CN101993697A

CN101993697A - Aligning agent for liquid crystal

Info

Publication number: CN101993697A
Application number: CN2010102493787A
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: 2011-03-30
Anticipated expiration: 2030-08-02
Also published as: CN101993697B; KR101565393B1; 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, it is good to the present invention relates to a kind of coating, formation membranous evenly and good, the also good liquid crystal aligning agent of yield rate when making liquid crystal orientation film.

Background technology

Present known liquid crystal display device can be divided into all kinds shown below according to the rerum natura of electrode structure and used liquid crystal molecule.

At 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 the used for liquid crystal display element substrate, again two these substrates are disposed relatively, and form the layer of nematic liquid crystal betwixt in the crack with positive dielectric anisotropy, form the box of sandwich structure, and the major axis of liquid crystal molecule reverses 90 ° (patent documentations 1) from a substrate continuously 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 counter electrode configuration that also known a kind of employing and TN type liquid crystal display device are same, but in electrode gap, inject the layer of nematic liquid crystal, and make mesomorphic phase for the vertical orientated substantially VA of substrate (vertical orientated) type display element (patent documentation 3) with negative dielectric anisotropy.This VA type display element can be made high-contrast and large-area display element.

On the other hand, also known a kind of by right with broach shape configured electrodes in the face of a plate base, and the liquid crystal drive direction only will apply electric field the time is as IPS (switching in the face) the type liquid crystal display device (patent documentation 4) of direction in the real estate, and the electrode structure that changes the IPS type, improve the aperture opening ratio of display element part, thereby improve FFS (fringing field conversion) the type liquid crystal display device (patent documentation 5) of brightness, their viewing angle characteristics separately are good.

In addition, it is little also to have developed view angle dependency, OCB (Optical Compensated Bend: optical compensation curved) the type liquid crystal display device (patent documentation 6) that the high-speed response of while image frame is good 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 that forms by polyamic acid or polyimide particularly, therefore its thermotolerance, physical strength, good with the affinity of liquid crystal etc. are used for many liquid crystal display device (patent documentation 1～4,7 and 8).This liquid crystal orientation film generally is to be coated on the substrate through will containing the liquid crystal aligning agent that forms liquid crystal orientation film with the state that is dissolved in solvent, removes the operation manufacturing of desolvating then.

Yet, pointed out when making liquid crystal orientation film, use under the situation of hitherto known liquid crystal aligning agent, with certain probability form film on to have produced printing such as the irregular or pore of printing bad, and the finished product rate deficiency when making liquid crystal orientation film.For example when flexible printing, carry out under the situation of continuous printing for long time, contained polymkeric substance is separated out to the anilox roll of printing press in the liquid crystal aligning agent, and causes printing bad.This printing is bad, can think the solvability deficiency owing to polymkeric substance contained in the liquid crystal aligning agent.That is to say, can think and have the polymkeric substance as the necessary various characteristics of liquid crystal orientation film such as liquid crystal aligning performance, thermotolerance, in any case all must have 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 is by coming out lentamente in the roller, thereby cause under the strong solution state of the polymkeric substance that generates, the mutual aggegation of polymer molecule, and observe polymkeric substance thus and separate out.

In addition, when this printing of generation is bad, peeled off the liquid crystal orientation film that has formed though use stripper, and substrate utilized again, to seek for the resources effective utilization, but by the formed liquid crystal orientation film of the low polymkeric substance of above-mentioned solvability, separability is also poor, therefore is difficult to such utilization.

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

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 that has 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 the liquid crystal aligning agent can not separated out yet, what form is membranous even and good, simultaneously, the liquid crystal aligning agent that the liquid crystal orientation film that has formed is peeled off easily.Because this liquid crystal aligning agent, the yield rate when making liquid crystal orientation film is good, is to expect in this area therefore.

Other purpose 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, reached by a kind of liquid crystal aligning agent, it contains from polyamic acid and makes at least a polymkeric substance of selecting the group of the formed polyimide formation of this polyamic acid dehydration closed-loop, and this polyamic acid is by making the 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, the connecting key that has " * " is connected with diamino-phenyl, R is that methylene radical, carbonatoms are that 2～10 alkylidene group or carbonatoms are 6～18 arylidene, R ^IFor carbonatoms is 1～6 alkyl, n is 0～4 integer, and Z is carbonyl or the represented group of following formula (Z-1),

In the formula (Z-1), R ^IIAnd R ^IIIBe that hydrogen atom or carbonatoms are 1～6 alkyl 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 the liquid crystal aligning agent can not separated out yet, what form is membranous even and good, simultaneously, and the liquid crystal aligning agent that the liquid crystal orientation film that has formed is peeled off easily.

This liquid crystal aligning agent of the present invention can be made membranous even and good liquid crystal orientation film with the high product yield rate, and simultaneously, the substrate yield rate when also helping to make liquid crystal display device improves.

Therefore, has 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 for example 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, by the formed film of polymkeric substance contained in this liquid crystal aligning agent, can also be used as the electronic material insulating film.

Embodiment

Below, the present invention is described in detail.

Liquid crystal aligning agent of the present invention contains at least a polymkeric substance of selecting from polyamic acid and group that the formed polyimide of this polyamic acid dehydration closed-loop is constituted, this polyamic acid be by the tetracarboxylic dianhydride with comprise above-mentioned formula (A ⁰) diamine reactant of represented compound obtains.

＜polyamic acid 〉

[tetracarboxylic dianhydride]

Tetracarboxylic dianhydride as being used for synthetic above-mentioned polyamic acid can enumerate for example butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, following formula (T-I) and (T-II)

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

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

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

These tetracarboxylic dianhydrides can be used alone or be used in combination of two or more.

As the tetracarboxylic dianhydride that can be used for synthetic polyamic acid of the present invention, comprise the butane tetracarboxylic acid dianhydride that is 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 basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5, the following formula (T-5)～(T-7) in the represented compound of 8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I)

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

(T-8)

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

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

Can be used for the tetracarboxylic dianhydride of synthetic polyamic acid of the present invention,, preferably contain 50 moles more than the %, more preferably contain 70 moles more than the %, and especially preferably contain the above aforesaid specific tetracarboxylic dianhydride of 80 moles of % with respect to whole tetracarboxylic dianhydrides.

Tetracarboxylic dianhydride as being used for synthetic polyamic acid of the present invention most preferably only uses aforesaid specific tetracarboxylic dianhydride.

[diamines]

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

As above-mentioned formula (A ⁰) in the carbonatoms of R be 2～10 alkylidene group, be preferably carbonatoms and be 2～6 straight-chain alkyl-sub-.It as the carbonatoms of R 6～18 arylidene, be preferably carbonatoms and be 6～10 arylidene, as its object lesson, for example can enumerate 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, xenyl-4,4 '-two bases, ditan 4,4 '-two bases, 3,3 '-dimethyl diphenyl base-4,4 '-two 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, be 2 preferably with respect to other group, 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, the 5-diketone, 1-[3-(3,5-diamino-phenoxy group)-propyl group]-tetramethyleneimine-2, the 5-diketone, 1-[4-(3,5-diamino-phenoxy group)-butyl]-tetramethyleneimine-2, the 5-diketone, 1-[5-(3,5-diamino-phenoxy group)-amyl group]-tetramethyleneimine-2, the 5-diketone, 1-[6-(3,5-diamino-phenoxy group)-hexyl]-tetramethyleneimine-2, the 5-diketone, 3,5-diamino-phenylformic acid 2-(2,5-dioxo-tetramethyleneimine-1-yl)-ethyl ester, 3,5-diamino-phenylformic acid 3-(2,5-dioxo-tetramethyleneimine-1-yl)-propyl ester, 3,5-diamino-phenylformic acid 4-(2,5-dioxo-tetramethyleneimine-1-yl)-butyl ester, 3,5-diamino-phenylformic acid 5-(2,5-dioxo-tetramethyleneimine-1-yl)-pentyl ester, 3,5-diamino-phenylformic acid 6-(2,5-dioxo-tetramethyleneimine-1-yl)-own ester, 1-[2-(2,4-diamino-phenoxy group)-ethyl]-tetramethyleneimine-2, the 5-diketone, 1-[3-(2,4-diamino-phenoxy group)-propyl group]-tetramethyleneimine-2, the 5-diketone, 1-[4-(2,4-diamino-phenoxy group)-butyl]-tetramethyleneimine-2, the 5-diketone, 1-[5-(2,4-diamino-phenoxy group)-amyl group]-tetramethyleneimine-2, the 5-diketone, 1-[6-(2,4-diamino-phenoxy group)-hexyl]-tetramethyleneimine-2, the 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-tetramethyleneimine-1-yl)-ethyl ester, 3,5-diamino-phenylformic acid 3-(2-oxo-tetramethyleneimine-1-yl)-propyl ester, 3,5-diamino-phenylformic acid 4-(2-oxo-tetramethyleneimine-1-yl)-butyl ester, 3,5-diamino-phenylformic acid 5-(2-oxo-tetramethyleneimine-1-yl)-pentyl ester, 3,5-diamino-phenylformic acid 6-(2-oxo-tetramethyleneimine-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 the formula (A), X, R and R ^IRespectively with above-mentioned formula (A ⁰) middle synonym, n is 0～2 integer) represented compound, n is 0 compound in the more preferably above-mentioned formula (A), and preferred especially the use is selected from 1-[2-(3,5-diamino-phenoxy group)-ethyl]-tetramethyleneimine-2, the 5-diketone, 1-[3-(3,5-diamino-phenoxy group)-propyl group]-tetramethyleneimine-2, the 5-diketone, 1-[4-(3,5-diamino-phenoxy group)-butyl]-tetramethyleneimine-2, the 5-diketone, 1-[5-(3,5-diamino-phenoxy group)-amyl group]-tetramethyleneimine-2, the 5-diketone, 1-[6-(3,5-diamino-phenoxy group)-hexyl]-tetramethyleneimine-2, the 5-diketone, 3,5-diamino-phenylformic acid 2-(2,5-dioxo-tetramethyleneimine-1-yl)-ethyl ester, 3,5-diamino-phenylformic acid 3-(2,5-dioxo-tetramethyleneimine-1-yl)-propyl ester, 3,5-diamino-phenylformic acid 4-(2,5-dioxo-tetramethyleneimine-1-yl)-butyl ester, 3,5-diamino-phenylformic acid 5-(2,5-dioxo-tetramethyleneimine-1-yl)-and pentyl ester and 3, at least a in the group that 5-diamino-phenylformic acid 6-(2,5-dioxo-tetramethyleneimine-1-yl)-own ester constitutes.

This above-mentioned formula (A ⁰) represented compound, can be by vitochemical ordinary method appropriate combination be synthesized.

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

Synthetic route a

Synthetic route b

Synthetic route c

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

The reaction that said synthesis route a is represented can be by making 1,3,5-trihydroxybenzene and diallyl amine, preferably reaction and carrying out in the presence of sodium bisulfite.This reaction can be under 5～40 ℃ temperature, carries out with 5～15 hours reaction times.By this reaction, can obtain compound (A-1-1a) as intermediate.

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

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

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

Synthetic route d

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

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

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

Synthetic route e

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

Compound (A-1a) by will having desirable radicals R and for example 2,4-dinitrobenzene fluorobenzene is dissolved in the suitable organic solvent, to wherein adding suitable alkali (for example triethylamine), and reaction system is heated to about 30～50 ℃, 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) is had and form amino can obtain target product thus.

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

Synthetic route f

Synthetic route g

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

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

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

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

Synthetic route h

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

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

Synthetic route i

By the compound (A-1j) and 2 that will have desirable radicals R, 4-dinitrobenzene fluorobenzene is dissolved in the suitable organic solvent, to wherein adding suitable alkali (for example triethylamine), and reaction system is heated to about 30～50 ℃, 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) is had and form amino can obtain target product thus.

Diamines as being used for synthetic polyamic acid of the present invention can only use the represented compound of above-mentioned formula (A), and also compound that can above-mentioned formula (A) is represented and other diamines are 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, the 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-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2, the 7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, two (4-amino-2-chloro-phenyl-) methane, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to the phenylene diisopropylidene) two (aniline), 4,4 '-(metaphenylene diisopropylidene) two (aniline), 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-3,3 '-two (trifluoromethyl) biphenyl, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, following formula (D-1)～(D-5)

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

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), 1,3-two (amino methyl) hexanaphthene, 1, aliphatie diamine and ester ring type diamines such as 4-two (amino methyl) hexanaphthene;

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

(in the formula (D-I), R ⁵For having 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 the formula (D-II), R ⁶For having 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) diamines of represented separately nitrogen-atoms beyond intramolecularly has 2 primary aminos and this primary amino such as compound;

Following formula (D-III)

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

Following formula (D-IV)

(in the 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, q be 1～20 integer) represented diamino organo-siloxanes such as compound etc.The phenyl ring that diamines and single-substituted diamines had of above-mentioned aromatic diamine, the nitrogen-atoms beyond intramolecularly has 2 primary aminos and this primary amino can be that 1～4 alkyl (being preferably methyl) replaces by the carbonatoms more than 1 or 2 also.In addition, the steroid backbone in the above-mentioned formula (D-III) is meant by being the skeleton of two keys more than 1 or 2 in pentamethylene base-formed skeleton of perhydro-phenanthrene nucleus or its carbon-carbon bond.

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

As other diamines that can be used for synthetic polyamic acid of the present invention, the preferred Ursol D that is selected from above-mentioned that uses, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino-diphenyl thioether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) two (aniline), 4,4 '-(metaphenylene diisopropylidene) two (aniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 1, the 4-diamino-cyclohexane, 4,4 '-methylene radical two (hexahydroaniline), 1,3-two (amino methyl) hexanaphthene, the represented separately compound of above-mentioned formula (D-1)～(D-5), 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, N, N '-two (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 separately compound and above-mentioned formula (D-IV) 1, at least a (below, be called " other specific diamines ") in the group that 3-two (3-aminopropyl)-tetramethyl disiloxane constitutes.

The diamines that can be used for synthetic polyamic acid of the present invention, with respect to whole diamines, preferably contain 3 moles more than the %, more preferably contain 5～90 moles of %, further preferably contain 3～70 moles of %, and especially preferably contain the represented compound of 8～50 moles of above-mentioned formulas of % (A).

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

The diamines that can be used for synthetic polyamic acid of the present invention preferably only is made of above-mentioned formula (A) represented compound and other specific diamines.

[synthesizing of polyamic acid]

Polyamic acid among the present invention can obtain by making tetracarboxylic dianhydride and the diamine reactant that comprises the represented compound of above-mentioned formula (A).

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

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

As operable organic solvent when synthesizing polyamides is sour, can enumerate for example 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 for example N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, N, dinethylformamide, 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 for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1,4-butyleneglycol, 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 for example ethyl lactate, n-Butyl lactate, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, methoxypropionic acid methyl esters, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate etc.;

As above-mentioned ether, can enumerate for example 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, 1,4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.;

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

In these organic solvents, the preferred use is selected from the group's (organic solvent of first group) that is made of non-proton property polar solvent and phenol and derivative thereof more than one, or be selected from aforementioned first group organic solvent more than one and be selected from more than one mixture in the group's (organic solvent of second group) that constitutes by alcohol, ketone, ether, halohydrocarbon and hydrocarbon.Under latter instance, the usage ratio of the organic solvent of second group, the total with respect to the organic solvent of the organic solvent of first group and second group is preferably below the 50 weight %, more preferably below the 40 weight %, and more preferably below the 30 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 the reaction soln can be separated the back and supply with the modulation of liquid crystal aligning agent, resupply the modulation of liquid crystal aligning agent after perhaps isolated polyamic acid can also being made with extra care.

When making the polyamic acid dehydration closed-loop form polyimide, above-mentioned reaction soln directly can be supplied with the dehydration closed-loop reaction, also polyamic acid contained in the reaction soln can be separated the back and supply with the dehydration closed-loop reaction, resupply the dehydration closed-loop reaction after perhaps isolated polyamic acid can also being made with extra care.

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

＜polyimide 〉

Polyimide among the present invention can be by making aforesaid polyamic acid dehydration closed-loop, carries out imidization and obtain.

Tetracarboxylic dianhydride as being used for synthetic above-mentioned polyimide can enumerate and the above-mentioned identical compound of tetracarboxylic dianhydride that can be used for synthesizing polyamides acid.Preferred tetracarboxylic dianhydride's kind and preferred usage ratio thereof are identical with the situation of polyamic acid.

As the diamines that can be used for synthetic polyimide of the present invention, can enumerate and the above-mentioned identical diamines of diamines that can be used for synthesizing polyamides acid.That is to say, the diamines that can be used for the contained polyimide of synthetic 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 also with above-mentioned formula (A) represented compound and above-mentioned other diamines.The kind of preferred other diamines and the preferred usage ratio of various diamines are identical with the situation of polyamic acid.

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

The dehydration closed-loop of polyamic acid preferably by the method for (i) heating polyamic acid, perhaps (ii) is dissolved in polyamic acid in the organic solvent, adds dewatering agent and dehydration closed-loop catalyzer in this solution, 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, the dehydration closed-loop reaction can't fully be carried out, and if temperature of reaction surpasses 200 ℃, the molecular weight and molecular weight of gained polyimide then.Reaction times is preferably 1.0～24 hours, and more preferably 1.0～12 hours.

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

Preparation of liquid crystal aligning agent can directly be supplied with it by the polyimide of gained in the aforesaid method (i), resupplies the preparation of liquid crystal aligning agent after perhaps also the polyimide of gained can being made with extra care.On the other hand, aforesaid method (ii) in, can obtain containing the reaction soln of polyimide.This reaction soln, it directly can be supplied with the preparation of liquid crystal aligning agent, also can after from reaction soln, removing dewatering agent and dehydration closed-loop catalyzer, supply with the preparation of liquid crystal aligning agent, polyimide can also be separated the preparation that liquid crystal aligning agent is supplied with in the back, resupply the preparation of liquid crystal aligning agent after perhaps isolating polyimide can also being made with extra care.From reaction soln, remove dewatering agent and dehydration closed-loop catalyzer, can adopt for example method such as solvent exchange.The separation of polyimide, refining can be taked to carry out as the separating of polyamic acid, the described same operation of process for purification with above.

The polymkeric substance of-end modified type-

Polyamic acid among 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 under the prerequisite of not damaging 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 in synthesizing polyamides when acid, adds molecular weight regulator and carry out in polymerization reaction system.As molecular weight regulator, can enumerate for example single acid anhydride, monoamine compound, monoisocyanates compound etc.

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

The usage ratio of molecular weight regulator, the total amount of employed tetracarboxylic dianhydride and diamines is preferably below 20 weight parts when synthetic with respect to the acid of 100 weight parts of polyamide, 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 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) is the polymers soln for the synthetic 10 weight % concentration of good solvent (for example gamma-butyrolactone, N-N-methyl-2-2-pyrrolidone N-etc.) that adopt this polymkeric substance, uses E type rotational viscosimeter 25 ℃ of values of being measured down.

＜other composition 〉

Liquid crystal orientation film of the present invention contains and is selected from least a as neccessary composition in the group that is made of aforesaid polyamic acid and the formed polyimide of imidization thereof, but also can contain other polymkeric substance as required.As this other composition, can enumerate other polymkeric substance for example, for example have a compound (below, be called " epoxy compounds "), functional silanes compound etc. of at least one epoxy group(ing) at intramolecularly

[other polymkeric substance]

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

Usage ratio as other polymkeric substance, (be meant above-mentioned tetracarboxylic dianhydride and the polyamic acid that comprises the diamine reactant gained of the represented compound of above-mentioned formula (A), make the total amount of the formed polyimide of this polyamic acid dehydration closed-loop and other polymkeric substance with respect to the total amount of polymkeric substance, down together), be preferably below the 90 weight %, 10～85 weight % more preferably, and 30～80 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, the 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-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl hexanaphthene, N, N-diglycidyl-hexahydroaniline etc.

The cooperation ratio of these epoxy compoundss, the total amount with respect to 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, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, 9-triethoxysilicane alkyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, 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 cooperation ratio of these functional silanes compounds, the total amount with respect to 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, other additive that preferably will be selected from least a polymkeric substance in the group that constitutes by aforesaid polyamic acid and polyimide and cooperate arbitrarily as required, dissolving is included in the organic solvent and constitutes.

As the organic solvent that can be used in the liquid crystal aligning agent of the present invention, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, 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 the liquid crystal aligning agent accounts for the ratio of liquid crystal aligning agent gross weight) is considered viscosity, volatility etc. and suitably selection, and is preferably the scope of 1～10 weight %.That is to say, as described later liquid crystal aligning agent of the present invention is coated on the substrate surface, and preferably by adding thermosetting as the filming of liquid crystal orientation film, but it is when solid component concentration less than 1 weight %, too small and be difficult to obtain the situation of good liquid crystal orientation film with this thickness of filming occurring; On the other hand, when solid component concentration surpassed 10 weight %, coating thickness was blocked up and be difficult to obtain the situation of good liquid crystal orientation film equally with occurring, and the viscosity that liquid crystal aligning agent perhaps will occur increases the situation that causes the coating characteristics variation.

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

Temperature when 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 aforesaid liquid crystal aligning agent of the present invention.

Liquid crystal display device of the present invention can be by for example operation manufacturing 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 a common.

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

(1-1) when making TN type, STN type or VA type liquid crystal display device, make two substrates that are provided with the nesa coating that forms pattern paired, and respectively liquid crystal aligning agent of the present invention is coated on separately the transparent conducting film formation face, then heat each coated face, formation is filmed.As coating process, can enumerate for example offset printing method, flexible printing method, ink jet printing method, rolling method, spin-coating method etc., but during owing to employing flexible printing method, can bring into play the present invention to greatest extent and the effect that polymkeric substance is separated out can not occur on anilox roll, therefore preferred.As substrate, can use for example 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.Simultaneously go up set nesa coating as substrate, 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 for example form patternless nesa coating after, by photoengraving form method of patterning, when forming nesa coating, use the method for mask etc. with desirable pattern.When the coating of liquid crystalline alignment agent, better for the adhesivity that makes substrate surface and nesa coating and film, can be embodied in and will form in the substrate surface on the surface of filming, be coated with the pre-treatment of functional silanes compound, functionality titanium compound etc. in advance.

Behind the coating of liquid crystalline alignment agent,, preferably preheat (prebake) for situations such as the alignment agent liquid that prevents to be coated with drip.The prebake temperature is preferably 30～200 ℃, and more preferably 40～150 ℃, and be preferably 40～100 ℃ especially.The prebake time is preferably 0.25～10 minute, and more preferably 0.5～5 minute.Then, desolvate in order to remove fully, and the purpose that makes the amido acid unit hot-imide in the polymerization process as required, (afterwards curing) operation burnt till.This burns till (afterwards curing) 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 making IPS type liquid crystal display device, respectively liquid crystal aligning agent of the present invention is coated on the broach shape and is provided with on the conducting film formation face of substrate of the nesa coating that forms pattern, and be not provided with on the one side of subtend substrate of conducting film, then heat each coated face, formation is filmed.Identical among coating process and above-mentioned (1-1).

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

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

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

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

Further, for as above-mentioned formed liquid crystal orientation film, carry out a part of irradiation ultraviolet radiation shown in patent documentation 9 (Japanese kokai publication hei 6-222366 communique) for example or the patent documentation 10 (Japanese kokai publication hei 6-281937 communique) to liquid crystal orientation film, thereby the processing that the pre-tilt angle that makes the liquid crystal orientation film subregion changes, shown in patent documentation 11 (Japanese kokai publication hei 5-107544 communique) after forming etchant resist on the part on liquid crystal orientation film surface, on the direction different, carry out grinding process with previous grinding process, remove the processing of etchant resist then, make liquid crystal orientation film on each zone, have 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 liquid crystal orientation film as mentioned above, and between two substrates of subtend configuration, dispose liquid crystal, make liquid crystal cell.When carrying out grinding process,, make polishing direction in respectively filming be the angle of regulation, for example quadrature or antiparallel mutually herein, with the configuration of two substrate subtends to filming.

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

First method is known in the past method.At first, two substrates are disposed relatively across gap (box gap), make separately liquid crystal orientation film relatively to, and use sealing agent that the peripheral position of two substrates is fit together, after in the box gap of dividing by substrate surface and sealing agent, injecting filling liquid crystal, the sealing filling orifice can be made liquid crystal cell thus.

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

Adopting under the situation of above-mentioned arbitrary method, is all wishing further the liquid crystal cell as above-mentioned manufacturing is heated to the temperature that used liquid crystal is isotropic phase, slowly cooling to room temperature then, the flow orientation when removing filling liquid crystal thus.

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

Herein, as sealing agent, can use and for example contain as the alumina balls of separator and the Resins, epoxy of solidifying agent etc.

As foregoing liquid crystal, can use for example nematic liquid crystal and dish shape type liquid crystal etc., wherein preferred nematic liquid crystal.When VA type liquid crystal cell, the nematic liquid crystal that preferably has negative dielectric anisotropy can use for example 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 that preferably has positive dielectric anisotropy can use for example biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.Can also add for example cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal; The chirality agent of selling with trade(brand)name C-15, CB-15 (manufacturing of メ Le Network company); To oxygen base Ben Yajiaji-strong dielectricity liquid crystal such as amino-2-methyl butyl laurate etc. is used in the last of the ten Heavenly stems.

As the polaroid of fitting on the liquid crystal cell outside surface, can enumerate with the 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 the polyvinyl alcohol stretch orientation and form.

Embodiment

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

The imidization rate of the soltion viscosity of each polymkeric substance and polyimide in the following synthesis example is measured respectively by the following method.

[soltion viscosity of polymkeric substance]

The soltion viscosity of polymkeric substance (mpas) is for adopting the described solvent of each synthesis example to be adjusted to the polymers soln of the polymer concentration % of each synthesis example regulation, using E type rotational viscosimeter 25 ℃ of values of being measured down.

[the imidization rate of polyimide]

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

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

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

The synthesis example of the compound that＜above-mentioned formula (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 the 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 stirred 8 hours, reacted.Use rotatory evaporator to concentrate the reaction mixture of gained, remove unreacted diallyl amine, add 10L toluene then, and with the organic layer of distilled water wash gained.Organic layer after using sal epsom to washing dewaters, and uses rotatory evaporator to remove then and desolvates, and 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 the 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, stir down at 0 ℃.Wherein splash into 312.0mL (2.3 moles) triethylamine through 30 fens clockwise, at room temperature stirred then 3 hours, react.In the reaction mixture of gained, add the 0.5L methylene dichloride, and with the organic layer of distilled water wash gained.Organic layer after using sal epsom to washing dewaters, and uses rotatory evaporator to concentrate then.In the colorless viscous liquid of gained, add 3L ethanol, fully stir, filter the white solid of separating out then and also 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 the 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 mineral oil after, vacuum-drying.To wherein adding the 3.0L tetrahydrofuran (THF), and stir down at 0 ℃.The compound (A-1-1a) that wherein splashes into the above-mentioned gained of 341.3g (1.2 moles) through 30 fens clockwise is dissolved in the solution in the 1.0L tetrahydrofuran (THF), stirs 15 minutes down at 0 ℃ then.To compound (A-1-1b) that wherein adds the above-mentioned gained of 317.8g (1.0 moles) and 32.2g (0.1 mole) Tetrabutylammonium bromide, at room temperature stirred then 10 hours again, react.After reaction finishes, in reaction mixture, add aqueous ammonium chloride solution, reach acidity after, use the 4.0L ethyl acetate to extract, obtain organic layer.After this organic layer washed, use sal epsom to dewater, and use rotatory evaporator to remove and desolvate, obtain crude product.Use column chromatography (weighting agent: silica gel, expansion solvent: hexane/ethyl acetate=4/1 (weight ratio)) the thick refining thing of refining gained, and from the cut of gained, remove and desolvate, obtain 262.1g (0.6 mole, yield rate is 58.6%) midbody compound (A-1-1c) for dark brown viscous liquids.

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

Under nitrogen atmosphere, in the 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 under 35 ℃ and reacted in 4 hours.After reaction finishes, with aqueous sodium carbonate washing reaction mixture, remove unreacted 1,3-dimethyl barbituric acid, and then use distilled water wash.Use the organic layer of dried over mgso gained, use rotatory evaporator to remove then and desolvate, obtain crude product.Use column chromatography (weighting agent: silica gel, expansion solvent: chloroform/ethanol=95/5 (weight ratio)) the thick refining thing of refining gained, and from the cut of gained, remove and desolvate, 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, the 5-diketone).

As required, 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 with above-mentioned scale.

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 the 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), stirred 10 hours down at 40 ℃, react.After reaction finishes, in reaction mixture, add the 2L ethyl acetate, use the organic layer of distilled water wash gained, and dewater, use rotatory evaporator to remove then and desolvate, obtain crude product with sal epsom.Use ethanol that the crude product of gained is carried out recrystallize, the filtered and recycled crystallization, and under 60 ℃, carry out vacuum-drying in 12 hours, obtain 206g (0.70 mole, yield rate is 70.0%) midbody compound (A-2-1k) into pale yellow powder.

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

Under nitrogen atmosphere, in the 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.Stir this mixture down at 0 ℃ on one side,, react Yi Bian, at room temperature stirred then 6 hours lentamente to wherein adding 600mL water.After reaction finishes, from reaction mixture, remove catalyzer, and use rotatory evaporator from this filtrate, to remove and desolvate, obtain crude product by the brownmillerite filtration.Use column chromatography (weighting agent: silica gel, launch solvent: the crude product of refining gained tetrahydrofuran (THF)), and from the cut of gained removal of solvent under reduced pressure, obtain 52.3g (0.22 mole, yield rate is 89%) compound (A-2-1) into dark brown liquid.

Synthesizing of＜polyimide 〉

Synthesis example PI-1

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate 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, the 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-two (3-aminopropyl) tetramethyl disiloxane and 9.6g (0.015 mole) 3,6-two (4-amino-benzene acyloxy) cholestane, and as 8.1g (0.030 mole) the octadecane amine of monoamine, be dissolved in the 960g N-N-methyl-2-2-pyrrolidone N-(NMP), under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of polyamic acid.This solution that takes a morsel adds NMP, and forming polyamic acid concentration is the solution of 10 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, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, with new gamma-butyrolactone the solvent in the system is carried out solvent exchange (by this solvent exchange operation, employed pyridine and diacetyl oxide in the dehydration closed-loop reaction are expelled to outside the system, down with), obtain containing the solution that the 15 weight % imidization rates of having an appointment are about 95% polyimide (PI-1).The take a morsel polyimide solution of gained adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 weight %, and the soltion viscosity of its mensuration is 70mPas.

Synthesis example PI-2

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, with as 38g (0.35 mole) Ursol D of diamines, the 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 among the 830g NMP, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of polyamic acid.This polyamic acid solution that takes a morsel adds NMP, and forming polyamic acid concentration is the solution of 10 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, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 weight % imidization rates of having an appointment are about 50% polyimide (PI-2) with new NMP.The take a morsel polyimide solution of gained adds NMP, and forming polyimide concentration is the solution of 10 weight %, and the soltion viscosity of its mensuration is 47mpas.

Synthesis example PI-3

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, with 32g (0.30 mole) Ursol D, 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 is dissolved among the 800g NMP, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of polyamic acid.This polyamic acid solution that takes a morsel adds NMP, and forming polyamic acid concentration is the solution of 10 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, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 weight % imidization rates of having an appointment are about 80% polyimide (PI-3) with new gamma-butyrolactone.The take a morsel polyimide solution of gained adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 weight %, and the soltion viscosity of its mensuration is 87mPas.

Synthesis example PI-4

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, with as 49g (0.45 mole) Ursol D of diamines and the compound (A-1-1) of the above-mentioned synthesis example A-1 gained of 13g (0.05 mole), be dissolved among the 1460g NMP, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of 10 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, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 weight % imidization rates of having an appointment are about 90% polyimide (PI-4) with new gamma-butyrolactone.The take a morsel polyimide solution of gained adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 weight %, and the soltion viscosity of its mensuration is 65mPas.

Synthesis example PI-5

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, with as 49g (0.45 mole) Ursol D of diamines and the compound (A-2-1) of the above-mentioned synthesis example A-2 gained of 12g (0.05 mole), be dissolved among the 1540g NMP, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of 10 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, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 weight % imidization rates of having an appointment are about 88% polyimide (PI-5) with new gamma-butyrolactone.The take a morsel polyimide solution of gained adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 weight %, and the soltion viscosity of its mensuration is 60mPas.

Synthesizing of＜other polymkeric substance 〉

[synthesizing of other polyamic acid]

Synthesis example PAR-1

Will be as tetracarboxylic dianhydride's 200g (1.0 moles) 1,2,3,4-tetramethylene tetracarboxylic dianhydride is 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, under 40 ℃, carry out reaction in 3 hours, obtain containing the solution of 10 weight % polyamic acids (PAR-1).The soltion viscosity of this polyamic acid solution is 160mPas.

[synthesizing of other polyimide]

Synthesis example PIR-1

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, with 38g (0.35 mole) Ursol D, 20g (0.1 mole) 4 as diamines, 4 '-diaminodiphenyl-methane and 26g (0.05 mole) 3 (3,5-diaminobenzene acyloxy) cholestane is dissolved among the 800g NMP, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of polyamic acid.Take a morsel this polyamic acid solution of gained adds NMP, and forming polyamic acid concentration is the solution of 10 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, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 weight % imidization rates of having an appointment are about 80% polyimide (PIR-1) with new gamma-butyrolactone.The take a morsel polyimide solution of gained adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 weight %, and the soltion viscosity of its mensuration is 87mPas.

Synthesis example PIR-2

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, with 54g (0.5 mole) Ursol D as diamines, be dissolved among the 1476g NMP, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of 10 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, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 weight % imidization rates of having an appointment are about 91% polyimide (PIR-2) with new gamma-butyrolactone.The take a morsel polyimide solution of gained adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 weight %, and the soltion viscosity of its mensuration is 64mPas.

Synthesis example PIR-3

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, with 6g (0.01 mole) 3 as diamines, 6-two (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 is dissolved among the 1647g NMP, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of 10 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, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 weight % imidization rates of having an appointment are about 89% polyimide (PIR-3) with new gamma-butyrolactone.The take a morsel polyimide solution of gained adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 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 above-mentioned synthesis example PIR-1, add gamma-butyrolactone (BL), N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether (BC) in the solution that contains polyimide (PIR-1) of gained, 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 the formation solvent composition is BL: NMP: BC=40: 30: 30 (weight ratio), solid component concentration are the solution of 6.0 weight %.The use aperture is that the strainer of 1 μ m filters this solution, the modulation liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

(1) evaluation of printing

For above-mentioned synthetic liquid crystal aligning agent, use liquid crystal orientation film printing press (Japan's description printing (strain) is made), it is coated on the transparency electrode face of the glass substrate that has the formed transparency electrode of ITO film, and on 80 ℃ hot plate, heat 1 minute (prebake) except that desolvating, and then on 200 ℃ hot plate, heating 10 minutes (afterwards curing), the formation average film thickness is

Film.Use 20 multiplying powers microscopic examination this film, investigation has pore-free and irregular and their degree of printing.Though the result does not observe pore, it is irregular to observe some printing.

The evaluation of the film uniformity of (2) filming

For above-mentioned formed filming, use contact pin type film thickness gauge (manufacturings of KLA テ Application コ one Le society), measure the thickness of substrate center part respectively and apart from the thickness of the close middle body 15mm position of substrate outboard end.With both film thickness differences be

Following average evaluation is film uniformity " well ", and film thickness difference is surpassed Average evaluation be film uniformity " defective ".

The separability evaluation of (3) filming

For above-mentioned formed filming, it was flooded 5 minutes changing in the stripper " TS-204 " that industry (strain) makes in Sanyo under 30 ℃, carry out strip operation.After peeling off, whether have the residue of filming on the visual investigation substrate.The average evaluation of the residue of filming is arranged is separability " well " with unconfirmed on the substrate, will confirm that it is separability " defective " that the average evaluation of the residue of filming is arranged, and in this comparative example, remaining filming on the part of substrate, its separability " defective ".

(4) printing is estimated continuously

In 1 minute, on the anilox roll of liquid crystal orientation film printing press (Japanese description printing (strain) is made), splash into the above-mentioned synthetic liquid crystal aligning agent of 0.2g on one side, on one side continuous rotation anilox roll.Per hour whether contained polymkeric substance separates out to anilox roll in liquid crystal aligning agent of visual observation.

In this comparative example, do not observe separating out of polymkeric substance in the experiment beginning after 1 hour, to separate out but after 2 hours, observe, experiment at this moment finishes.

Comparative example 2

[modulation of liquid crystal aligning agent]

In above-mentioned synthesis example PIR-2, add gamma-butyrolactone (BL) and ethylene glycol butyl ether (BC) in the solution that contains polyimide (PIR-2) of gained, 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 the formation solvent composition is BL: BC=88: 12 (weight ratios), solid component concentration are the solution of 6.0 weight %.The use aperture is that the strainer of 1 μ m filters this solution, the modulation liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

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

Comparative example 3

[modulation of liquid crystal aligning agent]

In above-mentioned synthesis example PIR-3, add gamma-butyrolactone (BL) and ethylene glycol butyl ether (BC) in the solution that contains polyimide (PIR-3) of gained, 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 the formation solvent composition is BL: B C=88: 12 (weight ratios), solid component concentration are the solution of 6.0 weight %.The use aperture is that the strainer of 1 μ m filters this solution, the 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 among the solution that contains polyimide (PI-1) of gained among the above-mentioned synthesis example PI-1 and the above-mentioned synthesis example PAR-1, make polyimide (PI-1): other polyamic acid (PAR-1)=20: 80 (weight ratio), and to wherein adding gamma-butyrolactone (BL), N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether (B C), again with respect to the total amount of 100 parts by weight polymer, adding is as 10 weight part N of epoxy compounds, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane also fully stirs, and the formation solvent composition is BL: NMP: BC=71: 17: 12 (weight ratio), solid component concentration is the solution of 6.0 weight %.The use aperture is that the strainer of 1 μ m filters this solution, the modulation liquid crystal aligning agent.

[evaluation of liquid crystal aligning agent]

(1) evaluation of printing

Use above-mentioned synthetic liquid crystal aligning agent and above-mentioned comparative example 1 similarly to form average film thickness to be

Film.Use 20 multiplying powers microscopic examination this film, investigation has pore-free and irregular and their degree of printing.Herein, irregular for printing, investigation is compared with filming of above-mentioned comparative example 1, whether improved the inhomogenous generation of printing, and the situation (that is to say, compare with filming of comparative example 1, print the little situation of inhomogenous degree) that will observe improvement is evaluated as " well ".

Evaluation result is shown in table 1.

The separability evaluation of filming in the evaluation of the film uniformity of (2) filming, (3) and (4) printing are continuously estimated

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

Evaluation result is shown in table 1 and table 2.

In addition, (4) printing are continuously estimated, and observe the 4th hour.

Embodiment 2

[modulation of liquid crystal aligning agent]

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

[evaluation of liquid crystal aligning agent]

Except using above-mentioned synthetic liquid crystal aligning agent and in the foregoing description 1, similarly estimate.

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

[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 among the solution that contains polyimide (PI-4) of gained among the above-mentioned synthesis example PI-4 and the above-mentioned synthesis example PAR-1, make polyimide (PI-4): other polyamic acid (PAR-1)=20: 80 (weight ratio), and to wherein adding gamma-butyrolactone (BL), N-N-methyl-2-2-pyrrolidone N-(NMP) and ethylene glycol butyl ether (BC), again with respect to the total amount of 100 parts by weight polymer, adding is as 10 weight part N of epoxy compounds, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane also fully stirs, and the formation solvent composition is BL: NMP: BC=83: 5: 12 (weight ratio), solid component concentration is the solution of 6.0 weight %.The use aperture is that the strainer of 1 μ m filters this solution, the 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 the solution that contains polyimide (PI-5) of gained among the above-mentioned synthesis example PI-5 to replace containing outside the solution of polyimide (PIR-2) and similarly modulate liquid crystal aligning agent in the comparative example 2.

[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, following content represented respectively in the abbreviation of the solvent in the table 1 solvent composition hurdle.

BL: gamma-butyrolactone

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

BC: ethylene glycol butyl ether

[table 2]

Table 2. is the result of printing evaluation continuously

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

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

3. liquid crystal aligning agent as claimed in claim 1 or 2, wherein above-mentioned tetracarboxylic dianhydride comprises 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride.

4. as each described liquid crystal aligning agent of claim 1～3, wherein above-mentioned polymkeric substance is a polyimide more than 30% for the imidization rate.

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

6. a liquid crystal display device is characterized in that having the described liquid crystal orientation film of claim 5.

7. make the tetracarboxylic dianhydride and comprise above-mentioned formula (A ⁰) polyamic acid of diamine reactant gained of represented compound.

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

9. by above-mentioned formula (A ⁰) represented compound.