CN102031122B - Liquid crystal orientation agent, liquid crystal display element, polyamide acids, polyimides, and compound - Google Patents

Liquid crystal orientation agent, liquid crystal display element, polyamide acids, polyimides, and compound Download PDF

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CN102031122B
CN102031122B CN201010510115.7A CN201010510115A CN102031122B CN 102031122 B CN102031122 B CN 102031122B CN 201010510115 A CN201010510115 A CN 201010510115A CN 102031122 B CN102031122 B CN 102031122B
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CN102031122A (en
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秋池利之
菅野尚基
阿部翼
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JSR Corp
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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    • 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

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Abstract

The invention relates to a liquid crystal alignment agent, a liquid crystal display element, polyamide acids, polyimides, and a compound. The liquid crystal alignment agent can provide excellent electrical properties and liquid crystal alignment performance of a liquid crystal alignment film do not become bad even through it is used at high temperature for a long time, and printing performance of the liquid crystal alignment agent is excellent. The liquid crystal alignment agent comprises at least one kind of polymer selected from the group consisting of polyamic acid and polyimide, wherein the polymer at least part in its molecule has a group represented by following formula (0). In the formula (0), RI represents an alkyl group having 3 to 12 carbon atoms or a fluoro alkyl group having 3 to 12 carbon atoms, XI represents a single bond or oxygen atom, RII represents 1,4-cyclohexylene or 1,4-phenylene, XII represents a single bond, oxygen atom or *-COO- (wherein, a linking bond with ''*'' link to RII), n is 0 or 1, XIII represents a group represented by following formula (XIII -1) or (XIII -2).

Description

Liquid crystal aligning agent, liquid crystal display device, polyamic acid, polyimide and compound
Technical field
The present invention relates to liquid crystal aligning agent, liquid crystal display device, polyamic acid, polyimide and compound.
Background technology
As the one of liquid crystal display device operation scheme, be known that the liquid crystal molecule that makes to have negative dielectric anisotropy vertical orientated vertical (Homeotropic) aligned liquid crystal display device on substrate.This operation scheme applies voltage between substrate, makes liquid crystal molecule in the time that the direction parallel with substrate tilts, and must make the direction of liquid crystal molecule in from substrate normal direction to real estate tilt (formation tilt angle).As the means of this use, propose for example to arrange at substrate surface the method for projection; The method of striped is set in transparency electrode; By using friction orientation film, by liquid crystal molecule from substrate normal direction, to the slightly method of low dip of a direction in real estate; Optical alignment method etc. (patent documentation 1～5).
Among above-mentioned, give the liquid crystal orientation film of tilt angle character by optical alignment method, even the liquid crystal aligning excellence at the initial stage of manufacture, but pass through life-time service, also there is the liquid crystal aligning performance problem of variation gradually, particularly pointed out that this trend of the liquid crystal display device using is obvious under hot conditions.
In addition, along with the digitizing of television transmission and the progress of height dynamic menu technique for fixing, the high-precision refinement of view data, high-quality fast development in recent years.In order correctly to reproduce this view data, demonstrate exquisite picture, the requirement of electrical property, particularly voltage retention to liquid crystal cell is higher and very strict compared with current liquid crystal cell.In addition, in order not only to improve the productive rate of product, and will contribute to cut down product cost, liquid crystal aligning agent also requires high printing performance.
[prior art document]
[patent documentation]
[patent documentation 1] TOHKEMY 2003-307736 communique
[patent documentation 2] TOHKEMY 2004-163646 communique
[patent documentation 3] TOHKEMY 2004-83810 communique
[patent documentation 4] Japanese kokai publication hei 9-211468 communique
[patent documentation 5] TOHKEMY 2003-114437 communique
[non-patent literature]
[non-patent literature 1] T.J.Scheffer et.al.J.Appl.Phys., vol.48, p1789 (1977)
[non-patent literature 2] F.Nakano et.al.JPN.J.Appl.Phys., vol.19, p2013 (1980)
Summary of the invention
The present invention is in order to address the above problem proposition, and its object is to provide a kind of liquid crystal aligning agent, and this liquid crystal aligning agent can provide electrical property excellence, even use for a long time under hot conditions, and the liquid crystal orientation film that liquid crystal aligning can variation yet; And the printing excellence of this liquid crystal aligning agent.
Another object of the present invention is to provide electrical property excellence, even use for a long time under hot conditions, and the manufacture method of the liquid crystal orientation film that liquid crystal aligning performance can variation yet.
Another object of the present invention is to provide display performance excellence, even use for a long time under hot conditions, and the liquid crystal display device that display performance can variation yet.
According to the present invention, above object and advantages of the present invention, the firstth, realize by a kind of liquid crystal aligning agent, this liquid crystal aligning agent contains at least one polymkeric substance of selecting in the group being made up of polyamic acid and polyimide, wherein, aforementioned polymer has the group shown in following formula (0) in its intramolecular at least a portion
Figure BSA00000308305800031
In formula (0), R ithat carbonatoms is the fluoro-alkyl that 3～12 alkyl or carbonatoms are 3～12, X isingly-bound or Sauerstoffatom, R iIisosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, X iIbe singly-bound, Sauerstoffatom or *-COO-(wherein, connecting key and the R of band " * " iIconnect), n is 0 or 1, X iIIfollowing formula (X iII-1) or (X iII-2) group shown in.
-CH＝CH-(X III-1)
-C≡C-(X III-2)
Above object and advantages of the present invention, the secondth, to realize by a kind of liquid crystal display device, this liquid crystal display device has the liquid crystal orientation film being formed by above-mentioned liquid crystal aligning agent.
According to the present invention, a kind of liquid crystal aligning agent is provided, this liquid crystal aligning agent can provide electrical property excellence, even use for a long time under hot conditions, the liquid crystal orientation film that liquid crystal aligning performance can variation yet; And the printing excellence of this liquid crystal aligning agent.There is the liquid crystal display device of the liquid crystal orientation film being formed by this liquid crystal aligning agent, display performance excellence, even and under hot conditions for a long time use, display performance can variation yet.
Embodiment
Below, the present invention is described in detail.
Liquid crystal aligning agent of the present invention contains at least one polymkeric substance of selecting in the group being made up of polyamic acid and polyimide, and wherein aforementioned polymer has the group shown in above-mentioned formula (0) at least a portion of its molecule.In this manual, this polymkeric substance is called " particular polymers " hereinafter.In this particular polymers, the group shown in above formula (0), may reside in the main chain of polymkeric substance, also may reside in the side chain of polymkeric substance, or can be present in the main chain and side chain of polymkeric substance simultaneously.
As the R in above-mentioned formula (0) i, be preferably carbonatoms and be 3～7 alkyl, or carbonatoms is 3～7 and the number of fluorine atoms fluoro-alkyl that is 3～5.As preferred R iobject lesson, can list for example n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, 4,4,4-tri-fluoro bases, 4,4,5,5,5-five fluorine amyl groups etc., among them, are particularly preferably n-propyl, normal-butyl, n-pentyl, n-hexyl or n-heptyl.
As the X in above formula (0) ibe preferably singly-bound;
As R iI, be preferably Isosorbide-5-Nitrae-cyclohexylidene;
As X iI, be preferably singly-bound;
Be preferably 0 as n.As X iII, be preferably above-mentioned formula (X iII-1) group shown in, particularly preferably above-mentioned formula (X iII-1) the two keys of C-C in are trans.Isosorbide-5-Nitrae-cyclohexylidene in above formula (0) is preferably formed chair form structure.
The liquid crystal orientation film being formed by the liquid crystal aligning agent of the present invention that contains this particular polymers with the group shown in above-mentioned formula (0) with rigidity liquid crystal unit structure, its electrical property excellence, even while use for a long time under hot conditions, the stability of liquid crystal property is also excellent.
Intramolecular at least a portion has the polyamic acid of the group shown in above-mentioned formula as above (0), can be by for example comprising tetracarboxylic dianhydride and the diamine reactant of the compound with the group shown in above-mentioned formula (0) and two acid anhydrides, or by tetracarboxylic dianhydride with comprise the diamine reactant with the group shown in above-mentioned formula (0) and two amino compounds and obtain;
There is the polyimide of the group shown in above-mentioned formula (0) in intramolecular at least a portion, for example can be by the polyamic acid dehydration closed-loop as above obtaining be obtained.
Be preferably at least one polymkeric substance of selecting in the group that the polyimide that forms by polyamic acid with by this polyamic acid dehydration closed-loop forms as the particular polymers containing in liquid crystal aligning agent of the present invention, wherein this polyamic acid is to make tetracarboxylic dianhydride and comprise the diamine reactant with the group shown in above-mentioned formula (0) and two amino compounds and obtain.
< polyamic acid >
As implied above, in the present invention, preferred polyamic acid is to make tetracarboxylic dianhydride and comprise the diamine reactant with the group shown in above-mentioned formula (0) and two amino compounds and obtain.
[tetracarboxylic dianhydride]
The tetracarboxylic dianhydride who uses as synthetic above-mentioned polyamic acid, can list for example butanetetra-carboxylic acid dianhydride, 1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,3-dichloro--1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,2,3,4-encircles penta tetracarboxylic dianhydride, 1,2,4,5-hexamethylene tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic base NSC 60134 dianhydride, 3,5,6-, tri-carboxyl norbornane base-2-acetic acid dianhydrides, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, two ring [2.2.2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] is pungent-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, 3,5,6-, tri-carboxyls-2-carboxymethyl norbornane-2:3,5:6-dianhydride, 4,9-dioxa three encircles [5.3.1.0 2,6] 11 carbon-3, aliphatics tetracarboxylic dianhydride and the ester ring type tetracarboxylic dianhydrides such as 5,8,10-tetraketone, following formula (T-I) and (T-II) compound that represents respectively,
Figure BSA00000308305800061
In above-mentioned formula, R 1and R 3respectively the divalent organic group with aromatic ring, R 2and R 4respectively hydrogen atom or alkyl, multiple R 2and R 4can be identical respectively, also can be different.
Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-xenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluoro isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phenyl phosphine oxide dianhydride, to phenylene-bis-(triphenyl phthalic acid) dianhydride, metaphenylene-bis-(triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol-bis-(trihemellitic acid acid anhydride), propylene glycol-bis-(trihemellitic acid acid anhydride), BDO-bis-(trihemellitic acid acid anhydride), 1,6-hexylene glycol-bis-(trihemellitic acid acid anhydride), 1,8-ethohexadiol-bis-(trihemellitic acid acid anhydride), 2,2-bis-(4-hydroxy phenyl) propane-bis-(trihemellitic acid acid anhydride), aromatic tetracarboxylic acid's dianhydrides such as the compound that following formula (T-1)～(T-4) represents respectively.
Figure BSA00000308305800071
Figure BSA00000308305800081
They can use separately one, or combine two or more uses.
For the synthesis of the tetracarboxylic dianhydride of preferred polyamic acid in the present invention, from making the liquid crystal orientation film forming show the viewpoint of better liquid crystal aligning, preferably comprise the butanetetra-carboxylic acid dianhydride of choosing in freely above-mentioned, 1, 2, 3, 4-ring butanetetra-carboxylic acid dianhydride, 1, 3-dimethyl-1, 2, 3, 4-ring butanetetra-carboxylic acid dianhydride, 1, 2, 3, 4-encircles penta tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic base NSC 60134 dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-5, 8-dimethyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, two ring [2.2.2]-Xin-7-alkene-2, 3, 5, 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] pungent-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyls-2-carboxymethyl norbornane-2:3, 5:6-dianhydride, 4, 9-dioxa three encircles [5.3.1.0 2,6] 11 carbon-3,5,8,10-tetraketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride, 2,3 ', 2,3 '-biphenyl tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5, in compound shown in 8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I), the compound that following formula (T-5)～(T-7) represents respectively
In the compound shown in above-mentioned formula (T-II), at least one (following, to be called " specific tetracarboxylic dianhydride ") of the group that the compound shown in following formula (T-8) forms.
Figure BSA00000308305800092
As specific tetracarboxylic dianhydride, particularly be preferably selected from by 1, 2, 3, 4-ring butanetetra-carboxylic acid dianhydride, 2, 3, 5-tricarboxylic base NSC 60134 dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] pungent-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2 dicarboxylic anhydrides, 3, 5, 6-tri-carboxyls-2-carboxymethyl norbornane-2:3, 5:6-dianhydride, 4, 9-dioxa three encircles [5.3.1.0 2,6] 11 carbon-3, at least one of the group that compound shown in 5,8,10-tetraketone, pyromellitic acid dianhydride and above-mentioned formula (T-5) forms, particularly preferably 2,3,5-tricarboxylic base NSC 60134 dianhydride.
For the synthesis of the tetracarboxylic dianhydride of preferred polyamic acid in the present invention, with respect to whole tetracarboxylic dianhydrides, more than preferably containing 20mol%, more than more preferably containing 50mol%, particularly preferably contain 80mol% as above specific tetracarboxylic dianhydride above.
The synthetic middle tetracarboxylic dianhydride of use as the preferred polyamic acid of the present invention most preferably only uses as above specific tetracarboxylic dianhydride.
[diamines]
For the synthesis of the diamines of preferred polyamic acid in the present invention, be to comprise the diamines with the group shown in above-mentioned formula (0) and two amino compounds.As the preferred example of this compound, can list the such as compound shown in following formula (1) etc.
Figure BSA00000308305800101
In formula (1), R i, X i, R iI, X iI, X iIIidentical with the definition in above-mentioned formula (0) respectively with n, R iIIbe that singly-bound, methylene radical or carbonatoms are 2～6 alkylidene group, wherein this alkylidene group can be replaced by hydroxyl, X iVbe singly-bound, Sauerstoffatom or *-OCO-(wherein, be with " *" connecting key and R iIIconnect), wherein, R iIIwhile being singly-bound, X iVit is singly-bound.
As the X in above formula (1) iVbe preferably singly-bound.Two amino in the diamino-phenyl of above-mentioned formula (1), are preferably 2,4-position, 2 with respect to other group, 5-position or 3,5-position.
As the preferred example of the compound shown in above-mentioned formula (1), can list compound that such as following formula (1-1)～(1-41) represents respectively etc.
Figure BSA00000308305800111
Figure BSA00000308305800121
Figure BSA00000308305800131
Figure BSA00000308305800141
Figure BSA00000308305800151
Figure BSA00000308305800161
In formula (1-1)～(1-41), R iidentical with the definition in above-mentioned formula (1), m is 1～6 integer, R iII-1it is propylene.In above-mentioned formula (1-1)～(1-41), the two keys of C-C are preferably trans.Among them, more preferably above-mentioned formula (1-1), (1-4)～(1-7), (1-10)～(1-13), (1-16)～(1-18), (1-29) and (1-30) compound that represents respectively, further preferred above-mentioned formula (1-4)～(1-6), (1-12), (1-18), (1-29) and (1-30) compound of expression respectively, the particularly preferably compound shown in above-mentioned formula (1-6).
Compound shown in above-mentioned formula (1) can be synthetic by appropriately combined vitochemical ordinary method.
For example, in above formula (1), R iIIfor methylene radical, X iIIfor above-mentioned formula (X iII-1) group shown in, X iVit is the compound of singly-bound, for example can pass through the compound shown in following formula (1-A) and dinitrobenzene benzyl chlorine, preferably under the existence of salt of wormwood, react, obtain after dinitrobenzene compound, use suitable reduction system, by the nitroreduction of this dinitrobenzene compound (hydrogenation), form amino and obtain.
Figure BSA00000308305800171
(in formula (1-A), R i, X i, R iI, X iIidentical with the definition in above-mentioned formula (1) respectively with n)
In above-mentioned formula (1), R iIIethylene, X iIIabove-mentioned formula (X iII-1) group shown in, X iVthe compound that is singly-bound for example can, by by the compound shown in above-mentioned formula (1-A) and thionyl chloride reaction, form after acyl chlorides, by following formula (1-B), and R iIIfor ethylene, X is the compound reaction of hydroxyl, obtains, after dinitrobenzene compound, using suitable reduction system, by the nitroreduction of this dinitrobenzene compound (hydrogenation), forms amino and obtains.
Figure BSA00000308305800172
In above-mentioned formula (1), R iIIsingly-bound, X iIIabove-mentioned formula (X iII-1) group shown in, X iVit is the compound of singly-bound, for example can be by the compound shown in above-mentioned formula (1-A) and thionyl chloride be reacted, form after acyl chlorides, react with dinitrophenol(DNP), obtain after dinitrobenzene compound, use suitable reduction system, by the nitroreduction of this dinitrobenzene compound (hydrogenation), form amino and obtain.
In above-mentioned formula (1), R iIIfor ethylene, X iIIabove-mentioned formula (X iII-1) group shown in, X iVbe *-OCO-(wherein, be with " *" connecting key and R iIIconnect) compound, for example can, by making the compound shown in following formula (1-C) and dinitrobenzoyl chloride reaction, obtain, after dinitrobenzene compound, using suitable reduction system, by the nitroreduction of this dinitrobenzene compound (hydrogenation), form amino and obtain.
Figure BSA00000308305800181
In formula (1-C), R i, X i, R iI, X iIidentical with the definition in above-mentioned formula (1) respectively with n.
In addition, by using in above-mentioned formula (1-C), methylene radical apparatus has the group-(CH of desirable m value 2) mthe compound of-replacement, can obtain corresponding desirable compound.
In above-mentioned formula (1), R iIImethylene radical or alkylidene group, X iIIabove-mentioned formula (X iII-1) group shown in, X iVbe the compound of Sauerstoffatom, for example, can, by by the compound shown in above-mentioned formula (1-A) and thionyl chloride reaction, form after acyl chlorides, as R iIIwith the compound reaction respectively at two ends of desirable methylene radical or alkylidene group with hydroxyl, form monohydroxy-alcohol, then by this monohydroxy-alcohol and the reaction of fluorodinitrobenzene phenol, de-HF, obtain after dinitrobenzene compound, use suitable reduction system, by the nitroreduction of this dinitrobenzene compound (hydrogenation), form amino and obtain.
The compound that above-mentioned formula (1-33)～(1-36) represents respectively, for example can pass through 3,5-bis-(N, N-diallyl amino) hydroxybenzene and the reaction of glycidyl chlorine, obtain 3,5-bis-(N, N-diallyl amino) glycidoxypropyl benzene, then, by this compound with there is desirable radicals R i, X i, R iIand X iIand the compound reaction shown in the following formula (1-D) of numerical value n, obtain after diallyl compound, preferably, under the existence of tetraphenyl palladium, by N, N-diallyl changes amino into and obtains.
The compound that above-mentioned formula (1-37)～(1-40) represents respectively, for example can be by having desirable radicals R i, X i, R iIand X iIand the compound shown in the above-mentioned formula (1-D) of numerical value n and the reaction of glycidyl chlorine, obtain midbody compound, then, by this midbody compound and the reaction of 3,5-bis-(N, N-diallyl amino) hydroxybenzene, obtain after diallyl compound, preferably, under the existence of tetraphenyl palladium, by N, N-diallyl changes amino into and obtains.
As the diamines for the synthesis of preferred polyamic acid in the present invention, can only use separately the compound shown in above-mentioned formula (1), also the compound shown in above-mentioned formula (1) and other diamines can be used in combination.
As other diamines that can use, can list for example P-pHENYLENE dI AMINE here, m-phenylenediamine, 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 '-diamino-diphenyl ether, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine base, 3,3 '-dimethyl-4,4 '-benzidine base, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine base, 3,3 '-bis-(trifluoromethyl)-4,4 '-benzidine base, 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 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] hexafluoorpropane, 2,2-bis-(4-aminophenyl) hexafluoorpropane, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] sulfone, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(3-amino-benzene oxygen) benzene, 9,9-bis-(4-aminophenyl)-10-hydrogen anthracene, 2,7 diamin of luorene, 9,9-dimethyl-2,7 diamin of luorene, 9,9-bis-(4-aminophenyl) fluorenes, 4,4 '-methylene radical-bis-(2-chloro aminobenzen), 2,2 ', 5,5 '-tetrachloro generation-4,4 '-benzidine base, 2,2 '-dichloro--4,4 '-diamino-5,5 '-dimethoxy-biphenyl base, 3,3 '-dimethoxy-4 ', 4 '-benzidine base, 4,4 '-(to phenylene isopropylidene) two (aniline), 4,4 '-(metaphenylene isopropylidene) two (aniline), 2,2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] hexafluoorpropane, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) xenyl, the aromatic diamines such as 4,4 '-bis-[(4-amino-2-trifluoromethyl) phenoxy group]-eight fluorodiphenyls,
1,1-m-xylene diamine, 1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, the sub-Dicyclopentadiene (DCPD) diamines of tetrahydrochysene, six hydrogen-4,7-methylene radical indenyl dimethylene diamines, three ring [6.2.1.0 2,7] hendecene dimethylene diamines, 4, aliphatie diamine and the ester ring type diamines such as 4 '-methylene radical two (cyclo-hexylamine);
2,3 diamino pyridine, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2,4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazines, Isosorbide-5-Nitrae-bis-(3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazines, 2,4-diamino-6-methoxyl group-1,3,5-triazines, 2,4-diamino-6-phenyl-1,3,5-triazines, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazines, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2,6-diaminopurine, 5,6-diaminostilbene, 3-dimethyl uracil, 3,5-diaminostilbene, 2,4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, Isosorbide-5-Nitrae-diamino piperazine, 3,6-proflavin, two (4-aminophenyl) phenyl amine, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, following formula (D-I) and (D-II) compound etc. that represents respectively have the diamines of the nitrogen-atoms beyond two primary amine groups and this primary amino in molecule,
Figure BSA00000308305800211
In formula (D-I), R 5any monovalent organic radical group that selects the ring structure with nitrogen atom of the group of free pyridine, pyrimidine, triazine, piperidines and piperazine formation, X 1it is divalent organic group;
In formula (D-II), R 6the divalent organic group that selects the ring structure with nitrogen atom of the group of free pyridine, pyrimidine, triazine, piperidines and piperazine formation, X 2respectively divalent organic group, multiple X 2can be identical respectively, also can be different.
The mono-substituted phenylenediamines such as the compound shown in following formula (D-III);
Figure BSA00000308305800212
(in formula (D-III), R 7be-O-,-COO-,-OCO-,-NHCO-,-CONH-or-CO-, R 8to have to select the alkyl that the skeleton of group that free steroid skeleton, trifluoromethyl, Trifluoromethoxyphen-l and difluorophenyl form or any monovalent organic radical of group group or carbonatoms are 6～30)
The diamino organo-siloxanes such as the compound shown in following formula (D-IV);
Figure BSA00000308305800213
(in formula (D-IV), R 9respectively that carbonatoms is 1～12 alkyl, multiple R 9can be identical respectively, also can be different, p is respectively 1～3 integer, q is 1～20 integer)
The compound that following formula (D-1)～(D-5) represents respectively etc.
Figure BSA00000308305800221
Figure BSA00000308305800231
Y in formula (D-4) is 2～12 integer, and the z in formula (D-5) is 1～5 integer.
As in synthetic the present invention when preferred polyamic acid, other diamines using together with the compound shown in above-mentioned formula (1), preferably include above-mentioned among, select free P-pHENYLENE dI AMINE, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to phenylene diisopropylidene) two (aniline), 4,4 '-(metaphenylene diisopropylidene) two (aniline), Isosorbide-5-Nitrae-cyclohexane diamine, 4,4 '-methylene radical two (cyclo-hexylamine), Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, the compound that above-mentioned formula (D-1)～(D-5) represents respectively, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, compound shown in following formula (D-6) in the compound that above-mentioned formula (D-I) represents,
Above-mentioned formula (D-II) represent compound in following formula (D-7) represent compound,
Figure BSA00000308305800233
And above-mentioned formula (D-III) represent compound in dodecyloxy-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2, at least one (following, be called " other specific diamines) of the group that the compound that 5-diaminobenzene and following formula (D-8)～(D-16) represent respectively forms.
Figure BSA00000308305800241
Figure BSA00000308305800251
Figure BSA00000308305800261
For the synthesis of the diamines of preferred polyamic acid in the present invention, with respect to whole diamines, more than preferably containing 1mol%, more than more preferably containing 20mol%, particularly preferably contain the compound shown in above-mentioned formula (1) more than 50mol%.
For the synthesis of the diamines of preferred polyamic acid in the present invention, can further contain other specific diamines as implied above, proportional as containing of other specific diamines, with respect to whole diamines, be preferably below 90mol%, more preferably below 80mol%, more preferably below 50mol%.
For the synthesis of the diamines of preferred polyamic acid in the present invention, preferably only formed by the compound shown in above-mentioned formula (1), or only formed by the compound shown in above-mentioned formula (1) and other specific diamines.
[synthesizing of polyamic acid]
In the present invention, preferred polyamic acid can obtain by the diamine reactant that makes tetracarboxylic dianhydride and comprise the compound shown in above-mentioned formula (1).
The tetracarboxylic dianhydride who uses in building-up reactions as polyamic acid and the usage ratio of diamines, with respect to the amino containing in monovalent diamine compound, tetracarboxylic dianhydride's anhydride group is the ratio of 0.2～2 equivalent preferably, more preferably the ratio of 0.3～1.2 equivalent.
The building-up reactions of polyamic acid in preferred organic solvent, preferably-20～150 DEG C, more preferably under the temperature condition of 0～100 DEG C, carry out.Be preferably 1～240 hour, more preferably 2～12 hours as the reaction times.Wherein, as organic solvent, as long as just there is no particular limitation can to dissolve synthetic polyamic acid, can list for example METHYLPYRROLIDONE, N, the non-proton property polar solvents such as N-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; The phenol solvents such as meta-cresol, xylenol, phenol, halogenated phenol.The total amount (b) that the consumption (a: when wherein organic solvent use together with lean solvent described later, refer to their total amount) of organic solvent is preferably tetracarboxylic dianhydride and diamine compound is the amount of 0.1～30 % by weight with respect to whole amounts (a+b) of reaction soln.
In above-mentioned organic solvent, can be can not separating out in the scope of polyamic acid of generation, use together with the alcohol that is conventionally identified with lean solvent as polyamic acid, ketone, ester, ether, halohydrocarbon, hydrocarbon etc.As the object lesson of this lean solvent, can list for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triglycol, ethylene glycol monomethyl ether, ethyl lactate, n-Butyl lactate, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, methyl acetate, ethyl acetate, butylacetate, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, oxalic acid diethyl ester, diethyl malonate, Anaesthetie Ether, Ethylene Glycol Methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, Ethylene Glycol Methyl ether acetic acid ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monomethyl ether acetic ester, TC acetic ester, tetrahydrofuran (THF), methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.
When synthesizing polyamides acid, when organic solvent is used together with above-mentioned lean solvent, as the usage ratio of lean solvent, with respect to the total amount of organic solvent and lean solvent, be preferably below 50 quality %, more preferably below 10 quality %.
As above, can obtain dissolving the reaction soln that polyamic acid forms.
This reaction soln can be directly used in prepares liquid crystal aligning agent, after the polyamic acid that also can contain in separating reaction solution, and for the preparation of liquid crystal aligning agent, or after the polyamic acid separating is refining, for the preparation of liquid crystal aligning agent.
When polyamic acid dehydration closed-loop is formed to polyimide, above-mentioned reaction soln can be directly used in to dehydration closed-loop reaction; Also the polyamic acid containing in can separating reaction solution reacts for dehydration closed-loop after separating; Or after the polyamic acid separating is refining, react for dehydration closed-loop.
The separation of polyamic acid can, by above-mentioned reaction soln is injected to a large amount of lean solvents, obtain precipitate, by the method for this precipitate drying under reduced pressure; Or the method by the solvent in vaporizer underpressure distillation reaction soln is carried out.In addition, also can be by this polyamic acid is dissolved in organic solvent again, the method for then separating out in lean solvent; Or by repeating the one or many vaporizer refining polyamic acid of the method that distillates that reduces pressure.
< polyimide >
In the present invention, preferred polyimide can be by obtaining polyamic acid dehydration closed-loop imidization as above.
The tetracarboxylic acid diamines using as synthetic above-mentioned polyimide, can list the synthetic middle identical compound of tetracarboxylic dianhydride using with above-mentioned polyamic acid.Preferred tetracarboxylic dianhydride's kind is also identical with the situation of polyamic acid with its preferred usage ratio.
As the diamines for the synthesis of preferred polyimide in the present invention, can list the identical diamines of diamines using with synthetic above-mentioned polyamic acid.Namely, comprise the compound shown in above-mentioned formula (1) for the synthesis of the diamines of the polyimide containing in liquid crystal aligning agent of the present invention, can only use the compound shown in above-mentioned formula (1), also the compound shown in above-mentioned formula (1) can be used together with above-mentioned other diamines.The preferred kind of other diamines is also identical with the situation of polyamic acid with the preferred usage ratio of each diamines.
In the present invention, preferred polyimide can be the complete imide compound of the amido acid structure fully dehydrating closed loop that has as the polyamic acid of raw material; Also can be a part of dehydration closed-loop of amido acid structure, amido acid structure and imide ring structure the part imide compound of depositing.The imide rate of the polyimide in the present invention is preferably more than 20%, and more preferably 40～80%.This imide rate is to represent that with percentage the quantity of imide ring structure occupies the ratio of the quantity of amido acid structure of polyimide and the total amount of the quantity of imide ring structure.Now, a part for imide ring can be different imide ring.Imide rate can for example,, by polyimide being dissolved into heavy-hydrogenated solvent (, in heavy-hydrogenated dimethyl sulfoxide (DMSO)), using tetramethylsilane as primary standard, be measured from room temperature 1the result of H-NMR, tries to achieve according to following mathematical expression (I).
Imide rate (%)={ 1-(A 1/ A 2) × α } × 100 (I)
In above-mentioned mathematical expression (I), A 1the peak area representing near the proton of the NH base occurring chemical shift 10ppm, A 2be the peak area representing from other proton, α is that the number of other proton is with respect to the ratio of the proton of the NH base in the precursor (polyamic acid) of a polyimide.
The dehydration closed-loop preferred (i) of polyamic acid is to pass through the method for heating polyamic acid, or (ii) polyamic acid is dissolved in organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer, the method for heating is carried out as required.
Be preferably 50～200 DEG C, more preferably 60～170 DEG C as the temperature of reaction in the method for the heating polyamic acid of above-mentioned (i).When temperature of reaction is less than 50 DEG C, cannot fully carry out dehydration closed-loop reaction; If temperature of reaction exceedes 200 DEG C, the molecular weight of the polyimide of gained may be low.As the reaction times, be preferably 1.0～24 hours, more preferably 1.0 hours～12 hours.
On the other hand, in the solution at polyamic acid of (ii), add in the method for dewatering agent and dehydration closed-loop catalyzer, as dewatering agent, can list the acid anhydrides such as such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.As the consumption of dewatering agent, determine according to desirable imide rate, with respect to the amido acid structure of 1mol polyamic acid, be preferably 0.01mol～20mol.In addition, as dehydration closed-loop catalyzer, can list the tertiary amines such as such as pyridine, trimethylpyridine, lutidine, triethylamine.But, be not limited to this.The dewatering agent using with respect to 1mol as the consumption of dehydration closed-loop catalyzer, is preferably 0.01～10mol.The consumption of above-mentioned dewatering agent, dehydration closed-loop catalyzer is more, and imide rate can be higher.As the organic solvent using in dehydration closed-loop reaction, can list the illustrative organic solvent of solvent that acid is used as synthesizing polyamides.Temperature of reaction as dehydration closed-loop reaction is preferably 0～180 DEG C, more preferably 10～150 DEG C.Be preferably 1.0～120 hours, more preferably 2.0 hours～30 hours as the reaction times.
The polyimide obtaining in aforesaid method (i) can be directly used in prepares liquid crystal aligning agent, or after the polyimide of gained is refining, for the preparation of liquid crystal aligning agent.On the other hand, in aforesaid method (ii), can obtain the reaction soln that contains polyimide.This reaction soln can be directly used in prepares liquid crystal aligning agent, also can be from reaction soln is removed dewatering agent and dehydration closed-loop catalyzer, for the preparation of liquid crystal aligning agent; Can also separate after polyimide, for the preparation of liquid crystal aligning agent; Or after the polyimide separating is refining, for the preparation of liquid crystal aligning agent.In order to remove dewatering agent and dehydration closed-loop catalyzer from reaction soln, for example, be applicable to using the methods such as solvent exchange.Separation, the refining above-mentioned same operation that can be undertaken by the separation as polyamic acid, process for purification of polyimide are carried out.
-polymkeric substance of end modified type-
In the present invention, above-mentioned polyamic acid and polyimide can be respectively the end modified property polymkeric substance of Molecular regulator amount.By using end modified type polymkeric substance, can not damage effect of the present invention and further improve coating property of liquid crystal aligning agent etc.This end modified type polymkeric substance, in the time of synthesizing polyamides acid, can be undertaken by add molecular weight regulator in polymerization reaction system.As molecular weight regulator, can list such as sour single acid anhydride, monoamine compound, monoisocyanates compound etc.
As the single acid anhydride of above-mentioned acid, can list such as maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.;
As above-mentioned monoamine compound, can list such as aniline, cyclo-hexylamine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octylamine, n-nonyl amine, positive decyl amine, n-undecane base amine, dodecyl amine, n-tridecane base amine, n-tetradecane base amine, Pentadecane base amine, n-hexadecyl amine, n-heptadecane base amine, Octadecane base amine, NSC 62789 base amine etc.;
As above-mentioned monoisocyanates compound, can list such as isocyanic acid phenylester, isocyanic acid naphthyl ester etc.
As the usage ratio of molecular weight regulator, the tetracarboxylic dianhydride who uses during with respect to synthesis of polyimides and the total of diamines 100 weight parts, be preferably below 20 weight parts, more preferably below 5 weight parts.
-soltion viscosity-
As above the polyamic acid obtaining or polyimide, in the time forming the solution of concentration 10 % by weight, preferably have the soltion viscosity of 20～800mPas, more preferably have the soltion viscosity of 30～500mPas.
The soltion viscosity (mPas) of above-mentioned polymkeric substance be use this polymkeric substance good solvent (for example, gamma-butyrolactone, METHYLPYRROLIDONE etc.), the polymers soln of concentration 10 % by weight to preparation, uses E type rotational viscosimeter, the value of measuring at 25 DEG C.
Other composition of < >
Liquid crystal orientation film of the present invention contains particular polymers as above as essential composition, also can contain as required other composition.As this other composition, can list polymkeric substance beyond particular polymers for example (following, be called " other polymkeric substance "), in molecule, there is compound (following, be called " epoxy compounds "), the functional silanes compound etc. of at least one epoxy group(ing).
[other polymkeric substance]
Above-mentioned other polymkeric substance can be for improving SOLUTION PROPERTIES and electrical property.As this other polymkeric substance, it is the as above polymkeric substance beyond particular polymers, the polyamic acid that can list for example tetracarboxylic dianhydride and do not obtain containing the diamine reactant of the compound shown in above-mentioned formula (1) is (following, be called " other polyamic acid "), the polyimide that this polyamic acid dehydration closed-loop is formed is (following, be called " other polyimide "), poly amic acid ester, polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.Among them, preferably other polyamic acid or other polyimide, more preferably other polyamic acid.
As other polymkeric substance usage ratio, (refer to the total amount of above-mentioned particular polymers and other polymkeric substance with respect to the total amount of polymkeric substance.Identical below), be preferably below 95 % by weight, more preferably 50～90 % by weight.
[epoxy compounds]
As above-mentioned epoxy compounds, can be used as and preferably list for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2, 2-bis-bromo neopentylglycol diglycidyl ethers, 1, 3, 5, 6-four glycidyl group-2, 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, 3-bis-(N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-amino methyl hexanaphthene etc.Amount to 100 weight parts with respect to polymkeric substance, the blending ratio of these compounds that contain epoxy group(ing) is preferably below 40 weight parts, more preferably 0.1～30 weight part.
[functional silanes compound]
As above-mentioned functional silanes compound, can list for example 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-uride propyl trimethoxy silicane, 3-uride propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, N-bis-(oxidation ethylidene)-3-TSL 8330, N-bis-(oxidation ethylidene)-APTES etc.
Amount to 100 weight parts with respect to polymkeric substance, the blending ratio of these functional silanes compounds is preferably below 40 weight parts.
< liquid crystal aligning agent >
Liquid crystal aligning agent of the present invention preferably dissolves other additive of as above particular polymers and any mixing as required to contain and form in organic solvent.
As the organic solvent that can use, can list the illustrative solvent of the solvent using in the building-up reactions as polyamic acid in liquid crystal aligning agent of the present invention.In addition, can also suitably select the building-up reactions as polyamic acid time, can use together solvent and illustrative lean solvent.As the preferred example of this organic solvent, can list for example METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, Ethylene Glycol Methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monomethyl ether acetic ester, TC acetic ester, diisobutyl ketone, propionic acid isopentyl ester, isopropylformic acid isopentyl ester, diisoamyl ether etc.They can use separately, or also can mix two or more uses.
The solid component concentration of liquid crystal aligning agent of the present invention is (in liquid crystal aligning agent, the gross weight of removing organic solvent composition in addition occupies the ratio of the gross weight of liquid crystal aligning agent), consider the suitably selection such as viscosity, volatility, be preferably the scope of 1～10 % by weight.Namely, liquid crystal aligning agent of the present invention can, by being coated to substrate surface, be removed organic solvent, form the film of liquid crystal orientation film, but in the time that solid component concentration is less than 1 % by weight, the thickness of this film is too small, may be difficult to obtain good liquid crystal orientation film; On the other hand, in the time that solid component concentration exceedes 10 % by weight, the thickness of film is excessive, may be difficult to equally obtain good liquid crystal orientation film, and the increase of the viscosity of liquid crystal aligning agent, coating character may be not enough.
The method that the scope of particularly preferred solid component concentration adopts during according to coated with liquid crystal alignment agent on substrate and different.For example, in the time using spin-coating method to carry out, solid component concentration is particularly preferably the scope of 1.5～4.5 % by weight.In the time using print process to carry out, solid component concentration is the scope of 3～9 % by weight, and thus, soltion viscosity is particularly preferably the scope of 12～50mPas.In the time using ink jet method to carry out, solid component concentration is the scope of 1～5 % by weight, and thus, soltion viscosity is particularly preferably the scope of 3～15mPas.
The formation method > of < liquid crystal orientation film
Liquid crystal aligning agent of the present invention is suitable for forming liquid crystal orientation film by optical alignment method.
As the method that forms liquid crystal orientation film, for example can list liquid crystal aligning agent is applied on substrate, form film, the direction tilting from relative coated surface is irradiated polarized light or non-polarized light ultraviolet ray at this film, or irradiate polarized ultraviolet from the direction that relative coated surface is vertical at this film, film is given to the method for liquid crystal aligning energy.
First,, by suitable coating processes such as such as rolling method, spin-coating method, print process, ink jet methods, the nesa coating side of substrate of pattern-like nesa coating is set, be coated with liquid crystal aligning agent of the present invention.Liquid crystal aligning agent of the present invention is due to printing excellence, adopting print process, particularly when adherography, can bring into play to greatest extent advantageous effects of the present invention, so preferably.After coating, by this coated face is preheated to (prebake), then roasting (curing afterwards) forms film.Prebake condition is for example at 40～120 DEG C, to carry out 0.1～5 minute, rear baking conditions preferably 120～300 DEG C, more preferably at 150～250 DEG C, preferably carry out 5～200 minutes, more preferably carry out 10～100 minutes.After the thickness of film after curing be preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
As aforesaid base plate, can use for example by the glass as float glass, soda-lime glass; The transparency carrier that plastics as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate etc. form etc.
Can use by SnO as aforementioned nesa coating 2form NESA film, by In 2o 3-SnO 2the ITO film forming etc.In order to form the pattern of these nesa coatings, can use photo-engraving process or forming the method etc. that uses mask when nesa coating.
When coated with liquid crystal alignment agent, in order to make the cohesiveness of substrate or nesa coating and film better, can, on substrate and nesa coating, apply in advance functional silanes compound, titanate compound etc.
Then, by irradiating the ultraviolet ray of polarized light or non-polarized light, give liquid crystal aligning energy to this film, aforementioned film becomes liquid crystal orientation film.Here, as radioactive rays, can use ultraviolet ray and the visible rays of the light of the wavelength that for example comprises 150nm～800nm, preferably comprise the ultraviolet ray of the light of the wavelength of 300nm～400nm.The radioactive rays that use during for polarized light (rectilinearly polarized light or partial poolarized light), can irradiate from the vertical direction of relative coated surface, also can irradiate from the direction tilting in order to give tilt angle.On the other hand, in the time irradiating non-polarized light, the direction that irradiation must be tilted from relative coated surface is carried out.
As the light source that irradiates radioactive rays, can use such as Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.The ultraviolet ray in aforementioned optimal wavelength region can obtain by mechanism that aforementioned light source is used together with such as spectral filter, diffraction grating etc. etc.
The irradiation dose of radioactive rays is preferably 1J/m 2above, be less than 10,000J/m 2, more preferably 10～3,000J/m 2.In addition, while giving liquid crystal aligning energy by optical alignment method on the film being formed by current known liquid crystal aligning agent, must 10,000J/m 2above radiation exposure amount.But, if use liquid crystal aligning agent of the present invention, even if radiation exposure amount when optical alignment method is 3,000J/m 2below, and then be 1,000J/m 2below, be further 300J/m 2below, also can give good liquid crystal aligning energy, the manufacturing cost that contributes to cut down liquid crystal display device.
In addition, " tilt angle " described in the present invention represents the angle that liquid crystal molecule tilts from the direction parallel with real estate.
The manufacture method > of < liquid crystal display device
Liquid crystal display device of the present invention has the liquid crystal orientation film being formed by liquid crystal aligning agent of the present invention.Liquid crystal display device of the present invention for example can be manufactured as follows.
Prepare two substrates that as above form liquid crystal orientation film, by configure liquid crystal between these two substrates, manufacture liquid crystal cell.In the time manufacturing liquid crystal cell, can list for example following two kinds of methods.
First method is current known method.First, in order to make the setting of each liquid crystal orientation film subtend, by gap (gap of box), by two substrate subtend configurations, use sealing agent, by the periphery position laminating of two substrates, in the box gap of being cut apart by substrate surface and sealing agent, inject after filling liquid crystal, sealing filling orifice, can manufacture liquid crystal cell.
Second method is the method that is called ODF (One Drop Fill, instillation) mode.Prescribed position on a substrate in two substrates that form liquid crystal orientation film, apply the sealing agent of for example ultraviolet light curable, then on liquid crystal aligning face, drip after liquid crystal, fit another substrate make liquid crystal orientation film subtend, then, in whole irradiating ultraviolet light of substrate, make sealant cures, can manufacture liquid crystal cell.
The in the situation that of any method, to wish then liquid crystal cell to be heated to after the isotropic temperature of liquid crystal of use, Slow cooling is to room temperature, the flow orientation while removing Liquid crystal pour.
Then,, by the outer surface laminating polaroid at liquid crystal cell, can obtain liquid crystal display device of the present invention.Here, when liquid crystal orientation film is horizontal alignment, form by adjustment in two substrates of liquid crystal orientation film, irradiate angle that the polarization direction of rectilinearly polarized light radioactive rays forms and the angle of each substrate and polaroid, can obtain having the liquid crystal display device of TN type or STN type liquid crystal cell.On the other hand, in the time that liquid crystal orientation film is vertical orientated property, the direction that makes to form the axle of the easy orientation in two substrates of liquid crystal orientation film forms liquid crystal cell abreast, the polaroid of fitting therein, and the axle shape angle at 45 ° that makes its polarization direction and be easily orientated, can form the liquid crystal display device with vertical alignment-type liquid crystal box.
As aforementioned sealing agent, can use and for example contain as the alumina balls of partition and the epoxy resin of solidifying agent etc.
As foregoing liquid crystal, preferably use such as nematic liquid crystal, dish-like liquid crystal etc.
In the time being TN type liquid crystal cell or STN type liquid crystal cell, preferably there is the nematic liquid crystal of positive dielectric anisotropy, can use such as biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.In addition, in foregoing liquid crystal, can further add cholesterol liquid crystals such as using such as chlorination beta-cholestanol, Cholesteryl pelargonate, cholesterol carbonic ether; The chiral reagent of selling with trade(brand)name " C-15 ", " CB-15 " (manufacture of メ ルク company); To oxygen base benzylidene-to Ferroelectric liquid Crystals such as amino-2-methyl butyl laurate etc. in the last of the ten Heavenly stems.
On the other hand, in the time being vertical alignment-type liquid crystal box, preferably there is the nematic liquid crystal of negative dielectric anisotropy, can use such as dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, schiff alkali class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.
The polaroid using as the outside of liquid crystal cell, can list limit polyvinyl alcohol is extended and is orientated, and limit is clamped and absorbed the polaroid that iodine is called the film formed polaroid of polarisation of " H film " or is formed by H film itself with cellulose acetate protective membrane.
The liquid crystal display device of the present invention of manufacturing like this, display performance excellence, even use for a long time under hot conditions, display performance can variation yet.
[embodiment]
The synthetic > of the compound shown in the above-mentioned formula of < (1)
Following synthesis example repeats by following synthetic route as required, the necessary amount when guaranteeing following synthesis example and polymkeric substance synthetic.
Synthesis example 1-1 (synthesizing of compound (1-4-1))
According to following synthetic route 1 synthetic compound (1-4-1).
Figure BSA00000308305800381
synthetic route 1
(1) compound (1-4-1A) is synthetic
In the there-necked flask of the 5L with reflux condensing tube, thermometer and nitrogen ingress pipe, add 4-(4-amyl group cyclohexyl) bromobenzene, 2.3g palladium, 12g tri-(o-tolyl) phosphine, 560mL triethylamine, the 82mL vinylformic acid and 2 of 310g, the N of 000mL, N-N,N-DIMETHYLACETAMIDE stirs and reacts for 3 hours at 120 DEG C.After reaction finishes, filter reaction mixture.In this filtrate, add 10L ethyl acetate, the organic layer obtaining is used dilute hydrochloric acid washed twice successively, wash with water after 3 times, by dried over mgso, decompression is lower to desolventizing, the solid obtaining, by the mixed solvent recrystallization being made up of ethyl acetate and tetrahydrofuran (THF), obtains the crystallization of 150g compound (1-4-1A).
(2) compound (1-4-1B) is synthetic
In the there-necked flask of the 500mL with agitator, thermometer and nitrogen ingress pipe, add 3 of the above-mentioned synthetic compound of 30g (1-4-1A), 22g, the N of 5-dinitrobenzene benzyl chlorine, 42g salt of wormwood, 30g sodium iodide and 150mL, dinethylformamide reacts 8 hours at 60 DEG C.After reaction finishes, add 300mL chloroform in reaction mixture, the organic layer obtaining washes with water 3 times, then uses dried over mgso.Concentrated this organic layer, reclaims the solid of separating out, and is used washing with alcohol, thereby obtains the pale yellow powder of 41g compound (1-4-1B).
(3) compound (1-4-1) is synthetic
In the there-necked flask of the 1L with agitator, thermometer and nitrogen ingress pipe, add the above-mentioned synthetic compound of 41g (1-4-1B), 192g tin chloride dihydrate and 400mL ethyl acetate, reflux under 4 hours and react.After reaction finishes, reaction mixture washs successively with potassium fluoride aqueous solution and water.Organic layer dried over mgso, then, removal of solvent under reduced pressure, the solid obtaining is from ethyl alcohol recrystallization, thereby obtains the faint yellow crystallization of 21g compound (1-4-1).
Synthesis example 1-2 (synthesizing of compound (1-22-1))
According to following synthetic route 2 synthetic compounds (1-22-1).
Figure BSA00000308305800401
synthetic route 2
(1) compound (1-22-1A) is synthetic
In the there-necked flask of the 500mL with return line, thermometer and nitrogen ingress pipe, add the 4-(4-(4 of 37g, 4,4-tri-fluoro butoxy) cyclohexyl) N of bromobenzene, 0.23g palladium, 1.2g tri-(o-tolyl) phosphine, 56mL triethylamine, 8.2mL vinylformic acid and 200mL, N-N,N-DIMETHYLACETAMIDE stirs and reacts for 3 hours at 120 DEG C.After reaction finishes, filter reaction mixture.In this filtrate, append 1L ethyl acetate, dilute hydrochloric acid washed twice and washing with water 3 times for the organic layer obtaining, with after dried over mgso, removal of solvent under reduced pressure, the solid of gained, by the mixed solvent recrystallization being formed by ethyl acetate and tetrahydrofuran (THF), obtains the crystallization of 18g compound (1-22-1A).
(2) compound (1-22-1B) is synthetic
In the there-necked flask of the 300mL with agitator, thermometer and nitrogen ingress pipe, add 3 of the above-mentioned synthetic compound of 18g (1-22-1A), 11g, the N of 5-dinitrobenzene benzyl chlorine, 21g salt of wormwood, 15g sodium iodide and 75mL, dinethylformamide reacts 8 hours at 60 DEG C.After reaction finishes, add 150mL chloroform in reaction mixture, the organic layer obtaining washes with water 3 times, then uses dried over mgso.Concentrated organic layer, reclaims the solid of separating out, and is used washing with alcohol, thereby obtains the pale yellow powder of 23g compound (1-22-1B).
(3) compound (1-22-1) is synthetic
In the there-necked flask of the 500mL with agitator, thermometer and nitrogen ingress pipe, add the above-mentioned synthetic compound of 23g (1-22-1B), 96g tin chloride dihydrate and 200mL ethyl acetate, reflux under 4 hours and react.After reaction finishes, reaction mixture washs successively with potassium fluoride aqueous solution and water.Organic layer dried over mgso, removal of solvent under reduced pressure, the solid obtaining is from ethyl alcohol recrystallization, thereby obtains the faint yellow crystallization of 10g compound (1-22-1).
Synthesis example 1-3 (synthesizing of compound (1-10-1))
According to following synthetic route 3, synthetic compound (1-10-1).
Figure BSA00000308305800421
synthetic route 3
(1) compound (1-10-1A) is synthetic
In the there-necked flask of the 500mL with return line, thermometer and nitrogen ingress pipe, add the N of compound (1-10-1G), 0.23g palladium, 1.2g tri-(o-tolyl) phosphine, 56mL triethylamine, 8.2mL vinylformic acid and the 200mL of 39g, N-N,N-DIMETHYLACETAMIDE stirs and reacts for 3 hours at 120 DEG C.After reaction finishes, filter reaction mixture.In filtrate, add 1L ethyl acetate, the organic layer obtaining is successively by dilute hydrochloric acid washed twice and washing with water 3 times, with after dried over mgso, removal of solvent under reduced pressure, the solid of gained, by the mixed solvent recrystallization being formed by ethyl acetate and tetrahydrofuran (THF), obtains the crystallization of 19g compound (1-10-1A).
(2) compound (1-10-1B) is synthetic
In the there-necked flask of the 300mL with agitator, thermometer and nitrogen ingress pipe, add 3 of the above-mentioned synthetic compound of 19g (1-10-1A), 11g, the N of 5-dinitrobenzene benzyl chlorine, 21g salt of wormwood, 15g sodium iodide and 75mL, dinethylformamide reacts 8 hours at 60 DEG C.After reaction finishes, add 150mL chloroform in reaction mixture, the organic layer obtaining washes with water 3 times, then uses dried over mgso.Concentrated organic layer, reclaims the solid of separating out, and is used washing with alcohol, thereby obtains the pale yellow powder of 24g compound (1-10-1B).
(3) compound (1-10-1) is synthetic
In the there-necked flask of the 500mL with agitator, thermometer and nitrogen ingress pipe, add the above-mentioned synthetic compound of 24g (1-10-1B), 96g tin chloride dihydrate and 200mL ethyl acetate, reflux under 4 hours and react.After reaction finishes, reaction mixture washs successively with potassium fluoride aqueous solution and water.Organic layer dried over mgso, then concentrated after, by ethyl alcohol recrystallization, thereby obtain the faint yellow crystallization of 12g compound (1-10-1).
Synthesis example 1-4 (synthesizing of compound (1-16-1))
According to following synthetic route 4 synthetic compounds (1-16-1).
Figure BSA00000308305800441
synthetic route 4
(1) compound (1-16-1A) is synthetic
In the eggplant type flask of the 300mL with return line and nitrogen ingress pipe, add the DMF of 21g compound (1-16-1G), 80mL thionyl chloride and 0.1mL, at 80 DEG C, stir and react for 1 hour.After reaction finishes, from reaction mixture distillates unreacted thionyl chloride, add 150mL methylene dichloride by decompression, the organic layer obtaining washes with water 3 times.This organic layer is with after dried over mgso, and removal of solvent under reduced pressure, after temporary transient dry solidification, adds 400mL tetrahydrofuran (THF), obtains the solution that contains compound (1-16-1A).
(2) compound (1-16-1B) is synthetic
In the there-necked flask of the 1L with dropping funnel and thermometer, add 16g p-Coumaric Acid, 24g salt of wormwood, 0.87g Tetrabutylammonium bromide, 200mL water and 100mL tetrahydrofuran (THF), it is ice-cold to below 5 DEG C.Spend therein within 3 hours, drip whole amounts of the solution of the compound (1-16-1A) that contains above-mentioned preparation, then stir and react for 1 hour.Reaction finish after, in reaction mixture, add dilute hydrochloric acid, make pH be below 4 after, add 3L toluene and 1L tetrahydrofuran (THF), the organic layer obtaining washes with water 3 times.This organic layer is with after dried over mgso, removal of solvent under reduced pressure, and the solid of gained is by the mixed solvent recrystallization being formed by ethanol and tetrahydrofuran (THF), thereby obtains 21g compound (1-16-1B).
(3) compound (1-16-1C) is synthetic
In the there-necked flask of the 300mL with agitator, thermometer and nitrogen ingress pipe, add 3 of the above-mentioned synthetic compound of 21g (1-16-1B), 11g, the N of 5-dinitrobenzene benzyl chlorine, 21g salt of wormwood, 15g sodium iodide and 75mL, dinethylformamide reacts 8 hours at 60 DEG C.After reaction finishes, add 300mL chloroform in reaction mixture, the organic layer obtaining washes with water 3 times, then uses dried over mgso.Concentrated organic layer, reclaims the solid of separating out, and is used washing with alcohol, thereby obtains the pale yellow powder of 28g compound (1-16-1C).
(4) compound (1-16-1) is synthetic
In the there-necked flask of the 1L with agitator, thermometer and nitrogen ingress pipe, add the above-mentioned synthetic compound of 26g (1-16-1C), 96g tin chloride dihydrate and 200mL ethyl acetate, reflux under 4 hours and react.After reaction finishes, reaction mixture washs successively with potassium fluoride aqueous solution and water.Organic layer dried over mgso, then concentrated after, by ethyl alcohol recrystallization, thereby obtain the faint yellow crystallization of 12g compound (1-16-1).
Synthesis example 1-5
Except in above-mentioned synthesis example 1-4, use the compound shown in the following formula of 17g (1-16-2G) to replace compound (1-16-1G) in addition, and synthesis example 1-4 similarly carry out,
Figure BSA00000308305800461
Thereby obtain the compound shown in the following formula of 11g (1-16-2) (compound (1-16-2)).
Figure BSA00000308305800462
Synthesis example 1-6
According to following synthetic route 5, synthetic compound (1-6-1).
Figure BSA00000308305800471
synthetic route 5
(1) compound (1-6-1A) is synthetic
In the there-necked flask of the 2L with dropping funnel, nitrogen ingress pipe and thermometer, add 45.2g (0.2moL) 2,4-dinitrobenzene guanidine-acetic acid and 300mL dehydration tetrahydrofuran (THF), use dropping funnel to spend the tetrahydrofuran solution that more than 2 hours drips boron-tetrahydrofuran complex of 600mL concentration 1mol/L, then, at room temperature stir and react for 3 hours.After reaction finishes, in reaction mixture, slowly add after the water of 400mL, add again ethyl acetate, after the organic layer obtaining washes with water, by dried over mgso, removal of solvent under reduced pressure, after dry solidification, by using ethyl acetate: toluene=1: after 1 silicagel column as developing solvent is refining, then by the mixed solvent recrystallization being formed by ethyl acetate and hexane, thereby obtain 38g compound (1-6-1A).
(2) compound (1-6-1B) is synthetic
In the eggplant type flask of the 500mL with nitrogen ingress pipe, add the N of 30g compound obtained above (1-4-1A), 21g compound (1-6-1A), 1.2g, N-dimethyl aminopyridine, 200mL methylene dichloride and N-(3-dimethylaminopropyl)-N '-ethyl carbon imide hydrochloride, ice-cold lower stirring 1 hour, then at room temperature, carry out diel reaction.After reaction finishes, wash reaction mixture with water, with after dried over mgso, removal of solvent under reduced pressure, dry solidification, the solid the obtaining mixed solvent recrystallization being formed by ethyl acetate and hexane, thus obtain 45g compound (1-6-1B).
(3) compound (1-6-1) is synthetic
In the there-necked flask of the 1L with reflux condensing tube, thermometer and nitrogen ingress pipe, add the above-mentioned synthetic compound of 45g (1-6-1B), 203g tin chloride dihydrate and 500mL ethyl acetate, reflux under 4 hours and react.After reaction finishes, reaction mixture washs successively with potassium fluoride aqueous solution and water.Organic layer dried over mgso, then concentrated after, by the mixed solvent recrystallization being formed by ethanol and tetrahydrofuran (THF), thereby obtain the faint yellow crystallization of 18g compound (1-6-1).
Synthesis example 1-7
According to following synthetic route 6 synthetic compounds (1-6-2).
Figure BSA00000308305800491
synthetic route 6
(1) compound (1-6-2B) is synthetic
In the eggplant type flask of the 500mL with nitrogen ingress pipe, add (1-6-1A), the N of 1.2g that in 34g compound (1-6-2A), 21g and above-mentioned synthesis example 1-6, similarly synthesize, N-dimethyl aminopyridine, 200mL methylene dichloride and N-(3-dimethylaminopropyl)-N '-ethyl carbon imide hydrochloride, under ice-cooled, stir 1 hour, more at room temperature react diel.After reaction finishes, in reaction mixture, add water, separatory, the organic layer obtaining is with after dried over mgso, and removal of solvent under reduced pressure, obtains 49g compound (1-6-2B).
(3) compound (1-6-2) is synthetic
In the there-necked flask of the 1L with return line, thermometer and nitrogen ingress pipe, add the above-mentioned synthetic compound of 49g (1-6-2B), 203g tin chloride dihydrate and 500mL ethyl acetate, reflux under 4 hours and react.After reaction finishes, reaction mixture washs successively with potassium fluoride aqueous solution and water.The organic layer of gained is with after dried over mgso, removal of solvent under reduced pressure, and the solid of gained is by the mixed solvent recrystallization being formed by ethanol and tetrahydrofuran (THF), thereby obtains the faint yellow crystallization of 20g compound (1-6-2).
Synthesis example 1-8
According to following synthetic route 7, synthetic compound (1-41-1).
Figure BSA00000308305800501
synthetic route 7
(1) compound (1-41-1B) is synthetic
In the eggplant type flask of the 300mL with reflux condensing tube and nitrogen ingress pipe, add the DMF of 30g compound (1-4-1A), 100mL thionyl chloride and 0.1mL, at 80 DEG C, react 1 hour.After reaction finishes, from reaction mixture distillates unreacted thionyl chloride, add 150mL methylene dichloride by decompression, the organic layer obtaining washes with water 3 times.This organic layer is with after dried over mgso, and removal of solvent under reduced pressure, after temporary transient dry solidification, adds 200mL tetrahydrofuran (THF), obtains the solution of the reaction product that contains compound (1-4-1A) and thionyl chloride.
On the other hand, with the there-necked flask of above-mentioned different 500mL in, add 38g propylene glycol, 11g triethylamine, 50mL tetrahydrofuran (THF), ice-cold to below 5 DEG C.Then, slowly drip the solution that keeps 5 DEG C of following reaction product that contain above-claimed cpd (1-4-1A) and thionyl chloride, then, at room temperature further stir and react for 1 hour.After reaction finishes, in reaction mixture, add ethyl acetate, the organic layer obtaining is used successively to hydrochloric acid and the water washing of 1mol/L, then with after dried over mgso, removal of solvent under reduced pressure, the dry solidification thing obtaining, by refining as the silicagel column that launches reagent using the mixed solvent of ethyl acetate and hexane formation, except desolventizing, obtains 29g compound (1-41-1B) from this cut.
(3) (1-41-1C) synthetic
In the there-necked flask of the 300mL with thermometer and nitrogen ingress pipe, add 2 of 29g (1-41-1B) obtained above, 16g, 4-dinitrobenzene fluorobenzene and 16g triethylamine, at room temperature stir diel and react.After reaction finishes, in reaction mixture, add 1L ethyl acetate, the organic layer obtaining is washed once and washed with water 3 times with dilute hydrochloric acid successively, with after dried over mgso, removal of solvent under reduced pressure, the dry solidification thing ethyl alcohol recrystallization obtaining, thus 37g compound (1-41-1C) obtained.
(4) compound (1-41-1) is synthetic
In the there-necked flask of the 1L with return line, thermometer and nitrogen ingress pipe, add the above-mentioned synthetic compound of 37g (1-41-1C), 160g tin chloride dihydrate and 400mL ethyl acetate, reflux under 4 hours and react.After reaction finishes, reaction mixture washs successively with potassium fluoride aqueous solution and water.The organic layer of gained is with after dried over mgso, removal of solvent under reduced pressure, and the solid obtaining is from ethyl alcohol recrystallization, thereby obtains the faint yellow crystallization of 18g compound (1-41-1).
Synthesis example 1-9,1-10 and 1-11
According to following synthetic route 8, synthetic compound (1-29-1), (1-29-2) and (1-30-1).
Figure BSA00000308305800531
synthetic route 8
Synthesis example 1-9
(1) compound (1-29-1B) is synthetic
In the eggplant type flask of the 200mL with return line and nitrogen ingress pipe, the compound (1-4-1A) that adds 30g and above-mentioned synthesis example 1-1 similarly to obtain, the DMF of 40mL thionyl chloride and 0.1mL, refluxes and reacts for 1 hour.After reaction finishes, Depressor response mixture, removes low boilers, obtains white powder.This white powder is dissolved in 100mL tetrahydrofuran (THF), sets it as A liquid.
On the other hand, in the there-necked flask of the 500mL with dropping funnel and thermometer, add 1,3-PD, 100mL tetrahydrofuran (THF) and the 21mL triethylamine of 73mL, it is ice-cooled.Then, use dropping funnel to divide and within two hours, drip therein after above-mentioned A liquid, be returned to room temperature, then react two hours.After reaction finishes, in reaction mixture, add 600mL ethyl acetate, the organic layer obtaining is once washed after 3 times with water separatory with the washing of dilute hydrochloric acid separatory successively, by dried over mgso, decompression is lower to desolventizing, obtains the white solid of 34g compound (1-29-1B).
(2) compound (1-29-1C) is synthetic
In the there-necked flask of the 500mL with thermometer and nitrogen ingress pipe, add 2 of 27g above-claimed cpd (1-29-1B), 15g, 4-dinitrobenzene fluorobenzene, 100mL tetrahydrofuran (THF) and 21mL triethylamine react 9 hours at 40 DEG C.After reaction finishes, in reaction mixture, add 300mL ethyl acetate, the organic layer obtaining is once washed after 3 times with water separatory with the washing of dilute hydrochloric acid separatory successively, decompression is lower to desolventizing, the white solid washing with alcohol obtaining, thus the white powder of 33g compound (1-29-1C) obtained.
(3) compound (1-29-1) is synthetic
In the there-necked flask of the 1L with thermometer and nitrogen ingress pipe, add after 32g above-claimed cpd (1-29-1C), 76g zinc powder, 12.4g ammonium chloride, 200mL ethanol and 200mL tetrahydrofuran (THF), divide therein and within 1 hour, slowly add 35mL water, directly at room temperature react 5 hours.After reaction finishes, filter reaction mixture, in the filtrate obtaining, add 750mL ethyl acetate, the organic layer water separatory obtaining is washed after 3 times, add ethanol, obtain mixing solutions.This mixing solutions is under reduced pressure concentrated, reclaims the white crystals of separating out, and by washing with alcohol, obtains the white crystals of 25g compound (1-29-1).
Synthesis example 1-10
(1) compound (1-29-2B) is synthetic
Except in above-mentioned synthesis example 1-1 (1), use 4-(the 4-heptyl cyclohexyl) bromobenzene of 337g to replace beyond 4-(4-amyl group cyclohexyl) bromobenzene, with synthesis example 1-1 (1) similarly, obtain 163g compound (1-4-3A).
Then, by synthesis example 1-9 (1), use 29g compound obtained above (1-4-3A) to replace compound (1-4-1A), obtain 37g compound (1-29-2B).
(2) compound (1-29-2C) is synthetic
By in synthesis example 1-9 (2), use 29g compound obtained above (1-29-2B) to replace compound (1-29-1B), obtain 36g compound (1-29-2C).
(3) compound (1-29-2) is synthetic
By in synthesis example 1-9 (3), use 32g compound obtained above (1-29-2C) to replace compound (1-29-1C), obtain 26g compound (1-29-2).
Synthesis example 1-11
(1) compound (1-30-1B) is synthetic
By in synthesis example 1-9 (1), use 38g compound (1-10-1A) to replace compound (1-4-1A), obtain 42g compound (1-30-1B)
(2) compound (1-30-1C) is synthetic
By in synthesis example 1-9 (2), use 33g compound obtained above (1-30-1B) to replace compound (1-29-1B), obtain 39g compound (1-30-1C).
(3) compound (1-30-1) is synthetic
By in synthesis example 1-9 (3), use 37g compound obtained above (1-30-1C) to replace compound (1-29-1C), obtain 28g compound (1-30-1).
Relatively synthesis example 1
According to following synthetic route R1 synthetic compound (R-1).
Figure BSA00000308305800561
(1) compound (R-1A) is synthetic
In the eggplant type flask of 1L, add the METHYLPYRROLIDONE of 4-HBA methyl esters, 182.4g salt of wormwood and the 320mL of 91.3g, at room temperature stir after 1 hour, add the 1-bromo pentane of 99.7g, at 100 DEG C, stir and react for 5 hours.After reaction finishes, in reaction mixture, add water, again precipitation.Reclaim this precipitation, add 48g sodium hydroxide and 400mL water, reflux 3 hours, reaction is hydrolyzed.After reaction finishes, in reaction mixture, add hydrochloric acid neutralization, reclaim the precipitation generating, by from ethyl alcohol recrystallization, obtain the white crystals of 102g compound (R-1A).
(2) compound (R-1B) is synthetic
Pack the 52g in above-mentioned synthetic compound (R-1A) into reaction vessel, add therein the DMF of 100mL thionyl chloride and 0.2mL, at 80 DEG C, stir and react for 1 hour.Then, under reduced pressure, from reaction mixture distillates unreacted thionyl chloride, add methylene dichloride, the organic layer obtaining washs with saturated sodium bicarbonate aqueous solution, with after dried over mgso, concentrated, then adds tetrahydrofuran (THF), forms solution.
Then, with the there-necked flask of above-mentioned different 2L in, add 4-hydroxycinnamic acid, 69g salt of wormwood, 2.4g TBuA, 250mL tetrahydrofuran (THF) and the 500mL water of 37g.Ice-cooled this aqueous solution on one side, limit slowly drips above-mentioned tetrahydrofuran solution therein, then stirs and reacts for 2 hours.After reaction finishes, add hydrochloric acid neutralization in reaction mixture, be extracted with ethyl acetate, the organic layer obtaining is with after dried over mgso, and decompression is lower to desolventizing, and the solid obtaining, from ethyl alcohol recrystallization, obtains the white crystals of 45g mixture (R-1B).
(3) compound (R-1C) is synthetic
In the there-necked flask of the 500mL with agitator, thermometer and nitrogen ingress pipe, add 3 of the above-mentioned synthetic compound of 35g (R-1C), 22g, the DMF of 5-dinitrobenzene benzyl chlorine, 42g salt of wormwood, 30g sodium iodide and 150mL reacts 8 hours at 60 DEG C.After reaction finishes, add 300mL chloroform in reaction mixture, the organic layer obtaining washes with water 3 times, then uses dried over mgso.Concentrated organic layer, reclaims the solid of separating out, and is used washing with alcohol, thereby obtains the pale yellow powder of 45g compound (R-1C).
(4) compound (R-1) is synthetic
In the there-necked flask of the 1L with agitator, thermometer and nitrogen ingress pipe, add the above-mentioned synthetic compound of 45g (R-1C), 192g tin chloride dihydrate and 400mL ethyl acetate, reflux under 4 hours and react.After reaction finishes, reaction mixture washs successively with potassium fluoride aqueous solution and water.Organic layer is with after dried over mgso, removal of solvent under reduced pressure, and the solid obtaining is from ethyl alcohol recrystallization, thereby obtains the faint yellow crystallization of 22g compound (R-1).
Relatively synthesis example 2 (synthesizing of compound (R-2))
According to following synthetic route R2, synthetic compound (R-2).
Figure BSA00000308305800581
synthetic route R2
In the eggplant type flask of the 300mL with reflux condensing tube and nitrogen ingress pipe, add the DMF of 30g compound (1-4-1A), 100mL thionyl chloride and 0.1mL, at 80 DEG C, react 1 hour.After reaction finishes, from reaction mixture distillates unreacted thionyl chloride, add 150mL methylene dichloride by decompression, the organic layer obtaining washes with water 3 times.This organic layer is with after dried over mgso, and removal of solvent under reduced pressure, after temporary transient dry solidification, adds 200mL tetrahydrofuran (THF), obtains the solution of the reaction product that contains compound (1-4-1A) and thionyl chloride.
Then, with the there-necked flask of above-mentioned different 500mL in, add 13g methacrylic acid hydroxyethyl ester, 11g triethylamine and 50mL tetrahydrofuran (THF), ice-cold to below 5 DEG C.Then, slowly drip the solution that keeps 5 DEG C of following reaction product that contain above-claimed cpd (1-4-1A) and thionyl chloride, at room temperature react 1 hour.After reaction finishes, in reaction mixture, add ethyl acetate, the organic layer obtaining is used successively to hydrochloric acid and the water washing of 1M, with after dried over mgso, after removal of solvent under reduced pressure, by refining as the silicagel column that launches reagent using the mixed solvent of ethyl acetate and hexanaphthene formation, then reduce pressure and remove desolventizing from this cut, obtain the transparent thick liquid of 40g compound (R-2).
The synthetic > of < particular polymers
[synthesizing of polyamic acid]
Synthesis example CPA-1
Using 7.0g as tetracarboxylic anhydride 2,3, the synthetic compound (1-4-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-1 of 13g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-1).The soltion viscosity of this polyamic acid solution is 2,000mPas.
Synthesis example CPA-2
Using 6.9g as tetracarboxylic anhydride 2,3, the synthetic compound (1-6-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-6 of 13.1g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-2).The soltion viscosity of this polyamic acid solution is 1,800mPas.
Synthesis example CPA-3
Using 6.2g as tetracarboxylic anhydride 2,3, the synthetic compound (1-10-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-3 of 13.8g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-3).The soltion viscosity of this polyamic acid solution is 2,100mPas.
Synthesis example CPA-4
Using 5.9g as tetracarboxylic anhydride 2,3, the synthetic compound (1-16-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-4 of 14.1g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-4).The soltion viscosity of this polyamic acid solution is 2,200mPas.
Synthesis example CPA-5
Using 6.1g as tetracarboxylic anhydride 2,3, the synthetic compound (1-16-2) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-5 of 13.9g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-5).The soltion viscosity of this polyamic acid solution is 2,200mPas.
Synthesis example CPA-6
Using 6.4g as tetracarboxylic anhydride 2,3, the synthetic compound (1-22-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-2 of 13.6g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-6).The soltion viscosity of this polyamic acid solution is 2,100mPas.
Synthesis example CPA-7
Using 6.8g as tetracarboxylic anhydride 2,3, the synthetic compound (1-6-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-6 of 12.4g is (with respect to the TCA of 1mol, be equivalent to 0.95mol) and the above-mentioned formula of 0.8g (D-10) shown in compound, be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-7).The soltion viscosity of this polyamic acid solution is 1,900mPas.
Synthesis example CPA-8
Using 6.4g as tetracarboxylic anhydride 2,3, the synthetic compound (1-6-2) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-7 of 13.6g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-8).The soltion viscosity of this polyamic acid solution is 1,700mPas.
Synthesis example CPA-9
Using 6.5g as tetracarboxylic anhydride 2,3, the synthetic compound (1-41-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-8 of 13.5g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-9).The soltion viscosity of this polyamic acid solution is 2,300mPas.
Synthesis example CPA-10
Using 6.5g as tetracarboxylic anhydride 2,3, the synthetic compound (1-29-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-9 of 14g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-10).The soltion viscosity of this polyamic acid solution is 2,200mPas.
Synthesis example CPA-11
Using 6.3g as tetracarboxylic anhydride 2,3, the synthetic compound (1-29-2) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-10 of 14g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-11).The soltion viscosity of this polyamic acid solution is 2,100mPas.
Synthesis example CPA-12
Using 5.8g as tetracarboxylic anhydride 2,3, the synthetic compound (1-30-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-11 of 14g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids (CPA-12).The soltion viscosity of this polyamic acid solution is 2,000mPas.
[synthesizing of polyimide]
Synthesis example CPI-1
Using 2.4g as tetracarboxylic anhydride 2,3, the synthetic compound (1-4-1) of 5-tricarboxylic base NSC 60134 dianhydride (TCA) and the above-mentioned synthesis example 1-1 of 4.6g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 28g, at 60 DEG C, react 4 hours, obtain the solution that contains 20 % by weight polyamic acids.The soltion viscosity of this polyamic acid solution is 2,000mPas.
Then, in above-mentioned polyamic acid solution, add METHYLPYRROLIDONE, 0.9g pyridine and the 1.0g diacetyl oxide of 65g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, intrasystem solvent carries out solvent exchange with new METHYLPYRROLIDONE and (operates by this solvent exchange, by the pyridine using in dehydration closed-loop reaction and diacetyl oxide except going to system), thereby obtain the solution of the polyimide (CPI-1) that about 45g contains 15 % by weight imide rates approximately 47%.
Get this polyimide solution for a small amount of point, after removal of solvent under reduced pressure, be dissolved in gamma-butyrolactone, to the solution of polymer concentration 8.0 % by weight that form, the soltion viscosity of measuring at 25 DEG C is 24mPas.
The synthetic > of other polymkeric substance of <
[synthesizing of other polyamic acid]
Synthesis example PA-1
Using all benzene tertacarbonic acid's dianhydride and the 98g (0.50mol) 1 of 109g (0.50mol) as tetracarboxylic dianhydride, 2,3,4-encircles butanetetra-carboxylic acid dianhydride and the 200g (1.0mol) 4 as diamines, 4-diamino-diphenyl ether, be dissolved in the METHYLPYRROLIDONE of 2,290g, at 40 DEG C, react after 3 hours, append 1, the METHYLPYRROLIDONE of 350g, obtains approximately 3, the solution that 590g contains 10 % by weight polyamic acids (PA-1).The soltion viscosity of this polyamic acid solution is 210mPas.
Synthesis example PA-2
Using the 98g (0.50mol) 1 as tetracarboxylic dianhydride, 2,3,4-ring butanetetra-carboxylic acid dianhydride and 109g (0.50mol) be benzene tertacarbonic acid's dianhydride and the 198g (1.0mol) 4 as diamines all, 4 '-diaminodiphenyl-methane, be dissolved into 2, in the METHYLPYRROLIDONE of 290g, at 40 DEG C, react after 3 hours, append 1, the METHYLPYRROLIDONE of 350g, obtains the solution that contains 10 % by weight polyamic acids (PA-2).The soltion viscosity of this polyamic acid solution is 135mPas.
Synthesis example PA-3
Using the 196g (1.0mol) 1 as tetracarboxylic dianhydride, 2,3,4-encircles butanetetra-carboxylic acid dianhydride and the 200g (1.0mol) 4 as diamines, 4 '-diamino-diphenyl ether, be dissolved into 2, in the METHYLPYRROLIDONE of 246g, at 40 DEG C, react after 4 hours, append 1, the METHYLPYRROLIDONE of 321g, obtains the solution that contains 10 % by weight polyamic acids (PA-3).The soltion viscosity of this polyamic acid solution is 220mPas.
Synthesis example PA-4
Using the 196g (1.0mol) 1 as tetracarboxylic dianhydride, 2,3,4-encircles butanetetra-carboxylic acid dianhydride and the 212g (1.0mol) 2 as diamines, 2 '-dimethyl-4,4 '-benzidine, be dissolved into 3, in the METHYLPYRROLIDONE of 670g, at 40 DEG C, react after 3 hours, obtain the solution that contains 10 % by weight polyamic acids (PA-4).The soltion viscosity of this polyamic acid solution is 170mPas.
Synthesis example PA-5
Using the 224g (1.0mol) 2 as tetracarboxylic dianhydride, 3,5-tricarboxylic base NSC 60134 dianhydride and as the 200g (1.0mol) 4 of diamines, 4 '-diamino-diphenyl ether, be dissolved into 2, in the METHYLPYRROLIDONE of 404g, at 40 DEG C, react after 4 hours, obtain the solution that contains polyamic acid (PA-5).Get this polyamic acid solution for a small amount of point, add METHYLPYRROLIDONE, form the solution of concentration 10 % by weight, the soltion viscosity of mensuration is 190mPas.
Synthesis example PA-6
Using as 2 of tetracarboxylic dianhydride's 6.5g, 3, the above-mentioned synthetic compound (R-1) of synthesis example 1 that compares of 5-tricarboxylic base NSC 60134 dianhydride and 13.5g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the METHYLPYRROLIDONE of 80g, at 60 DEG C, react after 4 hours, obtain the solution that contains 20 % by weight polyamic acids (PA-6).The soltion viscosity of this polyamic acid solution is 2,000mPas.
[synthesizing of polymethacrylate]
Synthesis example PMA-1
Being equipped with in the four-hole boiling flask of stirring rod, T-valve and thermometer, add the above-mentioned compound (R-2) that relatively synthesis example 2 obtain of 10g as monomer, then add 20g as the glycol ether ethyl-methyl ether of solvent, 0.5g as 2 of polymerization starter, 2 '-azo two (2,4-methyl pentane nitrile) and 0.2g are as the α-methylstyrenedimer of molecular weight regulator.It is seethed with excitement in nitrogen gas stream approximately 10 minutes, by after nitrogen replacement in system, under nitrogen environment, at 70 DEG C, react 5 hours, thereby obtain the solution that contains 32 % by weight polymkeric substance (PMA-1).To polymkeric substance (PMA-1) by the gel permeation chromatography (GPC) of following condition, measure weight-average molecular weight (Mw), the number-average molecular weight (Mn) of polystyrene conversion, trying to achieve molecular weight distribution (Mw/Mn) is, Mw=24,000, Mw/Mn=2.4, does not have to find the peak from residual monomer.
" HLC-8020 " that GPC determinator: East ソ mono-(strain) manufactures
Post TSK guardcolum α, TSK gel α-M and TSK gel α-2500 that post: manufactures East ソ mono-(strain) are connected in series use
Solvent: 3L dimethyl formamide is dissolved to the solution of 9.4g lithiumbromide monohydrate and 1.7g phosphoric acid, measure temperature: 35 DEG C
Reference material: monodisperse polystyrene
The preparation of < liquid crystal aligning agent and evaluation >
Embodiment 1
[preparation of liquid crystal aligning agent]
(1) preparation of liquid crystal aligning agent for printing evaluation
Using the solution that contains polyamic acid (CPA-1) obtaining as the above-mentioned synthesis example CPA-1 of particular polymers and the solution that contains polyamic acid (PA-1) that obtains as the above-mentioned synthesis example PA-1 of other polymkeric substance, taking the ratio of the amount of the polymkeric substance that contains in them as CPA-1: PA-1=20: 80 (weight ratio) mixes, then add METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (B C), form solvent composition NMP: B C=50: 50 (weight ratios), solid component concentration is the solution of 7 % by weight.This solution uses the strainer of aperture 1 μ m to filter, preparation printing liquid crystal aligning agent (P-1) for evaluation.
(2) preparation of liquid crystal aligning agent for liquid crystal display device manufacture
Except in the time that liquid crystal aligning agent is used in the above-mentioned printing evaluation of preparation, making solid component concentration is beyond 4 % by weight, similarly carry out with the preparation of liquid crystal aligning agent with above-mentioned printing evaluation, prepare liquid crystal display device liquid crystal aligning agent (A-1) for manufacture.
[evaluation of liquid crystal aligning agent]
Use two kinds of liquid crystal aligning agent of above-mentioned preparation, evaluate as follows.Evaluation result represents in table 2.
I. the evaluation of printing
Use liquid crystal orientation film printing press (Japan's description prints (strain) and manufactures), the printing that applies above-mentioned preparation on the transparent electrical pole-face of the glass substrate with by the film formed transparency electrode of ITO liquid crystal aligning agent (P-1) for evaluation, heating (prebake) 1 minute at 80 DEG C, except after desolventizing, at 200 DEG C, heat 60 minutes (curing afterwards), thereby form the film of thickness 60nm.To this film, by the microscopic examination of visual observation and 2.5 times of multiplying powers, research has or not printing spot and pin hole.Wherein, under visual observation and microscopic examination both of these case, the situation of all not observing printing spot and pin hole this two is evaluated as printing " good ";
When visual observation, all do not observe printing spot and pin hole the two, but when microscopic examination, observe at least one the situation in printing spot and pin hole, be evaluated as printing " well ";
By visual observation, observe at least one the situation in printing spot and pin hole, be evaluated as printing " bad ".
II. the manufacture of liquid crystal display device and evaluation
(1) manufacture of liquid crystal display device
On the transparent electrical pole-face of the glass substrate with by the film formed transparency electrode of ITO, pass through spin-coating method, the liquid crystal display device that is coated with above-mentioned preparation liquid crystal aligning agent (A-1) for manufacture, on the hot plate of 80 DEG C, after prebake 1 minute, in case in nitrogen replacement baking oven, at 200 DEG C, heat 1 hour, form the film of thickness 0.1 μ m.Then, on the surface of this film, use Hg-Xe lamp and Glan-Taylor prism, from the direction of 40 ° of substrate normal inclinations, irradiate the polarisation ultraviolet ray 200J/m of the bright line that contains wavelength 313nm 2, form liquid crystal orientation film.Repeat identical operation, manufacture a pair of (two) and have the substrate of liquid crystal orientation film.
The periphery of the face with liquid crystal orientation film of in aforesaid substrate, apply by silk screen printing after the epoxy resin binder of the alumina balls that added diameter 5.5 μ m, the liquid crystal orientation film of a pair of substrate is faced to configuration, crimping is so that the ultraviolet optical axis of each substrate, toward the projecting direction antiparallel of real estate, spends 1 hour by tackiness agent thermofixation at 150 DEG C.Then,, from liquid crystal injecting port, in the gap between substrate, fill after negative type liquid crystal (メ ルク company manufactures, MLC-6608), by epoxy adhesive encapsulated liquid crystals inlet.Then, the flow orientation when removing Liquid crystal pour, is heated after 150 DEG C, and Slow cooling is to room temperature.
Then, at the each outer side laminating polaroid of two substrates so that its polarization direction is mutually orthogonal, and and the ultraviolet optical axis of liquid crystal orientation film toward the direction of illumination shape of real estate angle at 45 °, manufacture liquid crystal display device.
(2) evaluation of liquid crystal display device
(2-1) evaluation of liquid crystal aligning
To the liquid crystal display device of above-mentioned manufacture, by observation by light microscope during at room temperature by 5V voltage ONOFF (applying releasing), the abnormal area that has or not light and shade to change.The situation of not observing abnormal area is evaluated as to liquid crystal aligning agent (vertical orientated property) " well ".
(2-2) evaluation of tilt angle
To the liquid crystal display device of above-mentioned manufacture respectively according to non-patent literature 1 (T.J.Scheffer et.al.J.Appl.Phys., vol.48, p1789 (1977)) and non-patent literature 2 (F.Nakano et.al.JPN.J.Appl.Phys., vol.19, p2013 (1980)) the middle method of recording, by using the crystallization rotational method of He-Ne laser, measure tilt angle.
(2-3) evaluation of voltage retention
To the liquid crystal display device of above-mentioned manufacture, in the envrionment temperature of 60 DEG C, apply after the voltage of 5V with the application time of 60 microseconds, the interval of 167 milliseconds, measure the voltage retention being applied to 167 milliseconds from removing.The model " VHR-1 " that determinator Shi Yong East Yang テ Network ニ カ Co., Ltd. manufactures.
(2-4) evaluation of High Temperature Pre inclination angle stability
The liquid crystal display device of above-mentioned manufacture is taken care of after 30 days at 70 DEG C, and above-mentioned (2-2) similarly, again measures tilt angle.To this measured value, in the time that the variable quantity from initial value is less than 1 °, be " well " by High Temperature Pre inclination angle estimation of stability, being when more than 1 °, High Temperature Pre inclination angle estimation of stability is " bad ".
Embodiment 2～16 and 18～21
Except in above-described embodiment 1, beyond the kind of particular polymers and other polymkeric substance and amount are respectively as expression 1 records, with embodiment 1 similarly, prepare respectively printing liquid crystal aligning agent (P-2) for evaluation～(P-16) and (P-18)～(P-21) and liquid crystal display device liquid crystal aligning agent (A-2) manufacture for～(A-16) with (A-18)～(A-21), evaluate.In addition, in embodiment 13, do not use other polymkeric substance, only use particular polymers.
Evaluation result is as shown in table 2.
Embodiment 17
Except in above-described embodiment 1, add after METHYLPYRROLIDONE and ethylene glycol butyl ether, then add 20 weight parts as beyond the compound shown in the following formula (E-1) of epoxy compounds,
Figure BSA00000308305800681
With embodiment 1 similarly, prepare respectively printing liquid crystal aligning agent (P-17) and liquid crystal display device liquid crystal aligning agent (A-17) for manufacture for evaluation, evaluate.
Evaluation result is as shown in table 2.
Comparative example 1
Except in above-described embodiment 1, do not use particular polymers, use beyond two kinds of other polymkeric substance shown in table 1, with embodiment 1 similarly, prepare respectively printing for evaluation liquid crystal aligning agent (RP-1) and liquid crystal display device for manufacture liquid crystal aligning agent (RA-1) evaluate.
Evaluation result is as shown in table 2.
Comparative example 2
In the solution that contains the above-mentioned relatively polymethacrylate (PMA-1) that synthesis example PMA-1 obtains, add N-methyl isophthalic acid-pyrrolidone (NMP) and ethylene glycol butyl ether, the printing of preparing respectively solvent composition NMP/ ethylene glycol butyl ether/gamma-butyrolactone/glycol ether ethyl-methyl ether=23/50/25/2 (weight ratio), the solid component concentration 7.0 % by weight liquid crystal display device that for evaluation, liquid crystal aligning agent (RP-2) and solid component concentration are 3.5% liquid crystal aligning agent (RA-2) for manufacture, evaluates.Evaluation result is as shown in table 2.
[table 1]
Figure BSA00000308305800691
[table 2]
Figure BSA00000308305800701

Claims (6)

1. a liquid crystal aligning agent, it is characterized in that: contain at least one polymkeric substance of selecting in the group being formed by polyamic acid and polyimide, wherein, aforementioned polymer has the group shown in following formula (0) in its intramolecular at least a portion side chain
Figure FDA0000465244320000011
In formula (0), R ithat carbonatoms is the fluoro-alkyl that 3～12 alkyl or carbonatoms are 3～12, X isingly-bound or Sauerstoffatom, R iIisosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, X iIbe singly-bound, Sauerstoffatom or *-COO-, wherein, connecting key and the R of band " * " iIconnect, n is 0 or 1, X iIIfollowing formula (X iII-1) group shown in,
Figure FDA0000465244320000012
2. the liquid crystal aligning agent of recording according to claim 1, wherein aforementioned polymer is at least one polymkeric substance of selecting the group that forms of the polyamic acid from being obtained by tetracarboxylic dianhydride and diamine reactant and polyimide that this polyamic acid dehydration closed-loop is formed, this diamines comprises the compound shown in following formula (1)
Figure FDA0000465244320000013
In formula (1), R i, X i, R iI, X iI, X iIIidentical with the definition in the formula described in claim 1 (0) respectively with n, R iIIbe that singly-bound, methylene radical or carbonatoms are 2～6 alkylidene group, wherein this alkylidene group can be replaced by hydroxyl, X iVbe singly-bound, Sauerstoffatom or *-OCO-, wherein, connecting key and the R of band " * " iIIconnect, wherein, R iIIx while being singly-bound iVit is singly-bound.
3. a liquid crystal display device, is characterized in that: have the liquid crystal orientation film that the liquid crystal aligning agent recorded by claim 1 or 2 forms.
4. a polyamic acid, this polyamic acid is obtained by tetracarboxylic dianhydride and the diamine reactant that comprises the compound shown in the formula described in claim 2 (1).
5. a polyimide, this polyimide is to be formed with the polyamic acid dehydration closed-loop that the diamine reactant that comprises the compound shown in the formula described in claim 2 (1) obtains by tetracarboxylic dianhydride.
6. the compound shown in the formula described in claim 2 (1).
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JP5668907B2 (en) * 2009-12-25 2015-02-12 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
KR101831008B1 (en) * 2010-07-05 2018-02-21 닛산 가가쿠 고교 가부시키 가이샤 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same
KR101333710B1 (en) * 2011-05-11 2013-11-27 제일모직주식회사 Liquid　crystal alignment　agent, liquid　crystal alignment film manufactured using the same, and liquid　crystal display device including the liquid　crystal alignment film
CN104350418B (en) * 2012-03-21 2017-05-03 日产化学工业株式会社 Liquid-crystal alignment agent, liquid-crystal alignment film, and liquid-crystal display element
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CN110803990B (en) * 2018-08-04 2023-08-08 石家庄诚志永华显示材料有限公司 Compound, liquid crystal composition, liquid crystal display element and liquid crystal display
JP2020173424A (en) * 2019-04-08 2020-10-22 Jsr株式会社 Liquid crystal element, manufacturing method therefor, and liquid crystal composition
WO2023085390A1 (en) * 2021-11-12 2023-05-19 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000250047A (en) * 1999-03-03 2000-09-14 Jsr Corp Liquid crystal aligning agent
EP0683418B1 (en) * 1994-05-17 2003-07-16 JSR Corporation Liquid crystal aligning agent and liquid crystal display device
JP2007191447A (en) * 2006-01-20 2007-08-02 Jsr Corp New diamine compound and method for producing the same
WO2009051207A1 (en) * 2007-10-19 2009-04-23 Jsr Corporation Liquid crystal-aligning agent, and method for production of liquid crystal alignment film
WO2009054545A1 (en) * 2007-10-26 2009-04-30 Jsr Corporation Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101235412B1 (en) * 2004-12-28 2013-02-20 닛산 가가쿠 고교 가부시키 가이샤 Liquid-crystal alignment material for vertical alignment, liquid-crystal alignment film, and liquid-crystal display element employing the same
JP4775796B2 (en) * 2006-03-14 2011-09-21 独立行政法人物質・材料研究機構 Liquid crystal alignment film, liquid crystal alignment agent, and liquid crystal display element
JP5057056B2 (en) 2007-08-03 2012-10-24 Ｊｓｒ株式会社 Liquid crystal aligning agent, method for producing liquid crystal aligning film, polyamic acid, polyimide and diamine compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0683418B1 (en) * 1994-05-17 2003-07-16 JSR Corporation Liquid crystal aligning agent and liquid crystal display device
JP2000250047A (en) * 1999-03-03 2000-09-14 Jsr Corp Liquid crystal aligning agent
JP2007191447A (en) * 2006-01-20 2007-08-02 Jsr Corp New diamine compound and method for producing the same
WO2009051207A1 (en) * 2007-10-19 2009-04-23 Jsr Corporation Liquid crystal-aligning agent, and method for production of liquid crystal alignment film
WO2009054545A1 (en) * 2007-10-26 2009-04-30 Jsr Corporation Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device

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