As molecular weight regulator, can enumerate for example single acid anhydride, monoamine compound, monoisocyanates compound etc.
As above-mentioned single acid anhydride, can enumerate for example maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.As above-mentioned monoamine compound, can enumerate for example aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane amine, n-hexadecane amine, n-heptadecane amine, Octadecane amine, NSC 62789 amine etc.As above-mentioned monoisocyanates compound, can enumerate for example phenylcarbimide, isocyanic acid naphthyl ester etc.
The usage rate of molecular weight regulator, the total amount of employed tetracarboxylic dianhydride and diamines is preferably below 5 weight parts, more preferably below 2 weight parts when synthetic with respect to the acid of 100 weight parts of polyamide.
-soltion viscosity-
The polyamic acid that as above makes or imide amination polymer when it being made into concentration when being the solution of 10 weight %, preferably have the soltion viscosity of 20～800mPas, more preferably have the soltion viscosity of 30～500mPas.
The soltion viscosity of above-mentioned polymkeric substance (mPas) is the polymers soln to 10 weight % concentration of the good solvent (for example gamma-butyrolactone, N-N-methyl-2-2-pyrrolidone N-etc.) that adopts this polymkeric substance modulation, with E type rotational viscosimeter 25 ℃ of values of measuring down.
＜other additives 〉
Liquid crystal aligning agent of the present invention contains at least a polymkeric substance in the group that the imide amination polymer that is selected from aforesaid polyamic acid and dehydration closed-loop thereof and obtains constitutes as essential composition, and can also contain other compositions as required.As this other compositions, can enumerate compound (hereinafter referred to as " epoxy compounds ") that for example other polymkeric substance, intramolecularly have at least 1 epoxy group(ing), functional silanes compound etc.
[other polymkeric substance]
Be to make to contain 2,3, the polyamic acid that the tetracarboxylic dianhydride of 5-tricarboxylic basic ring amyl group acetic acid dianhydride makes with the diamine reactant of the compound that contains above-mentioned formula (1) expression and the polymkeric substance beyond the imide amination polymer thereof, for example, the polyamic acid (hereinafter referred to as " other polyamic acids ") that the tetracarboxylic dianhydride is made with the diamine reactant of the compound that does not contain above-mentioned formula (1) expression, its imide amination polymer (hereinafter referred to as " other imide amination polymers "), poly amic acid ester, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.Wherein, as other polymkeric substance, the preferred use is selected from least a in the group that other polyamic acids and other imide amination polymers constitute.
Aforesaid polyamic acid and imide amination polymer thereof except using the tetracarboxylic dianhydride and not containing the diamines of the compound that above-mentioned formula (1) represents, can synthesize according to the synthetic method of above-mentioned polyamic acid and imide amination polymer thereof respectively.As the raw material of this moment, as used tetracarboxylic dianhydride, preferably contain the tetracarboxylic dianhydride of at least a (hereinafter referred to as " specific tetracarboxylic dianhydride ") in the group that is selected from ester ring type tetracarboxylic dianhydride and pyromellitic acid dianhydride formation.As specific tetracarboxylic dianhydride, be preferably selected from 1,2 especially, 3,4-tetramethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-, three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-, two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8, at least a in the group that 10-tetraketone and pyromellitic acid dianhydride constitute.As the tetracarboxylic dianhydride for the synthesis of other polyamic acids or its imide amination polymer, preferably with respect to whole tetracarboxylic dianhydrides, contain the above aforesaid specific tetracarboxylic dianhydride of 40 moles of %, more preferably contain 80 moles more than the %.
As the diamines for the synthesis of other polyamic acids or its imide amination polymer, the preferred use is selected from aromatic diamine and 4, at least a diamines in the group that 4 '-methylene radical two (hexahydroaniline) constitutes, especially preferably contain and be selected from Ursol D, 4,4 '-diaminodiphenylmethane, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-(to the phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, 1, the 4-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline), 1,4-two (4-amino-benzene oxygen) benzene and 4, at least a diamines in the group that 4 '-two (4-amino-benzene oxygen) biphenyl constitutes.As the diamines for the synthesis of other polyamic acids or its imide amination polymer, preferably with respect to whole diamines, contain above aforesaid aromatic diamine and 4 of being selected from of 40 moles of %, at least a in the group that 4 '-methylene radical two (hexahydroaniline) constitutes especially preferably contains 80 moles more than the %.
As other polymkeric substance, more preferably use other polyamic acids.
When liquid crystal aligning agent of the present invention contains other polymkeric substance, the ratio that contains as other polymkeric substance, total amount with respect to above-mentioned polyamic acid and imide amination polymer and other polymkeric substance, be preferably below the 95 weight %, more preferably 50～90 weight %, more preferably 65～85 weight %.
As above-mentioned epoxy compounds, preferably can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl hexanaphthene etc.The mixture ratio of these epoxy compounds (refers to the total amount of polyamic acid contained in the liquid crystal aligning agent and imide amination polymer thereof and other polymkeric substance with respect to the total amount of 100 parts by weight polymer.Be preferably below 40 weight parts, more preferably 0.1～30 weight part, more preferably 5～25 weight parts down together).
As above-mentioned functional silanes compound, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-3-aminopropyltriethoxywerene werene etc.
The mixture ratio of these functional silanes compounds with respect to 100 parts by weight polymer total amounts, is preferably below 40 weight parts.
＜liquid crystal aligning agent 〉
Liquid crystal aligning agent of the present invention contains at least a polymkeric substance in the group that is selected from aforesaid polyamic acid and imide amination polymer formation thereof and chooses other additives that cooperate as required wantonly.
The particularly preferred liquid crystal aligning agent of the present invention is: contain aforesaid imide amination polymer and epoxy compounds liquid crystal aligning agent, contain the liquid crystal aligning agent of aforesaid imide amination polymer and other polyamic acids or contain imide amination polymer and the liquid crystal aligning agent of other polyamic acids and epoxy compounds.
Liquid crystal aligning agent of the present invention is contained in above-mentioned each composition preferred dissolution in the organic solvent and constitutes.
As operable organic solvent in the liquid crystal aligning agent of the present invention, can enumerate as solvent used in the polyamic acid building-up reactions and illustrative solvent.In addition, but can also suitably select coupling as the building-up reactions of polyamic acid the time coupling and illustrative poor solvent.Preferred example as this organic solvent, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.They can use separately, perhaps also can two or more mixing use.
The solids content concn of liquid crystal aligning agent of the present invention (the total weight of the composition in the liquid crystal aligning agent except organic solvent accounts for the ratio of liquid crystal aligning agent gross weight) is considered viscosity, volatility etc. and is suitably selected, and is preferably the scope of 1～10 weight %.That is to say that liquid crystal aligning agent of the present invention is by being coated on substrate surface with it, remove organic solvent, formation is filmed as liquid crystal orientation film, and is when solids content concn less than 1 weight %, too small and be difficult to obtain the situation of good liquid crystal orientation film with this thickness of filming occurring; On the other hand, when solids content concn surpassed 10 weight %, coating thickness was blocked up and be difficult to obtain the situation of good liquid crystal orientation film equally with occurring, and the viscosity that liquid crystal aligning agent can occur increases the situation that causes applying degradation.
Particularly preferred solids content concn scope, the method that adopts when liquid crystal aligning agent is coated on substrate and difference.For example, when adopting spin-coating method, the scope of preferred especially 1.5～4.5 weight %.When adopting print process, especially preferably making solids content concn is the scope of 3～9 weight %, like this, can make soltion viscosity drop on the scope of 12～50mPas.When adopting ink jet method, especially preferably making solids content concn is the scope of 1～5 weight %, like this, can make soltion viscosity drop on the scope of 3～15mPas.
As above Tiao Zhi liquid crystal aligning agent of the present invention can be specially adapted to form the liquid crystal orientation film of vertical alignment-type liquid crystal display device.
＜liquid crystal display device 〉
Liquid crystal display device of the present invention has the liquid crystal orientation film that is formed by aforesaid liquid crystal aligning agent of the present invention.Liquid crystal display device of the present invention is preferably the vertical alignment-type liquid crystal display device with vertical alignment-type liquid crystal box.
Liquid crystal display device of the present invention can be by for example following method manufacturing.
(1) adopts for example methods such as rolling method, spin-coating method, print process, ink jet method, liquid crystal aligning agent of the present invention is coated on the substrate one side that is provided with the nesa coating that forms pattern, then, film by the formation of heating applicator surface.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Plastics transparency carriers processed such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyester ring type alkene, polyester ring type hydrogenation of olefin thing.Simultaneously go up the nesa coating that arranges as substrate, can use stannic oxide (SnO 2) system NESA film (U.S. PPG register of company trade mark), Indium sesquioxide-stannic oxide (In 2O 3-SnO 2) the ITO film etc. of system.Form the making of nesa coating of pattern, for example can adopt after substrate forms patternless nesa coating, form required method of patterning by photoengraving; When nesa coating forms, adopt the mask with required pattern directly to form the method etc. of the nesa coating of pattern-like.When the coating of liquid crystal aligning agent, in order further to improve the adhesivity of formed liquid crystal orientation film and substrate surface, can also on substrate, apply for example functional silanes compound, functionality titanium compound etc. in advance.Behind the coated with liquid crystal alignment agent, the purpose for the sagging grade of alignment agent liquid that prevents from applying preferably preheats (prebake).The prebake temperature is preferably 30～200 ℃, and more preferably 40～150 ℃, preferred especially 40～100 ℃.The prebake time is preferably 0.5～10 minute, more preferably 1～5 minute.Then, for purposes such as complete desolventizings, burn till (afterwards curing) operation.This back stoving temperature is preferably 80～300 ℃, more preferably 120～250 ℃.After the time of curing be preferably 5～180 minutes, more preferably 10～120 minutes.
Liquid crystal aligning agent of the present invention forms filming as alignment films by removing organic solvent after applying, and be polyamic acid or have the imide ring structure simultaneously and during the imide amination polymer of amido acid structure when polymkeric substance contained in the liquid crystal aligning agent of the present invention, can also after filming, formation make it carry out the dehydration closed-loop reaction by further heating, to form filming of further imidization.
Here the thickness of film (liquid crystal orientation film) of Xing Chenging is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) prefabricated two substrates that as above form liquid crystal orientation film by arrange liquid crystal between these two substrates, are made liquid crystal cell.The manufacturing of liquid crystal cell can be enumerated two kinds of for example following methods.
First method is previously known method.At first, by two substrates are oppositely arranged by gap (box gap), make separately liquid crystal orientation film relatively to, fitted with sealing agent in the peripheral position of two substrates, after annotating the topping up crystalline substance in the box gap that is 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 the substrate in two substrates that form liquid crystal orientation film, coating is ultra-violet solidified sealant material for example, again after the liquid crystal aligning face drips liquid crystal, another piece substrate of fitting, make liquid crystal orientation film to subtend, to whole irradiation ultraviolet radiation of substrate, make sealant cures then, can make liquid crystal cell.Liquid crystal aligning agent of the present invention owing to can form the good liquid crystal orientation film of vertical orientated property, even thereby when having the ODF of employing method and making vertical alignment-type liquid crystal display device, also can make the advantage that can not produce the liquid crystal display device of ODF spot.
Adopting under the situation of above-mentioned arbitrary method, all needing to slowly cool to room temperature by then liquid crystal cell being heated to after used liquid crystal is the temperature of isotropic phase, the flow orientation when removing liquid crystal and filling.
Then, by the polaroid of fitting at the outer surface of liquid crystal cell, can make liquid crystal display device of the present invention.
Here, as sealing agent, can use Resins, epoxy that for example contains as the alumina balls of solidifying agent and separator etc.
As liquid crystal, can enumerate nematic liquid crystal and dish shape type liquid crystal.The nematic liquid crystal that wherein preferably has negative dielectric anisotropic can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.And, can also further add for example cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal; Chirality agent with trade(brand)name " C-15 ", " CB-15 " (production of メ Le Network society) sale; To oxygen base Ben Yajiaji-to ferroelectric liquid crystals such as amino-2-methyl butyl laurate etc. and using in the last of the ten Heavenly stems.
As the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol is extended that the light polarizing film 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 of＜above-mentioned formula (1) expression 〉
Synthesis example 1-1
[synthesizing of the compound of above-mentioned formula (1-1) expression]
Synthesizing of compound (1-1-1)
Synthesized compound (1-1-1) according to following synthetic route 2.
Figure G2009102243577D00351
Synthetic route 2
Synthesizing of compound (1-1-1A)
In the three-necked flask of the 3L that stirrer, nitrogen ingress pipe and thermometer are housed, add 200g compound (2-1), 89g potassium tert.-butoxide, 26g Tetrabutylammonium bromide and 1500ml tetrahydrofuran (THF), stir 3 hours (with it as reaction solution A) down ice-cooled.
In addition, in the three-necked flask of the 5L that addition funnel, nitrogen ingress pipe, thermometer and agitator are housed, add 160g 2,4-dinitrobenzene and 800ml tetrahydrofuran (THF), under ice-cooled, through slowly dripping above-mentioned reaction solution A more than 1 hour, at room temperature carry out to former state reaction in 12 hours.After reaction finishes, after the reaction mixture filtration, inject the water of 10L, reclaim the precipitation that generates.Should precipitate wash with methyl alcohol and Virahol after, use the mixed solvent by hexanaphthene and hexane to carry out recrystallization, obtain 180g compound (1-1-1A).
Synthesizing of compound (1-1-1)
In the three-necked flask of the 2L that return line, nitrogen ingress pipe and thermometer are housed, add the compound (1-1-1A) that makes more than the 180g, palladium carbon, 1.5L ethanol and the 750ml tetrahydrofuran (THF) of 12g 5 weight %, then, the ammoniacal liquor that adds 49g 28 weight %, added 243g hydrazine monohydrate again through 5 minutes, former state ground stirred after 1 hour, carried out reaction in 6 hours under 70 ℃.Reaction joins reaction mixture in the water of 15L after finishing, and reclaims the precipitation that generates.Should precipitate with ethanol and carry out recrystallization, obtain 83g compound (1-1-1).
Synthesis example 1-2
[synthesizing of the compound of above-mentioned formula (1-2) expression]
Synthesizing of compound (1-2-1)
Synthesized compound (1-2-1) according to following synthetic route 3.
Figure G2009102243577D00371
Synthetic route 3
Synthesizing of compound (1-2-1A)
In the three-necked flask of the 5L that agitator, addition funnel, thermometer and nitrogen ingress pipe are housed, add 151g compound (2-1), 2.5L toluene and 115g 3,5 dinitrobenzoylchloride.At the ice-cooled 80ml pyridine that drips down, at room temperature carry out reaction in 7 hours then.After reaction finishes, with 2.5L water reaction mixture is carried out 4 washings repeatedly.Then with the organic layer dried over mgso, and after concentrating, use the mixed solvent of being formed by ethanol and tetrahydrofuran (THF) to carry out recrystallization, obtain 105g compound (1-2-1A)
Synthesizing of compound (1-2-1)
In the three-necked flask of the 5L that agitator, addition funnel, thermometer and nitrogen ingress pipe are housed, the palladium carbon that adds the compound (1-2-1A), 1L ethanol, 0.5L tetrahydrofuran (THF) and the 5g 5 weight % that make more than the 89g, with under the water cooling, drip 48ml hydrazine monohydrate.After at room temperature stirring 1 hour, under 70 ℃, carry out reaction in 1 hour.After removing by filter palladium carbon, add the 2.5L ethyl acetate, repeat 3 washings with 2.5L water.After concentrating organic layer, carry out recrystallization by ethanol, obtain 70g compound (1-2-1).
Synthesizing of＜imide amination polymer 〉
Synthesis example PI-1
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 41.0g (makes among the above-mentioned synthesis example 1-1 as the compound (1-1-1) of diamines.Down together) 13.1g (with respect to 1 mole of TCA, being equivalent to 0.2 mole) and Ursol D 15.8 are dissolved in the 280g N-N-methyl-2-2-pyrrolidone N-, carry out reaction in 4 hours under 60 ℃, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 2366mPas.
Then, in the gained polyamic acid solution, append 650g N-N-methyl-2-2-pyrrolidone N-, add 14.5g pyridine and 18.7g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by being carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, (by this solvent exchange operation, the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction are removed to system by the solvent in the system.Down with), obtain containing 20 weight % imidization rates and be the solution of 50% imide amination polymer (A-1).
Synthesis example PI-2
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 36.3g, as compound (1-1-1) 23.2g of diamines (with respect to 1 mole of TCA, be equivalent to 0.4 mole) and Ursol D 10.5g be dissolved in the 280g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 2352mPas.
Then, in the gained polyamic acid solution, append 650g N-N-methyl-2-2-pyrrolidone N-, add 12.8g pyridine and 16.5g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 50% imide amination polymer (A-2).
Synthesis example PI-3
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 41.0g, as compound (1-1-1) 13.1g of diamines (with respect to 1 mole of TCA, be equivalent to 0.2 mole) and Ursol D 15.8 be dissolved in the 280g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 2338mPas.
Then, in the gained polyamic acid solution, append 650g N-N-methyl-2-2-pyrrolidone N-, add 29.0g pyridine and 37.4g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 80% imide amination polymer (A-3).
Synthesis example PI-4
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 36.3g, as compound (1-1-1) 23.2g of diamines (with respect to 1 mole of TCA, be equivalent to 0.4 mole) and Ursol D 10.5g be dissolved in the 280g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 2231mPas.
Then, in the gained polyamic acid solution, append 650g N-N-methyl-2-2-pyrrolidone N-, add 25.6g pyridine and 33.1g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 80% imide amination polymer (A-4).
Synthesis example PI-5
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 18.2g, as compound (1-1-1) 6.0g of diamines (with respect to 1 mole of TCA, be equivalent to 0.2 mole), the compound 4.4g of above-mentioned formula (D-10) expression is (with respect to 1 mole of TCA, be equivalent to 0.1 mole) and Ursol D 6.4g be dissolved in the 140g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 1980mPas.
Then, in the gained polyamic acid solution, append 325g N-N-methyl-2-2-pyrrolidone N-, add 6.4g pyridine and 8.3g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 51% imide amination polymer (A-5).
Synthesis example PI-6
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 40.5g (makes among the above-mentioned synthesis example 1-2 as the compound (1-2-1) of diamines.Down together) 14.1g (with respect to 1 mole of TCA, being equivalent to 0.2 mole) and Ursol D 15.7g are dissolved in the 280g N-N-methyl-2-2-pyrrolidone N-, carry out reaction in 4 hours under 60 ℃, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 1605mPas.
Then, in the gained polyamic acid solution, append 650g N-N-methyl-2-2-pyrrolidone N-, add 14.2g pyridine and 18.3g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 50% imide amination polymer (A-6).
Synthesis example PI-7
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 35.4g, as compound (1-2-1) 24.4g of diamines (with respect to 1 mole of TCA, be equivalent to 0.4 mole) and Ursol D 10.2g be dissolved in the 280g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 1214mPas.
Then, in the gained polyamic acid solution, append 650g N-N-methyl-2-2-pyrrolidone N-, add 12.5g pyridine and 16.1g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 51% imide amination polymer (A-7).
Synthesis example PI-8
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 40.4g, as compound (1-2-1) 13.9g of diamines (with respect to 1 mole of TCA, be equivalent to 0.2 mole) and Ursol D 15.6g be dissolved in the 280g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 1538mPas.
Then, in the gained polyamic acid solution, append 650g N-N-methyl-2-2-pyrrolidone N-, add 28.5g pyridine and 36.8g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 83% imide amination polymer (A-8).
Synthesis example PI-9
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 35.4g, as compound (1-2-1) 24.4g of diamines (with respect to 1 mole of TCA, be equivalent to 0.4 mole) and Ursol D 10.2g be dissolved in the 280g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 1231mPas.
Then, in the gained polyamic acid solution, append 650g N-N-methyl-2-2-pyrrolidone N-, add 25.0g pyridine and 32.2g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 79% imide amination polymer (A-9).
Synthesis example PI-10
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride (TCA) 18.3g, as compound (1-2-1) 6.3g of diamines (with respect to 1 mole of TCA, be equivalent to 0.2 mole), the compound 4.3g of above-mentioned formula (D-10) expression is (with respect to 1 mole of TCA, be equivalent to 0.1 mole) and Ursol D 6.2g be dissolved in the 140g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 1180mPas.
Then, in the gained polyamic acid solution, append 325g N-N-methyl-2-2-pyrrolidone N-, add 6.5g pyridine and 8.3g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 52% imide amination polymer (A-10).
Synthesizing of＜other polyamic acids 〉
Synthesis example PA-1
Will be as tetracarboxylic dianhydride's pyromellitic acid dianhydride 109g (0.50 mole) and 1,2,3,4-tetramethylene tetracarboxylic dianhydride 98g (0.50 mole), as 4 of diamines, 4-diamino-diphenyl ether 200g (1.0 moles) is dissolved in the 2290g N-N-methyl-2-2-pyrrolidone N-, after carrying out reaction in 3 hours under 40 ℃, append 1350g N-N-methyl-2-2-pyrrolidone N-, obtain the solution that about 3990g contains 10 other polyamic acids of weight % (B-1).
The soltion viscosity of these other polyamic acid solutions is 180mPas.
Synthesis example PA-2
Will be as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride 98g (0.50 mole) and pyromellitic acid dianhydride 109g (0.50 mole), as 4 of diamines, 4 '-diaminodiphenyl-methane 198g (1.0 moles) is dissolved in the 2290g N-N-methyl-2-2-pyrrolidone N-, after carrying out reaction in 3 hours under 40 ℃, append 1350g N-N-methyl-2-2-pyrrolidone N-, obtain the solution that about 4000g contains 10 other polyamic acids of weight % (B-2).
The soltion viscosity of these other polyamic acid solutions is 113mPas.
Synthesis example PA-3
Will be as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride 196g (1.0 moles), as 4 of diamines, 4 '-diamino-diphenyl ether 200g (1.0 moles) is dissolved in the 2246g N-N-methyl-2-2-pyrrolidone N-, after carrying out reaction in 4 hours under 40 ℃, append 1321g N-N-methyl-2-2-pyrrolidone N-, obtain the solution that about 3900g contains 10 other polyamic acids of weight % (B-3).
The soltion viscosity of these other polyamic acid solutions is 189mPas.
Synthesis example PA-4
Will be as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride 196g (1.0 moles), as 2 of diamines, 2 '-dimethyl-4,4 '-benzidine 212g (1.0 moles) is dissolved in the 3670g N-N-methyl-2-2-pyrrolidone N-, under 40 ℃, carry out reaction in 3 hours, obtain the solution that about 4020g contains 10 other polyamic acids of weight % (B-4).
The soltion viscosity of these other polyamic acid solutions is 144mPas.
Synthesis example PA-5
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224g (1.0 moles), as 4 of diamines, 4 '-diamino-diphenyl ether 200g (1.0 moles) is dissolved in the 2404gN-N-methyl-2-2-pyrrolidone N-, under 40 ℃, carry out reaction in 4 hours, append 1412g N-N-methyl-2-2-pyrrolidone N-, obtain the solution that about 4200g contains 10 other polyamic acids of weight % (B-5).
The soltion viscosity of these other polyamic acid solutions is 162mPas.
Synthesis example PA-6
Will be as 1 of tetracarboxylic anhydride, 2,3,4-tetramethylene tetracarboxylic dianhydride 54g, as compound (1-1-1) 21g of diamines (with respect to 1 mole 1,2,3,4-tetramethylene tetracarboxylic dianhydride is equivalent to 0.2 mole) and Ursol D 25g be dissolved in the 400g N-N-methyl-2-2-pyrrolidone N-, at room temperature carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids (B-6).Soltion viscosity to this measured in solution under 25 ℃ is 2870mPas.
Synthesis example PA-7
Will be as the pyromellitic acid acid anhydride 56g of tetracarboxylic anhydride, as compound (1-1-1) 20g of diamines (with respect to 1 mole of pyromellitic acid acid anhydride, be equivalent to 0.2 mole) and Ursol D 24g be dissolved in the 400g N-N-methyl-2-2-pyrrolidone N-, at room temperature carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids (B-7).Soltion viscosity to this measured in solution under 25 ℃ is 3240mPas.
Synthesis example PA-8
Will be as 1 of tetracarboxylic anhydride, 2,3,4-tetramethylene tetracarboxylic dianhydride 57g, as compound (1-2-1) 23g of diamines (with respect to 1 mole 1,2,3,4-tetramethylene tetracarboxylic dianhydride is equivalent to 0.2 mole) and Ursol D 25g be dissolved in the 420g N-N-methyl-2-2-pyrrolidone N-, at room temperature carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids (B-8).Soltion viscosity to this measured in solution under 25 ℃ is 1770mPas.
Synthesis example PA-9
Will be as the pyromellitic acid acid anhydride 60g of tetracarboxylic anhydride, as compound (1-2-1) 21g of diamines (with respect to 1 mole of pyromellitic acid acid anhydride, be equivalent to 0.2 mole) and Ursol D 24g be dissolved in the 420g N-N-methyl-2-2-pyrrolidone N-, at room temperature carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids (B-9).Soltion viscosity to this measured in solution under 25 ℃ is 1840mPas.
Synthesizing of＜other imide amination polymers 〉
Synthesis example PI-11
Will be as compound (compound (the F)) 22.7g of tetracarboxylic dianhydride's following formula (F) expression, as compound (1-1-1) 5.5g of diamines (with respect to 1 mole compound (F), be equivalent to 0.2 mole) and Ursol D 6.7g be dissolved in the 140g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 1950mPas.
Then, in the gained polyamic acid solution, append 325g N-N-methyl-2-2-pyrrolidone N-, add 6.0g pyridine and 7.7g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 50% imide amination polymer (R-1).
Synthesis example PI-12
Will be as compound (compound (the F)) 22.6g of the above-mentioned formula (F) of tetracarboxylic anhydride expression, as compound (1-2-1) 5.8g of diamines (with respect to 1 mole compound (F), be equivalent to 0.2 mole) and Ursol D 6.5g be dissolved in the 140g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 1050mPas.
Then, in the gained polyamic acid solution, append 325g N-N-methyl-2-2-pyrrolidone N-, add 6.0g pyridine and 7.7g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 48% imide amination polymer (R-2).
Synthesis example PI-13
Get the solution 175g that contains polyamic acid (B-6) (be converted into polyamic acid (B-6) and be equivalent to 35g) that makes among the above-mentioned synthesis example PA-6, dilute to wherein adding the 325gN-N-methyl-2-2-pyrrolidone N-, add 7.7g pyridine and 9.9g acetic anhydride again, at room temperature carry out the dehydration closed-loop reaction.Polymkeric substance is insoluble and separated out.
Synthesis example PI-14
Get the solution 175g that contains polyamic acid (B-7) (be converted into polyamic acid (B-7) and be equivalent to 35g) that makes among the above-mentioned synthesis example PA-7, dilute to wherein adding the 325gN-N-methyl-2-2-pyrrolidone N-, add 7.2g pyridine and 9.3g acetic anhydride again, at room temperature carry out the dehydration closed-loop reaction.Polymkeric substance is insoluble and separated out.
Synthesis example PI-15
Get the solution 175g that contains polyamic acid (B-8) (be converted into polyamic acid (B-8) and be equivalent to 35g) that makes among the above-mentioned synthesis example PA-8, dilute to wherein adding the 325gN-N-methyl-2-2-pyrrolidone N-, add 7.7g pyridine and 9.9g acetic anhydride again, at room temperature carry out the dehydration closed-loop reaction.Polymkeric substance is insoluble and separated out.
Synthesis example PI-16
Get the solution 175g that contains polyamic acid (B-9) (be converted into polyamic acid (B-9) and be equivalent to 35g) that makes among the above-mentioned synthesis example PA-9, dilute to wherein adding the 325gN-N-methyl-2-2-pyrrolidone N-, add 7.3g pyridine and 9.4g acetic anhydride again, at room temperature carry out the dehydration closed-loop reaction.Polymkeric substance is insoluble and separated out.
Synthesis example PI-17
Will be as compound (compound (the G)) 43g of the following formula (G) of tetracarboxylic anhydride expression, as compound (1-1-1) 12g of diamines (with respect to 1 mole compound (G), be equivalent to 0.2 mole) and Ursol D 15g be dissolved in the 280g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 4 hours, obtain containing the solution of 20 weight % polyamic acids.Soltion viscosity to this measured in solution under 25 ℃ is 2050mPas.
Figure G2009102243577D00471
Then, in the gained polyamic acid solution, append 650g N-N-methyl-2-2-pyrrolidone N-, add 14g pyridine and 17g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, obtain containing 20 weight % imidization rates and be the solution of 52% imide amination polymer (R-3).
The modulation of＜liquid crystal aligning agent and evaluation 〉
[modulation of printing evaluation usefulness liquid crystal aligning agent and the evaluation of printing]
Embodiment 1
[the printing evaluation modulation of liquid crystal aligning agent]
Only get and be converted into wherein contained imide amination polymer (A-1) and be equivalent to the solution that contains imide amination polymer (A-1) that makes in the above-mentioned synthesis example 1 of amount of 100 weight parts, to wherein adding 20 weight part N, N, N ', N '-four glycidyl group-m-xylene diamine is as epoxy compounds, add N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether (BC) again, being made into solvent composition is NMP: BC=60: 40 (weight ratios), solids content concn are the solution of 7 weight %.Be that the filter of 1 μ m filters with this solution with the aperture, modulate liquid crystal aligning agent (P-1).
[printing evaluation]
(Japan's description printing (strain) is made to adopt the liquid crystal orientation film printing press, " オ Application グ ス ト ロ one マ one S40L-532 " type), under the condition of the liquid crystal aligning agent amount of dripping for round 20 (about 0.2g) of anilox roll (Anilox Roll), liquid crystal aligning agent (P-1) with above modulation is coated on the transparency electrode face of the glass substrate that has ITO film transparency electrode processed.Here, the amount of dripping of above-mentioned liquid crystal aligning agent is compared with the amount of dripping that adopts usually for the printing press of same model (coming and going 30 (about 0.3g)), and amount of liquid is less, is harsher printing condition.
Substrate behind the coated with liquid crystal alignment agent after heating (prebake) desolventizing in 1 minute under 80 ℃, is heated 10 minutes (afterwards curing) down at 180 ℃ again, and forming thickness is filming of 80nm.
This is filmed carry out visual observations, investigation has corrugationless (pin hole) and printing spot, this moment pin hole and print spot and all do not observe, the printing of above-mentioned liquid crystal aligning agent (P-1) is good.
[the liquid crystal cell manufacturing modulation of liquid crystal aligning agent]
In above-mentioned [the printing evaluation modulation of liquid crystal aligning agent], the solution solids content concn before making filtration is the 4 weight %, with the above-mentioned liquid crystal aligning agent (S-1) that similarly modulates.
[manufacturing of liquid crystal cell]
Adopting spin coater that the liquid crystal aligning agent (S-1) of above modulation is coated in thickness is on the ITO film nesa coating processed that arranges on the one side of glass substrate of 1mm, under 80 ℃, carrying out 1 minute prebake on the hot-plate, cured 30 minutes after under 230 ℃, forming thickness is film (liquid crystal orientation film) of 0.08 μ m again.Repeat this operation, produce a pair of (two) have liquid crystal orientation film at nesa coating substrate.
On each outer rim with liquid crystal orientation film of above-mentioned a pair of substrate, coating makes the liquid crystal aligning face carry out overlapping and pressing relatively to ground after having added the epoxy resin binder of alumina balls that diameter is 3.5 μ m, and tackiness agent is solidified.Then, by liquid crystal injecting port to fill between a pair of substrate nematic liquid crystal (メ Le Network society produces, MLC-6608) after, with the acrylic acid or the like Photocurable adhesive liquid crystal injecting port is sealed, produce the vertical alignment-type liquid crystal box.
[evaluation of liquid crystal cell]
(1) evaluation of voltage retention
Under 60 ℃, in the time span of 16.7 microseconds, the liquid crystal cell of above manufacturing is applied the voltage of 5V, application time is 60 microseconds, measures then from voltage and removes voltage retention after 16.7 milliseconds.The results are shown in table 2.
(2) sunproof evaluation
Above-mentioned liquid crystal cell being placed under the state of the distance of 40 watts of type white fluorescent lamp 5cm, open luminescent lamp, shine 1000 hours light after, with the evaluation of above-mentioned voltage retention in measure voltage retention again under the identical condition.At this moment, when the value of the voltage retention of irradiation after 1000 hours, compare with initial stage voltage retention value, less than ± 2% o'clock, photostabilization was evaluated as " well ".When being ± 2% when above, photostabilization is evaluated as " bad ".
(3) stable on heating evaluation
To with the above liquid crystal cell of similarly making, at first, under 167 milliseconds time span, apply the voltage of 5V, application time is 60 microseconds, measures then from voltage and removes voltage retention after 167 milliseconds.The numerical value of this moment is as initial stage voltage retention (VHR BF).
Measure VHR BFAfter, liquid crystal display device is placed 100 ℃ baking oven, apply 1000 hours thermal stresses.Then liquid crystal display device is at room temperature left standstill be cooled to room temperature after, under the condition identical with the mensuration of above-mentioned initial stage voltage retention, measure the voltage retention (VHR apply after the thermal stresses AF).
Obtain the velocity of variation (Δ VHR) that thermal stresses applies the voltage retention of front and back by following formula (II), this velocity of variation less than 5%, thermotolerance is evaluated as " well ", more than 5%, thermotolerance is evaluated as " bad ".
ΔVHR(％)＝((VHR BF-VHR AF)÷VHR BF)×100 (II)
Evaluation result is listed in table 2.
(4) evaluation of anti-burning screen property
To with the above liquid crystal cell of similarly making, after applying the voltage of 20 hours 5V under 60 ℃, measure residual DC voltage, when this value is 0～500mV, anti-burning screen property is evaluated as " excellent ", and when surpassing 500mV and be 1000mV when following, anti-burning is shielded property and is evaluated as " well ".
Evaluation result is listed in table 2.
Embodiment 2～9
In above-described embodiment 1, use the solution of the polymkeric substance contain kind shown in the table 1 and amount to replace containing the solution of imide amination polymer (A-1) respectively, epoxy compounds N, N, N ', the consumption of N '-four glycidyl group-m-xylene diamine is as shown in table 1 respectively, in addition, modulate liquid crystal aligning agent (P-2)～(P-9) and the liquid crystal cell manufacturing liquid crystal aligning agent (S-2)～(S-9) of printing evaluation usefulness respectively similarly to Example 1, and carry out manufacturing and the evaluation of printing evaluation and liquid crystal cell.
Evaluation result is listed in table 1 and table 2.
Embodiment 10
[modulation of printing evaluation usefulness liquid crystal aligning agent and the evaluation of printing]
To be converted into imide amination polymer (A-1) and be equivalent to the solution that contains imide amination polymer (A-1) that makes in the above-mentioned synthesis example 1 of amount of 20 weight parts, with be converted into the solution that contains polyamic acid (B-1) that polyamic acid (B-1) is equivalent to make in the above-mentioned synthesis example 6 of amount of 80 weight parts and mix, to wherein adding the N of 20 weight parts as epoxy compounds, N, N ', N '-four glycidyl group-m-xylene diamine, add N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether (BC) again, being made into solvent composition is NMP: BC=60: 40 (weight ratios), solids content concn is the solution of 7 weight %.Be that the filter of 1 μ m filters with this solution with the aperture, modulate the liquid crystal aligning agent (P-10) of printing evaluation usefulness.
Except the liquid crystal aligning agent (P-10) that adopts above modulation, carry out the evaluation of printing similarly to Example 1.
Evaluation result is listed in table 1.
[liquid crystal cell is made modulation and the evaluation with liquid crystal aligning agent]
In above-mentioned [the printing evaluation modulation of liquid crystal aligning agent], except the solids content concn that filters preceding solution is 4 weight %, with the above-mentioned liquid crystal cell manufacturing liquid crystal aligning agent (S-10) that similarly modulates.
Except the liquid crystal aligning agent (S-10) that adopts above modulation, make liquid crystal cell similarly to Example 1 and estimate.
Evaluation result is listed in table 2.
Embodiment 11～22
In above-described embodiment 10, use and contain the imide amination polymer of kind shown in the table 1 and amount and the solution of polyamic acid respectively, epoxy compounds N, N, N ', the consumption of N '-four glycidyl group-m-xylene diamine is as shown in table 1 respectively, in addition, modulate liquid crystal aligning agent (P-11)～(P-22) and the liquid crystal cell manufacturing liquid crystal aligning agent (S-11)～(S-22) of printing evaluation usefulness respectively similarly to Example 10, and carry out manufacturing and the evaluation of printing evaluation and liquid crystal cell.
Evaluation result is listed in table 1 and table 2.
Embodiment 23～31
In above-described embodiment 1, use the solution of the polymkeric substance contain kind shown in the table 1 and amount to replace containing the solution of imide amination polymer (A-1) respectively, epoxy compounds N, N, N ', the consumption of N '-four glycidyl group-m-xylene diamine is as shown in table 1 respectively, in addition, modulate liquid crystal aligning agent (P-23)～(P-31) and the liquid crystal cell manufacturing liquid crystal aligning agent (S-23)～(S-31) of printing evaluation usefulness respectively similarly to Example 1, and carry out manufacturing and the evaluation of printing evaluation and liquid crystal cell.
Evaluation result is listed in table 1 and table 2.
Embodiment 32～44
In above-described embodiment 10, use and contain the imide amination polymer of kind shown in the table 1 and amount and the solution of polyamic acid respectively, epoxy compounds N, N, N ', the consumption of N '-four glycidyl group-m-xylene diamine is as shown in table 1 respectively, in addition, modulate liquid crystal aligning agent (P-32)～(P-44) and the liquid crystal cell manufacturing liquid crystal aligning agent (S-32)～(S-44) of printing evaluation usefulness respectively similarly to Example 10, and carry out manufacturing and the evaluation of printing evaluation and liquid crystal cell.
Evaluation result is listed in table 1 and table 2.
Comparative example 1
In above-described embodiment 1, except containing the solution that contains imide amination polymer (R-1) that makes among the above-mentioned synthesis example PI-11, use replaces containing the solution of imide amination polymer (A-1), modulate the liquid crystal aligning agent (RP-1) of printing evaluation usefulness similarly to Example 1, and carry out the printing evaluation.As a result, the printing spot is observed in filming of formation, and printing is " bad ".
Comparative example 2
In above-described embodiment 1, except containing the solution that contains imide amination polymer (R-2) that makes among the above-mentioned synthesis example PI-12, use replaces containing the solution of imide amination polymer (A-1), modulate the liquid crystal aligning agent (RP-2) of printing evaluation usefulness similarly to Example 1, and carry out the printing evaluation.As a result, the printing spot is observed in filming of formation, and printing is " bad ".
Comparative example 3
In above-described embodiment 1, use contains the solution that the solution that contains polyamic acid (B-6) that makes among the above-mentioned synthesis example PA-6 replaces containing imide amination polymer (A-1), and do not use epoxy compounds, in addition, modulate the liquid crystal aligning agent (RP-3) of printing evaluation usefulness and the liquid crystal aligning agent (RS-3) of liquid crystal cell manufacturing usefulness similarly to Example 1 respectively, and carry out the printing evaluation, and the manufacturing of liquid crystal cell and voltage retention, stable on heating evaluation.At this moment, printing is " well ", and voltage retention is 98%, and thermotolerance is " bad ".
Comparative example 4
In above-described embodiment 1, use contains the solution that the solution that contains polyamic acid (B-7) that makes among the above-mentioned synthesis example PA-7 replaces containing imide amination polymer (A-1), and do not use epoxy compounds, in addition, modulate the liquid crystal aligning agent (RP-4) of printing evaluation usefulness and the liquid crystal aligning agent (RS-4) of liquid crystal cell manufacturing usefulness similarly to Example 1 respectively, and carry out the printing evaluation, and the manufacturing of liquid crystal cell and voltage retention, photostabilization, stable on heating evaluation.At this moment, printing is " well ", and voltage retention is 96%, and photostabilization and thermotolerance are " bad ".
Comparative example 5
In above-described embodiment 1, use contains the solution that the solution that contains polyamic acid (B-8) that makes among the above-mentioned synthesis example PA-8 replaces containing imide amination polymer (A-1), and do not use epoxy compounds, in addition, modulate the liquid crystal aligning agent (RP-5) of printing evaluation usefulness and the liquid crystal aligning agent (RS-5) of liquid crystal cell manufacturing usefulness similarly to Example 1 respectively, and carry out the printing evaluation, and the manufacturing of liquid crystal cell and voltage retention, stable on heating evaluation.At this moment, printing is " well ", and voltage retention is 98%, and thermotolerance is " bad ".
Comparative example 6
In above-described embodiment 1, use contains the solution that the solution that contains polyamic acid (B-9) that makes among the above-mentioned synthesis example PA-9 replaces containing imide amination polymer (A-1), and do not use epoxy compounds, in addition, modulate the liquid crystal aligning agent (RP-6) of printing evaluation usefulness and the liquid crystal aligning agent (RS-6) of liquid crystal cell manufacturing usefulness similarly to Example 1 respectively, and carry out the printing evaluation, and the manufacturing of liquid crystal cell and voltage retention, photostabilization, stable on heating evaluation.At this moment, printing is " well ", and voltage retention is 96%, and photostabilization and thermotolerance are " bad ".
Comparative example 7
In above-described embodiment 1, use contains the solution that the solution that contains imide amination polymer (R-3) that makes among the above-mentioned synthesis example PI-17 replaces containing imide amination polymer (A-1), and do not use epoxy compounds, in addition, modulate the liquid crystal aligning agent (RP-7) of printing evaluation usefulness similarly to Example 1, and carry out the printing evaluation, at this moment, observed the printing spot, printing is " bad ".
Table 1
Table 1 (continuing)
Figure G2009102243577D00551
Table 2
Figure G2009102243577D00561
Table 2 (continuing)
Figure G2009102243577D00571

Claims (6)

1. liquid crystal aligning agent, it is characterized in that containing at least a polymkeric substance in the group that is selected from polyamic acid and imide amination polymer formation thereof, this polyamic acid is to contain 2 by making, the tetracarboxylic dianhydride of 3,5-tricarboxylic basic ring amyl group acetic acid dianhydride makes with the diamine reactant of the compound that contains following formula (1) expression, and with respect to whole tetracarboxylic dianhydrides, 2, the content of 3,5-tricarboxylic basic ring amyl group acetic acid dianhydride is 20 moles more than the %
In the formula (1), R IFor the optional carbonatoms that can be replaced by fluorine atom is 3～20 alkyl, R IIFor-O-* ,-COO-* or-OCO-*, wherein, the connecting key of band " * " links to each other with phenyl ring.
2. the described liquid crystal aligning agent of claim 1, wherein above-mentioned diamines is selected from Ursol D for further containing, 4,4 '-diaminodiphenylmethane, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-(to the phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, 1, the 4-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline), 1,4-two (4-amino-benzene oxygen) benzene and 4, at least a diamines in the group that 4 '-two (4-amino-benzene oxygen) biphenyl constitutes.
3. claim 1 or 2 described liquid crystal aligning agent, it further contains and is selected from least a polymkeric substance that makes in the group that polyamic acid that the tetracarboxylic dianhydride makes with the diamine reactant of the compound that does not contain above-mentioned formula (1) expression and imide amination polymer thereof constitute.
4. a liquid crystal display device is characterized in that having the liquid crystal orientation film that is formed by each described liquid crystal aligning agent of claim 1～3.
5. the described liquid crystal display device of claim 4, it is vertical orientating type.
6. a polyamic acid or its imide amination polymer, be to contain 2 by making, 3, the tetracarboxylic dianhydride of 5-tricarboxylic basic ring amyl group acetic acid dianhydride makes with the diamine reactant of the compound that contains above-mentioned formula (1) expression, and with respect to whole tetracarboxylic dianhydrides, the content of 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride is 20 moles more than the %.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1211263A (en) * 1996-02-15 1999-03-17 日产化学工业株式会社 diaminobenzene derivatives, polyimides prepared therefrom, and alignment film for liquid crystals
CN101057177A (en) * 2004-12-22 2007-10-17 日产化学工业株式会社 Liquid-crystal alignment material and liquid-crystal display element employing the same
WO2008010528A1 (en) * 2006-07-18 2008-01-24 Nissan Chemical Industries, Ltd. Liquid crystal orienting agent and liquid crystal oriented film and liquid crystal display element using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1211263A (en) * 1996-02-15 1999-03-17 日产化学工业株式会社 diaminobenzene derivatives, polyimides prepared therefrom, and alignment film for liquid crystals
CN101057177A (en) * 2004-12-22 2007-10-17 日产化学工业株式会社 Liquid-crystal alignment material and liquid-crystal display element employing the same
WO2008010528A1 (en) * 2006-07-18 2008-01-24 Nissan Chemical Industries, Ltd. Liquid crystal orienting agent and liquid crystal oriented film and liquid crystal display element using the same

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