CN101993697B

CN101993697B - Aligning agent for liquid crystal

Info

Publication number: CN101993697B
Application number: CN201010249378.7A
Authority: CN
Inventors: 阿久津光男; 阿部翼; 林英治; 福间聪司; 米田笃史; 泉谦一
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2009-08-10
Filing date: 2010-08-02
Publication date: 2014-03-19
Anticipated expiration: 2030-08-02
Also published as: KR101565393B1; CN101993697A; KR20110016390A

Abstract

The present invention relates to an aligning agent for liquid crystal having a good coating property, even when being continuously printed for a long time, polymers contained in the aligning agent for liquid crystal will not be separated, quality of a formed film is uniform and good, simultaneously, a formed liquid crystal aligning film is easy to peel. The aligning agent for liquid crystal contains at least one polymer selected from a group composed of polyamic acid and polyimides formed by dewatering and closed loop of the polyamic acid, the polyamic acid is obtained by diamine reaction of tetracarboxylic acid dianhydride and a specific compound containing a compound represented by formula (A), in the formula (A), X represents *-O- or *-COO- (wherein a connection key with * is connected with a diamino phenyl group), R is methane, alkylidene containing 2 to 20 of carbon atoms or arylidene containing 6 to 18 of carbon atoms, RI is alkyl containing 1 to 6 of carbon atoms, and n is an integer from 0 to 2.

Description

Liquid crystal aligning agent

Technical field

The present invention relates to a kind of liquid crystal aligning agent.More specifically, the present invention relates to a kind of coating good, formation membranous evenly and good, the yield rate when manufacturing liquid crystal orientation film is good liquid crystal aligning agent also.

Background technology

Current known liquid crystal display device, can be divided into all kinds shown below according to the physical property of electrode structure and liquid crystal molecule used.

First, known a kind of TN type liquid crystal display device with so-called TN type (twisted-nematic) liquid crystal cell, it is to form liquid crystal orientation film being provided with on the substrate surface of nesa coating, as used for liquid crystal display element substrate, again two these substrates are configured relatively, and form betwixt the layer of the nematic liquid crystal with positive dielectric anisotropy in gap, form the box of sandwich structure, and the major axis of liquid crystal molecule reverses 90 ° (patent documentations 1) continuously from a substrate to another piece substrate, and a kind ofly compare with TN type liquid crystal display device, can realize STN (supertwist is to row) the type liquid crystal display device (patent documentation 2) of high duty ratio.Further, the also same counter electrode configuration of known a kind of employing and TN type liquid crystal display device, but in electrode gap, inject the layer of the nematic liquid crystal with negative dielectric anisotropy, and make mesomorphic phase for the substantially vertical orientated VA of substrate (vertical orientated) type display element (patent documentation 3).This VA type display element, can manufacture high-contrast and large-area display element.

On the other hand, also known a kind of by the face of a plate base with comb teeth-shaped configured electrodes pair, and the IPS of the liquid crystal drive direction direction in real estate when applying electric field (switching in face) type liquid crystal display device (patent documentation 4) only, and the electrode structure that changes IPS type, improve the aperture opening ratio of display element part, thereby FFS (fringing field conversion) the type liquid crystal display device (patent documentation 5) that improves brightness, their viewing angle characteristics are separately good.

In addition, also developed view angle dependency little, OCB (Optical Compensated Bend: optical compensation curved) the type liquid crystal display device (patent documentation 6) that the high-speed response of image frame is good simultaneously etc.

Material as liquid crystal orientation film in these liquid crystal display device, known have resin materials such as polyamic acid, polyimide, polymeric amide and polyester, the liquid crystal orientation film particularly being formed by polyamic acid or polyimide, its thermotolerance, physical strength, good with the affinity of liquid crystal etc., therefore for many liquid crystal display device (patent documentation 1～4,7 and 8).This liquid crystal orientation film, be generally through containing the liquid crystal aligning agent that forms liquid crystal orientation film and be coated on substrate to be dissolved in the state of solvent, then except the operation of desolventizing is manufactured.

Yet, pointed out when manufacturing liquid crystal orientation film, use in the situation of hitherto known liquid crystal aligning agent, with certain probability form film on to have produced the printings such as the irregular or pore of printing bad, and the finished product rate when manufacturing liquid crystal orientation film is not enough.For example, when flexible printing, carry out in the situation of continuous printing for long time, in liquid crystal aligning agent, contained polymkeric substance is separated out to the anilox roll of printing press, and causes printing bad.This printing is bad, can think because the solvability of polymkeric substance contained in liquid crystal aligning agent is not enough.That is to say, can think and there are liquid crystal aligning performance, thermotolerance etc. as the polymkeric substance of the necessary various characteristics of liquid crystal orientation film, in any case all must there is upright and outspoken component part in its molecule, therefore its poorly soluble with respect to general organic solvent, thus, when carrying out continuous printing for long time, organic solvent comes out lentamente in roller, thereby cause under the strong solution state of the polymkeric substance generating, the mutual aggegation of polymer molecule, and observe thus polymkeric substance and separate out.

In addition, when this printing of generation is bad, although use stripper, peeled off the liquid crystal orientation film having formed, and substrate is recycled, to seek the effective utilization for resource, but by the formed liquid crystal orientation film of the low polymkeric substance of above-mentioned solvability, separability is also poor, be therefore difficult to such utilization.

In this area, in order to take into account as the performance guarantee of liquid crystal orientation film and for the solvability of solvent, study constantly all the year round, yet finished product rate while manufacturing liquid crystal orientation film still has certain limit.

Therefore, expect that a kind of to print bad probability of occurrence extremely low, even and just in case to have produced printing bad, the liquid crystal aligning agent of the liquid crystal orientation film having formed also can be peeled off at an easy rate.

Prior art

[patent documentation]

[patent documentation 1] Japanese kokai publication hei 4-153622 communique

[patent documentation 2] Japanese kokai publication sho 60-107020 communique

[patent documentation 3] Japanese kokai publication hei 11-258605 communique

[patent documentation 4] Japanese kokai publication sho 56-91277 communique

[patent documentation 5] TOHKEMY 2008-216572 communique

[patent documentation 6] TOHKEMY 2009-48211 communique

No. 5928733 specification sheets of [patent documentation 7] United States Patent (USP)

[patent documentation 8] Japanese kokai publication sho 62-165628 communique

[patent documentation 9] Japanese kokai publication hei 6-222366 communique

[patent documentation 10] Japanese kokai publication hei 6-281937 communique

[patent documentation 11] Japanese kokai publication hei 5-107544 communique

Summary of the invention

The present invention In view of the foregoing makes, its objective is that a kind of coating is provided is good, even and when carrying out continuous printing for long time, polymkeric substance contained in liquid crystal aligning agent can not separated out yet, what form is membranous even and good, meanwhile, the liquid crystal aligning agent that the liquid crystal orientation film having formed is easily peeled off.Due to this liquid crystal aligning agent, the yield rate when manufacturing liquid crystal orientation film is good, is therefore to expect in this area.

Other object of the present invention and advantage, can be learned by the following description.

According to the present invention, above-mentioned purpose of the present invention, by a kind of liquid crystal aligning agent, reached, at least one polymkeric substance that it contains from polyamic acid and makes to select the group of the formed polyimide formation of this polyamic acid dehydration closed-loop, this polyamic acid is by making tetracarboxylic dianhydride and comprising following formula (A ⁰) diamine reactant of represented compound obtains,

Formula (A ⁰) in, X is *-O-or *-COO-, above-mentioned in, with the connecting key of " * ", be connected with diamino-phenyl, R is the arylidene that methylene radical, the carbonatoms alkylidene group that is 2～10 or carbonatoms are 6～18, R ⁱfor the carbonatoms alkyl that is 1～6, the integer that n is 0～4, Z is carbonyl or the represented group of following formula (Z-1),

In formula (Z-1), R ^iIand R ^iIIbe the alkyl that hydrogen atom or carbonatoms are 1～6 independently of one another.

According to the present invention, provide a kind of coating good, even and when carrying out continuous printing for long time, polymkeric substance contained in liquid crystal aligning agent can not separated out yet, what form is membranous even and good, meanwhile, and the liquid crystal aligning agent that the liquid crystal orientation film having formed is easily peeled off.

This liquid crystal aligning agent of the present invention, can manufacture membranous even and good liquid crystal orientation film with high product yield rate, and meanwhile, the substrate yield rate while also contributing to manufacture liquid crystal display device improves.

Therefore, there is the liquid crystal display device by the formed liquid crystal orientation film of liquid crystal aligning agent of the present invention, can show with high-quality, and cheap, therefore go for various display unit such as clock and watch, portable game machine, word processor, notebook computer, auto-navigation system, camcorder, portable data assistance, digital camera, mobile phone, various indicating meter, LCD TV.

In addition, the contained formed film of polymkeric substance in this liquid crystal aligning agent, can also be used as electronic material insulating film.

Embodiment

Below, the present invention is described in detail.

Liquid crystal aligning agent of the present invention, at least one polymkeric substance that contains from polyamic acid and make to select the group of the formed polyimide formation of this polyamic acid dehydration closed-loop, this polyamic acid is by tetracarboxylic dianhydride and comprises above-mentioned formula (A ⁰) diamine reactant of represented compound obtains.

< polyamic acid >

[tetracarboxylic dianhydride]

As can, for the synthesis of the tetracarboxylic dianhydride of above-mentioned polyamic acid, enumerating for example butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-bis-is chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic base NSC 60134 dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, 3,5,6-, tri-carboxyls-2-carboxymethyl norbornane-2:3,5:6-dianhydride, 4,9-dioxa, three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, following formula (T-I) and (T-II)

(in formula, R ¹and R ³respectively do for oneself and there is the divalent organic group of aromatic nucleus, R ²and R ⁴respectively do for oneself hydrogen atom or alkyl, a plurality of R of existence ²and R ⁴separately can be identical, also can be different) the represented aliphatics tetracarboxylic dianhydrides such as compound and ester ring type tetracarboxylic dianhydride separately;

Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dianhydride, to phenylene-bis-(triphenyl phthalic acid) dianhydride, metaphenylene-bis-(triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol-bis-(dehydration trimellitate), propylene glycol-bis-(dehydration trimellitate), BDO-bis-(dehydration trimellitate), 1,6-hexylene glycol-bis-(dehydration trimellitate), 1,8-ethohexadiol-bis-(dehydration trimellitate), 2,2-bis-(4-hydroxyphenyl) propane-bis-(dehydration trimellitate), following formula (T-1)～(T-4)

Represented aromatic tetracarboxylic acid's dianhydrides such as compound separately.The alkyl (being preferably methyl) that the phenyl ring of above-mentioned aromatic tetracarboxylic acid's dianhydride can be also 1～4 by one or more carbonatoms replaces.

These tetracarboxylic dianhydrides can use separately a kind of or be used in combination of two or more.

As can be for the synthesis of the tetracarboxylic dianhydride of polyamic acid of the present invention, comprise the butane tetracarboxylic acid dianhydride being selected from above-mentioned, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic base NSC 60134 dianhydride, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, 3,5,6-, tri-carboxyls-2-carboxymethyl norbornane-2:3,5:6-dianhydride, 4,9-dioxa, three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1, following formula (T-5) in the represented compound of 4,5,8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I)～(T-7)

Following formula in the represented compound of represented compound and above-mentioned formula (T-II) separately

(T-8)

At least one in the group that represented compound forms (following, to be called " specific tetracarboxylic dianhydride "), the viewpoint that can show good liquid crystal aligning from the liquid crystal orientation film forming is considered, is preferred.

As specific tetracarboxylic dianhydride, more preferably be selected from 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic base NSC 60134 dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyls-2-carboxymethyl norbornane-2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3, at least one in the group that the represented compound of 5,8,10-tetraketone, pyromellitic acid dianhydride and above-mentioned formula (T-5) forms, and be particularly preferably 2,3,5-tricarboxylic base NSC 60134 dianhydride.

Can with respect to whole tetracarboxylic dianhydrides, preferably contain more than 50 % by mole for the synthesis of the tetracarboxylic dianhydride of polyamic acid of the present invention, more preferably contain more than 70 % by mole, and particularly preferably contain 80 % by mole of above specific tetracarboxylic dianhydrides as above.

As can, for the synthesis of the tetracarboxylic dianhydride of polyamic acid of the present invention, most preferably only using specific tetracarboxylic dianhydride as above.

[diamines]

Can, for the synthesis of the diamines of polyamic acid of the present invention, comprise above-mentioned formula (A ⁰) represented compound.

As above-mentioned formula (A ⁰) in the carbonatoms of the R alkylidene group that is 2～10, be preferably carbonatoms and be 2～6 straight-chain alkyl-sub-.The arylidene that is 6～18 as the carbonatoms of R, be preferably carbonatoms and be 6～10 arylidene, as its object lesson, can enumerate for example Isosorbide-5-Nitrae-phenylene, 1,3-phenylene, 1,2-phenylene, xenyl-4,4 '-bis-bases, ditan 4,4 '-bis-bases, 3,3 '-dimethyl diphenyl base-4,4 '-bis-bases etc.

And preferred separately, above-mentioned formula (A ⁰) in R be that carbonatoms is 2～6 straight-chain alkyl-sub-; Z is carbonyl or methylene radical; N is 0～2 integer.Above-mentioned formula (A ⁰) in diamino-phenyl in two amino, with respect to other group, be preferably 2,4-position or 3,5-position.

As this above-mentioned formula (A ⁰) object lesson of represented compound, can enumerate for example 1-[2-(3,5-diamino-phenoxy group)-ethyl]-tetramethyleneimine-2,5-diketone, 1-[3-(3,5-diamino-phenoxy group)-propyl group]-tetramethyleneimine-2,5-diketone, 1-[4-(3,5-diamino-phenoxy group)-butyl]-tetramethyleneimine-2,5-diketone, 1-[5-(3,5-diamino-phenoxy group)-amyl group]-tetramethyleneimine-2,5-diketone, 1-[6-(3,5-diamino-phenoxy group)-hexyl]-tetramethyleneimine-2,5-diketone, 3,5-diamino-phenylformic acid 2-(2,5-dioxo-pyrrolidin-1-yl)-ethyl ester, 3,5-diamino-phenylformic acid 3-(2,5-dioxo-pyrrolidin-1-yl)-propyl ester, 3,5-diamino-phenylformic acid 4-(2,5-dioxo-pyrrolidin-1-yl)-butyl ester, 3,5-diamino-phenylformic acid 5-(2,5-dioxo-pyrrolidin-1-yl)-pentyl ester, 3,5-diamino-phenylformic acid 6-(2,5-dioxo-pyrrolidin-1-yl)-own ester, 1-[2-(2,4-diamino-phenoxy group)-ethyl]-tetramethyleneimine-2,5-diketone, 1-[3-(2,4-diamino-phenoxy group)-propyl group]-tetramethyleneimine-2,5-diketone, 1-[4-(2,4-diamino-phenoxy group)-butyl]-tetramethyleneimine-2,5-diketone, 1-[5-(2,4-diamino-phenoxy group)-amyl group]-tetramethyleneimine-2,5-diketone, 1-[6-(2,4-diamino-phenoxy group)-hexyl]-tetramethyleneimine-2,5-diketone, 1-[2-(3,5-diamino-phenoxy group)-ethyl]-2-pyrroles's a heatable brick bed ketone, 1-[3-(3,5-diamino-phenoxy group)-propyl group]-2-Pyrrolidone, 1-[4-(3,5-diamino-phenoxy group)-butyl]-2-Pyrrolidone, 1-[5-(3,5-diamino-phenoxy group)-amyl group]-2-Pyrrolidone, 1-[6-(3,5-diamino-phenoxy group)-hexyl]-2-Pyrrolidone, 3,5-diamino-phenylformic acid 2-(2-oxo-pyrrolidin-1-yl)-ethyl ester, 3,5-diamino-phenylformic acid 3-(2-oxo-pyrrolidin-1-yl)-propyl ester, 3,5-diamino-phenylformic acid 4-(2-oxo-pyrrolidin-1-yl)-butyl ester, 3,5-diamino-phenylformic acid 5-(2-oxo-pyrrolidin-1-yl)-pentyl ester, 3,5-diamino-phenylformic acid 6-(2-oxo-pyrrolidin-1-yl)-own ester, 1-[2-(2,4-diamino-phenoxy group)-ethyl]-2-Pyrrolidone, 1-[3-(2,4-diamino-phenoxy group)-propyl group]-2-Pyrrolidone, 1-[4-(2,4-diamino-phenoxy group)-butyl]-2-Pyrrolidone, 1-[5-(2,4-diamino-phenoxy group)-amyl group]-2-Pyrrolidone, 1-[6-(2,4-diamino-phenoxy group)-hexyl]-2-Pyrrolidone etc.

As above-mentioned formula (A ⁰) represented compound, be preferably following formula (A)

(in formula (A), X, R and R ⁱrespectively with above-mentioned formula (A ⁰) middle synonym, n is 0～2 integer) represented compound, the compound that more preferably in above-mentioned formula (A), n is 0, and particularly preferably use and be selected from 1-[2-(3, 5-diamino-phenoxy group)-ethyl]-tetramethyleneimine-2, 5-diketone, 1-[3-(3, 5-diamino-phenoxy group)-propyl group]-tetramethyleneimine-2, 5-diketone, 1-[4-(3, 5-diamino-phenoxy group)-butyl]-tetramethyleneimine-2, 5-diketone, 1-[5-(3, 5-diamino-phenoxy group)-amyl group]-tetramethyleneimine-2, 5-diketone, 1-[6-(3, 5-diamino-phenoxy group)-hexyl]-tetramethyleneimine-2, 5-diketone, 3, 5-diamino-phenylformic acid 2-(2, 5-dioxo-pyrrolidin-1-yl)-ethyl ester, 3, 5-diamino-phenylformic acid 3-(2, 5-dioxo-pyrrolidin-1-yl)-propyl ester, 3, 5-diamino-phenylformic acid 4-(2, 5-dioxo-pyrrolidin-1-yl)-butyl ester, 3, 5-diamino-phenylformic acid 5-(2, 5-dioxo-pyrrolidin-1-yl)-pentyl ester and 3, 5-diamino-phenylformic acid 6-(2, at least one in the group of 5-dioxo-pyrrolidin-1-yl)-own ester formation.

This above-mentioned formula (A ⁰) represented compound, can be by synthesizing vitochemical ordinary method is appropriately combined.

For example, in above-mentioned formula (A), X is-O-, and n is 0, and diamino-phenyl is the compound of 3,5-diamino-phenyl, for example, can synthesize according to following synthetic route a～c.

synthetic route a

synthetic route b

synthetic route c

(in said synthesis route, synonym in R and above-mentioned formula (A))

The reaction that said synthesis route a is represented, can be by making phloroglucinol and diallyl amine, preferably reaction and carrying out under the existence of sodium bisulfite.This reaction, can be at the temperature of 5～40 ℃, carries out with the reaction times of 5～15 hours.By this reaction, can obtain the compound (A-1-1a) as intermediate.

The reaction that said synthesis route b is represented, can be by thering is compound (A-1a) and for example parachloroben-zenesulfonyl chloride of desirable radicals R, preferably in suitable solvent, be pre-mixed, and slowly add wherein the method for suitable alkali (for example triethylamine) and carry out.The interpolation of alkali is preferably carried out at the temperature of for example-5～5 ℃ of low temperature.Then, reaction system is heated to 10～30 ℃ of left and right, then continues reaction about 2～4 hours, can obtain thus midbody compound (A-1b).

In said synthesis route c, obtain the reaction of midbody compound (A-1c), can be by by the compound obtaining as mentioned above (A-1-1a) and compound (A-1b), preferably under the existence of potassium hydride KH and Tetrabutylammonium bromide, and preferred preferred reaction 8～15 hours and carrying out at the temperature of-5～5 ℃.Then the compound of gained like this (A-1c) is sloughed to allyl group, can obtain target product.De-allyl reaction, can be by by compound (A-1c), preferably under the existence of 1,3-dimethyl barbituric acid and four (triphen phosphino-) palladium, and preferred preferred reaction 2～6 hours and carrying out at the temperature of 20～40 ℃.

In above-mentioned formula (A), X is *-COO-(wherein, being connected with diamino-phenyl with the connecting key of " * "), and n is 0, and diamino-phenyl is the compound of 3,5-diamino-phenyl, for example, can synthesize according to following synthetic route d.

synthetic route d

(in said synthesis route, synonym in R and above-mentioned formula (A))

It can be by having the compound (A-1a) of desirable radicals R and for example 3, and 5-dinitrobenzoyl chloride is dissolved in suitable organic solvent, and slowly adds wherein the method for suitable alkali (for example triethylamine) and carry out.The interpolation of alkali, preferably at low temperature, for example, carries out at the temperature of-5～5 ℃.Then, reaction system is heated to 10～30 ℃ of left and right, then continues reaction about 2～4 hours, can obtain thus midbody compound (A-1d).Then, by using suitable reduction system, for example zinc, ammonium chloride and water, the nitro that reduction (hydrogenation) compound (A-1d) has and form amino, can obtain target product thus.

In above-mentioned formula (A), X is-O-, and n is 0, and diamino-phenyl is the compound of 2,4-diamino-phenyl, for example, can synthesize according to following synthetic route e.

synthetic route e

(in said synthesis route, synonym in R and above-mentioned formula (A))

By thering are the compound (A-1a) of desirable radicals R and for example 2,4-dinitrobenzene fluorobenzene is dissolved in suitable organic solvent, add wherein suitable alkali (for example triethylamine), and reaction system is heated to 30～50 ℃ of left and right, carry out reaction about 8～15 hours, can obtain midbody compound (A-1e).Then, by using suitable reduction system, for example zinc, ammonium chloride and water, the nitro that reduction (hydrogenation) compound (A-1d) has and form amino, can obtain target product thus.

At above-mentioned formula (A ⁰) in, X is-O-, and n is that 0, Z is methylene radical, and diamino-phenyl is the compound of 3,5-diamino-phenyl, for example, can synthesize according to following synthetic route f and g.

synthetic route f

synthetic route g

(in said synthesis route, R and above-mentioned formula (A ⁰) middle synonym)

The reaction that said synthesis route f is represented, can be by thering is compound (A-1f) and for example parachloroben-zenesulfonyl chloride of desirable radicals R, preferably in suitable solvent, be pre-mixed, and slowly add wherein the method for suitable alkali (for example triethylamine) and carry out.The interpolation of alkali is preferably carried out at the temperature of for example-5～5 ℃ of low temperature.Then, reaction system is heated to 10～30 ℃ of left and right, then continues reaction about 2～4 hours, can obtain thus midbody compound (A-1g).

In said synthesis route g, obtain the reaction of midbody compound (A-1h), can be by by the compound obtaining as mentioned above (A-1-1a) and compound (A-1f), preferably under the existence of potassium hydride KH and Tetrabutylammonium bromide, and preferred preferred reaction 8～15 hours and carrying out at the temperature of-5～5 ℃.Then the compound of gained like this (A-1h) is sloughed to allyl group, can obtain target product.De-allyl reaction, can be by by compound (A-1h), preferably under the existence of 1,3-dimethyl barbituric acid and four (triphen phosphino-) palladium, and preferred preferred reaction 2～6 hours and carrying out at the temperature of 20～40 ℃.

At above-mentioned formula (A ⁰) in, X is-COO-, and Z is methylene radical, and n is 0, and diamino-phenyl is the compound of 3,5-diamino-phenyl, for example, can synthesize according to following synthetic route h.

synthetic route h

(in said synthesis route, R and above-mentioned formula (A ⁰) middle synonym)

It can be by having the compound (A-1f) of desirable radicals R and for example 3, and 5-dinitrobenzoyl chloride is dissolved in suitable organic solvent, and slowly adds wherein the method for suitable alkali (for example triethylamine) and carry out.The interpolation of alkali is preferably carried out at the temperature of for example-5～5 ℃ of low temperature.Then, reaction system is heated to 10～30 ℃ of left and right, then continues reaction about 2～4 hours, can obtain thus midbody compound (A-1i).Then, by using suitable reduction system, for example zinc, ammonium chloride and water, the nitro that reduction (hydrogenation) compound (A-1i) has and form amino, can obtain target product thus.

In addition, at above-mentioned formula (A ⁰) in, X is-O-, and Z is methylene radical, and n is 0, and diamino-phenyl is the compound of 2,4-diamino-phenyl, for example, can synthesize according to following synthetic route i.

synthetic route i

(in said synthesis route, R and above-mentioned formula (A ⁰) middle synonym)

By thering is the compound (A-1j) and 2 of desirable radicals R, 4-dinitrobenzene fluorobenzene is dissolved in suitable organic solvent, add wherein suitable alkali (for example triethylamine), and reaction system is heated to 30～50 ℃ of left and right, proceed reaction about 8～15 hours, can obtain midbody compound (A-1k).Then, by using suitable reduction system, for example zinc, ammonium chloride and water, the nitro that reduction (hydrogenation) compound (A-1k) has and form amino, can obtain target product thus.

As the diamines for the synthesis of polyamic acid of the present invention, can only use the represented compound of above-mentioned formula (A), also represented compound and other diamines of above-mentioned formula (A) can be used in combination.

As operable other diamines herein, can enumerate for example Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formylaniline, 4,4 '-diaminodiphenyl oxide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diamino benzophenone, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, two [4-(4-amino-benzene oxygen) phenyl] sulfone, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 1,3-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(3-amino-benzene oxygen) benzene, 9,9-bis-(4-aminophenyl)-10-hydrogen anthracene, 2,7 diamin of luorene, 9,9-dimethyl-2,7 diamin of luorene, 9,9-bis-(4-aminophenyl) fluorenes, two (4-amino-2-chloro-phenyl-) methane, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-bis-is chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to phenylene diisopropylidene) two (aniline), 4,4 '-(metaphenylene diisopropylidene) two (aniline), 2,2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-3,3 '-bis-(trifluoromethyl) biphenyl, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 4,4 '-bis-[(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, following formula (D-1)～(D-5)

(integer that the y in formula (D-4) is 2～12, the integer that the z in formula (D-5) is 1～5) be represented aromatic diamines such as compound separately;

1,1-m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine, heptamethylene diamines, eight methylene diamine, nine methylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0 ^2,7]-11 alkylidene group dimethyl diamines, 4,4 '-methylene radical two (hexahydroaniline), 1, aliphatie diamine and the ester ring type diamines such as 3-bis-(amino methyl) hexanaphthene, Isosorbide-5-Nitrae-bis-(amino methyl) hexanaphthene;

2,3 diamino pyridine, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2,4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazines, Isosorbide-5-Nitrae-bis-(3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazines, 2,4-diamino-6-methoxyl group-1,3,5-triazines, 2,4-diamino-6-phenyl-1,3,5-triazines, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazines, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2,6-diaminopurine, 5,6-diaminostilbene, 3-dimethyl uracil, 3,5-diaminostilbene, 2,4-triazole, 3,8-diamino-6-phenylphenanthridineand, Isosorbide-5-Nitrae-diamino piperazine, 3,6-proflavin, N, N '-bis-(4-aminophenyl) aniline, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-dimethyl-p-diaminodiphenyl and following formula (D-I) and (D-II)

(in formula (D-I), R ⁵for thering is 1 valency organic group of the nitrogen atom ring texture in the group that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine formation, X ¹organic group for divalent;

In formula (D-II), R ⁶for thering is the divalent organic group of the nitrogen atom ring texture in the group that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine formation, X ²respectively the do for oneself organic group of divalent, a plurality of X of existence ²separately can be identical, also can be different) separately represented compound etc. in molecule, there is the diamines of the nitrogen-atoms beyond 2 primary aminos and this primary amino;

Following formula (D-III)

(in formula (D-III), R ⁷for be selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-or-CO-, R ⁸for thering is skeleton in the group that the steroid backbone of being selected from, trifluoromethyl, Trifluoromethoxyphen-l and difluorophenyl form or 1 valency organic group of group or the alkyl that carbonatoms is 6～30) the represented single-substituted diamines such as compound;

Following formula (D-IV)

(in formula (D-IV), R ⁹the carbonatoms of respectively doing for oneself is 1～12 alkyl, a plurality of R of existence ⁹separately can be identical, also can be different, respectively do for oneself 1～3 integer of p, the integer that q is 1～20) represented diamino organo-siloxanes such as compound etc.Above-mentioned aromatic diamine, the diamines in molecule with the nitrogen-atoms beyond 2 primary aminos and this primary amino and the phenyl ring that single-substituted diamines has, the alkyl (being preferably methyl) that can be also 1～4 by 1 or 2 above carbonatomss replaces.In addition, the steroid backbone in above-mentioned formula (D-III), refers to 1 or 2 above skeletons for two keys in the formed skeleton of pentamethylene base-perhydro-phenanthrene nucleus or its carbon-carbon bond.

These diamines, can be used singly or in combination of two or more.

As can be for the synthesis of other diamines of polyamic acid of the present invention, preferably use the Ursol D being selected from above-mentioned, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino-diphenyl thioether, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to phenylene diisopropylidene) two (aniline), 4,4 '-(metaphenylene diisopropylidene) two (aniline), Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene radical two (hexahydroaniline), 1,3-bis-(amino methyl) hexanaphthene, above-mentioned formula (D-1)～(D-5) is represented compound separately, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, following formula (D-6) in the represented compound of above-mentioned formula (D-I)

Following formula (D-7) in the represented compound of represented compound, above-mentioned formula (D-II)

Dodecyloxy-2 in the represented compound of represented compound and above-mentioned formula (D-III), 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-2,5-diaminobenzene, following formula (D-8)～(D-15)

In the represented compound of represented compound and above-mentioned formula (D-IV) 1 separately, at least one in the group that 3-bis-(3-aminopropyl)-tetramethyl disiloxane forms (following, to be called " other specific diamines ").

Can be for the synthesis of the diamines of polyamic acid of the present invention, with respect to whole diamines, preferably contain more than 3 % by mole, more preferably contain 5～90 % by mole, further preferably contain 3～70 % by mole, and particularly preferably contain the represented compound of 8～50 % by mole of above-mentioned formulas (A).

Can, for the synthesis of the diamines of polyamic acid of the present invention, preferably, except the represented compound of above-mentioned formula (A), also contain other specific diamines as above.As the usage ratio of other specific diamines at this moment, with respect to whole diamines, be preferably more than 5 % by mole, more preferably 10～97 % by mole, more preferably 30～95 % by mole, and be particularly preferably 50～92 % by mole.

Can, for the synthesis of the diamines of polyamic acid of the present invention, preferably only by the represented compound of above-mentioned formula (A) and other specific diamines, be formed.

[synthesizing of polyamic acid]

Polyamic acid in the present invention, can obtain by the diamine reactant that makes tetracarboxylic dianhydride and comprise the represented compound of above-mentioned formula (A).

Supply with the tetracarboxylic dianhydride and the usage ratio of diamines of polyamic acid building-up reactions, with respect to 1 equivalent amino contained in diamines, tetracarboxylic dianhydride's anhydride group is preferably the ratio of 0.2～2 equivalent, and the ratio of 0.3～1.2 equivalent more preferably.

The building-up reactions of polyamic acid, preferably in organic solvent, and preferably at-20 ℃～150 ℃, more preferably under the temperature condition of 0～100 ℃, and preferably carries out 0.1～24 hour, more preferably carries out 0.5～12 hour.

As operable organic solvent when synthesizing polyamides is sour, can enumerate such as non-proton property polar solvent, phenol and derivative thereof, alcohol, ketone, ester, ether, halon, hydrocarbon etc.

As above-mentioned non-proton property polar solvent, can enumerate such as METHYLPYRROLIDONE, N,N-dimethylacetamide, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc.;

As above-mentioned amphyl, for example can enumerate between sylvan, xylenol, halogenated phenol;

As above-mentioned alcohol, can enumerate such as methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triglycol, ethylene glycol monomethyl ether etc.;

As above-mentioned ketone, can enumerate for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone;

As above-mentioned ester, can enumerate such as ethyl lactate, n-Butyl lactate, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, methoxy methyl propionate, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate etc.;

As above-mentioned ether, can enumerate such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether, glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF) etc.;

As above-mentioned halohydrocarbon, can enumerate for example methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.;

As above-mentioned hydrocarbon, can enumerate such as hexane, heptane, octane, benzene,toluene,xylene, isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.

In these organic solvents, preferably use more than one in choosing group's (organic solvent of the first group) that freely non-proton property polar solvent and phenol and derivative thereof form, or be selected from aforementioned the first group organic solvent more than one and select more than one the mixture in group's (organic solvent of the second group) that free alcohol, ketone, ether, halohydrocarbon and hydrocarbon form.Under latter instance, the usage ratio of the organic solvent of the second group, the total with respect to the organic solvent of the first group and the organic solvent of the second group, is preferably below 50 % by weight, more preferably below 40 % by weight, and more preferably below 30 % by weight.

As mentioned above, can obtain dissolving the formed reaction soln of polyamic acid.

This reaction soln, can directly supply with the modulation of liquid crystal aligning agent, also polyamic acid contained in reaction soln can be separated to the modulation of rear supply liquid crystal aligning agent, or after isolated polyamic acid can also being refined, resupply the modulation of liquid crystal aligning agent.

When making polyamic acid dehydration closed-loop form polyimide, above-mentioned reaction soln directly can be supplied with to dehydration closed-loop reaction, also polyamic acid contained in reaction soln can be separated to rear supply dehydration closed-loop reaction, or resupply dehydration closed-loop reaction after isolated polyamic acid can also being refined.

The separation of polyamic acid, can obtain precipitate by above-mentioned reaction soln is put in a large amount of poor solvents, then the method for this precipitate of drying under reduced pressure, or uses the method that vaporizer distillates the organic solvent decompression in reaction soln and carry out.In addition, can then with poor solvent, make its method of separating out by this polyamic acid is dissolved in organic solvent again, or the method for the operation of using once or several times vaporizer to reduce pressure to distillate, refining polyamic acid.

< polyimide >

Polyimide in the present invention, can, by making polyamic acid dehydration closed-loop as above, carry out imidization and obtain.

As can, for the synthesis of the tetracarboxylic dianhydride of above-mentioned polyimide, enumerating and above-mentioned compound that can be identical for the synthesis of the tetracarboxylic dianhydride of polyamic acid.Preferred tetracarboxylic dianhydride's kind and preferred usage ratio thereof are identical with the situation of polyamic acid.

As can, for the synthesis of the diamines of polyimide in the present invention, enumerating and above-mentioned diamines that can be identical for the synthesis of the diamines of polyamic acid.That is to say, can be for the synthesis of the diamines of polyimide contained in liquid crystal aligning agent of the present invention, comprise the represented compound of above-mentioned formula (A), and can only use the represented compound of above-mentioned formula (A), also can be used together the represented compound of above-mentioned formula (A) and above-mentioned other diamines.The preferred kind of other diamines and the preferred usage ratio of various diamines are identical with the situation of polyamic acid.

Polyimide in the present invention, can be the amido acid structure fully dehydrating closed loop that the polyamic acid as raw material is had and the complete imide compound obtaining, or can be also the amido acid structure that only a part of dehydration closed-loop in amido acid structure obtained and imide ring structure the part imide compound of depositing.Polyimide in the present invention, its imide rate is preferably more than 30%, and more preferably more than 50%.This imide rate is to represent that with percentage imide ring structure number is with respect to the value of the amido acid structure number of polyimide and the total amount proportion of imide ring structure number.At this moment, a part for imide ring can be also different imide ring.

The dehydration closed-loop of polyamic acid, preferably by the method for (i) heating polyamic acid, or (ii) is dissolved in polyamic acid in organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer, and the method for heating as required and carrying out.

Temperature of reaction in the method for above-mentioned (i) heating polyamic acid, is preferably 50～200 ℃, and more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, dehydration closed-loop reaction cannot fully be carried out, and if temperature of reaction surpasses 200 ℃, the molecular weight and molecular weight of gained polyimide.In the reaction times, be preferably 1.0～24 hours, and more preferably 1.0～12 hours.

On the other hand, above-mentioned (ii) adds in the method for dewatering agent and dehydration closed-loop catalyzer in the solution of polyamic acid, as dewatering agent, can use acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.The usage ratio of dewatering agent, determines according to desirable imide rate, but preferably with respect to the amido acid structure of 1 mole of polyamic acid, is 0.01～20 mole.As dehydration closed-loop catalyzer, can use tertiary amines such as pyridine, collidine, two picolins, triethylamine, but be not limited to these.The usage ratio of dehydration closed-loop catalyzer, with respect to 1 mole of dewatering agent used, is preferably 0.01～10 mole.The usage quantity of above-mentioned dewatering agent and dehydration closed-loop agent is more, can improve imide rate.As can be for the organic solvent of dehydration closed-loop reaction, can enumerate as organic solvent used in polyamic acid synthetic and illustrative organic solvent.The temperature of reaction of dehydration closed-loop reaction, is preferably 0～180 ℃, and more preferably 10～150 ℃.In the reaction times, be preferably 1.0～120 hours, and more preferably 2.0～30 hours.

In aforesaid method (i), the polyimide of gained, can directly supply with the preparation of liquid crystal aligning agent by it, or after also the polyimide of gained can being refined, resupplies the preparation of liquid crystal aligning agent.On the other hand, in aforesaid method (ii), can obtain the reaction soln that contains polyimide.This reaction soln, it directly can be supplied with to the preparation of liquid crystal aligning agent, also can remove dewatering agent and dehydration closed-loop catalyzer from reaction soln after, supply with the preparation of liquid crystal aligning agent, polyimide separation can also be supplied with afterwards to the preparation of liquid crystal aligning agent, or after separated polyimide can also being refined, be resupplied the preparation of liquid crystal aligning agent.From reaction soln, remove dewatering agent and dehydration closed-loop catalyzer, can adopt such as methods such as solvent exchanges.The separation of polyimide, refining, can take and as the same operation described in separated, the process for purification of polyamic acid, carry out above.

-polymkeric substance of end modified type-

Polyamic acid in the present invention and polyimide can be the polymkeric substance that has carried out the end modified type of molecular-weight adjusting separately.By using the polymkeric substance of end modified type, can, not damaging under the prerequisite of effect of the present invention, further improve the coating characteristics of liquid crystal aligning agent etc.The polymkeric substance of this end modified type, can be by synthesizing polyamides when acid, to adding molecular weight regulator in polymerization reaction system, carries out.As molecular weight regulator, can enumerate such as single acid anhydride, monoamine compound, monoisocyanates compound etc.

As above-mentioned single acid anhydride, can enumerate such as maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.; As above-mentioned monoamine compound, can enumerate such as aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane amine, n-hexadecane amine, n-heptadecane amine, Octadecane amine, NSC 62789 amine etc.; As above-mentioned monoisocyanates compound, can enumerate such as phenylcarbimide, isocyanic acid naphthyl ester etc.

The usage ratio of molecular weight regulator, the tetracarboxylic dianhydride who uses while synthesizing with respect to 100 weight parts of polyamide acid and the total amount of diamines, be preferably below 20 weight parts, and more preferably below 10 weight parts.

-soltion viscosity-

As above the polyamic acid of gained or polyimide, when formation concentration is the solution of 10 % by weight, preferably has the soltion viscosity of 20～800mPas, and more preferably have the soltion viscosity of 30～500mPas.

The soltion viscosity of above-mentioned polymkeric substance (mPas), for the polymers soln of 10 % by weight concentration that adopts good solvent (such as gamma-butyrolactone, the METHYLPYRROLIDONE etc.) modulation of this polymkeric substance, the value of using E type rotational viscosimeter to measure at 25 ℃.

Other composition of < >

Liquid crystal orientation film of the present invention, contains at least one in the choosing group that freely polyamic acid as above and the formed polyimide of imidization thereof form as neccessary composition, but also can contain as required other polymkeric substance.As this other composition, can enumerate for example other polymkeric substance, the compound (following, to be called " epoxy compounds ") for example in molecule with at least one epoxy group(ing), functional silanes compound etc.

[other polymkeric substance]

Above-mentioned other polymkeric substance, can be for improving solution properties and electrical specification.This other polymkeric substance, to make the polyamic acid of tetracarboxylic dianhydride and the diamine reactant gained that comprises the represented compound of above-mentioned formula (A) and make the polymkeric substance beyond the formed polyimide of this polyamic acid dehydration closed-loop, for example make tetracarboxylic dianhydride (following with the polyamic acid that does not comprise the diamine reactant gained of the represented compound of above-mentioned formula (A), be called " other polyamic acid "), make the formed polyimide of this polyamic acid dehydration closed-loop (following, be called " other polyimide "), poly amic acid ester, polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.Wherein, preferably other polyamic acid or other polyimide, and more preferably other polyamic acid.

Usage ratio as other polymkeric substance, with respect to the total amount of polymkeric substance (refer to above-mentioned tetracarboxylic dianhydride and the diamine reactant gained that comprises the represented compound of above-mentioned formula (A) polyamic acid, make the total amount of the formed polyimide of this polyamic acid dehydration closed-loop and other polymkeric substance, lower same), be preferably below 90 % by weight, 10～85 % by weight more preferably, and 30～80 % by weight more preferably.

[epoxy compounds]

As above-mentioned epoxy compounds, preferably can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, 3-bis-(N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl hexanaphthene, N, N-diglycidyl-hexahydroaniline etc.

The mixing ratio of these epoxy compoundss, with respect to the total amount of 100 parts by weight polymer, is preferably below 40 weight parts, and 0.1～30 weight part more preferably.

[functional silanes compound]

As above-mentioned functional silanes compound, can enumerate for example 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-APTES, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilicane alkyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, 9-triethoxysilicane alkyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, glycidyl ether oxygen ylmethyl Trimethoxy silane, glycidyl ether oxygen ylmethyl triethoxyl silane, 2-glycidyl ether oxygen base ethyl trimethoxy silane, 2-glycidyl ether oxygen base ethyl triethoxysilane, 3-glycidyl ether oxygen base propyl trimethoxy silicane, 3-glycidyl ether oxygen base propyl-triethoxysilicane etc.

The mixing ratio of these functional silanes compounds, with respect to the total amount of 100 parts by weight polymer, is preferably below 2 weight parts, and 0.02～0.2 weight part more preferably.

Liquid crystal aligning agent of the present invention, preferably by least one polymkeric substance in the choosing group that freely polyamic acid as above and polyimide form and other additive coordinating arbitrarily as required, dissolves and is included in organic solvent and forms.

As the organic solvent can be used in liquid crystal aligning agent of the present invention, can enumerate for example METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, NSC 11801, propylene carbonate etc.They may be used alone, or two or more mixed.

The solid component concentration of liquid crystal aligning agent of the present invention (the total weight of the composition beyond desolventizing in liquid crystal aligning agent accounts for the ratio of liquid crystal aligning agent gross weight), considers viscosity, volatility etc. and suitably selection, and is preferably the scope of 1～10 % by weight.That is to say, as described later liquid crystal aligning agent of the present invention is coated on substrate surface, and preferably by adding thermosetting as the filming of liquid crystal orientation film, but when solid component concentration less than 1 % by weight, will occur that this thickness of filming is too small and be difficult to obtain the situation of good liquid crystal orientation film; On the other hand, when solid component concentration surpasses 10 % by weight, will occur that coating thickness is blocked up and be difficult to equally obtain the situation of good liquid crystal orientation film, or the viscosity that occurs liquid crystal aligning agent is increased to the situation that causes coating characteristics variation.

The scope of particularly preferred solid component concentration, the method adopting during according to coating of liquid crystalline alignment agent on substrate and difference.For example, when adopting spin-coating method, particularly preferably solid component concentration is the scope of 1.5～4.5 % by weight.When adopting print process, particularly preferably making solid component concentration is the scope of 3～9 % by weight, and thus, can make soltion viscosity is the scope of 12～50mPas.When adopting ink jet method, particularly preferably making solid component concentration is the scope of 1～5 % by weight, and thus, can make soltion viscosity is the scope of 3～15mPas.

Temperature while modulating liquid crystal aligning agent of the present invention, is preferably 10～50 ℃, and more preferably 20～30 ℃.

< liquid crystal display device >

Liquid crystal display device of the present invention, has by the formed liquid crystal orientation film of liquid crystal aligning agent of the present invention as above.

Liquid crystal display device of the present invention, can be by for example operation manufacture of following (1) to (3).Operation (1), according to desirable operation scheme, the substrate of its use is also different.Each operation scheme of operation (2) and (3) is common.

(1) first liquid crystal aligning agent of the present invention is coated on substrate, then heats coated face, on substrate, form and film.

(1-1) when manufacturing TN type, STN type or VA type liquid crystal display device, two substrates that make to be provided with the nesa coating that forms pattern are paired, and liquid crystal aligning agent of the present invention is coated on transparent conducting film formation face separately respectively, then heat each coated face, formation is filmed.As coating process, can enumerate such as offset printing method, flexible printing method, ink jet printing method, rolling method, spin-coating method etc., but owing to adopting flexible printing method, can bring into play to greatest extent the present invention and there will not be polymkeric substance to the effect of separating out in anilox roll, therefore preferably.As substrate, can use glass such as float glass, soda-lime glass herein; Polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene) etc. are by the formed transparency carrier of plastics.As substrate, simultaneously go up set nesa coating, can use by stannic oxide (SnO ₂) form NESA film (U.S. PPG register of company trade mark), by Indium sesquioxide-stannic oxide (In ₂o ₃-SnO ₂) the ITO film that forms etc., in order to obtain forming the nesa coating of pattern, can adopt and for example form after patternless nesa coating, by photoengraving form the method for pattern, when forming nesa coating, use the method for the mask with desirable pattern etc.When coating of liquid crystalline alignment agent, better for the adhesivity that makes substrate surface and nesa coating and film, can be embodied in substrate surface and will form on the surface of filming, be coated with in advance the pre-treatment of functional silanes compound, functionality titanium compound etc.

After coating of liquid crystalline alignment agent, in order to prevent the situations such as the alignment agent liquid of coating drips, preferably preheat (prebake).Prebake temperature, is preferably 30～200 ℃, and more preferably 40～150 ℃, and be particularly preferably 40～100 ℃.The prebake time, is preferably 0.25～10 minute, and more preferably 0.5～5 minute.Then, in order to remove desolventizing completely, and the object that makes as required the amido acid unit hot-imide in polymerization process, burn till (curing afterwards) operation.This burns till (curing afterwards) temperature, is preferably 80～300 ℃, and more preferably 120～250 ℃.After cure the time, be preferably 5～200 minutes, and more preferably 10～100 minutes.The thickness of thus formed film, is preferably 0.001～1 μ m, and 0.005～0.5 μ m more preferably.

(1-2) on the other hand, when manufacturing IPS type liquid crystal display device, respectively liquid crystal aligning agent of the present invention is coated on comb teeth-shaped and is provided with on the conducting film formation face of substrate of the nesa coating that forms pattern, and do not arrange in the one side of subtend substrate of conducting film, then heat each coated face, formation is filmed.Identical in coating process and above-mentioned (1-1).

At this moment substrate, the material of nesa coating used are, the preferred thickness of filming of the pre-treatment of the formation pattern method of nesa coating, substrate, the heating means after coating of liquid crystalline alignment agent and formation is identical with above-mentioned (1-1).

(2) when the liquid crystal display device of manufacturing by method of the present invention is the liquid crystal display device of VA type, can will directly be used as liquid crystal orientation film as above-mentioned formed filming, but also can after carrying out grinding process described below, supply with according to hope use.

On the other hand, during liquid crystal display device beyond manufacturing VA type, by as above-mentioned formed filming implement grinding process and form liquid crystal orientation film.

Grinding process, can by use reeled the roller of the formed cloth of fiber such as nylon, artificial silk, cotton on certain orientation to as above-mentioned formed coated surface rub and implement.Thus, to filming, give the alignment capability of liquid crystal molecule, thereby form liquid crystal orientation film.

Further, for as above-mentioned formed liquid crystal orientation film, carry out a part of irradiation ultraviolet radiation to liquid crystal orientation film shown in patent documentation 9 (Japanese kokai publication hei 6-222366 communique) for example or patent documentation 10 (Japanese kokai publication hei 6-281937 communique), thereby the processing that the pre-tilt angle that makes liquid crystal orientation film subregion changes, forming after etchant resist in the part on liquid crystal orientation film surface as shown in patent documentation 11 (Japanese kokai publication hei 5-107544 communique), in the different direction of the grinding process from previous, carry out grinding process, then remove the processing of etchant resist, make liquid crystal orientation film on each region, there is different liquid crystal aligning abilities, thereby can improve the field-of-view characteristics of the liquid crystal display device of gained.

(3) prepare two substrates that form as mentioned above liquid crystal orientation film, and configure liquid crystal between two substrates of subtend configuration, manufacture liquid crystal cell.When carrying out grinding process to filming, by the configuration of two substrate subtends, make polishing direction in respectively filming be mutually the angle of regulation, for example quadrature or antiparallel herein.

In order to configure liquid crystal between two substrates, can enumerate for example following two kinds of methods.

First method is in the past known method.First, two substrates are configured relatively across gap (box gap), make liquid crystal orientation film separately relatively to, and use sealing agent that the periphery position of two substrates is fit together, in the box gap of being divided by substrate surface and sealing agent, inject after filling liquid crystal, sealing filling orifice, can manufacture liquid crystal cell thus.

Second method is the method that is called ODF (One Drop Fill) mode.Regulation position on a substrate in two substrates that form liquid crystal orientation film, coating is ultra-violet solidified sealing material for example, liquid crystal again drips on liquid crystal aligning face, then another piece substrate of fitting, make liquid crystal orientation film relatively to, then to whole irradiation ultraviolet radiation of substrate, make sealant cures, can manufacture liquid crystal cell thus.

In the situation that adopting above-mentioned either method, all wishes further, to as the liquid crystal cell of above-mentioned manufacturing, to be heated to the temperature that liquid crystal used is isotropic phase, then slowly cool to room temperature, the flow orientation while removing filling liquid crystal thus.

Then, by the polaroid of fitting, can obtain liquid crystal display device of the present invention thus on the outer surface of liquid crystal cell.

Herein, as sealing agent, can use such as containing as the alumina balls of separator and the epoxy resin of solidifying agent etc.

As foregoing liquid crystal, can use such as nematic liquid crystal and dish shape type liquid crystal etc., wherein preferred nematic liquid crystal.When VA type liquid crystal cell, preferably there is the nematic liquid crystal of negative dielectric anisotropy, can use such as dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.When TN type liquid crystal cell or STN type liquid crystal cell, the nematic liquid crystal preferably with positive dielectric anisotropy, can be used such as biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.In these liquid crystal, can also add cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate; The chirality agent of selling with trade(brand)name C-15, CB-15 (manufacture of メル Network company); To oxygen base α-tolylene-Ferroelectric liquid Crystals such as amino-2-methyl butyl laurate etc. are used in the last of the ten Heavenly stems.

As the polaroid of fitting on liquid crystal cell outside surface, can enumerate with rhodia protective membrane and clamp polaroid or the formed polaroid of H film self that absorbs the light polarizing film that is referred to as " H film " of iodine gained when making polyvinyl alcohol stretch orientation and form.

Embodiment

Below, by embodiment, be described more specifically the present invention, but the present invention is not restricted to these embodiment.

The imide rate of the soltion viscosity of each polymkeric substance and polyimide in following synthesis example, measures respectively by the following method.

[soltion viscosity of polymkeric substance]

The soltion viscosity of polymkeric substance (mpas) is for the solvent described in each synthesis example of employing, to be adjusted to the polymers soln of the polymer concentration % of each synthesis example regulation, the value of using E type rotational viscosimeter to measure at 25 ℃.

[the imide rate of polyimide]

The solution that contains the polyimide of gained in each synthesis example that minute takes a morsel is also fed in pure water, and gained precipitation at room temperature fully after drying under reduced pressure, is dissolved in deuterate dimethyl sulfoxide (DMSO), and usings tetramethylsilane as primary standard, at room temperature measures ¹h-NMR frequency spectrum, by this measurement result, (1) is calculated and is obtained according to the following equation.

Imide rate (%)=(1-A ¹/ A ²* α) * 100 (1)

(in formula (1), A ¹for coming from the peak area of NH matrix, A near chemical shift 10ppm ²for coming from the peak area of other protons, α is the proton with respect to 1 NH base in polyimide precursor (polyamic acid), the number ratio of other protons).

The synthesis example > of the compound that the above-mentioned formula of < (A) is represented

Synthesis example A-1

According to following synthetic route 1a～1c,

synthetic route 1a

synthetic route 1b

synthetic route 1c

Synthetic 1-[2-(3,5-diamino-phenoxy group)-ethyl]-tetramethyleneimine-2,5-diketone (compound (A-1-1)).

[synthesizing of compound (A-1-1a)]

Under nitrogen atmosphere, in 20L there-necked flask, mix 1261.1g (10.0 moles) 1,3,5-trihydroxybenzene, 4858.0g (50.0 moles) diallyl amine and 1248.7g (12.0 moles) sodium bisulfite, at room temperature stir 8 hours, reacts.Use the reaction mixture of the concentrated gained of rotatory evaporator, remove unreacted diallyl amine, then add 10L toluene, and with the organic layer of distilled water wash gained.Organic layer after using magnesium sulfate to washing dewaters, and then uses rotatory evaporator to remove desolventizing, obtains 2701.8g (9.5 moles, yield rate is 95.0%) midbody compound (A-1-1a).

[synthesizing of compound (A-1-1b)]

Under nitrogen atmosphere, in 5L there-necked flask, mix 214.7g (1.5 moles) N-(2-hydroxyethyl) succsinic acid imide, 422.1g (2.0 moles) parachloroben-zenesulfonyl chloride and 1L methylene dichloride, at 0 ℃, stir.Through 30 minutes, splash into wherein 312.0mL (2.3 moles) triethylamine, then at room temperature stir 3 hours, react.In the reaction mixture of gained, add 0.5L methylene dichloride, and with the organic layer of distilled water wash gained.Organic layer after using magnesium sulfate to washing dewaters, and then uses rotatory evaporator to concentrate.In the colorless viscous liquid of gained, add 3L ethanol, fully stir, then filter the white solid of separating out and reclaim, obtain 420.7g (1.3 moles, yield rate is 88.3%) midbody compound (A-1-1b).

[synthesizing of compound (A-1-1c)]

Under nitrogen atmosphere, in 5.0L there-necked flask, use petroleum ether 174.0g (being scaled to pure potassium hydride KH is 1.3 moles) potassium hydride KH (30 weight wt% mineral oil suspension), remove after mineral oil vacuum-drying.Add wherein 3.0L tetrahydrofuran (THF), and stir at 0 ℃.The compound (A-1-1a) that splashed into wherein the above-mentioned gained of 341.3g (1.2 moles) through 30 minutes is dissolved in the solution in 1.0L tetrahydrofuran (THF), then at 0 ℃, stirs 15 minutes.The compound (A-1-1b) and 32.2g (0.1 mole) Tetrabutylammonium bromide that add wherein the more above-mentioned gained of 317.8g (1.0 moles), then at room temperature stir 10 hours, reacts.After reaction finishes, in reaction mixture, add aqueous ammonium chloride solution, reach after acidity, use 4.0L ethyl acetate to extract, obtain organic layer.After this organic layer is washed, use magnesium sulfate to dewater, and use rotatory evaporator to remove desolventizing, obtain crude product.Use column chromatography (weighting agent: silica gel, developing solvent: hexane/ethyl acetate=4/1 (weight ratio)) the thick refining thing of refining gained, and from the cut of gained except desolventizing, obtain 262.1g (0.6 mole, yield rate the is 58.6%) midbody compound (A-1-1c) for dark brown viscous liquids.

[synthesizing of compound (A-1-1)]

Under nitrogen atmosphere, in 5.0L there-necked flask, the compound (A-1-1c), the 274.5g (1.8 moles) 1 that mix the above-mentioned gained of 239.8g (0.6 mole), 3-dimethyl barbituric acid, 13.5g (0.012 mole) four (triphen phosphino-) palladium (0) and 2.5L methylene dichloride stir and react for 4 hours at 35 ℃.After reaction finishes, with aqueous sodium carbonate washing reaction mixture, remove unreacted 1,3-dimethyl barbituric acid, and then use distilled water wash.The organic layer that uses dried over mgso gained, is then used rotatory evaporator to remove desolventizing, obtains crude product.Use column chromatography (weighting agent: silica gel, developing solvent: chloroform/ethanol=95/5 (weight ratio)) the thick refining thing of refining gained, and from the cut of gained except desolventizing, obtain (0.16 mole of 33.9g for brown powder, yield rate is 26.9%) (1-[2-(3 for compound (A-1-1), 5-diamino-phenoxy group)-ethyl]-tetramethyleneimine-2,5-diketone).

As required, with above-mentioned scale, repeat the various operations of above-mentioned synthesis example A-1, to guarantee the compound (A-1-1) of the synthetic aequum of aftermentioned polyimide.

Synthesis example A-2

According to following synthetic route 2,

synthetic route 2

Synthetic 1-[2-(2,4-diamino-phenoxy group)-ethyl]-2-Pyrrolidone (compound (A-2-1)).

[synthesizing of compound (A-2-1k)]

Under nitrogen atmosphere, in 2L there-necked flask, mix 129.2g (1.0 moles) 1-(2-hydroxyethyl)-2-Pyrrolidone, 186.1g (1.0 moles) 2,4-dinitrobenzene fluorobenzene, 280mL triethylamine and 500mL tetrahydrofuran (THF), at 40 ℃, stir 10 hours, react.After reaction finishes, in reaction mixture, add 2L ethyl acetate, with the organic layer of distilled water wash gained, and dewater with magnesium sulfate, then use rotatory evaporator to remove desolventizing, obtain crude product.Use ethanol to carry out recrystallize to the crude product of gained, filtered and recycled crystallization, and at 60 ℃, carry out vacuum-drying in 12 hours, obtain 206g (0.70 mole, yield rate the is 70.0%) midbody compound (A-2-1k) into pale yellow powder.

[synthesizing of compound (A-2-1)]

Under nitrogen atmosphere, in 5L there-necked flask, mix 73.8g (0.25 mole) above-mentioned intermediate (A-2-1k), 327.0g (5 moles) zinc, 53.5g (1 mole) ammonium chloride and 2.5L ethanol.At 0 ℃, stir this mixture on one side, Yi Bian add wherein lentamente 600mL water, then at room temperature stir 6 hours, react.After reaction finishes, by brownmillerite, filter and from reaction mixture, remove catalyzer, and use rotatory evaporator from this filtrate, to remove desolventizing, obtain crude product.Use column chromatography (weighting agent: silica gel, developing solvent: the tetrahydrofuran (THF)) crude product of refining gained, and from the cut of gained removal of solvent under reduced pressure, obtain 52.3g (0.22 mole, yield rate the is 89%) compound (A-2-1) into dark brown liquid.

The synthetic > of < polyimide

Synthesis example PI-1

Using the 110g as tetracarboxylic dianhydride (0.50 mole) 2, 3, 5-tricarboxylic base NSC 60134 dianhydride and 160g (0.50 mole) 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, with 91g (0.84 mole) Ursol D as diamines, the compound (A-1-1) of the above-mentioned synthesis example A-1 gained of 8g (0.03 mole), 25g (0.10 mole) 1, 3-bis-(3-aminopropyl) tetramethyl disiloxane and 9.6g (0.015 mole) 3, 6-bis-(4-amino-benzene acyloxy) cholestane, and as 8.1g (0.030 mole) octadecylamine of monoamine, be dissolved in 960g METHYLPYRROLIDONE (NMP), at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains polyamic acid.This solution that takes a morsel, adds NMP, and forming polyamic acid concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 60mPas.

Then, in the polyamic acid solution of gained, append 2700g NMP, and add 400g pyridine and 410g diacetyl oxide, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new gamma-butyrolactone, the solvent in system being carried out to solvent exchange (operates by this solvent exchange, the pyridine and the diacetyl oxide that in dehydration closed-loop reaction, use are expelled to outside system, lower with), obtain being about containing the 15 % by weight imide rates of having an appointment the solution of 95% polyimide (PI-1).The take a morsel polyimide solution of gained, adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 70mPas.

Synthesis example PI-2

Using the 110g as tetracarboxylic dianhydride (0.50 mole) 2,3,5-tricarboxylic base NSC 60134 dianhydride, with 38g (0.35 mole) Ursol D as diamines, compound (A-1-1) and the 52g (0.10 mole) 3 (3 of the above-mentioned synthesis example A-1 gained of 13g (0.05 mole), 5-diaminobenzene acyloxy) cholestane, be dissolved in 830g NMP, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains polyamic acid.This polyamic acid solution that takes a morsel, adds NMP, and forming polyamic acid concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 60mPas.

Then, in the polyamic acid solution of gained, append 1900g NMP, and add 40g pyridine and 51g diacetyl oxide, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new NMP, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 % by weight imide rates of having an appointment are about 50% polyimide (PI-2).The take a morsel polyimide solution of gained, adds NMP, and forming polyimide concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 47mpas.

Synthesis example PI-3

Using the 110g as tetracarboxylic dianhydride (0.50 mole) 2,3,5-tricarboxylic base NSC 60134 dianhydride, with 32g (0.30 mole) Ursol D, the 20g (0.1 mole) 4 as diamines, the compound (A-1-1) of 4 '-diaminodiphenyl-methane, the above-mentioned synthesis example A-1 gained of 13g (0.05 mole) and 26g (0.05 mole) 3 (3,5-diaminobenzene acyloxy) cholestane, be dissolved in 800g NMP, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains polyamic acid.This polyamic acid solution that takes a morsel, adds NMP, and forming polyamic acid concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 60mPas.

Then, in the polyamic acid solution of gained, append 1800g NMP, and add 80g pyridine and 100g diacetyl oxide, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new gamma-butyrolactone, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 % by weight imide rates of having an appointment are about 80% polyimide (PI-3).The take a morsel polyimide solution of gained, adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 87mPas.

Synthesis example PI-4

Using the 110g as tetracarboxylic dianhydride (0.50 mole) 2,3,5-tricarboxylic base NSC 60134 dianhydride, with 49g (0.45 mole) Ursol D as diamines and the compound (A-1-1) of the above-mentioned synthesis example A-1 gained of 13g (0.05 mole), be dissolved in 1460g NMP, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains 10 % by weight polyamic acids.The soltion viscosity of this polyamic acid solution is 65mPas.

Then, in the polyamic acid solution of gained, append 1625g NMP, and add 200g pyridine and 150g diacetyl oxide, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new gamma-butyrolactone, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 % by weight imide rates of having an appointment are about 90% polyimide (PI-4).The take a morsel polyimide solution of gained, adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 65mPas.

Synthesis example PI-5

Using the 110g as tetracarboxylic dianhydride (0.50 mole) 2,3,5-tricarboxylic base NSC 60134 dianhydride, with 49g (0.45 mole) Ursol D as diamines and the compound (A-2-1) of the above-mentioned synthesis example A-2 gained of 12g (0.05 mole), be dissolved in 1540g NMP, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains 10 % by weight polyamic acids.The soltion viscosity of this polyamic acid solution is 73mPas.

Then, in the polyamic acid solution of gained, append 1710g NMP, and add 194g pyridine and 150g diacetyl oxide, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new gamma-butyrolactone, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 % by weight imide rates of having an appointment are about 88% polyimide (PI-5).The take a morsel polyimide solution of gained, adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 60mPas.

The synthetic > of other polymkeric substance of <

[synthesizing of other polyamic acid]

Synthesis example PAR-1

Using the 200g as tetracarboxylic dianhydride (1.0 moles) 1,2,3,4-tetramethylene tetracarboxylic dianhydride, with the 210g (1.0 moles) 2 as diamines, 2 '-dimethyl-4,4 '-benzidine, be dissolved in 370g NMP and the formed mixed solvent of 3300g gamma-butyrolactone, at 40 ℃, carry out reaction in 3 hours, obtain the solution that contains 10 % by weight polyamic acids (PAR-1).The soltion viscosity of this polyamic acid solution is 160mPas.

[synthesizing of other polyimide]

Synthesis example PIR-1

Using the 110g as tetracarboxylic dianhydride (0.50 mole) 2,3,5-tricarboxylic base NSC 60134 dianhydride, with 38g (0.35 mole) Ursol D, the 20g (0.1 mole) 4 as diamines, 4 '-diaminodiphenyl-methane and 26g (0.05 mole) 3 (3,5-diaminobenzene acyloxy) cholestane, is dissolved in 800g NMP, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains polyamic acid.Take a morsel this polyamic acid solution of gained, adds NMP, and forming polyamic acid concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 60mPas.

Then, in the polyamic acid solution of gained, append 1800g NMP, and add 160g pyridine and 200g diacetyl oxide, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new gamma-butyrolactone, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 % by weight imide rates of having an appointment are about 80% polyimide (PIR-1).The take a morsel polyimide solution of gained, adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 87mPas.

Synthesis example PIR-2

Using the 110g as tetracarboxylic dianhydride (0.50 mole) 2,3,5-tricarboxylic base NSC 60134 dianhydride, with 54g (0.5 mole) Ursol D as diamines, be dissolved in 1476g NMP, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains 10 % by weight polyamic acids.The soltion viscosity of this polyamic acid solution is 63mpas.

Then, in the polyamic acid solution of gained, append 1640g NMP, and add 200g pyridine and 150g diacetyl oxide, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new gamma-butyrolactone, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 % by weight imide rates of having an appointment are about 91% polyimide (PIR-2).The take a morsel polyimide solution of gained, adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 64mPas.

Synthesis example PIR-3

Using the 110g as tetracarboxylic dianhydride (0.50 mole) 2,3,5-tricarboxylic base NSC 60134 dianhydride, with the 6g (0.01 mole) 3 as diamines, 6-bis-(4-amino-benzene acyloxy) cholestane, 17g (0.04 mole) 4-(4 '-trifluoromethoxy benzoyloxy group) cyclohexyl-3,5-diaminobenzoic acid ester and 48g (0.45 mole) Ursol D, be dissolved in 1647g NMP, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains 10 % by weight polyamic acids.The soltion viscosity of this polyamic acid solution is 70mPas.

Then, in the polyamic acid solution of gained, append 1830g NMP, and add 200g pyridine and 150g diacetyl oxide, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new gamma-butyrolactone, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 % by weight imide rates of having an appointment are about 89% polyimide (PIR-3).The take a morsel polyimide solution of gained, adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 % by weight, and the soltion viscosity of its mensuration is 72mPas.

The modulation of < liquid crystal aligning agent and evaluation >

Comparative example 1

[modulation of liquid crystal aligning agent]

In the solution that contains polyimide (PIR-1) of gained in above-mentioned synthesis example PIR-1, add gamma-butyrolactone (BL), METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (BC), again with respect to 100 weight part polyimide (PIR-1), add 10 weight part N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane also fully stirs, and formation solvent composition is BL: NMP: BC=40: 30: 30 (weight ratio), solid component concentration are the solution of 6.0 % by weight.Use aperture is that the strainer of 1 μ m filters this solution, modulation liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

(1) evaluation of printing

Liquid crystal aligning agent for above-mentioned modulation, use liquid crystal orientation film printing press (Japan's description printing (strain) is manufactured), be coated on the transparent electrical pole-face with the glass substrate of the formed transparency electrode of ITO film, and on the hot plate of 80 ℃, heat 1 minute (prebake) except desolventizing, and then on the hot plate of 200 ℃, heating 10 minutes (curing afterwards), formation average film thickness is film.Use 20 multiplying powers microscopic examination this film, investigation has pore-free and printing is irregular and their degree.Although result is not observe pore, observe some printing irregular.

(2) evaluation of the film uniformity of filming

For above-mentioned formed filming, use contact pin type film thickness gauge (manufacture of KLAテンコYiル society), measure respectively the thickness of substrate center part and the thickness near middle body 15mm position apart from substrate outboard end.By both film thickness differences, be

following average evaluation is film uniformity " well ", and film thickness difference is surpassed

average evaluation be film uniformity " defective ".

(3) the separability evaluation of filming

For above-mentioned formed filming, Qi 30℃Xia Sanyo is changed into middle the dipping 5 minutes of stripper " TS-204 " that industry (strain) is manufactured, carry out strip operation.After peeling off, on visual investigation substrate, whether have the residue of filming.To have the average evaluation of the residue of filming be separability " well " by unconfirmed on substrate, will confirm that having the average evaluation of the residue of filming is separability " defective ", and in this comparative example, remaining filming in a part for substrate, its separability " defective ".

(4) continuous printing evaluation

On one side in 1 minute to the liquid crystal aligning agent that splashes into the above-mentioned modulation of 0.2g in the anilox roll of liquid crystal orientation film printing press (Japan's description printing (strain) is manufactured), on one side continuous rotation anilox roll.In liquid crystal aligning agent of visual observation per hour, whether contained polymkeric substance separates out to anilox roll.

In this comparative example, after experiment starts 1 hour, not observe separating out of polymkeric substance, but observed and separate out after 2 hours, at this moment experiment finishes.

Comparative example 2

[modulation of liquid crystal aligning agent]

In the solution that contains polyimide (PIR-2) of gained in above-mentioned synthesis example PIR-2, add gamma-butyrolactone (BL) and ethylene glycol butyl ether (BC), again with respect to 100 weight part polyimide (PIR-2), add 10 weight part N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane also fully stirs, and formation solvent composition is BL: BC=88: 12 (weight ratios), solid component concentration are the solution of 6.0 % by weight.Use aperture is that the strainer of 1 μ m filters this solution, modulation liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

Except using the liquid crystal aligning agent of above-mentioned modulation, and in above-mentioned comparative example 1, carry out equally the evaluation of printing, the film uniformity of filming, separability and continuous printing for long time.Evaluation result is shown in table 1 and table 2.

Comparative example 3

[modulation of liquid crystal aligning agent]

In the solution that contains polyimide (PIR-3) of gained in above-mentioned synthesis example PIR-3, add gamma-butyrolactone (BL) and ethylene glycol butyl ether (BC), again with respect to 100 weight part polyimide (PIR-3), add 10 weight part N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane also fully stirs, and formation solvent composition is BL: B C=88: 12 (weight ratios), solid component concentration are the solution of 6.0 % by weight.Use aperture is that the strainer of 1 μ m filters this solution, modulation liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

Embodiment 1

[modulation of liquid crystal aligning agent]

The solution that contains other polyamic acid (PAR-1) that mixes gained in the solution that contains polyimide (PI-1) of gained in above-mentioned synthesis example PI-1 and above-mentioned synthesis example PAR-1, make polyimide (PI-1): other polyamic acid (PAR-1)=20: 80 (weight ratio), and add wherein gamma-butyrolactone (BL), METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (B C), again with respect to the total amount of 100 parts by weight polymer, add the 10 weight part N as epoxy compounds, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane also fully stirs, formation solvent composition is BL: NMP: BC=71: 17: 12 (weight ratio), solid component concentration is the solution of 6.0 % by weight.Use aperture is that the strainer of 1 μ m filters this solution, modulation liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

(1) evaluation of printing

Use the liquid crystal aligning agent of above-mentioned modulation, and above-mentioned comparative example 1 similarly forms average film thickness and is film.Use 20 multiplying powers microscopic examination this film, investigation has pore-free and printing is irregular and their degree.Herein, irregular for printing, investigation is compared with filming of above-mentioned comparative example 1, whether improved and printed irregular generation, and the situation (that is to say, compare with filming of comparative example 1, print the situation that irregular degree is little) of observing improvement is evaluated as to " well ".

Evaluation result is shown in table 1.

(2) the separability evaluation of filming in the evaluation of the film uniformity of filming, (3) and (4) continuous printing evaluation

For filming of above-mentioned formation, and evaluation, the separability evaluation of filming and the continuous printing evaluation of above-mentioned comparative example 1 film uniformity of similarly filming.

Evaluation result is shown in table 1 and table 2.

In addition, (4) continuous printing evaluation, observes the 4th hour.

Embodiment 2

[modulation of liquid crystal aligning agent]

In the solution that contains polyimide (PI-2) of gained in above-mentioned synthesis example PI-2, add METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (BC), again with respect to 100 weight part polyimide (PI-2), add the 10 weight part N as epoxy compounds, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane also fully stirs, and formation solvent composition is NMP: BC=50: 50 (weight ratios), solid component concentration are the solution of 6.0 % by weight.Use aperture is that the strainer of 1 μ m filters this solution, modulation liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

Except using the liquid crystal aligning agent of above-mentioned modulation, and similarly evaluate in above-described embodiment 1.

Evaluation result is shown in table 1 and table 2.

Embodiment 3

[modulation of liquid crystal aligning agent]

Except in above-mentioned comparative example 1, use outside the solution that the solution that contains polyimide (PI-3) of gained in above-mentioned synthesis example PI-3 replaces containing polyimide (PIR-1), and in comparative example 1, similarly modulate liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

Evaluation result is shown in table 1 and table 2.

Embodiment 4

[modulation of liquid crystal aligning agent]

The solution that contains other polyamic acid (PAR-1) that mixes gained in the solution that contains polyimide (PI-4) of gained in above-mentioned synthesis example PI-4 and above-mentioned synthesis example PAR-1, make polyimide (PI-4): other polyamic acid (PAR-1)=20: 80 (weight ratio), and add wherein gamma-butyrolactone (BL), METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (BC), again with respect to the total amount of 100 parts by weight polymer, add the 10 weight part N as epoxy compounds, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane also fully stirs, formation solvent composition is BL: NMP: BC=83: 5: 12 (weight ratio), solid component concentration is the solution of 6.0 % by weight.Use aperture is that the strainer of 1 μ m filters this solution, modulation liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

Evaluation result is shown in table 1 and table 2.

Embodiment 5

[modulation of liquid crystal aligning agent]

Except in above-mentioned comparative example 2, use outside the solution that the solution that contains polyimide (PI-5) of gained in above-mentioned synthesis example PI-5 replaces containing polyimide (PIR-2), and in comparative example 2, similarly modulate liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

Evaluation result is shown in table 1 and table 2.

[table 1]

The composition of table 1. liquid crystal aligning agent and printing and the evaluation result of filming

In addition, the abbreviation of the solvent in table 1 solvent composition hurdle, represents respectively following content.

BL: gamma-butyrolactone

NMP:N-N-methyl-2-2-pyrrolidone N-

BC: ethylene glycol butyl ether

[table 2]

The result that table 2. continuous printing is evaluated

Comparative example 1

Comparative example 2

Comparative example 3

Embodiment 1

Embodiment 2

Embodiment 3

Embodiment 4

Embodiment 5

1 hour

Do not separate out

2 hours

Separate out

Do not separate out

3 hours

-

Do not separate out

4 hours

-

Do not separate out

Claims

1. a liquid crystal aligning agent, is characterized in that containing from polyamic acid and at least one polymkeric substance that makes to select the group of the formed polyimide formation of this polyamic acid dehydration closed-loop, and this polyamic acid is by making tetracarboxylic dianhydride and comprising following formula (A ⁰) diamine reactant of represented compound obtains,

Formula (A ⁰) in, X is ^*-O-or ^*-COO-, above-mentioned in, with the connecting key of " * ", be connected with diamino-phenyl, R is the arylidene that methylene radical, the carbonatoms alkylidene group that is 2～10 or carbonatoms are 6～18, R ⁱfor the carbonatoms alkyl that is 1～6, the integer that n is 0～4, Z is carbonyl or the represented group of following formula (Z-1),

2. liquid crystal aligning agent as claimed in claim 1, wherein above-mentioned formula (A ⁰) represented compound is the represented compound of following formula (A),

In formula (A), X, R and R ⁱrespectively with above-mentioned formula (A ⁰) middle synonym, the integer that n is 0～2.

3. liquid crystal aligning agent as claimed in claim 1 or 2, wherein above-mentioned tetracarboxylic dianhydride comprises 2,3,5-tricarboxylic base NSC 60134 dianhydride.

4. liquid crystal aligning agent as claimed in claim 1 or 2, wherein above-mentioned polymkeric substance is that imide rate is more than 30% polyimide.

5. adopt the formed liquid crystal orientation film of liquid crystal aligning agent described in claim 1～4 any one.

6. a liquid crystal display device, is characterized in that having liquid crystal orientation film claimed in claim 5.

7. make tetracarboxylic dianhydride and comprise the formula (A described in claim 1 ⁰) polyamic acid of diamine reactant gained of represented compound.

8. make tetracarboxylic dianhydride and comprise the formula (A described in claim 1 ⁰) the formed polyimide of polyamic acid dehydration closed-loop of diamine reactant gained of represented compound.

9. by the formula (A described in claim 1 ⁰) represented compound.