CN102031122A - 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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CN102031122A
CN102031122A CN2010105101157A CN201010510115A CN102031122A CN 102031122 A CN102031122 A CN 102031122A CN 2010105101157 A CN2010105101157 A CN 2010105101157A CN 201010510115 A CN201010510115 A CN 201010510115A CN 102031122 A CN102031122 A CN 102031122A
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liquid crystal
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polyamic acid
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CN102031122B (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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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

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Abstract

The invention discloses a liquid crystal orientation agent, a liquid crystal display element, polyamide acids, polyimides, and a compound. The liquid crystal orientation agent can provide an excellent electrical property, possesses a liquid crystal orientation film which allows no deterioration of liquid crystal orientation property even under high temperature and long time usage and an excellent printing property. The liquid crystal orientation agent includes at least one kind of polymers selected from a group constituted by polyamide acids and polyimides, wherein the said polymer internally contains in at least one portion of its molecule a group expressed by the following formula (0). In formula (0), R1 is alkyl with a carbon atomicity ranging from 3 to 12 or fluoro alkyl with a carbon atomicity ranging from 3 to 12, X1 being a singly-bound or an oxygen atom, RII beign 1, 4-cyclohexylene or 1, 4-phenylene, XII being a singly-bound, an oxygen atom or * -COO-(wherein, a connection key with * is connected to RII), n being 0 or 1, XIII being a group expressed by the following formula (XIII-I) or (XIII-2). -CH=CH-(XIII-1)-C C-(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
A kind of as the liquid crystal display device operation scheme is known that to make liquid crystal molecule vertical orientated vertical (Homeotropic) the aligned liquid crystal display device on substrate with negative dielectric anisotropy.This operation scheme applies voltage between substrate, make liquid crystal molecule when the direction parallel with substrate tilts, and must make liquid crystal molecule from the direction inclination (formation tilt angle) of substrate normal direction in real estate.As the means of this use, proposed for example to be provided with the method for projection at substrate surface; The method of striped is set on transparency electrode; By using the friction orientation film, with liquid crystal molecule from the substrate normal direction, the method for the direction slight inclination 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 manufacturing, but pass through life-time service, also have the liquid crystal aligning performance problem of variation gradually, pointed out that particularly this trend of the liquid crystal display device that uses is obvious under hot conditions.
In addition, along with the progress of the digitizing of television transmission and height dynamic menu technique for fixing, in recent years the height of view data become more meticulous, high-qualityization fast development.In order correctly to reproduce this view data, demonstrate exquisite picture, the requirement of the electrical property of liquid crystal cell, particularly voltage retention is compared higher and very strict with present liquid crystal cell.In addition, in order not only will to improve the productive rate of product, and will help 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 purpose is to provide a kind of liquid crystal aligning agent, and this liquid crystal aligning agent can provide the electrical property excellence, even under hot conditions, use for a long time, 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 provides the electrical property excellence, even under hot conditions, use for a long time, and the manufacture method of the liquid crystal orientation film that the liquid crystal aligning performance can variation yet.
Another purpose of the present invention provides the display performance excellence, even under hot conditions, use for a long time, and the liquid crystal display device that display performance can variation yet.
According to the present invention, above-mentioned purpose of the present invention and advantage, the firstth, realize by a kind of liquid crystal aligning agent, this liquid crystal aligning agent contains at least a polymkeric substance of selecting in the group that is made of polyamic acid and polyimide, wherein, aforementioned polymer has the group shown in the following formula (0) in its intramolecular at least a portion
Figure BSA00000308305800031
In the formula (0), R IBe that carbonatoms is that 3～12 alkyl or carbonatoms are 3～12 fluoro-alkyl, X IBe singly-bound or Sauerstoffatom, R IIBe 1,4-cyclohexylidene or 1,4-phenylene, X IIBe singly-bound, Sauerstoffatom or *-COO-(wherein, the connecting key and the R of band " * " IIConnect), n is 0 or 1, X IIIBe following formula (X III-1) or (X III-2) group shown in.
-CH＝CH-(X III-1)
-C≡C-(X III-2)
Above-mentioned purpose of the present invention and advantage, the secondth, realize that by a kind of liquid crystal display device this liquid crystal display device has the liquid crystal orientation film that is 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 the electrical property excellence, even under hot conditions, use for a long time, the liquid crystal orientation film that the liquid crystal aligning performance can variation yet; And the printing excellence of this liquid crystal aligning agent.Liquid crystal display device with the liquid crystal orientation film that forms by this liquid crystal aligning agent, the display performance excellence, even and under hot conditions, use for a long time, 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 a polymkeric substance of selecting in the group that is made of polyamic acid and polyimide, and wherein aforementioned polymer has the group shown in the 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 the following formula (0) may reside in the main chain of polymkeric substance, also may reside in the side chain of polymkeric substance, perhaps can be present in simultaneously in the main chain and side chain of polymkeric substance.
As the R in the above-mentioned formula (0) I, be preferably carbonatoms and be 3～7 alkyl, perhaps carbonatoms be 3～7 and number of fluorine atoms be 3～5 fluoro-alkyl.As preferred R IObject lesson, can list for example n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, 4,4,4-three fluoro bases, 4,4,5,5,5-five fluorine amyl groups etc. among them, are preferably n-propyl, normal-butyl, n-pentyl, n-hexyl or n-heptyl especially.
As the X in the following formula (0) IBe preferably singly-bound;
As R II, be preferably 1, the 4-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, preferred especially above-mentioned formula (X III-1) the two keys of the C-C in are trans.In the following formula (0) 1, the 4-cyclohexylidene is preferably formed the chair form structure.
By containing the liquid crystal orientation film that this liquid crystal aligning agent of the present invention with particular polymers with the group shown in the above-mentioned formula (0) of rigidity liquid crystal unit structure forms, its electrical property excellence, even when using 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 the aforesaid above-mentioned formula (0), can perhaps obtain with the diamine reactant that comprises compound by for example comprising the tetracarboxylic dianhydride and the diamine reactant of compound with the group shown in the above-mentioned formula (0) and two acid anhydrides with the group shown in the above-mentioned formula (0) and two amino by the tetracarboxylic dianhydride;
Have the polyimide of the group shown in the above-mentioned formula (0) in intramolecular at least a portion, for example can obtain by the polyamic acid dehydration closed-loop that will as above obtain.
Be preferably at least a polymkeric substance of selecting in the group that is made of polyamic acid and polyimide that this polyamic acid dehydration closed-loop is formed as the particular polymers that contains in the liquid crystal aligning agent of the present invention, wherein this polyamic acid is that tetracarboxylic dianhydride and the diamine reactant that comprises the compound with the group shown in the above-mentioned formula (0) and two amino are obtained.
＜polyamic acid 〉
As implied above, preferred polyamic acid is that tetracarboxylic dianhydride and the diamine reactant that comprises the compound with the group shown in the above-mentioned formula (0) and two amino are obtained among the present invention.
[tetracarboxylic dianhydride]
Tetracarboxylic dianhydride as synthetic above-mentioned polyamic acid uses 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 basic ring amyl group acetate dianhydride, 3,5,6-three carboxyl norbornane bases-2-acetate dianhydride, 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, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2, the 5-dioxotetrahydrofuryl)-and 3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, two ring [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] suffering-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0 2,6] 11 carbon-3,5,8,10-tetraketone, following formula (T-I) and aliphatics tetracarboxylic dianhydride and the ester ring type tetracarboxylic dianhydrides such as compound that (T-II) represent respectively;
Figure BSA00000308305800061
In the above-mentioned formula, R 1And R 3Be respectively divalent organic group with aromatic ring, R 2And R 4Be respectively hydrogen atom or alkyl, the R of a plurality of existence 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, 1,4,5,8-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 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-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-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol-two (trihemellitic acid acid anhydride), propylene glycol-two (trihemellitic acid acid anhydride), 1,4-butyleneglycol-two (trihemellitic acid acid anhydride), 1,6-hexylene glycol-two (trihemellitic acid acid anhydride), 1,8-ethohexadiol-two (trihemellitic acid acid anhydride), 2,2-two (4-hydroxy phenyl) propane-two (trihemellitic acid acid anhydride), aromatic tetracarboxylic acid's dianhydrides such as compound that following formula (T-1)～(T-4) is represented respectively.
Figure BSA00000308305800071
Figure BSA00000308305800081
They can be used alone, or make up two or more uses.
The tetracarboxylic dianhydride who is used for the preferred polyamic acid of synthetic the present invention shows the viewpoint of better liquid crystal aligning from the liquid crystal orientation film that makes formation, preferably comprises the butanetetra-carboxylic acid dianhydride that is selected from by in 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 basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, two ring [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] suffering-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [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, 1,4,5, in the compound shown in 8-naphthalene tetracarboxylic acid dianhydride, the above-mentioned formula (T-I), the compound that following formula (T-5)～(T-7) is represented respectively
In the compound shown in the above-mentioned formula (T-II), at least a (below, be called " specific tetracarboxylic dianhydride ") of the group that compound shown in the following formula (T-8) constitutes.
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 basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] suffering-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-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0 2,6] 11 carbon-3,5,8, the group that compound shown in 10-tetraketone, pyromellitic acid dianhydride and the above-mentioned formula (T-5) constitutes at least a, preferred especially 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride.
Be used for the tetracarboxylic dianhydride of the preferred polyamic acid of synthetic the present invention,, preferably contain more than the 20mol%, more preferably contain more than the 50mol%, especially preferably contain as above specific tetracarboxylic dianhydride more than the 80mol% with respect to whole tetracarboxylic dianhydrides.
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]
Being used for the diamines of the preferred polyamic acid of synthetic the present invention, is the diamines that comprises the compound with the group shown in the above-mentioned formula (0) and two amino.As the preferred example of this compound, can list the compound shown in for example following formula (1) etc.
In the formula (1), R I, X I, R II, X II, X IIIIdentical with the definition in the 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 IIIWhen being singly-bound, X IVIt is singly-bound.
As the X in the following formula (1) IVBe preferably singly-bound.Two amino in the diamino-phenyl of above-mentioned formula (1) are preferably 2 with respect to other group, 4-position, 2,5-position or 3,5-position.
As the preferred example of the compound shown in the above-mentioned formula (1), can list compound that for example following formula (1-1)～(1-41) represents respectively etc.
Figure BSA00000308305800111
Figure BSA00000308305800121
Figure BSA00000308305800131
Figure BSA00000308305800151
Figure BSA00000308305800161
In the formula (1-1)～(1-41), R IIdentical with the definition in the above-mentioned formula (1), m is 1～6 integer, R III-1It is propylene.In the 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 the compound of (1-30) representing respectively, further preferred above-mentioned formula (1-4)～(1-6), (1-12), (1-18), (1-29) and the compound of (1-30) representing respectively, the compound shown in the preferred especially above-mentioned formula (1-6).
Compound shown in the above-mentioned formula (1) can be synthetic by the vitochemical ordinary method of appropriate combination.
For example, in the following formula (1), R IIIBe methylene radical, X IIIBe above-mentioned formula (X III-1) group shown in, X IVBe single bonded compound, for example can preferably in the presence of salt of wormwood, react by with compound shown in the following formula (1-A) and dinitrobenzene benzyl chlorine, after obtaining the dinitrobenzene thing, use suitable reduction system,, form amino and obtain the nitroreduction (hydrogenation) of this dinitrobenzene thing.
Figure BSA00000308305800171
(in the formula (1-A), R I, X I, R II, X IIIdentical with the definition in the above-mentioned formula (1) respectively with n)
In the above-mentioned formula (1), R IIIBe ethylene, X IIIBe above-mentioned formula (X III-1) group shown in, X IVBe that single bonded compound for example can pass through compound shown in the above-mentioned formula (1-A) and thionyl chloride reaction, behind the formation acyl chlorides, in following formula (1-B), R IIIBe ethylene, X is the compound reaction of hydroxyl, obtain the dinitrobenzene thing after, uses suitable reduction system, with the nitroreduction (hydrogenation) of this dinitrobenzene thing, formation amino obtains.
Figure BSA00000308305800172
In the above-mentioned formula (1), R IIIBe singly-bound, X IIIBe above-mentioned formula (X III-1) group shown in, X IVBe single bonded compound, for example can pass through with compound shown in the above-mentioned formula (1-A) and thionyl chloride reaction, behind the formation acyl chlorides, with dinitrophenol(DNP) reaction, obtain the dinitrobenzene thing after, use suitable reduction system, with the nitroreduction (hydrogenation) of this dinitrobenzene thing, form amino and obtain.
In the above-mentioned formula (1), R IIIBe ethylene, X IIIBe above-mentioned formula (X III-1) group shown in, X IVBe *-OCO-(wherein, be with " *" connecting key and R IIIConnect) compound, for example can be by making the reaction of compound shown in the following formula (1-C) and dinitrobenzoyl chloride, obtain the dinitrobenzene thing after, uses suitable reduction system, with the nitroreduction (hydrogenation) of this dinitrobenzene thing, formation amino obtains.
Figure BSA00000308305800181
In the formula (1-C), R I, X I, R II, X IIIdentical with the definition in the above-mentioned formula (1) respectively with n.
In addition, by using in the above-mentioned formula (1-C), the methylene radical apparatus has the group-(CH of desirable m value 2) mThe compound of-replacement can obtain corresponding desirable compound.
In the above-mentioned formula (1), R IIIBe methylene radical or alkylidene group, X IIIBe above-mentioned formula (X III-1) group shown in, X IVBe the compound of Sauerstoffatom, for example can pass through with compound shown in the above-mentioned formula (1-A) and thionyl chloride reaction, behind the formation acyl chlorides, as R IIIHas the compound reaction of hydroxyl respectively with two ends at desirable methylene radical or alkylidene group, form monohydroxy-alcohol, then with this monohydroxy-alcohol and the reaction of fluorodinitrobenzene phenol, take off HF, after obtaining the dinitrobenzene thing, use suitable reduction system,, form amino and obtain the nitroreduction (hydrogenation) of this dinitrobenzene thing.
The compound that above-mentioned formula (1-33)～(1-36) is represented respectively, for example can pass through 3,5-two (N, N-diallyl amino) hydroxybenzene and glycidyl chlorine reaction, obtain 3,5-two (N, N-diallyl amino) glycidoxypropyl benzene, then, with this compound with have a desirable radicals R I, X I, R IIAnd X IIAnd the compound shown in the following formula (1-D) of numerical value n reaction, obtain the diallyl thing after, preferably in the presence of the tetraphenyl palladium, with N, the N-diallyl changes amino into and obtains.
Figure BSA00000308305800191
The compound that above-mentioned formula (1-37)～(1-40) is represented respectively for example can be by having desirable radicals R I, X I, R IIAnd X IIAnd compound shown in the above-mentioned formula (1-D) of numerical value n and the reaction of glycidyl chlorine, obtain midbody compound, then, with this midbody compound and 3, the reaction of 5-two (N, N-diallyl amino) hydroxybenzene, after obtaining the diallyl thing, preferably in the presence of the tetraphenyl palladium, with N, the N-diallyl changes amino into and obtains.
Diamines as being used for the preferred polyamic acid of synthetic the present invention can only use the compound shown in the above-mentioned formula (1) separately, also the compound shown in the above-mentioned formula (1) and other diamines can be used in combination.
As other diamines that can here use, can list for example P-pHENYLENE dI AMINE, 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, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine base, 3,3 '-dimethyl-4,4 '-benzidine base, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine base, 3,3 '-two (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-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] hexafluoorpropane, 2,2-two (4-aminophenyl) hexafluoorpropane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2,7 diamin of luorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene radical-two (2-chloro aminobenzen), 2,2 ', 5,5 '-tetrachloro is for-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 the phenylene isopropylidene) two (aniline), 4,4 '-(metaphenylene isopropylidene) two (aniline), 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] hexafluoorpropane, 4,4 '-diamino-2,2 '-two (trifluoromethyl) xenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoros are for aromatic diamines such as biphenyl;
1,1-m-xylene diamine, 1,3-propylene diamine, 1,4-butanediamine, 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 inferior 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, 4,4 '-methylene radical two aliphatie diamine and ester ring type diamines such as (cyclo-hexylamine);
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2,4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3, the 5-triazine, 2,4-diamino-6-methoxyl group-1,3, the 5-triazine, 2,4-diamino-6-phenyl-1,3, the 5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2,6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3,5-diaminostilbene, 2, the 4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, 1,4-diamino piperazine, 3, the 6-proflavin, two (4-aminophenyl) phenyl amine, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, the following formula (D-I) and (D-II) diamines of the nitrogen-atoms of the compound etc. of expression beyond intramolecularly has two primary amine groups and this primary amino respectively;
In the formula (D-I), R 5Be any monovalent organic radical group that is selected from the ring structure with nitrogen atom of the group that constitutes by pyridine, pyrimidine, triazine, piperidines and piperazine, X 1It is divalent organic group;
In the formula (D-II), R 6Be the divalent organic group that is selected from the ring structure with nitrogen atom of the group that constitutes by pyridine, pyrimidine, triazine, piperidines and piperazine, X 2Be respectively divalent organic group, the X of a plurality of existence 2Can be identical respectively, also can be different.
Mono-substituted phenylenediamines such as compound shown in the following formula (D-III);
Figure BSA00000308305800212
(in the formula (D-III), R 7Be-O-,-COO-,-OCO-,-NHCO-,-CONH-or-CO-, R 8Be that to have any monovalent organic radical group of the skeleton that is selected from the group that is made of steroid skeleton, trifluoromethyl, Trifluoromethoxyphen-l and fluoro phenyl or group or carbonatoms be 6～30 alkyl)
Diamino organo-siloxanes such as compound shown in the following formula (D-IV);
Figure BSA00000308305800213
(in the formula (D-IV), R 9Be respectively that carbonatoms is 1～12 alkyl, the R of a plurality of existence 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) is represented respectively etc.
Figure BSA00000308305800221
Figure BSA00000308305800231
Y in the formula (D-4) is 2～12 integer, and the z in the formula (D-5) is 1～5 integer.
As among synthetic the present invention during preferred polyamic acid, other diamines that uses together with the compound shown in the above-mentioned formula (1), preferably include above-mentioned among, be selected from by P-pHENYLENE dI AMINE, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) two (aniline), 4,4 '-(metaphenylene diisopropylidene) two (aniline), 1, the 4-cyclohexane diamine, 4,4 '-methylene radical two (cyclo-hexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, the compound that above-mentioned formula (D-1)～(D-5) is represented respectively, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, compound shown in the following formula (D-6) in the compound of above-mentioned formula (D-I) expression;
Figure BSA00000308305800232
The compound of following formula (D-7) expression in the compound of above-mentioned formula (D-II) expression,
Figure BSA00000308305800233
And the dodecyloxy-2 in the compound of above-mentioned formula (D-III) expression, 4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2, at least a (below, be called " other specific diamines) of the group that compound that 5-diaminobenzene and following formula (D-8)～(D-16) are represented respectively constitutes.
Figure BSA00000308305800241
Figure BSA00000308305800261
Be used for the diamines of the preferred polyamic acid of synthetic the present invention,, preferably contain more than the 1mol%, more preferably contain more than the 20mol%, especially preferably contain the compound shown in the above above-mentioned formula (1) of 50mol% with respect to whole diamines.
Be used for the diamines of the preferred polyamic acid of synthetic 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 the 90mol%, more preferably below the 80mol%, more preferably below the 50mol%.
The diamines that is used for the preferred polyamic acid of synthetic the present invention, preferred only by the formation of the compound shown in the above-mentioned formula (1), perhaps only constitute by the compound shown in the above-mentioned formula (1) and other specific diamines.
[synthesizing of polyamic acid]
Preferred polyamic acid can obtain by making tetracarboxylic dianhydride and the diamine reactant that comprises the compound shown in the above-mentioned formula (1) among the present invention.
The tetracarboxylic dianhydride who uses in the building-up reactions as polyamic acid and the usage ratio of diamines, with respect to the amino that contains in the monovalent diamine compound, tetracarboxylic dianhydride's anhydride group preferred 0.2～2 normal ratio, more preferably 0.3～1.2 normal ratio.
The building-up reactions of polyamic acid in preferred organic, preferably-20～150 ℃, more preferably carry out under 0～100 ℃ the temperature condition.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 the synthetic polyamic acid, can list for example N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N, non-proton property polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; Phenol solvents such as meta-cresol, xylenol, phenol, halogenated phenol.The total amount (b) that the consumption of organic solvent (a: when wherein organic solvent and lean solvent described later being used together, be meant their total amount) is preferably tetracarboxylic dianhydride and diamine compound is the amount of 0.1～30 weight % with respect to whole amounts (a+b) of reaction soln.
In the above-mentioned organic solvent, can be in the scope of the polyamic acid that can not separate out generation and the alcohol that is identified usually as the lean solvent of polyamic acid, ketone, ester, ether, halohydrocarbon, hydrocarbon etc. use together.Object lesson as this lean solvent, can list for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, triglycol, the glycol monomethyl methyl 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, the ethylene glycol n-propyl ether, the 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, the diethylene glycol monomethyl ether acetic ester, the TC acetic ester, tetrahydrofuran (THF), methylene dichloride, 1, the 2-ethylene dichloride, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.
Synthesizing polyamides when acid, when organic solvent and above-mentioned lean solvent are used together,, with respect to the total amount of organic solvent and lean solvent, be preferably below the 50 quality %, more preferably below the 10 quality % as the usage ratio of lean solvent.
As above, can obtain dissolving the reaction soln that polyamic acid forms.
This reaction soln can be directly used in the preparation liquid crystal aligning agent, also behind the polyamic acid that can contain, is used to prepare liquid crystal aligning agent in separating reaction solution, after perhaps isolating polyamic acid being made with extra care, is used to prepare liquid crystal aligning agent.
When the polyamic acid dehydration closed-loop is formed polyimide, above-mentioned reaction soln can be directly used in the dehydration closed-loop reaction; After the polyamic acid that contains in also can separating reaction solution separates, be used for the dehydration closed-loop reaction; After perhaps isolating polyamic acid being made with extra care, be used for the dehydration closed-loop reaction.
The separation of polyamic acid can obtain precipitate, with the method for this precipitate drying under reduced pressure by above-mentioned reaction soln is injected a large amount of lean solvents; Perhaps undertaken by the method for the solvent in the vaporizer underpressure distillation reaction soln.In addition, also can be by this polyamic acid being dissolved in the organic solvent once more the method for in lean solvent, separating out then; Perhaps make with extra care polyamic acid with vaporizer decompression distilled method by repeating one or many.
＜polyimide 〉
Preferred polyimide can be by obtaining aforesaid polyamic acid dehydration closed-loop imidization among the present invention.
As the tetracarboxylic acid diamines that synthetic above-mentioned polyimide uses, can list the synthetic middle identical compound of tetracarboxylic dianhydride that uses with above-mentioned polyamic acid.Preferred tetracarboxylic dianhydride's kind is identical with its preferred usage ratio also situation with polyamic acid.
As the diamines that is used for the preferred polyimide of synthetic the present invention, can list the identical diamines of diamines that uses with synthetic above-mentioned polyamic acid.Just, the diamines that is used for the polyimide that synthetic liquid crystal aligning agent of the present invention contains comprises the compound shown in the above-mentioned formula (1), can only use the compound shown in the above-mentioned formula (1), also the compound shown in the above-mentioned formula (1) and above-mentioned other diamines can be used together.Also the situation with polyamic acid is identical for the kind of preferred other diamines and the preferred usage ratio of each diamines.
Preferred polyimide can be the complete imidization thing as the amido acid structure fully dehydrating closed loop that polyamic acid had of raw material among the present invention; Also can be a part of dehydration closed-loop of amido acid structure, amido acid structure and imide ring structure and the part imidization thing of depositing.The imidization rate of the polyimide among the present invention is preferably more than 20%, and more preferably 40～80%.This imidization rate is to represent that with percentage the quantity of imide ring structure occupies the ratio of total amount of the quantity of the quantity of amido acid structure of polyimide and imide ring structure.At this moment, the part of imide ring can be different imide ring.The imidization rate can be by being dissolved into polyimide heavy-hydrogenated solvent (for example, in the heavy-hydrogenated dimethyl sulfoxide (DMSO)),, measures under the room temperature as primary standard with tetramethylsilane 1The result of H-NMR, (I) tries to achieve according to following mathematical expression.
Imidization rate (%)={ 1-(A 1/ A 2) * α } * 100 (I)
In the above-mentioned mathematical expression (I), A 1Be the peak area of expression near the proton of the NH base that occurs the chemical shift 10ppm, A 2Be the peak area of expression from other proton, α is the ratio of the number of other proton with respect to the proton of the NH base in the precursor (polyamic acid) of a polyimide.
The dehydration closed-loop of polyamic acid preferred (i) perhaps (ii) is dissolved in polyamic acid in the organic solvent with the method by the heating polyamic acid, adds dewatering agent and dehydration closed-loop catalyzer in this solution, and Jia Re method is carried out as required.
Be preferably 50～200 ℃, more preferably 60～170 ℃ as the temperature of reaction in the method for the heating polyamic acid of above-mentioned (i).Temperature of reaction can't fully be carried out the dehydration closed-loop reaction during less than 50 ℃; If temperature of reaction surpasses 200 ℃, then 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 solution (ii), add in the method for dewatering agent and dehydration closed-loop catalyzer,, can list for example acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride as dewatering agent at polyamic acid.As the consumption of dewatering agent, determine that according to desirable imidization rate the amido acid structure with respect to the 1mol polyamic acid is preferably 0.01mol～20mol.In addition, as the dehydration closed-loop catalyzer, can list for example tertiary amines such as pyridine, trimethylpyridine, lutidine, triethylamine.But, be not limited to this.With respect to the dewatering agent that 1mol uses, be preferably 0.01～10mol as the dehydration closed-loop catalyst consumption.Above-mentioned dewatering agent, dehydration closed-loop catalyst consumption are many more, and the imidization rate can be high more.As the organic solvent that uses in the dehydration closed-loop reaction, can list the illustrative organic solvent of solvent that acid is used as synthesizing polyamides.Temperature of reaction as the dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.Be preferably 1.0～120 hours, more preferably 2.0 hours～30 hours as the reaction times.
The polyimide that obtains in the aforesaid method (i) can be directly used in it preparation liquid crystal aligning agent, after perhaps the polyimide of gained being made with extra care, is used to prepare liquid crystal aligning agent.On the other hand, aforesaid method (ii) in, can obtain containing the reaction soln of polyimide.This reaction soln can be directly used in it preparation liquid crystal aligning agent, also can remove dewatering agent and dehydration closed-loop catalyzer from reaction soln after, be used to prepare liquid crystal aligning agent; After polyimide can also be separated, be used to prepare liquid crystal aligning agent; After perhaps isolating polyimide being made with extra care, be used to prepare liquid crystal aligning agent.In order to remove dewatering agent and dehydration closed-loop catalyzer from reaction soln, for example be fit to use methods such as solvent exchange.The separation of polyimide, the refining above-mentioned same operation that can be undertaken by separation, the process for purification as polyamic acid are carried out.
The 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 regulating molecular weight.By using end modified type polymkeric substance, can not damage effect of the present invention and further improve coating character of liquid crystal aligning agent etc.This end modified type polymkeric substance can be undertaken by add molecular weight regulator in polymerization reaction system when synthesizing polyamides acid.As molecular weight regulator, can list for example sour single acid anhydride, monoamine compound, monoisocyanates compound etc.
As the single acid anhydride of above-mentioned acid, can list for example maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.;
As above-mentioned monoamine compound, can list for example 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 for example isocyanic acid phenylester, isocyanic acid naphthyl ester etc.
As the usage ratio of molecular weight regulator, tetracarboxylic dianhydride who uses during with respect to synthesis of polyimides and the total of diamines 100 weight parts are preferably below 20 weight parts, more preferably below 5 weight parts.
-soltion viscosity-
Polyamic acid that as above obtains or polyimide preferably have the soltion viscosity of 20～800mPas when forming the solution of concentration 10 weight %, more preferably have the soltion viscosity of 30～500mPas.
The soltion viscosity of above-mentioned polymkeric substance (mPas) is to use the good solvent (for example, gamma-butyrolactone, N-N-methyl-2-2-pyrrolidone N-etc.) of this polymkeric substance, to the polymers soln of concentration 10 weight % of preparation, uses E type rotational viscosimeter, 25 ℃ of values of measuring down.
＜other composition 〉
Liquid crystal orientation film of the present invention contains the essential composition of particular polymers conduct as above, also can contain other composition as required.As this other composition, can list polymkeric substance beyond the particular polymers for example (below, be called " other polymkeric substance "), have compound (below, be called " epoxy compounds "), functional silanes compound of at least one epoxy group(ing) etc. at intramolecularly.
[other polymkeric substance]
Above-mentioned other polymkeric substance can be used to improve SOLUTION PROPERTIES and electrical property.As this other polymkeric substance, it is the as above polymkeric substance beyond the particular polymers, can list tetracarboxylic dianhydride for example and do not contain the polyamic acid that the diamine reactant of the compound shown in the above-mentioned formula (1) obtains (below, be called " other polyamic acid "), polyimide that this polyamic acid dehydration closed-loop is formed (below, 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, (be meant the total amount of above-mentioned particular polymers and other polymkeric substance with respect to the total amount of polymkeric substance.Below identical), be preferably below the 95 weight %, more preferably 50～90 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, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-two bromo neopentylglycol diglycidyl ethers, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-amino methyl hexanaphthene etc.Amount to 100 weight parts with respect to polymkeric substance, these blending ratios that contain the compound of epoxy group(ing) are 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, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-uride propyl trimethoxy silicane, 3-uride propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three 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-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxidation ethylidene)-3-TSL 8330, N-two (oxidation ethylidene)-3-aminopropyltriethoxywerene werene 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 as above particular polymers and as required arbitrarily other additive of blended preferably in organic solvent, dissolve and contain and constitute.
As the organic solvent that can in liquid crystal aligning agent of the present invention, use, can list the illustrative solvent of the solvent that uses in the building-up reactions as polyamic acid.In addition, can use solvent together and illustrative lean solvent in the time of can also suitably selecting building-up reactions as polyamic acid.As the preferred example of this organic solvent, can list for example N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, the glycol monomethyl methyl ether, n-Butyl lactate, butylacetate, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, the 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, the diethylene glycol monomethyl ether acetic ester, the TC acetic ester, diisobutyl ketone, propionic acid isopentyl ester, isopropylformic acid isopentyl ester, diisoamyl ether etc.They can use separately, perhaps also can mix two or more uses.
The solid component concentration of liquid crystal aligning agent of the present invention (in the 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) is considered suitably selection such as viscosity, volatility, is preferably the scope of 1～10 weight %.Just, liquid crystal aligning agent of the present invention can be removed organic solvent by it is coated to substrate surface, form filming of liquid crystal orientation film, but during less than 1 weight %, this thickness of filming is too small, may be difficult to obtain good liquid crystal orientation film at solid component concentration; On the other hand, when solid component concentration surpassed 10 weight %, the thickness of filming was excessive, may be difficult to equally obtain good liquid crystal orientation film, and the viscosity of liquid crystal aligning agent increased coating character possibility deficiency.
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, when using spin-coating method to carry out, solid component concentration is preferably the scope of 1.5～4.5 weight % especially.When using print process to carry out, solid component concentration is the scope of 3～9 weight %, and thus, soltion viscosity is preferably the scope of 12～50mPas especially.When using ink jet method to carry out, solid component concentration is the scope of 1～5 weight %, and thus, soltion viscosity is preferably the scope of 3～15mPas especially.
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 the substrate, formation is filmed, the direction that tilts from relative coated surface is in the ultraviolet ray of this film irradiation polarized light or non-polarized light, perhaps film at this and shine polarized ultraviolet, give the method for liquid crystal aligning energy to filming from the vertical direction of relative coated surface.
At first, by for example suitable coating processes such as rolling method, spin-coating method, print process, ink jet method,, be coated with liquid crystal aligning agent of the present invention in the nesa coating side of the substrate that the pattern-like nesa coating is set.Liquid crystal aligning agent of the present invention is adopting print process because the printing excellence, particularly during adherography, can bring into play advantageous effects of the present invention to greatest extent, so preferred.After the coating, by this coated face is preheated (prebake), roasting then (afterwards curing) forms and films.The prebake condition for example is to carry out under 40～120 ℃ 0.1～5 minute, after cure condition optimization 120～300 ℃, more preferably under 150～250 ℃, preferably carried out 5～200 minutes, more preferably carried out 10～100 minutes.After the thickness of filming after curing be preferably 0.001～1 μ m, 0.005～0.5 μ m more preferably.
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 as aforementioned nesa coating by SnO 2The NESA film that forms, by In 2O 3-SnO 2The ITO film that forms etc.In order to form the pattern of these nesa coatings, can use photo-engraving process or when forming nesa coating, use the method etc. of mask.
During the coated with liquid crystal alignment agent, better for the cohesiveness that makes substrate or nesa coating and film, can on substrate and nesa coating, apply functional silanes compound, titanate compound etc. in advance.
Then, by shining the ultraviolet ray of polarized light or non-polarized light, this is filmed give the liquid crystal aligning energy, aforementioned filming becomes liquid crystal orientation film.Here,, can use the ultraviolet ray and the visible rays of the light of the wavelength that for example comprises 150nm～800nm, preferably comprise the ultraviolet ray of light of the wavelength of 300nm～400nm as radioactive rays.The radioactive rays that use are during as polarized light (rectilinearly polarized light or partial poolarized light), can be from the vertical direction irradiations of relative coated surface, and also can be in order to give tilt angle from the direction irradiation of tilting.On the other hand, when the irradiation non-polarized light, irradiation must be carried out from the direction that relative coated surface tilts.
Light source as the irradiation radioactive rays can use for example 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 zone can obtain by mechanism that aforementioned light source and for example spectral filter, diffraction grating etc. are used together etc.
The irradiation dose of radioactive rays is preferably 1J/m 2More than, less than 10,000J/m 2, more preferably 10～3,000J/m 2In addition, by optical alignment method form by present known liquid crystal aligning agent film on give liquid crystal aligning can the time, must 10,000J/m 2Above radiation exposure amount.But, if use liquid crystal aligning agent of the present invention, even the radiation exposure amount during optical alignment method is 3,000J/m 2Below, and then be 1,000J/m 2Below, further be 300J/m 2Below, also can give good liquid crystal aligning energy, the manufacturing cost that helps to cut down liquid crystal display device.
In addition, the expression of " tilt angle " described in the present invention liquid crystal molecule is from the angle of the direction inclination 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 that is formed by liquid crystal aligning agent of the present invention.Liquid crystal display device of the present invention for example can followingly be made.
Prepare two substrates that as above form liquid crystal orientation film,, make liquid crystal cell by between these two substrates, disposing liquid crystal.When making liquid crystal cell, can list for example following two kinds of methods.
First method is present known method.At first, in order to make each liquid crystal orientation film subtend setting, by gap (gap of box), with two substrate subtend configurations, use sealing agent, fitted in the peripheral position of two substrates, in the box gap of cutting apart by substrate surface and sealing agent, inject filling liquid crystal after, the sealing filling orifice can be made liquid crystal cell.
Second method is the method that is called ODF (One Drop Fill, instillation) mode.Prescribed position on the substrate in two substrates that form liquid crystal orientation film, apply for example sealing agent of ultraviolet light curable, then after dripping liquid crystal on the liquid crystal aligning face, fit another substrate and make the liquid crystal orientation film subtend, then, whole irradiating ultraviolet light at substrate makes sealant cures, can make liquid crystal cell.
Under the situation of any method, after wishing then liquid crystal cell to be heated to the isotropic temperature of liquid crystal of use, slow cool to room temperature, the flow orientation when removing the liquid crystal injection.
Then, the outer surface applying polaroid by at liquid crystal cell can obtain liquid crystal display device of the present invention.Here, when liquid crystal orientation film is horizontal alignment, in two substrates that adjust to form liquid crystal orientation film, the angle that the polarization direction of irradiation 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, when liquid crystal orientation film is vertical orientated property, make the direction of the axle of the easy orientation in two substrates that form liquid crystal orientation film constitute liquid crystal cell abreast, the polaroid of fitting therein, and the axle shape angle at 45 that makes its polarization direction and be orientated easily, can form 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 Resins, epoxy of solidifying agent etc.
As foregoing liquid crystal, preferably use for example nematic liquid crystal, dish-like liquid crystal etc.
When being TN type liquid crystal cell or STN type liquid crystal cell, the nematic liquid crystal that preferably has positive dielectric anisotropy can use for example biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, in the foregoing liquid crystal, can further add and use for example cholesterol liquid crystals such as chlorination beta-cholestanol, Cholesteryl pelargonate, cholesterol carbonic ether; Chiral reagent with trade(brand)name " C-15 ", " CB-15 " (manufacturing of メ Le Network company) sale; To oxygen base benzylidene-to strong dielectricity liquid crystal such as amino-2-methyl butyl laurate etc. in the last of the ten Heavenly stems.
On the other hand, when being the vertical alignment-type liquid crystal box, the nematic liquid crystal that preferably has negative dielectric anisotropy can use for example 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.
As the polaroid that use in the outside of liquid crystal cell, can list the limit with polyvinyl alcohol extension orientation, the limit is clamped absorption iodine with the cellulose acetate protective membrane and is called the film formed polaroid of polarisation of " H film " or the polaroid that is formed by H film itself.
The liquid crystal display device of the present invention of Zhi Zaoing like this, the display performance excellence, even use for a long time under hot conditions, display performance can variation yet.
[embodiment]
Synthesizing of compound shown in the＜above-mentioned formula (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 that has reflux condensing tube, thermometer and nitrogen ingress pipe, 4-(the 4-amyl group cyclohexyl) bromobenzene, 2.3g palladium, 12g three (o-tolyl) phosphine, 560mL triethylamine, the 82mL vinylformic acid and 2 that add 310g, the N of 000mL, the N-N,N-DIMETHYLACETAMIDE stirs under 120 ℃ and reacted in 3 hours.After reaction finishes, filter reaction mixture.In this filtrate, add the 10L ethyl acetate, the organic layer that obtains is used the dilute hydrochloric acid washed twice successively, after washing 3 times with water, use dried over mgso, decompression removes down and desolvates, the mixed solvent recrystallization of the solid that obtains by being made 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 that has 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 reacted 8 hours down at 60 ℃.After reaction finishes, add the 300mL chloroform in reaction mixture, the organic layer that obtains washes with water 3 times, then uses dried over mgso.Concentrate this organic layer, reclaim the solid of separating out, it is used washing with alcohol, thereby obtain 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 that has 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 and react under 4 hours.After reaction finished, reaction mixture washed successively with potassium fluoride aqueous solution and water.The organic layer dried over mgso, then, removal of solvent under reduced pressure, the solid that obtains 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 that has return line, thermometer and nitrogen ingress pipe, (4-(4 for the 4-of adding 37g, 4,4-three fluoro butoxy) N of bromobenzene, 0.23g palladium, 1.2g three (o-tolyl) phosphine, 56mL triethylamine, 8.2mL vinylformic acid and 200mL cyclohexyl), the N-N,N-DIMETHYLACETAMIDE stirs under 120 ℃ and reacted in 3 hours.After reaction finishes, filter reaction mixture.In this filtrate, append the 1L ethyl acetate, the organic layer that obtains is with dilute hydrochloric acid washed twice and washing with water 3 times, after dried over mgso, removal of solvent under reduced pressure, the mixed solvent recrystallization of the solid of gained by 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 that has 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 reacted 8 hours down at 60 ℃.After reaction finishes, add the 150mL chloroform in reaction mixture, the organic layer that obtains washes with water 3 times, then uses dried over mgso.Concentrate organic layer, reclaim the solid of separating out, it is used washing with alcohol, thereby obtain 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 that has 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 and react under 4 hours.After reaction finished, reaction mixture washed successively with potassium fluoride aqueous solution and water.The organic layer dried over mgso, removal of solvent under reduced pressure, the solid that obtains 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 that has return line, thermometer and nitrogen ingress pipe, the N that adds compound (1-10-1G), 0.23g palladium, 1.2g three (o-tolyl) phosphine, 56mL triethylamine, 8.2mL vinylformic acid and the 200mL of 39g, the N-N,N-DIMETHYLACETAMIDE stirs under 120 ℃ and reacted in 3 hours.After reaction finishes, filter reaction mixture.In filtrate, add the 1L ethyl acetate, the organic layer that obtains is successively with dilute hydrochloric acid washed twice and washing with water 3 times, after dried over mgso, removal of solvent under reduced pressure, the mixed solvent recrystallization of the solid of gained by 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 that has 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 reacted 8 hours down at 60 ℃.After reaction finishes, add the 150mL chloroform in reaction mixture, the organic layer that obtains washes with water 3 times, then uses dried over mgso.Concentrate organic layer, reclaim the solid of separating out, it is used washing with alcohol, thereby obtain 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 that has 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 and react under 4 hours.After reaction finished, reaction mixture washed successively with potassium fluoride aqueous solution and water.The organic layer dried over mgso after then concentrating, by ethyl alcohol recrystallization, thereby obtains 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 that has return line and nitrogen ingress pipe, add the N of 21g compound (1-16-1G), 80mL thionyl chloride and 0.1mL, dinethylformamide stirs under 80 ℃ and reacted in 1 hour.After reaction finishes, distillate unreacted thionyl chloride by decompression from reaction mixture after, add the 150mL methylene dichloride, the organic layer that obtains washes with water 3 times.This organic layer with dried over mgso after, removal of solvent under reduced pressure behind the temporary transient dry solidification, adds the 400mL tetrahydrofuran (THF), obtains containing the solution of compound (1-16-1A).
(2) compound (1-16-1B) is synthetic
In the there-necked flask of the 1L that has 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 ℃.Spend the whole amounts that dripped the solution of the compound (1-16-1A) that contains above-mentioned preparation in 3 hours therein, restir reacted in 1 hour.After reaction finishes, in reaction mixture, add dilute hydrochloric acid, make pH be 4 below after, adding 3L toluene and 1L tetrahydrofuran (THF), the organic layer that obtains washes with water 3 times.This organic layer with dried over mgso after, removal of solvent under reduced pressure, the mixed solvent recrystallization of the solid of gained by forming by ethanol and tetrahydrofuran (THF), thereby obtain 21g compound (1-16-1B).
(3) compound (1-16-1C) is synthetic
In the there-necked flask of the 300mL that has 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 reacted 8 hours down at 60 ℃.After reaction finishes, add the 300mL chloroform in reaction mixture, the organic layer that obtains washes with water 3 times, then uses dried over mgso.Concentrate organic layer, reclaim the solid of separating out, it is used washing with alcohol, thereby obtain 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 that has 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 and react under 4 hours.After reaction finished, reaction mixture washed successively with potassium fluoride aqueous solution and water.The organic layer dried over mgso after then concentrating, by ethyl alcohol recrystallization, thereby obtains 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) 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 that has 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 of the boron-tetrahydrofuran complex that drips 600mL concentration 1mol/L more than 2 hours, then, at room temperature stir and reacted in 3 hours.After reaction finishes, after in reaction mixture, slowly adding the water of 400mL, add ethyl acetate again, after the organic layer that obtains washes with water, use dried over mgso, removal of solvent under reduced pressure, behind the dry solidification, by using ethyl acetate: toluene=1: 1 as the silicagel column that launches solvent refining after, the mixed solvent recrystallization by forming again by ethyl acetate and hexane, thus obtain 38g compound (1-6-1A).
(2) compound (1-6-1B) is synthetic
In the eggplant type flask of the 500mL that has nitrogen ingress pipe, the N that adds the above-mentioned compound that obtains of 30g (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 stirring down 1 hour, then at room temperature, carry out the diel reaction.Reaction washes reaction mixture with water after finishing, after dried over mgso, and removal of solvent under reduced pressure, dry solidification, the solid that the obtains mixed solvent recrystallization that forms 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 that has 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 and react under 4 hours.After reaction finished, reaction mixture washed successively with potassium fluoride aqueous solution and water.The organic layer dried over mgso after then concentrating, by the mixed solvent recrystallization that is formed by ethanol and tetrahydrofuran (THF), thereby obtains 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 that has nitrogen ingress pipe, add among 34g compound (1-6-2A), 21g and the above-mentioned synthesis example 1-6 N of synthetic (1-6-1A), 1.2g similarly, N-dimethyl aminopyridine, 200mL methylene dichloride and N-(3-dimethylaminopropyl)-N '-ethyl carbon imide hydrochloride, under ice-cooled, stirred 1 hour, and at room temperature reacted diel again.After reaction finishes, in reaction mixture, add entry, separatory, the organic layer that obtains with dried over mgso after, 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 that has 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 and react under 4 hours.After reaction finished, reaction mixture washed successively with potassium fluoride aqueous solution and water.The organic layer of gained with dried over mgso after, removal of solvent under reduced pressure, the mixed solvent recrystallization of the solid of gained by forming by ethanol and tetrahydrofuran (THF), thereby obtain 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 that has reflux condensing tube and nitrogen ingress pipe, add the N of 30g compound (1-4-1A), 100mL thionyl chloride and 0.1mL, dinethylformamide reacted 1 hour down at 80 ℃.After reaction finishes, distillate unreacted thionyl chloride by decompression from reaction mixture after, add the 150mL methylene dichloride, the organic layer that obtains washes with water 3 times.This organic layer with dried over mgso after, removal of solvent under reduced pressure behind the temporary transient dry solidification, adds the 200mL tetrahydrofuran (THF), obtains containing the solution of the reaction product of 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 ℃.Then, slowly drip the solution that keeps the reaction product that contains above-claimed cpd (1-4-1A) and thionyl chloride below 5 ℃, then, at room temperature further stir and reacted in 1 hour.After reaction finishes, in reaction mixture, add ethyl acetate, the organic layer that obtains is used successively hydrochloric acid and the water washing of 1mol/L, then with after the dried over mgso, removal of solvent under reduced pressure, the dry solidification thing that obtains is refining as the silicagel column that launches reagent by the mixed solvent that forms with ethyl acetate and hexane, removes from this cut and desolvates, and obtains 29g compound (1-41-1B).
(3) (1-41-1C) synthetic
In the there-necked flask of the 300mL that has thermometer and nitrogen ingress pipe, add 2 of above-mentioned (1-41-1B) that obtains of 29g, 16g, 4-dinitrobenzene fluorobenzene and 16g triethylamine at room temperature stir diel and react.After reaction finishes, in reaction mixture, add the 1L ethyl acetate, the organic layer that obtains is washed once and washes with water 3 times with dilute hydrochloric acid successively, after dried over mgso, removal of solvent under reduced pressure, the dry solidification thing ethyl alcohol recrystallization that obtains, thus obtain 37g compound (1-41-1C).
(4) compound (1-41-1) is synthetic
In the there-necked flask of the 1L that has 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 and react under 4 hours.After reaction finished, reaction mixture washed successively with potassium fluoride aqueous solution and water.The organic layer of gained with dried over mgso after, removal of solvent under reduced pressure, the solid that obtains 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 that has return line and nitrogen ingress pipe, add the compound (1-4-1A) that 30g and above-mentioned synthesis example 1-1 similarly obtain, the N of 40mL thionyl chloride and 0.1mL, dinethylformamide refluxes and reacted in 1 hour.After reaction finished, the decompression reaction mixture was removed low boilers, obtains white powder.This white powder is dissolved in the 100mL tetrahydrofuran (THF), with it as A liquid.
On the other hand, in the there-necked flask of the 500mL that has dropping funnel and thermometer, add 1 of 73mL, ammediol, 100mL tetrahydrofuran (THF) and 21mL triethylamine are ice-cooled with it.Then, after using dropping funnel to divide to drip above-mentioned A liquid in two hours therein, be returned to room temperature, reacted again two hours.After reaction finishes, in reaction mixture, add the 600mL ethyl acetate, to the organic layer that obtains successively with the washing of dilute hydrochloric acid separatory once with water separatory washing 3 times after, use dried over mgso, decompression removes down and desolvates, and 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 that has 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 reacted 9 hours down at 40 ℃.After reaction finishes, in reaction mixture, add the 300mL ethyl acetate, to the organic layer that obtains successively with the washing of dilute hydrochloric acid separatory once with water separatory washing 3 times after, decompression removes down and desolvates, the white solid washing with alcohol that obtains, 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 that has thermometer and nitrogen ingress pipe, after adding 32g above-claimed cpd (1-29-1C), 76g zinc powder, 12.4g ammonium chloride, 200mL ethanol and 200mL tetrahydrofuran (THF), divide therein slowly to add 35mL water in 1 hour, directly at room temperature reacted 5 hours.After reaction finished, filter reaction mixture in the filtrate that obtains, added the 750mL ethyl acetate, after the organic layer water separatory washing that obtains 3 times, added ethanol, obtained mixing solutions.This mixing solutions under reduced pressure concentrates, and 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 (1) of above-mentioned synthesis example 1-1, use 4-(the 4-heptyl cyclohexyl) bromobenzene of 337g to replace beyond 4-(the 4-amyl group cyclohexyl) bromobenzene and synthesis example 1-1 (1) similarly, obtain 163g compound (1-4-3A).
Then,, use the above-mentioned compound that obtains of 29g (1-4-3A) to replace compound (1-4-1A), obtain 37g compound (1-29-2B) by in (1) of synthesis example 1-9.
(2) compound (1-29-2C) is synthetic
By in (2) of synthesis example 1-9, use the above-mentioned compound that obtains of 29g (1-29-2B) to replace compound (1-29-1B), obtain 36g compound (1-29-2C).
(3) compound (1-29-2) is synthetic
By in (3) of synthesis example 1-9, use the above-mentioned compound that obtains of 32g (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 (1) of synthesis example 1-9, 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 (2) of synthesis example 1-9, use the above-mentioned compound that obtains of 33g (1-30-1B) to replace compound (1-29-1B), obtain 39g compound (1-30-1C).
(3) compound (1-30-1) is synthetic
By in (3) of synthesis example 1-9, use the above-mentioned compound that obtains of 37g (1-30-1C) to replace compound (1-29-1C), obtain 28g compound (1-30-1).
Compare 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 N-N-methyl-2-2-pyrrolidone N-of 4-methyl hydroxybenzoate, 182.4g salt of wormwood and the 320mL of 91.3g, at room temperature stir 1 hour after, add the 1-bromo pentane of 99.7g, stir down at 100 ℃ and reacted in 5 hours.Reaction adds entry after finishing in reaction mixture, once more precipitation.Reclaim this precipitation, add 48g sodium hydroxide and 400mL water, refluxed 3 hours, reaction is hydrolyzed.After reaction finishes, in reaction mixture, add the hydrochloric acid neutralization, reclaim the precipitation that generates,, obtain the white crystals of 102g compound (R-1A) by from ethyl alcohol recrystallization.
(2) compound (R-1B) is synthetic
With the reaction vessel of packing into of the 52g in the above-mentioned synthetic compound (R-1A), add the N of 100mL thionyl chloride and 0.2mL therein, dinethylformamide stirs down at 80 ℃ and to react in 1 hour.Then, under reduced pressure, distillate unreacted thionyl chloride from reaction mixture after, add methylene dichloride, the organic layer that obtains washs with saturated sodium bicarbonate aqueous solution, after dried over mgso, concentrates, and adds tetrahydrofuran (THF) then, 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 in one side, the limit slowly drips above-mentioned tetrahydrofuran solution therein, stirs then and reacts in 2 hours.After reaction finishes, in reaction mixture, add the hydrochloric acid neutralization, use ethyl acetate extraction, the organic layer that obtains with dried over mgso after, except that desolvating, the solid that obtains obtains the white crystals of 45g mixture (R-1B) from ethyl alcohol recrystallization down in decompression.
(3) compound (R-1C) is synthetic
In the there-necked flask of the 500mL that has agitator, thermometer and nitrogen ingress pipe, add 3 of the above-mentioned synthetic compound of 35g (R-1C), 22g, the N of 5-dinitrobenzene benzyl chlorine, 42g salt of wormwood, 30g sodium iodide and 150mL, dinethylformamide reacted 8 hours down at 60 ℃.After reaction finishes, add the 300mL chloroform in reaction mixture, the organic layer that obtains washes with water 3 times, then uses dried over mgso.Concentrate organic layer, reclaim the solid of separating out, it is used washing with alcohol, thereby obtain the pale yellow powder of 45g compound (R-1C).
(4) compound (R-1) is synthetic
In the there-necked flask of the 1L that has 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 and react under 4 hours.After reaction finished, reaction mixture washed successively with potassium fluoride aqueous solution and water.Organic layer with dried over mgso after, removal of solvent under reduced pressure, the solid that obtains is from ethyl alcohol recrystallization, thereby obtains the faint yellow crystallization of 22g compound (R-1).
Compare 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 that has reflux condensing tube and nitrogen ingress pipe, add the N of 30g compound (1-4-1A), 100mL thionyl chloride and 0.1mL, dinethylformamide reacted 1 hour down at 80 ℃.After reaction finishes, distillate unreacted thionyl chloride by decompression from reaction mixture after, add the 150mL methylene dichloride, the organic layer that obtains washes with water 3 times.This organic layer with dried over mgso after, removal of solvent under reduced pressure behind the temporary transient dry solidification, adds the 200mL tetrahydrofuran (THF), obtains containing the solution of the reaction product of 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 ℃.Then, slowly drip the solution that keeps the reaction product that contains above-claimed cpd (1-4-1A) and thionyl chloride below 5 ℃, at room temperature reacted 1 hour.After reaction finishes, in reaction mixture, add ethyl acetate, the organic layer that obtains is used successively hydrochloric acid and the water washing of 1M, after dried over mgso, after the removal of solvent under reduced pressure, refining by the mixed solvent that forms with ethyl acetate and hexanaphthene as the silicagel column that launches reagent, reduce pressure then to remove and desolvate from this cut, obtain the transparent thick liquid of 40g compound (R-2).
Synthesizing of＜particular polymers 〉
[synthesizing of polyamic acid]
Synthesis example CPA-1
With 7.0g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-1 synthetic of 13g compound (1-4-1) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-1).The soltion viscosity of this polyamic acid solution is 2,000mPas.
Synthesis example CPA-2
With 6.9g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-6 synthetic of 13.1g compound (1-6-1) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-2).The soltion viscosity of this polyamic acid solution is 1,800mPas.
Synthesis example CPA-3
With 6.2g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-3 synthetic of 13.8g compound (1-10-1) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-3).The soltion viscosity of this polyamic acid solution is 2,100mPas.
Synthesis example CPA-4
With 5.9g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-4 synthetic of 14.1g compound (1-16-1) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-4).The soltion viscosity of this polyamic acid solution is 2,200mPas.
Synthesis example CPA-5
With 6.1g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-5 synthetic of 13.9g compound (1-16-2) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-5).The soltion viscosity of this polyamic acid solution is 2,200mPas.
Synthesis example CPA-6
With 6.4g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-2 synthetic of 13.6g compound (1-22-1) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-6).The soltion viscosity of this polyamic acid solution is 2,100mPas.
Synthesis example CPA-7
With 6.8g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-6 synthetic of 12.4g compound (1-6-1) are (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 N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-7).The soltion viscosity of this polyamic acid solution is 1,900mPas.
Synthesis example CPA-8
With 6.4g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-7 synthetic of 13.6g compound (1-6-2) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-8).The soltion viscosity of this polyamic acid solution is 1,700mPas.
Synthesis example CPA-9
With 6.5g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-8 synthetic of 13.5g compound (1-41-1) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-9).The soltion viscosity of this polyamic acid solution is 2,300mPas.
Synthesis example CPA-10
With 6.5g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-9 synthetic of 14g compound (1-29-1) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-10).The soltion viscosity of this polyamic acid solution is 2,200mPas.
Synthesis example CPA-11
With 6.3g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-10 synthetic of 14g compound (1-29-2) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-11).The soltion viscosity of this polyamic acid solution is 2,100mPas.
Synthesis example CPA-12
With 5.8g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-11 synthetic of 14g compound (1-30-1) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids (CPA-12).The soltion viscosity of this polyamic acid solution is 2,000mPas.
[synthesizing of polyimide]
Synthesis example CPI-1
With 2.4g as 2 of tetracarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetate dianhydride (TCA) and the above-mentioned synthesis example 1-1 synthetic of 4.6g compound (1-4-1) are (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 28g, reacted 4 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids.The soltion viscosity of this polyamic acid solution is 2,000mPas.
Then, in above-mentioned polyamic acid solution, add N-N-methyl-2-2-pyrrolidone N-, 0.9g pyridine and the 1.0g diacetyl oxide of 65g, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, intrasystem solvent carries out solvent exchange (by this solvent exchange operation with new N-N-methyl-2-2-pyrrolidone N-, with the pyridine that uses in the dehydration closed-loop reaction and diacetyl oxide except that going to system), thereby obtain the solution that about 45g contains the polyimide (CPI-1) of 15 weight % imidization rates about 47%.
Get this polyimide solution a small amount of the branch, after the removal of solvent under reduced pressure, be dissolved in the gamma-butyrolactone, and to the solution of the polymer concentration 8.0 weight % that form, be 24mPas at 25 ℃ of soltion viscosities of measuring down.
Synthesizing of＜other polymkeric substance 〉
[synthesizing of other polyamic acid]
Synthesis example PA-1
Will be as equal benzene tertacarbonic acid's dianhydride of tetracarboxylic dianhydride's 109g (0.50mol) and 98g (0.50mol) 1,2,3,4-ring butanetetra-carboxylic acid dianhydride and as the 200g (1.0mol) 4 of diamines, 4-diamino-diphenyl ether, be dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 290g, after reacting 3 hours under 40 ℃, append 1, the N-N-methyl-2-2-pyrrolidone N-of 350g obtains approximately 3, and 590g contains the solution of 10 weight % polyamic acids (PA-1).The soltion viscosity of this polyamic acid solution is 210mPas.
Synthesis example PA-2
Will be as tetracarboxylic dianhydride's 98g (0.50mol) 1,2,3,4-ring butanetetra-carboxylic acid dianhydride and 109g (0.50mol) be benzene tertacarbonic acid's dianhydride and as the 198g (1.0mol) 4 of diamines, 4 '-diaminodiphenyl-methane all, be dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 290g, append 1 after 3 hours in reaction under 40 ℃, the N-N-methyl-2-2-pyrrolidone N-of 350g obtains containing the solution of 10 weight % polyamic acids (PA-2).The soltion viscosity of this polyamic acid solution is 135mPas.
Synthesis example PA-3
Will be as tetracarboxylic dianhydride's 196g (1.0mol) 1,2,3,4-ring butanetetra-carboxylic acid dianhydride and as the 200g (1.0mol) 4 of diamines, 4 '-diamino-diphenyl ether, be dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 246g, append 1 after 4 hours in reaction under 40 ℃, the N-N-methyl-2-2-pyrrolidone N-of 321g obtains containing the solution of 10 weight % polyamic acids (PA-3).The soltion viscosity of this polyamic acid solution is 220mPas.
Synthesis example PA-4
Will be as tetracarboxylic dianhydride's 196g (1.0mol) 1,2,3,4-ring butanetetra-carboxylic acid dianhydride and as the 212g (1.0mol) 2 of diamines, 2 '-dimethyl-4,4 '-benzidine, be dissolved into 3, in the N-N-methyl-2-2-pyrrolidone N-of 670g, after 3 hours, obtain containing the solution of 10 weight % polyamic acids (PA-4) in reaction under 40 ℃.The soltion viscosity of this polyamic acid solution is 170mPas.
Synthesis example PA-5
Will be as tetracarboxylic dianhydride's 224g (1.0mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as the 200g (1.0mol) 4 of diamines, 4 '-diamino-diphenyl ether, be dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 404g, after 4 hours, obtain containing the solution of polyamic acid (PA-5) in reaction under 40 ℃.Get this polyamic acid solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of concentration 10 weight %, and the soltion viscosity of mensuration is 190mPas.
Synthesis example PA-6
Will be as 2 of tetracarboxylic dianhydride's 6.5g, 3, the above-mentioned relatively synthesis example 1 synthetic compound (R-1) of 5-tricarboxylic basic ring amyl group acetate dianhydride and 13.5g is (with respect to the TCA of 1mol, be equivalent to 1.0mol), be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, after 4 hours, obtain containing the solution of 20 weight % polyamic acids (PA-6) in reaction under 60 ℃.The soltion viscosity of this polyamic acid solution is 2,000mPas.
[synthesizing of polymethacrylate]
Synthesis example PMA-1
In the four-hole boiling flask that stirring rod, T-valve and thermometer are housed, add the compound (R-2) that 10g obtains as monomeric above-mentioned relatively synthesis example 2, add then 20g as the glycol ether ethyl-methyl ether of solvent, 0.5g as 2 of polymerization starter, 2 '-azo two (2, the 4-methyl pentane nitrile) and 0.2g are as the α-Jia Jibenyixierjuwu of molecular weight regulator.It was seethed with excitement in nitrogen gas stream about 10 minutes, behind nitrogen replacement in the system, under nitrogen environment, reacted 5 hours down, thereby obtain containing the solution of 32 weight % polymkeric substance (PMA-1) at 70 ℃.To the gel permeation chromatography (GPC) of polymkeric substance (PMA-1) by following condition, measure weight-average molecular weight (Mw), the number-average molecular weight (Mn) of polystyrene conversion, try to achieve molecular weight distribution (Mw/Mn) and be Mw=24,000, Mw/Mn=2.4 does not have the peak of discovery from residual monomer.
" HLC-8020 " that GPC determinator: East ソ one (strain) made
Post TSK guardcolum α, TSK gel α-M that post: makes East ソ one (strain) and TSK gel α-2500 use that is connected in series
Solvent:, measure temperature: 35 ℃ to the solution of 3L dimethyl formamide dissolving 9.4g lithiumbromide monohydrate and 1.7g phosphoric acid
Reference material: monodisperse polystyrene
The preparation of＜liquid crystal aligning agent and evaluation 〉
Embodiment 1
[preparation of liquid crystal aligning agent]
(1) the printing evaluation preparation of liquid crystal aligning agent
Solution that contains polyamic acid (CPA-1) that will obtain and the solution that contains polyamic acid (PA-1) that obtains as the above-mentioned synthesis example PA-1 of other polymkeric substance as the above-mentioned synthesis example CPA-1 of particular polymers, ratio with the amount of the polymkeric substance that contains in them is CPA-1: PA-1=20: 80 (weight ratios) are mixed, add N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether (B C) then, form solvent composition NMP: B C=50: 50 (weight ratios), solid component concentration are the solution of 7 weight %.This solution uses the strainer of aperture 1 μ m to filter, preparation printing evaluation liquid crystal aligning agent (P-1).
(2) the liquid crystal display device manufacturing preparation of liquid crystal aligning agent
Except when liquid crystal aligning agent is used in the above-mentioned printing evaluation of preparation, making solid component concentration is beyond the 4 weight % and above-mentioned printing evaluation is similarly carried out with the preparation of liquid crystal aligning agent, preparation liquid crystal display device manufacturing liquid crystal aligning agent (A-1).
[evaluation of liquid crystal aligning agent]
Use two kinds of liquid crystal aligning agent of above-mentioned preparation, the following evaluation.Evaluation result is represented in table 2.
I. the evaluation of printing
Use liquid crystal orientation film printing press (Japan's description seal (strain) is made), the printing evaluation of the above-mentioned preparation of coating is with liquid crystal aligning agent (P-1) on having by the transparency electrode face of the glass substrate of the film formed transparency electrode of ITO, heated (prebake) 1 minute down at 80 ℃, except that after desolvating, heat 60 minutes (afterwards curing) down at 200 ℃, thereby form filming of thickness 60nm.This is filmed by the microscopic examination of visual observation and 2.5 times of multiplying powers, and 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 ";
All do not observe during visual observation printing spot and pin hole the two, but during microscopic examination, observe at least a situation in printing spot and the pin hole, be evaluated as printing " well ";
By visual observation, observe at least a situation in printing spot and the pin hole, be evaluated as printing " bad ".
II. the manufacturing of liquid crystal display device and evaluation
(1) manufacturing of liquid crystal display device
On the transparency electrode face that has by the glass substrate of the film formed transparency electrode of ITO, pass through spin-coating method, be coated with the liquid crystal display device manufacturing liquid crystal aligning agent (A-1) of above-mentioned preparation, on 80 ℃ hot plate, after the prebake 1 minute, in case in the nitrogen replacement baking oven, under 200 ℃, heated 1 hour, and formed filming of thickness 0.1 μ m.Then, on this surface of filming, use Hg-Xe lamp and Glan-Taylor prism, from the direction of 40 ° of substrate normal inclinations, irradiation contains the polarisation ultraviolet ray 200J/m of the bright line of wavelength 313nm 2, form liquid crystal orientation film.Repeat identical operations, make the substrate that a pair of (two) have liquid crystal orientation film.
The periphery of one face in aforesaid substrate with liquid crystal orientation film, apply the epoxy resin binder of the alumina balls that added diameter 5.5 μ m by silk screen printing after, 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 with the tackiness agent thermofixation down at 150 ℃.Then, from liquid crystal injecting port, in the gap between substrate, fill negative type liquid crystal (メ Le Network company makes, MLC-6608) after, by epoxy adhesive encapsulated liquid crystals inlet.Then, the flow orientation when injecting in order to remove liquid crystal, be heated 150 ℃ after, slow cool to room temperature.
Then, at each outer side applying 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 angle at 45 of real estate, make 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 manufacturing, by observation by light microscope during at room temperature with 5V voltage ONOFF (applying releasing), the abnormal area that has or not light and shade to change.The situation that to not observe abnormal area is evaluated as liquid crystal aligning agent (vertical orientated property) " well ".
(2-2) evaluation of tilt angle
To the liquid crystal display device of above-mentioned manufacturing 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)) method of record in, 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 manufacturing, in 60 ℃ envrionment temperature, apply the voltage of 5V with the application time of 60 microseconds, 167 milliseconds interval after, measure from releasing and be applied to voltage retention after 167 milliseconds.The model " VHR-1 " that determinator Shi Yong East Yang テ Network ニ カ Co., Ltd. makes.
(2-4) evaluation of high temperature tilt angle stability
With the liquid crystal display device of above-mentioned manufacturing 70 ℃ down keeping after 30 days and above-mentioned (2-2) similarly, measure tilt angle once more.To this measured value, during less than 1 °, be " well " from the variable quantity of initial value with high temperature tilt angle estimation of stability, be more than 1 ° the time, high temperature tilt angle estimation of stability is " bad ".
Embodiment 2～16 and 18～21
Except in the foregoing description 1, the kind of particular polymers and other polymkeric substance and amount are respectively as beyond 1 record of expression, with embodiment 1 similarly, prepare respectively the printing evaluation with liquid crystal aligning agent (P-2)～(P-16) and (P-18)～(P-21) and the liquid crystal display device manufacturing with liquid crystal aligning agent (A-2)～(A-16) and (A-18)～(A-21), estimate.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 the foregoing description 1, behind adding N-N-methyl-2-2-pyrrolidone N-and the ethylene glycol butyl ether, add 20 weight parts again as beyond the compound shown in the following formula (E-1) of epoxy compounds,
Figure BSA00000308305800681
With embodiment 1 similarly, prepare the printing evaluation respectively with liquid crystal aligning agent (P-17) and liquid crystal display device manufacturing usefulness liquid crystal aligning agent (A-17), estimate.
Evaluation result is as shown in table 2.
Comparative example 1
Except in the foregoing description 1, do not use particular polymers, use beyond two kinds of other polymkeric substance shown in the table 1 and embodiment 1 similarly, prepare the printing evaluation respectively and estimate with liquid crystal aligning agent (RA-1) with liquid crystal aligning agent (RP-1) and liquid crystal display device manufacturing.
Evaluation result is as shown in table 2.
Comparative example 2
In the solution that contains the polymethacrylate (PMA-1) that above-mentioned relatively synthesis example PMA-1 obtains, add N-methyl isophthalic acid-pyrrolidone (NMP) and ethylene glycol butyl ether, the printing evaluation for preparing solvent composition NMP/ ethylene glycol butyl ether/gamma-butyrolactone/glycol ether ethyl-methyl ether=23/50/25/2 (weight ratio), solid component concentration 7.0 weight % respectively with liquid crystal aligning agent (RP-2) and solid component concentration be 3.5% liquid crystal display device manufacturing with liquid crystal aligning agent (RA-2), estimate.Evaluation result is as shown in table 2.
[table 1]
Figure BSA00000308305800691
[table 2]

Claims (6)

1. liquid crystal aligning agent, it is characterized in that: contain at least a polymkeric substance of selecting in the group that is made of polyamic acid and polyimide, wherein, aforementioned polymer has the group shown in the following formula (0) in its intramolecular at least a portion,
Figure FSA00000308305700011
In the formula (0), R IBe that carbonatoms is that 3～12 alkyl or carbonatoms are 3～12 fluoro-alkyl, X IBe singly-bound or Sauerstoffatom, R IIBe 1,4-cyclohexylidene or 1,4-phenylene, X IIBe singly-bound, Sauerstoffatom or *-COO-, wherein, band " *" connecting key and R IIConnect, n is 0 or 1, X IIIBe following formula (X III-1) or (X III-2) group shown in,
-CH＝CH-?(X III-1)
-C≡C- (X III-2)。
2. the liquid crystal aligning agent of putting down in writing according to claim 1, wherein aforementioned polymer is at least a polymkeric substance of selecting from the group that the polyamic acid that is obtained by tetracarboxylic dianhydride and diamine reactant and the polyimide that this polyamic acid dehydration closed-loop is formed constitute, this diamines comprises the compound shown in the following formula (1)
Figure FSA00000308305700012
In the formula (1), R I, X I, R II, X III, X IIIIdentical with the definition in the above-mentioned formula (0) respectively with n, R IIIBe that singly-bound, methylene radical or carbonatoms are 1～6 alkylidene group, wherein this alkylidene group can be replaced by hydroxyl, X IVBe singly-bound, Sauerstoffatom or *-OCO-, wherein, band " *" connecting key and R IIIConnect, wherein, R IIIX when being singly-bound IVIt is singly-bound.
3. a liquid crystal display device is characterized in that: have the liquid crystal orientation film that is formed by claim 1 or 2 liquid crystal aligning agent of being put down in writing.
4. polyamic acid, this polyamic acid are by the tetracarboxylic dianhydride and comprise that the diamine reactant of the compound shown in the above-mentioned formula (1) obtains.
5. polyimide, this polyimide are will and comprise the polyamic acid dehydration closed-loop that the diamine reactant of the compound shown in the above-mentioned formula (1) obtains by the tetracarboxylic dianhydride to form.
6. the compound shown in the above-mentioned formula (1).
CN201010510115.7A 2009-10-06 2010-09-30 Liquid crystal orientation agent, liquid crystal display element, polyamide acids, polyimides, and compound Active CN102031122B (en)

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