CN103343015B

CN103343015B - Liquid crystal aligned agent, liquid crystal aligned film, liquid crystal display element, polyamic acid, imiding polymer and compound

Info

Publication number: CN103343015B
Application number: CN201310279345.0A
Authority: CN
Inventors: 平井刚; 秋池利之; 林英治; 菅野尚基
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2009-03-18
Filing date: 2010-03-16
Publication date: 2015-02-25
Anticipated expiration: 2030-03-16
Also published as: TWI448486B; JP5516863B2; CN101838537A; CN103343015A; CN101838537B; KR20100105460A; JP2010244015A; TW201038625A; KR101588905B1

Abstract

The present invention relates to a liquid crystal aligned agent, a liquid crystal aligned film, a liquid crystal display element, polyamic acid, imiding polymer and a compound. The invention provides a liquid crystal aligned agent which has lower decrease of voltage stability after photoradiation and has excellent reliability. The liquid crystal aligned agent comprises at least one polymer selected from the group consisting of polyamic acid obtained from reaction of tetracarboxylic acid with diamine and its imiding polymer, in which the said diamine comprises a compound (A) containing cyclic amine structure or phenol structure and two amino group; the two carbon atoms adjoining to the said cyclic structure could be substituted by two hydrocarbon groups which interrupted by oxygen atom, sulfur atom, carbonyl group or ester bond on the way; and at least one of the carbon in the ortho-site corresponding to the hydroxyl group of the said phenol structure could be substituted by the hydrocarbon group which interrupted by oxygen atom, sulfur atom, carbonyl group or ester bond on the way.

Description

Liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, polyamic acid, imide amination polymer and compound

The present invention is the denomination of invention of application on March 16th, 2010 is the divisional application of No. 201010134551.9 application for a patent for invention of " liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, polyamic acid, imide amination polymer and compound ".

Technical field

The present invention relates to liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, polyamic acid, imide amination polymer and compound.In more detail, relate to following liquid crystal aligning agent, excellent liquid crystal display device, this liquid crystal aligning agent because of the reduction of the voltage retention that light produces little, liquid crystal orientation film excellent in reliability can be formed, the reduction of the voltage retention because of light generation of this liquid crystal display device is little, and display quality can not be deteriorated.

Background technology

Liquid crystal display device according to the physical property of the liquid crystal molecule of electrode structure and use, can be categorized as following shown in various patterns.

As liquid crystal display device, the TN type liquid crystal display device (patent documentation 1) with so-called TN (Twisted Nematic: twisted-nematic) type liquid crystal cell can be listed, compared with TN type liquid crystal display device, STN (Super Twisted Nematic: supertwist is to row) the type liquid crystal display device (patent documentation 2) etc. of high duty ratio can be realized, wherein this TN type liquid crystal display device forms liquid crystal orientation film on the substrate surface being provided with nesa coating, as substrate used for liquid crystal display element, its 2 pieces are oppositely arranged, the nematic liquid crystal layer with positive dielectric anisotropy is formed betwixt in gap, form the box of sandwich structure, the major axis of this liquid crystal molecule is turned round continuously from one piece of substrate to another block substrate and is turn 90 degrees.

In addition, VA (Vertical Alignment: vertical orientated) type display element can also be listed, this display element is and TN type liquid crystal display device similarly subtend configuration electrode, in electrode gap, inject the layer with the nematic liquid crystal of negative dielectric anisotropy, make the generally perpendicularly orientation formation of liquid crystal opposing substrate.VA type display element can form high-contrast and large-area display element (patent documentation 3).

On the other hand, also develop IPS (In-Plane Switching: switch in face) type liquid crystal display device (patent documentation 4 and 5), this liquid crystal display device, by being configured in one piece of substrate surface by electrode pair comb teeth-shaped, applies the only direction in the face of substrate, liquid crystal drive direction during electric field; And FFS (Fringe Field Switching: fringing field switches) type liquid crystal display device (patent documentation 6), this liquid crystal display device changes the electrode structure of IPS type liquid crystal display device, improve the aperture opening ratio of display element part, improve brightness, their respective perspective nature are all excellent.

In addition, further developed the OCB (Optical Compensated Bend: optical compensation curved) type liquid crystal display device (patent documentation 7) etc. of the little and image frame high-speed response excellence of view angle dependency.

As the material of the liquid crystal orientation film in these various liquid crystal display device, known has the resin materials such as polyamic acid, polyimide, polymeric amide, polyester, particularly, the excellences such as the affinity of the liquid crystal aligning film heat resistance, physical strength and the liquid crystal that are formed by polyamic acid or polyimide, so use (patent documentation 8) in the liquid crystal display device of majority.

In this liquid crystal aligning agent, in recent years, to the performance of function can not be reduced because of rayed, require also than increasing to some extent in the past.Its problem is as follows.

In the manufacturing process of liquid crystal display device, bringing into use based on shortening technique and the viewpoint improving yield rate is liquid crystal drop add mode, namely ODF (One Drop Fill) mode.ODF mode is different from the current method in the liquid crystal cell of the sky using Thermocurable sealing agent to be installed by Liquid crystal pour in advance, after the sealing agent of the needed position coating ultraviolet light curable of the side substrate being coated with liquid crystal orientation film, liquid crystal drop is added in needed position, after another baseplate-laminating, whole irradiating ultraviolet light, make sealant cures, manufacture the method for liquid crystal cell.The UV-light of now irradiating, normally at every 1 square centimeter, is the intensity of more than several joules.Namely, in the manufacturing process of liquid crystal display device, under liquid crystal orientation film is exposed to this strong UV-light together with liquid crystal.

If the purposes according to liquid crystal display device changes target, compared with the notebook computer, watch-dog indicating meter etc. of the main application as existing liquid crystal display device, the cycle of the new and old replacement of LCD TV obviously universal is in recent years longer, need the life-span more grown, can for longer periods be exposed in backlight illumination.In addition, except commercial use, in the liquid crystal display device of the liquid crystal projection apparatus purposes raised as the demand of home theater in recent years, use the light source that the exposure intensities such as metal halide lamp are very high.In addition, the navigating instrument liquid crystal display device of the mobile office instrument use such as mobile telephone and vehicle-mounted use is exposed to and comprises in the sunlight of intensive ultraviolet, in order to improve sense of vision, must improve backlight illumination.

So, in liquid crystal display device, along with the improvement, multi-usage etc. of its manufacturing process, also cannot use in the rayed of high strength, long-time driving etc. so far unimaginable severe rugged environment.

Liquid crystal orientation film known is at present noted the patience of the environment of this harshness not enough.

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Unexamined Patent Publication 4-153622 publication

[patent documentation 2] Japanese Laid-Open Patent Publication 60-107020 publication

[patent documentation 3] Japanese Unexamined Patent Publication 11-258605 publication

[patent documentation 4] Japanese Laid-Open Patent Publication 56-91277 publication

[patent documentation 5] US5,928,733

[patent documentation 6] Japanese Unexamined Patent Publication 2002-082357 publication

[patent documentation 7] Japanese Unexamined Patent Publication 9-105957 publication

[patent documentation 8] Japanese Laid-Open Patent Publication 62-165628 publication

[patent documentation 9] Japanese Unexamined Patent Publication 6-222366 publication

[patent documentation 10] Japanese Unexamined Patent Publication 6-281937 publication

[patent documentation 11] Japanese Unexamined Patent Publication 5-107544 publication

Summary of the invention

The present invention proposes based on the problems referred to above, and its object is to provides the reduction of the voltage retention because of rayed generation little, can form the liquid crystal aligning agent of liquid crystal orientation film excellent in reliability.

Another object of the present invention is to provide the reduction of the voltage retention because of light generation little, the liquid crystal display device of the excellence that display quality can not be deteriorated.

Other object of the present invention and advantage can be clear and definite by following explanation.

According to the present invention, above object and advantages of the present invention first are realized by a kind of liquid crystal aligning agent, this liquid crystal aligning agent comprises at least a kind of polymkeric substance in the group being selected from and being made up of polyamic acid and imide amination polymer thereof, this polyamic acid is obtained by tetracarboxylic dianhydride and diamine reactant, it is characterized in that: aforementioned diamines comprises and has cyclic amine structure or phenol structure and 2 amino compounds (A), wherein this cyclic amine structure is that 2 carbon atoms adjacent on nitrogen-atoms are separately by can in centre by Sauerstoffatom, sulphur atom, the cyclic amine structure of 2 alkyl replacements at carbonyl or ester bond interval, this phenol structure be relative to hydroxyl be in the carbon at ortho position at least 1 by can in centre by Sauerstoffatom, sulphur atom, the phenol structure of the alkyl replacement at carbonyl or ester bond interval.

Above object and advantages second point of the present invention is that the liquid crystal display device by having the liquid crystal orientation film formed by above-mentioned liquid crystal aligning agent realizes.

Even if liquid crystal aligning agent of the present invention can be formed irradiate backlight for a long time, the liquid crystal orientation film that voltage retention also can not reduce.The liquid crystal display device of the present invention with the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention can show to high-quality, even if when driving for a long time, display character also can not be deteriorated.Therefore, liquid crystal display device of the present invention can effectively for various device, such as, be adapted at using in the display unit such as clock and watch, pocket game machine, word processor, notebook computer, onboard navigation system, pick up camera, portable information terminal, digital camera, mobile telephone, various watch-dog, LCD TV.

Embodiment

Below, the present invention is described in detail.

Liquid crystal aligning agent of the present invention contains at least a kind of polymkeric substance in the group being selected from and being made up of polyamic acid and imide amination polymer thereof, and this polyamic acid is obtained by tetracarboxylic dianhydride and the diamine reactant containing compound as above (A).

[tetracarboxylic dianhydride]

As the tetracarboxylic dianhydride used for the synthesis of above-mentioned polyamic acid, such as aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc. can be listed.As their object lesson, wherein as aliphatics tetracarboxylic dianhydride, such as butane tetracarboxylic acid dianhydride etc. can be listed;

As ester ring type tetracarboxylic dianhydride, such as 1 can be listed, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic acid anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl norcamphane-2:3, 5:6-dianhydride, 2, 4, 6, 8-tetracarboxylic two ring [3.3.0] octane-2:3, 5:6-dicarboxylic anhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone etc.,

As aromatic tetracarboxylic acid's dianhydride, such as pyromellitic acid dianhydride etc. can be listed; In addition the tetracarboxylic dianhydride recorded in Japanese Patent Application 2009-66252 can be used.

As the tetracarboxylic dianhydride for the synthesis of foregoing polyamides acid, the tetracarboxylic dianhydride of ester ring type tetracarboxylic dianhydride is preferably comprised among them, be more preferably containing being selected from 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 1,2, at least a kind of tetracarboxylic dianhydride of the group that 3,4-tetramethylene tetracarboxylic dianhydride is formed, is particularly preferably containing 2, the tetracarboxylic dianhydride of 3,5-tricarboxylic cyclopentyl acetic acid dianhydride.

As the tetracarboxylic dianhydride for the synthesis of above-mentioned polyamic acid, be more preferably and be selected from 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 1,2, the content of at least a kind in the group that 3,4-tetramethylene tetracarboxylic dianhydride is formed is more than 10mol% relative to whole tetracarboxylic dianhydride, is more preferably more than 20mol%; Most preferably only containing at least a kind that is selected from the group of 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 1,2,3,4-tetramethylene tetracarboxylic dianhydride formation.

[diamines]

The diamines of inclusion compound (A) for the synthesis of the diamines of polyamic acid in the present invention, this compound (A) to have on nitrogen-atoms 2 adjacent carbon atoms separately by can in centre by the cyclic amine structure that 2 alkyl at Sauerstoffatom, sulphur atom, carbonyl or ester bond interval replace, or relative at least 1 in the carbon that hydroxyl is ortho position by can in centre by the phenol structure that the alkyl at Sauerstoffatom, sulphur atom, carbonyl or ester bond interval replaces, and 2 amino.

Above-claimed cpd (A) is when the compound for having cyclic amine structure, as the alkyl replaced on the carbon atom of this cyclic amine nitrogen-atoms adjacent, can list such as carbonatoms be 1 ~ 6 alkyl, carbonatoms be 6 ~ 20 aryl, carbonatoms be the aralkyl etc. of 7 ~ 20.Wherein, these alkyl can in centre by Sauerstoffatom, sulphur atom, carbonyl or ester bond interval.

On the other hand, when above-claimed cpd (A) is the compound with phenol structure, as being the alkyl that the carbon at ortho position replaces at relative hydroxyl, can list such as carbonatoms is the alkyl of 4 ~ 16.But this alkyl can in centre by Sauerstoffatom, sulphur atom, carbonyl or ester bond interval.

As this compound (A), the compound shown in following formula (A1) can be listed respectively as the compound with cyclic amine structure; List the compound shown in following formula (A2) as the compound with phenol structure.

In formula (A1), R ⁱhydrogen atom, the carbonatoms alkyl that is 1 ~ 6, the carbonatoms aryl that is 6 ~ 20, carbonatoms be 7 ~ 13 aralkyl or 1,3-dioxobutyl,

X ¹be singly-bound, carbonyl or ^*-CONH-(wherein, connecting key and piperidine ring combination with " * "),

R ^iI~ R ^veach carbonatoms be naturally 1 ~ 6 alkyl, carbonatoms be 6 ~ 12 aryl or carbonatoms be the aralkyl of 7 ~ 13, the alkoxyl group that the phenyl ring that wherein aforesaid aryl and aralkyl have can be 1 ~ 4 by formyl radical or carbonatoms replaces,

X ²~ X ⁵each singly-bound naturally, carbonyl, ^*-CH ₂-CO-or ^*-CH ₂-CH (OH)-(wherein, connecting key and piperidine ring combination with " * "),

In formula (A2), R ^vIbe centre can be the alkyl of 4 ~ 16 by the carbonatoms at Sauerstoffatom, sulphur atom, carbonyl or ester bond interval, R ^vIIbe hydrogen atom or centre can be the alkyl of 1 ~ 16 by the carbonatoms at Sauerstoffatom, sulphur atom, carbonyl or ester bond interval,

X in formula (A1) and (A2) ⁶be respectively Sauerstoffatom, ^*-OCO-, following formula (X ⁶-1)

(formula (X ⁶-1) in, a is the integer of 1 ~ 12, and b is the integer of 0 ~ 5)

Shown group (wherein, hereinbefore, connecting key with " * " is and piperidine ring in formula (A1), is combine respectively with the phenyl ring with hydroxyl in formula (A2)), methylene radical or carbonatoms be the alkylidene group of 2 ~ 6.

As the R in above formula (A1) ⁱcarbonatoms be the alkyl of 1 ~ 6, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl etc. can be listed.

As R ⁱcarbonatoms be the aromatic group of 6 ~ 20, aryl and other aromatic group that carbonatoms is 6 ~ 12 can be listed, be the aryl of 6 ~ 12 as aforementioned carbonatoms, such as phenyl, 3-difluorophenyl, 3-chloro-phenyl-, 4-chloro-phenyl-, 4-isopropyl phenyl, 4-n-butylphenyl, 3-chloro-4-aminomethyl phenyl etc. can be listed;

As other aryl aforementioned, such as 4-pyridyl, 2-phenyl-4-quinolyl, 2-(4 '-tert-butyl-phenyl)-4-quinolyl, 2-(2 '-thio-phenyl)-4-quinolyl etc. can be listed.

As R ⁱcarbonatoms be the aralkyl of 7 ~ 13, such as benzyl etc. can be listed.

As the R in above formula (A1) ⁱand X ¹combination, by the radicals R that they flock together ⁱ-X ¹-, such as methyl can be listed, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl, formyl radical, ethanoyl, phenyl, benzyl, 1, 3-dioxobutyl, 4-PYRIDYLCARBONYL, benzoyl, 2-phenyl-4-quinolyl, 2-(4 '-tert-butyl-phenyl)-4-quinolyl, 2-(2 '-thio-phenyl)-4-quinolyl, formula-CONH-Ph (wherein, Ph is phenyl, 3-difluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-isopropyl phenyl, 4-n-butylphenyl or 3-chloro-4-aminomethyl phenyl) shown in group etc.

As the R in above formula (A1) ^iI~ R ^vcarbonatoms be the alkyl of 1 ~ 6, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl etc. can be listed;

Be the aryl of 6 ~ 12 as carbonatoms, the alkoxyl group that the phenyl ring that wherein this aryl has can be 1 ~ 4 by formyl radical or carbonatoms replaces, and can list such as phenyl, 4-Fonnylphenyl, 3,4,5-trimethoxyphenyls etc.;

Be the aralkyl of 7 ~ 13 as carbonatoms, the alkoxyl group that the phenyl ring that wherein this aralkyl has can be 1 ~ 4 by formyl radical or carbonatoms replaces, and can list such as benzyl etc.

As the R in above formula (A1) ^iIand X ², R ^iIIand X ³, R ^iVand X ⁴and R ^vand X ⁵combination, by the radicals R that they flock together ^iI-X ²-, R ^iII-X ³-, R ^iV-X ⁴-or R ^v-X ⁵-; such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl, phenyl, benzyl, benzoyl, 4-formylbenzoyl, 2-hydroxyl-2-phenylethyl, 2-oxo-2-(3 can be listed respectively; 4,5-trimethoxyphenyl) ethyl etc.

As the X in above formula (A1) ⁶carbonatoms be the alkylidene group of 2 ~ 6, such as trimethylene, hexamethylene etc. can be listed.As X ⁶be preferably Sauerstoffatom or ^*-OCO-(wherein, with connecting key and the piperidine ring combination of " * ").

Be attached to 2 amino of above formula (A1) phenyl ring, be preferably relative radicals X ⁶, in 2,4-position or 3,5-position.

As the compound shown in above formula (A1), particularly preferably be the R in above formula (A1) ⁱfor hydrogen atom or methyl, R ^iI~ R ^vall methyl, X ¹~ X ⁵all the compound of singly-bound, the namely compound shown in following formula (A1-1).

In formula (A1-1), R ⁱhydrogen atom or methyl, X ⁶identical with the definition in above formula (A1).

2 amino in above formula (A1-1) are relative radicals X preferably ⁶be 2,4-position or 3,5-position.As the compound shown in above formula (A1), the most preferably compound that represents respectively of following formula (A1-1-1) ~ (A1-1-4).

Compound shown in this above formula (A1), easily can be synthesized by the vitochemical ordinary method of combination.

Such as, in above formula (A1), X ⁶for ^*the compound of-OCO-(wherein, connecting key and piperidine ring combination with " * "), can pass through following formula (P-1)

(in formula (P-1), R ⁱ~ R ^vand X ¹~ X ⁵identical with the definition in above formula (A1) respectively) after the compound that represents and dinitrobenzoyl chloride reaction, by suitable reduction system, such as hydrazine and palladium carbon, be converted to amino to synthesize by nitro.

In addition, in above formula (A1), X ⁶for Sauerstoffatom compound can by by the compound shown in above formula (P-1) under the existence of the suitable alkali such as potassium t-butoxide, after DNCB reaction, by suitable reduction system, such as hydrazine and palladium carbon, be converted to amino to synthesize by nitro.

As the R in above formula (A2) ^vIand R ^vIIcentre can be the alkyl of 4 ~ 16 by the carbonatoms at Sauerstoffatom, sulphur atom, carbonyl or ester bond interval, can be the alkyl of 4 ~ 16 by the carbonatoms at sulphur atom interval in the middle of being preferably respectively, the such as tertiary butyl, 1-methyl pentadecyl, octylsulfo methyl etc. can be listed, among them, be particularly preferably the tertiary butyl.As radicals R ^vIIposition on phenyl ring, 1 have hydroxyl, 2 for radicals R ^vItime, preferably at 5 or 6.

As the X in above formula (A2) ⁶, be preferably above formula (X ⁶-1) group shown in, particularly at above formula (X ⁶-1) in, preferred a to be 2, b be 1 group.

As the compound shown in above formula (A2), the R particularly preferably in above formula (A2) ^vIand R ^vIIall the compound of the tertiary butyl, the namely compound shown in following formula (A2-1).

(in formula (A2-1), X ⁶identical with the definition in above formula (A2)).

2 amino in above formula (A2-1) are relative radicals X preferably ⁶it is 3,5.As the compound shown in above formula (A2), most preferably be the compound shown in following formula (A2-1-1).

Compound shown in this above formula (A2), easily can be synthesized by the vitochemical ordinary method of combination.

Such as, in above formula (A2), radicals X ⁶for above formula (X ⁶-1) compound of the group (wherein, b is 1) shown in can by having desired radicals R ^vIand R ^vIIreplacement 4-HBA successively with thionyl chloride, have desired methylene radical chain length a (gathering) methylene glycol reaction, obtain the alkylol cpd as intermediate, after this intermediate and dinitrobenzoyl chloride reaction, by suitable reduction system, such as hydrazine and palladium carbon, be converted to amino to synthesize by nitro.

As the diamines for the synthesis of polyamic acid of the present invention, only can use compound (A), or also compound (A) and other diamines can be used together.

As other diamines that can here use, can list such as aliphatie diamine, ester ring type diamines, aromatic diamine (but, except compound that above formula (A1) and (A2) represent separately.Identical below), diamino organo-siloxane etc.

As their object lesson, wherein as aliphatie diamine, such as 1,1-m-xylene diamine, 1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine etc. can be listed;

As ester ring type diamines, such as Isosorbide-5-Nitrae-diamino-cyclohexane, 4 can be listed, 4 '-methylene radical two (cyclo-hexylamine), 1,3-bis-(amino methyl) hexanaphthene etc.;

As aromatic diamine, such as P-pHENYLENE dI AMINE can be listed, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(p-phenylenediisopropylidene) pentanoic, 4,4 '-(metaphenylene two isopropylidene) pentanoic, Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) xenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, N, N '-two (4-aminophenyl)-N, N '-dimethyl p-diaminodiphenyl, Isosorbide-5-Nitrae-two-(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxyaniline-2,5-diaminobenzene,

Pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane base oxygen base-3,5-diaminobenzene, cholesteryl oxygen base-3,5-diaminobenzene, cholestane base oxygen base-2,4-diaminobenzene, cholesteryl oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, 3,6-bis-(4-aminobenzoic acyl-oxygen base) cholestane, 3,6-bis-(4-amino-benzene oxygen) cholestane, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3,5-diaminobenzoic acid ester, 1,1-bis-(4-((aminophenyl) methyl) phenyl)-4-butyl cyclohexane, 1,1-bis-(4-((aminophenyl) methyl) phenyl)-4-heptylcyclohexane, 1,1-bis-(4-((amino-benzene oxygen) methyl) phenyl)-4-heptylcyclohexane, 1,1-bis-(4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) compound etc. shown in hexanaphthene and following formula (D-1),

(in formula (D-1), X ⁱto be carbonatoms be 1 ~ 3 alkyl, ^*-O-, ^*-COO-or ^*-OCO-(wherein, combining with the connecting key of " * " and diamino-phenyl), x be 0 or 1, y be 0 ~ 2 integer, z is the integer of 1 ~ 20).

As diamino organo-siloxane, such as 1,3-bis-(3-aminopropyl)-tetramethyl disiloxane etc. can be listed respectively, the diamines recorded in Japanese Patent Application 2009-66252 can be used in addition.

X in above formula (D-1) ⁱbe preferably carbonatoms be 1 ~ 3 alkyl, ^*-O-or ^*-COO-(wherein, with connecting key and the diamino-phenyl combination of " * ").As group C _zh _2z+1-object lesson, such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc. can be listed.Preferred other group relatively of 2 amino in diamino-phenyl is in 2,4-position or 3,5-position.

As the object lesson of the compound shown in above formula (D-1), the compound etc. that such as following formula (D-1-1) ~ (D-1-4) represents respectively can be listed.

In above formula (D-1), be 0 when x and y is preferably different.

These other diamines can be used alone, or combine two or more.

The preferred relatively all diamines of diamines for the synthesis of polyamic acid of the present invention contain the compound (A) of more than 0.1mol%, more preferably containing 0.1 ~ 80mol%, particularly preferably containing 1 ~ 50mol%.

[synthesis of polyamic acid]

Polyamic acid of the present invention can by obtaining by tetracarboxylic dianhydride with containing, for example the diamine reactant of upper compound (A).

For the tetracarboxylic dianhydride of the building-up reactions of polyamic acid and the usage ratio of diamines, preferably relative to the amino of 1 equivalent diamines, the anhydride group of tetracarboxylic dianhydride is the ratio of 0.2 ~ 2 equivalent, is more preferably the ratio of 0.3 ~ 1.2 equivalent.

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

As the organic solvent that can use when synthesizing above-mentioned polyamic acid, such as aprotic polar solvent, phenol and its derivatives, alcohol, ketone, ester, ether, halohydrocarbon, hydrocarbon etc. can be listed.As above-mentioned aprotic polar solvent, such as METHYLPYRROLIDONE, N,N-dimethylacetamide, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, 4-methyl urea, HMPA etc. can be listed.As above-mentioned amphyl, such as meta-cresol, xylenol, halogenated phenol etc. can be listed.As above-mentioned alcohol, such as methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triglycol, ethylene glycol monomethyl ether etc. can be listed.As above-mentioned ketone, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone can be listed.As above-mentioned ester, ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methoxypropionic acid methyl ester, ethyl-ethoxypropionate, oxalic acid diethyl ester, diethyl malonate can be listed.As above-mentioned ether, Anaesthetie Ether, Ethylene Glycol Methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetate, tetrahydrofuran (THF) can be listed.As above-mentioned halohydrocarbon, such as methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene can be listed.As above-mentioned hydrocarbon, such as hexane, heptane, octane, benzene,toluene,xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether can be listed.

In these organic solvents, preferred use is selected from more than a kind of group's (first group's organic solvent) that aprotic polar solvent and phenol and derivative thereof are formed, or be selected from more than a kind of organic solvent of aforementioned first group with the mixture of more than a kind of group's (second group's organic solvent) being selected from alcohol, ketone, ester, ether, halohydrocarbon and hydrocarbon.In the case of the latter, the usage ratio of second group's organic solvent, relative to the total amount of first group's organic solvent and second group's organic solvent, is preferably less than 50 % by weight, is more preferably less than 40 % by weight, and more preferably less than 30 % by weight.

As above the reaction soln dissolving polyamic acid formation can be obtained.

This reaction soln can be directly used in prepares liquid crystal aligning agent, after the polyamic acid that also can contain in separating reaction solution, for the preparation of liquid crystal aligning agent, or after being refined by the polyamic acid be separated, for the preparation of liquid crystal aligning agent.

When polyamic acid dehydration closed-loop is formed imide amination polymer, above-mentioned reaction soln can be directly used in dehydration closed-loop reaction; After the polyamic acid that also can contain in separating reaction solution is separated, react for dehydration closed-loop; Or after the polyamic acid be separated is refined, react for dehydration closed-loop.

The separation of polyamic acid by above-mentioned reaction soln is injected a large amount of lean solvents, can obtain precipitate, by the method for this precipitate drying under reduced pressure; Or undertaken by the method for the organic solvent in vaporizer underpressure distillation reaction soln.In addition, also can by this polyamic acid be dissolved in organic solvent again, the method then separated out in lean solvent; Or polyamic acid is dissolved in organic solvent again, by after the solution washing that formed, with vaporizer by the organic solvent underpressure distillation removing in this solution, repeats this operation 1 time or method repeatedly refines polyamic acid.

< imide amination polymer >

Imide amination polymer of the present invention can by obtaining polyamic acid dehydration closed-loop as above, imidization.

As the tetracarboxylic dianhydride for the synthesis of above-mentioned imide amination polymer, the compound identical with the tetracarboxylic dianhydride used when synthesizing above-mentioned polyamic acid can be listed.Kind and the preferred usage ratio thereof of preferred tetracarboxylic dianhydride are also identical with the situation of polyamic acid.

As the diamines for the synthesis of imide amination polymer of the present invention, the diamines identical with the diamines synthesizing the use of above-mentioned polyamic acid can be listed.Namely, synthesizing the diamines that imide amination polymer of the present invention uses is diamines containing, for example upper compound (A), only can use compound (A), also compound (A) and other diamines can be used together.The kind of other diamines preferred is also identical with the situation of polyamic acid with the preferred usage ratio of each diamines.

Imide amination polymer in the present invention can be the complete imide compound that the amido acid structure fully dehydrating closed loop had as the polyamic acid of raw material is formed; Also can be only by amido acid structure part dehydration closed-loop, have the part imide compound of amido acid structure and imide ring structure concurrently.The preferred imide rate of imide amination polymer of the present invention is more than 20%, is more preferably 30 ~ 90%, is particularly preferably 40 ~ 80%.This described imide rate is the total amount relative to the quantity of the amido acid structure of imide amination polymer and the quantity of imide ring structure, the value that the ratio that the quantity of imide ring structure occupies represents with percentage.In addition, a part for imide ring can be different imide ring.

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

Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i) is preferably 50 ~ 200 DEG C, is more preferably 60 ~ 170 DEG C.When temperature of reaction is less than 50 DEG C, fully cannot carry out dehydration closed-loop reaction; If temperature of reaction is more than 200 DEG C, then the molecular weight of the imide amination polymer of gained may be low.Reaction times is preferably 1.0 ~ 24 hours, is more preferably 1.0 ~ 12 hours.

On the other hand, add in the method for dewatering agent and dehydration closed-loop catalyzer in polyamic acid solution at above-mentioned (ii), as dewatering agent, the acid anhydrides such as such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride can be used.The consumption of dewatering agent is determined according to desired imide rate, but relative to the amido acid structure of 1mol polyamic acid, is preferably 0.01 ~ 20mol.In addition, as dehydration closed-loop catalyzer, the tertiary amines such as such as pyridine, trimethylpyridine, lutidine, triethylamine can be used.But be not limited to this.The dewatering agent that the consumption of dehydration closed-loop catalyzer uses relative to 1mol, is preferably 0.01 ~ 10mol.The consumption of above-mentioned dewatering agent, dehydration closed-loop agent is more, and imide rate is higher.As the organic solvent used in dehydration closed-loop reaction, the illustrative organic solvent of solvent used as synthesizing polyamides acid can be listed.The temperature of reaction of dehydration closed-loop reaction is preferably 0 ~ 180 DEG C, is more preferably 10 ~ 150 DEG C.Reaction times is preferably 1.0 ~ 120 hours, is more preferably 2.0 ~ 30 hours.

The imide amination polymer obtained in aforesaid method (i) can be directly used in prepares liquid crystal aligning agent, or after the imide amination polymer of gained is refined, for the preparation of liquid crystal aligning agent.On the other hand, in aforesaid method (ii), can obtain containing imide amination polymer reaction soln.This reaction soln can be directly used in prepares liquid crystal aligning agent, after also can removing dewatering agent and dehydration closed-loop catalyzer from reaction soln, for the preparation of liquid crystal aligning agent; After can also being separated imide amination polymer, for the preparation of liquid crystal aligning agent; Or after the imide amination polymer be separated is refined, for the preparation of liquid crystal aligning agent.In order to from reaction soln removing dewatering agent and dehydration closed-loop catalyzer, such as, be applicable to using the methods such as solvent exchange.The separation of imide amination polymer, refining can by the separation of polyamic acid, process for purification and the above-mentioned operation equally carried out is carried out.

-end modified type polymkeric substance-

Polyamic acid in liquid crystal aligning agent of the present invention and imide amination polymer thereof can be the end modified type polymkeric substance of Molecular regulator amount respectively.By using end modified type to be polymerized, effect of the present invention can not be damaged, improving the coating character of liquid crystal aligning agent further.This end modified type polymkeric substance, when synthesizing polyamides acid, can add molecular weight regulator and carry out in polymerization reaction system.As molecular weight regulator, such as sour single acid anhydride, monoamine compound, monoisocyanate compound etc. can be listed.

As the single acid anhydride of above-mentioned acid, such as maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc. can be listed.As above-mentioned monoamine compound, such as aniline, cyclo-hexylamine, n-butylamine, n-pentyl amine, n-hexyl amine, n-heptyl amine, n-octylamine, n-nonyl amine, positive decyl amine, n-undecane base amine, dodecyl amine, n-tridecane base amine, n-tetradecane base amine, Pentadecane base amine, n-hexadecyl amine, n-heptadecane base amine, Octadecane base amine, NSC 62789 base amine etc. can be listed.As above-mentioned monoisocyanate compound, such as phenyl isocyanate, isocyanic acid naphthyl ester etc. can be listed.

Amount to 100 weight parts relative to the tetracarboxylic dianhydride used during synthesizing polyamides acid and diamines, the usage ratio of molecular weight regulator is preferably below 20 weight parts, is more preferably below 10 weight parts.

-soltion viscosity-

As above the polyamic acid obtained and imide amination polymer thereof, when they being formed respectively the solution of concentration 10 % by weight, preferably having the soltion viscosity of 20 ~ 800mPas, more preferably having the soltion viscosity of 30 ~ 500mPas.

The soltion viscosity (mPas) of above-mentioned polymkeric substance is to using the good solvent of this polymkeric substance (such as, gamma-butyrolactone, METHYLPYRROLIDONE etc.) polymers soln of concentration 10 % by weight prepared, use E type rotational viscosimeter, the value measured at 25 DEG C.

Other additive of < >

Liquid crystal orientation film of the present invention contains at least a kind of polymkeric substance of the polyamic acid be selected from as above and the group formed by the polymkeric substance of its imidization as essential component, but also can contain other composition as required.As this other composition, can list such as other polymkeric substance, there is the compound (hereinafter referred to as " epoxy compounds "), functional silanes compound etc. of at least 1 epoxy group(ing) in molecule.

Other polymkeric substance above-mentioned may be used for improving SOLUTION PROPERTIES and electrical property.This other polymkeric substance is the polymkeric substance beyond the polyamic acid that obtains of the diamine reactant of tetracarboxylic dianhydride and inclusion compound (A) and imide amination polymer thereof, can list the imide amination polymer, poly amic acid ester, polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc. of such as tetracarboxylic dianhydride and the polyamic acid do not obtained containing the diamine reactant of compound (A), this polyamic acid.

As above-mentioned epoxy compounds, such as ethylene glycol diglycidylether can be listed, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-bis-bromo neopentylglycol diglycidyl ether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, 3-bis-(N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-cyclo-hexylamine etc. are as preferred material.

Amount to 100 weight parts relative to polymkeric substance, the blending ratio of these epoxy compoundss is preferably below 40 weight parts, is more preferably 0.1 ~ 30 weight part.

As above-mentioned functional silanes compound, such as 3-TSL 8330 can be listed, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-uride propyl trimethoxy silicane, 3-uride propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, 9-trimethoxysilyl-3,6-diaza methyl pelargonate, 9-triethoxysilyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, glycidoxypropyl methyltrimethoxy silane, glycidoxypropyl Union carbide A-162, 2-glycidoxypropyl ethyl trimethoxy silane, 2-glycidoxypropyl ethyl triethoxysilane, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane etc.

Amount to 100 weight parts relative to polymkeric substance, the blending ratio of these functional silanes compounds is preferably below 2 weight parts, is more preferably 0.02 ~ 0.2 weight part.

< liquid crystal aligning agent >

Liquid crystal aligning agent of the present invention, by least a kind of polymkeric substance be selected from the group of as above polyamic acid and imide amination polymer formation thereof and other additive mixed arbitrarily as required, dissolves containing and forms in preferred organic solvent.

As the organic solvent that can use in liquid crystal aligning agent of the present invention, such as METHYLPYRROLIDONE can be listed, γ-hexalactone, γ-hexanolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, Ethylene Glycol Methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate etc.They may be used alone, can also be 2 or more kinds in combination.

Solid component concentration (gross weight of the composition beyond the solvent of liquid crystal aligning agent occupies the ratio of the gross weight of liquid crystal aligning agent) in liquid crystal aligning agent of the present invention considers that viscosity, volatility etc. are suitably selected, and is preferably the scope of 1 ~ 10 % by weight.Namely, liquid crystal aligning agent of the present invention as described later, is coated to substrate surface, and preferably by the film adding thermosetting liquid crystal orientation film, but when solid component concentration is less than 1 % by weight, the thickness of this film is too small, cannot obtain good liquid crystal orientation film; On the other hand, when solid component concentration is more than 10 % by weight, the thickness of film is excessive, cannot obtain good liquid crystal orientation film, and the viscosity of liquid crystal aligning agent increases, coating properties deteriorate.

The scope of particularly preferred solid component concentration is different according to the method used during coated with liquid crystal alignment agent on substrate.Such as, when being applied by spin-coating method, solid component concentration is particularly preferably the scope of 1.5 ~ 4.5 % by weight.When being applied by print process, solid component concentration is the scope of 3 ~ 9 % by weight, and thus, soltion viscosity is particularly preferably the scope of 12 ~ 50mPas.When being applied by ink jet method, solid component concentration is the scope of 1 ~ 5 % by weight, and thus, soltion viscosity is particularly preferably the scope of 3 ~ 15mPas.

Temperature when allocating liquid crystal aligning agent of the present invention is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.

< liquid crystal display device >

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

Liquid crystal display device of the present invention such as can by following (1) ~ (3) operation manufacture.Operation (1) is according to desired operational mode, and the preferred coating method of the substrate of use, liquid crystal aligning agent is different with the Heating temperature after liquid crystal aligning agent coating.Operation (2) and (3) communicate under each operational mode.

(1) first, substrate applies liquid crystal aligning agent of the present invention, then by heating applicator surface, substrate forms film.

(1-1) when manufacturing TN type, STN type or VA type liquid crystal display device, the 2 pieces of substrates being provided with the nesa coating forming pattern are formed a pair, in the forming surface of its each transparent conductive film, liquid crystal aligning agent of the present invention is applied respectively preferably by adherography, spin-coating method or ink jet printing method, then, film is formed by heating each applicator surface.Wherein, as substrate, can use such as by the glass such as float glass, soda-lime glass; The transparency carrier that the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(alicyclic hydrocarbon) are formed.As the nesa coating arranged in the one side of substrate, can use by stannic oxide (SnO ₂) the NESA film (registered trademark of PPG company of the U.S.), the indium oxide-tin oxide (In that are formed ₂o ₃-SnO ₂) ito film etc. that formed, in order to obtain the nesa coating forming pattern, can by such as being formed without after figure nesa coating, by the method for photoetch formation pattern; When forming nesa coating, the method etc. with the mask of desired pattern is used to obtain.During coated with liquid crystal alignment agent, in order to make the cohesiveness of substrate surface and nesa coating and film better, in substrate surface, can should be formed on the face of film, applying functional silanes compound, functionality titanium compound etc. in advance and carrying out pre-treatment.

After coated with liquid crystal alignment agent, based on the alignment agent stream of liquid droplets preventing from applying, preferably carry out preheating (prebake).The temperature of prebake is preferably 30 ~ 200 DEG C, is more preferably 40 ~ 150 DEG C, is particularly preferably 40 ~ 100 DEG C.The time of prebake is preferably 0.25 ~ 10 minute, is more preferably 0.5 ~ 5 minute.Afterwards, based on completely except desolventizing, the object of amido acid structure hot-imide will existed in polymkeric substance as required, carries out ablating work procedure (curing afterwards).This is fired (curing afterwards), and temperature is preferably 80 ~ 300 DEG C, is more preferably 120 ~ 250 DEG C.After the time of curing be preferably 5 ~ 200 minutes, be more preferably 10 ~ 100 minutes.So, the thickness of the film of formation is preferably 0.001 ~ 1 μm, is more preferably 0.005 ~ 0.5 μm.

(1-2) on the other hand, when manufacturing IPS type liquid crystal display device, preferably arrange the nesa coating forming interdigitated electrode structure pattern substrate conducting film forming surface with do not arrange in the one side of subtend substrate of conducting film, liquid crystal aligning agent of the present invention is applied respectively by adherography, spin-coating method or ink jet printing method, then, heat each applicator surface, form film thus.

Heating means after the material of the substrate now used and nesa coating, the pattern formation method of nesa coating, the pre-treatment of substrate and coated with liquid crystal alignment agent are identical with above-mentioned (1-1).

The preferred thickness of the film formed is identical with above-mentioned (1-1).

(2), when the liquid crystal display device manufactured by method of the present invention is VA type liquid crystal display device, the film as above formed can directly use as liquid crystal orientation film, uses after also desirably can carrying out following friction treatment.

On the other hand, when manufacturing the liquid crystal display device beyond VA type, by carrying out friction treatment to the film of above-mentioned formation, form liquid crystal orientation film.

Friction treatment is the coated surface to as above being formed, and by winding such as by the roller of the fibroplastic cloth such as nylon, artificial silk, cotton, carries out in certain orientation friction.Thus, the orientation of liquid crystal molecule can pay film, forms liquid crystal orientation film.

Further, as above the liquid crystal orientation film formed is processed, by making each region of liquid crystal orientation film, there is different liquid crystal aligning energy, the perspective nature of the liquid crystal display device of gained can be improved, wherein the process that liquid crystal film carries out is comprised: it is such that such as patent documentation 9 (Japanese Unexamined Patent Publication 6-222366 publication) or patent documentation 10 (Japanese Unexamined Patent Publication 6-281937 publication) represent, to a part of irradiation ultraviolet radiation of liquid crystal orientation film, change the process of the pre-tilt angle in the region of a part for liquid crystal orientation film; As shown in patent documentation 11 (Japanese Unexamined Patent Publication 5-107544 publication), after etchant resist is formed to the part on liquid crystal orientation film surface, on the direction different with friction treatment before, after carrying out friction treatment, the process of removing etchant resist.

(3) prepare 2 pieces of substrates as above forming liquid crystal orientation film, configure liquid crystal, manufacture liquid crystal cell by between 2 pieces of substrates configure in subtend.Here, when carrying out friction treatment to film, 2 pieces of substrate subtend configurations, such as, to make frictional direction phase predetermined angular, the orthogonal or antiparallel each other of each film.

Manufacture liquid crystal cell and can list such as following 2 kinds of methods.

First method is method known at present.First, arrange to make each liquid crystal orientation film subtend, by gap (gap of box), by 2 pieces of substrate subtend configurations, use sealing agent, the peripheral part of 2 pieces of substrates is fitted, inject filling liquid crystal in the box gap split by substrate surface and sealing agent after, sealing filling orifice, can manufacture liquid crystal cell.

Second method is the method being called ODF (One Drop Fill) mode.Prescribed position on a substrate in the 2 pieces of substrates forming liquid crystal orientation film, apply such as ultraviolet light curable sealing material, then after dripping liquid crystal on liquid crystal aligning face, another substrate of fitting makes liquid crystal orientation film subtend, then, in whole irradiating ultraviolet light of substrate, make sealant cures, manufacture liquid crystal cell.

When any one method, to the liquid crystal cell as above manufactured, after reheating the isotropic temperature of liquid crystal used, progressively cool to room temperature, flow orientation during removing Liquid crystal pour.

Then, by the outer surface laminating polaroid at liquid crystal cell, liquid crystal display device of the present invention can be obtained.

Wherein, as sealing agent, the epoxy resin etc. such as containing solidifying agent and the alumina balls as partition can be listed.

As foregoing liquid crystal, such as nematic liquid crystal, dish-like liquid crystal etc. can be used, preferred nematic liquid crystal among them.When for VA type liquid crystal cell, preferably there is the nematic liquid crystal of negative dielectric anisotropy, such as dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, schiff alkali class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc. can be used.When for TN type liquid crystal cell or STN type liquid crystal cell, preferably there is the nematic liquid crystal of positive dielectric anisotropy, such as biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, two can be used octane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.In these liquid crystal, cholesterol liquid crystals such as using such as chlorination beta-cholestanol (cholestyl chloride), Cholesteryl pelargonate, cholesterol carbonic ether can be added further; With the chiral reagent that trade(brand)name C-15, CB-15 (manufacture of メルク society) sell; To oxygen base benzylidene-to Ferroelectric liquid Crystals etc. such as amino-2-methyl butyl laurates in the last of the ten Heavenly stems.

As the polaroid fitting to liquid crystal cell outside surface, limit can be listed and polyvinyl alcohol to be extended orientation, absorb the polaroid that light polarizing film that iodine is referred to as " H film " is formed or the polaroid formed by H film itself while clamp with cellulose acetate protective membrane.

[embodiment]

Below, by embodiment, the present invention is further illustrated, but the present invention is not subject to the restriction of these embodiments.The soltion viscosity of the polymkeric substance in embodiment and comparative example, the imide rate of imide amination polymer are by following method evaluation.

[soltion viscosity of polymkeric substance]

The polymers soln that the soltion viscosity (mPas) of polymkeric substance indicates each synthesis example, uses E type rotational viscosimeter, measures at 25 DEG C.

[the imide rate of imide amination polymer]

Solution containing imide amination polymer is dropped in pure water, after the precipitation of gained at room temperature abundant drying under reduced pressure, be dissolved in heavy-hydrogenated dimethyl sulfoxide (DMSO), by using tetramethylsilane as primary standard, at room temperature measure ¹h-NMR, tries to achieve imide rate from following formula (1).

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

(in mathematical expression (1), A ¹the peak area of the proton from the NH base shown near chemical shift 10ppm, A ²be the peak area from other proton, α is the ratio of number relative to the proton of the NH base in the precursor (polyamic acid) of 1 imide amination polymer of other proton).

The synthesis example > of < compound (A)

Synthesis example 1

According to following synthetic route 1, synthetic compound (A1-1-1).

synthetic route 1

(1) synthesis of compound (A1-1-1a)

In the there-necked flask of 500mL with dropping funnel, nitrogen ingress pipe and thermometer, add 2,2,6,6-tetramethyl--4-piperidine alcohols and the 250mL pyridine of 16g, ice-cooled.Under ice-cooling, in this solution, the 3,5 dinitrobenzoylchloride of point 30 minutes dropping 23g is dissolved into the solution that 100mL tetrahydrofuran (THF) is formed, and directly at room temperature stirs 3 hours.Afterwards, add 1L ethyl acetate in the reactive mixture, separatory washing in the water of 500mL.Then, after organic layer dried over mgso, concentrated, solidification, recrystallization in ethanol, obtains the pale yellow crystals of 28g compound (A1-1-1a).

(2) synthesis of compound (A1-1-1)

In the there-necked flask of 500mL with return line, nitrogen ingress pipe and thermometer, add 28g compound obtained above (A1-1-1a), the 5 % by weight palladium carbon of 0.5g, 290mL ethanol and 20mL hydrazine 1 hydrate, at room temperature stir after 1 hour, then stir at 70 DEG C and react for 1 hour.After reaction terminates, filter after reaction mixture removing palladium carbon, add 1.6L ethyl acetate, wash with the moisture liquid of 800mL.

After organic layer dried over mgso, decompression is lower to desolventizing, and the mixed solvent recrystallization of dried product ethyl acetate and hexane, obtains the white crystals of 16g compound (A1-1-1).

Synthesis example 2

According to following synthetic route 2, synthetic compound (A1-1-2).

synthetic route 2

(1) synthesis of compound (A1-1-2a)

In the there-necked flask of 500mL with dropping funnel, nitrogen ingress pipe and thermometer, 1,2,2,6, the 6-pentamethyl--4-piperidine alcohols and the 16.6mL triethylamine that add 17g are dissolved in the solution of 100mL tetrahydrofuran (THF) formation, ice-cooled.Under ice-cooling, the 3,5 dinitrobenzoylchloride points 30 minutes dripping 23g in this solution is dissolved into the solution that 100mL tetrahydrofuran (THF) is formed, and after being warmed up to room temperature, then stirring and reacts for 3 hours.After reaction terminates, add 300mL ethyl acetate in the reactive mixture, aqueous sodium hydroxide solution and the water of the organic layer 1mol/L of gained wash successively.Then, with dry over magnesium sulfate, decompression is lower to desolventizing, mixed solvent (ethanol: tetrahydrofuran (THF)=50:50 (the weight ratio)) recrystallization that the solid of gained is formed by ethanol and tetrahydrofuran (THF), obtains the pale yellow crystals of 29g compound (A1-1-2a).

(2) synthesis of compound (A1-1-2)

In the there-necked flask of 500mL with return line, nitrogen ingress pipe and thermometer, add 28g compound obtained above (A1-1-2a), the 5 % by weight palladium carbon of 1.9g, 290mL ethanol and 20mL hydrazine 1 hydrate, at room temperature stir after 1 hour, then stir at 70 DEG C and react for 1 hour.After reaction terminates, filter reaction mixture, after removing palladium carbon, add 1.6L ethyl acetate, with the organic layer of the water washing gained of 800mL.After this organic layer dried over mgso, decompression is lower to desolventizing, the solid of gained, by mixed solvent (ethyl acetate: hexane=50:50 (the weight ratio)) recrystallization of ethyl acetate and hexane, obtains the white crystals of 17g compound (A1-1-2).

Synthesis example 3

According to following synthetic route 3 (1) and 3 (2) synthetic compound (A2-1-1).

synthetic route 3 (1)

synthetic route 3 (2)

(1) synthesis of compound (A2-1-1b)

In the there-necked flask of the 500mL with dropping funnel, nitrogen ingress pipe and thermometer, add the DMF of 3, the 5-di-tert-butyl-4-hydroxybenzoic acids of 13g and 20ml thionyl chloride, 0.6mL, stir at 80 DEG C and react for 1 hour.After reaction terminates, under decompression, after reaction mixture distillation removing thionyl chloride, add 100mL methylene dichloride in residue, obtain organic layer.This organic layer distilled water wash, after dried over mgso, under reduced pressure except desolventizing, the dissolution of solid of gained, in 40mL tetrahydrofuran (THF), forms solution.

With above-mentioned different having in the 500mL there-necked flask of dropping funnel, nitrogen ingress pipe and thermometer, add 27.7mL ethylene glycol, 7.67mL triethylamine, 40mL tetrahydrofuran (THF), Homogeneous phase mixing, formed solution., drip the above-mentioned tetrahydrofuran solution containing the reactant of 3,5-di-tert-butyl-4-hydroxybenzoic acid and thionyl chloride wherein, stir 1 hour at 0 DEG C, react.After reaction terminates, add 300mL ethyl acetate in the reactive mixture, the organic layer washed with water of gained, after dried over mgso, concentrated, obtain crystalline solid, this solid by filtration reclaims, and with hexanes wash, obtains 10g compound (A2-1-1a).

In the there-necked flask of 500mL with dropping funnel, nitrogen ingress pipe and thermometer, compound (A2-1-1a) obtained above for 9.2g and 5.23mL triethylamine are dissolved in 50mL tetrahydrofuran (THF), drip 3 of 7.6g wherein, after 5-dinitrobenzoyl chloride is dissolved into the solution obtained in 50mL tetrahydrofuran (THF), at room temperature stir 1 hour, react.After reaction terminates, add 200mL ethyl acetate in the reactive mixture, the organic layer washed with water of gained, after dried over mgso, under reduced pressure except desolventizing, the solid ethyl alcohol recrystallization of gained, obtains the crystallization of 12g compound (A2-1-1b).

(2) synthesis of compound (A2-1-1)

In the 500mL there-necked flask with return line, nitrogen ingress pipe and thermometer, add 12g compound obtained above (A2-1-1b), 0.6g 5 % by weight palladium carbon, 70mL ethanol and 70mL tetrahydrofuran (THF) mixing.Wherein, drip 6mL hydrazine 1 hydrate, at room temperature stir after 1 hour, then stir 2 hours at 70 DEG C, react.After reaction terminates, after crossing filter palladium carbon from reaction mixture, add 200mL ethyl acetate, with the organic layer of the water washing gained of 200mL.This organic layer concentrated, refining by column chromatography (packing material: silica gel launches to dissolve: chloroform), under reduced pressure, remove desolventizing from the cut of gained, obtain the white solid of 10g compound (A2-1-1).

The synthesis example > of < polymkeric substance

Synthesis example 4

Using 110g (0.50mol) as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and the compound (A1-1-1), 38g (0.35mol) P-pHENYLENE dI AMINE and the 52g (0.10mol) 3 that obtain as the above-mentioned synthesis example 1 of 15g (0.05mol) of diamines, 5-diaminobenzoic acid-3-cholestane base ester is dissolved in the METHYLPYRROLIDONE of 800g, react 6 hours at 60 DEG C, obtain polyamic acid solution.Divide the polyamic acid solution getting gained on a small quantity, add METHYLPYRROLIDONE, form the solution of polyamic acid concentration 10 % by weight, the soltion viscosity of mensuration is 60mPas.

Then, in the polyamic acid solution of gained, add the METHYLPYRROLIDONE of 1,800g, add 39g pyridine and 50g diacetyl oxide, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, (in this operation, the pyridine used in dehydration closed-loop reaction and diacetyl oxide are except going to system with new METHYLPYRROLIDONE solvent exchange for the solvent in system.Identical below), obtain the solution of the imide amination polymer (PI-1) containing 15 % by weight imide rates about 50%.Divide the solution getting above-mentioned imide amination polymer on a small quantity, add METHYLPYRROLIDONE, form the solution of polyimide fluidized polymer concentration 10 % by weight, the soltion viscosity of mensuration is 87mPas.

Synthesis example 5

Using 110g (0.50mol) as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and the compound (A1-1-2), the 46g (0.3mol) 3 that obtain as the above-mentioned synthesis example 2 of 15g (0.05mol) of diamines, 5-diaminobenzoic acid and 39g (0.075mol) 3,5-diaminobenzoic acid-3-cholestane base ester and 37g (0.075mol) cholestane base oxygen base-2,4-diaminobenzene is dissolved in the METHYLPYRROLIDONE of 800g, react 6 hours at 60 DEG C, obtain polyamic acid solution.Divide the polyamic acid solution getting gained on a small quantity, add METHYLPYRROLIDONE, form the solution of polyamic acid concentration 10 % by weight, the soltion viscosity of mensuration is 50mPas.

Then, in the polyamic acid solution of gained, add the METHYLPYRROLIDONE of 1,800g, add 39g pyridine and 50g diacetyl oxide, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, the new METHYLPYRROLIDONE solvent exchange of the solvent in system, obtains the solution of the imide amination polymer (PI-2) containing 15 % by weight imide rates about 60%.Divide the solution getting above-mentioned imide amination polymer on a small quantity, add METHYLPYRROLIDONE, form the solution of polyimide fluidized polymer concentration 10 % by weight, the soltion viscosity of mensuration is 70mPas.

Synthesis example 6

Using 110g (0.50mol) as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and the compound (A2-1-1), the 46g (0.3mol) 3 that obtain as the above-mentioned synthesis example 3 of 21g (0.05mol) of diamines, 5-diaminobenzoic acid and 39g (0.075mol) 3,5-diaminobenzoic acid-3-cholestane base ester and 37g (0.075mol) cholestane base oxygen base-2,4-diaminobenzene is dissolved in the METHYLPYRROLIDONE of 800g, react 6 hours at 60 DEG C, obtain polyamic acid solution.Divide the polyamic acid solution getting gained on a small quantity, add METHYLPYRROLIDONE, form the solution of polyamic acid concentration 10 % by weight, the soltion viscosity of mensuration is 52mPas.

Then, in the polyamic acid solution of gained, add the METHYLPYRROLIDONE of 1,800g, add 39g pyridine and 50g diacetyl oxide, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, the new METHYLPYRROLIDONE solvent exchange of the solvent in system, obtains the solution of the imide amination polymer (PI-3) containing 15 % by weight imide rates about 50%.Divide the solution getting above-mentioned imide amination polymer on a small quantity, add METHYLPYRROLIDONE, form the solution of polyimide fluidized polymer concentration 10 % by weight, the soltion viscosity of mensuration is 72mPas.

The comparison synthesis example > of < polymkeric substance

Relatively synthesis example 1

Except using 43g (0.40mol) P-pHENYLENE dI AMINE and 52g (0.10mol) 3 as diamines, outside 5-diaminobenzoic acid-3-cholestane base ester, with above-mentioned synthesis example 2 similarly, obtain the solution of imide amination polymer (PI-4) containing 15 % by weight imide rates about 50%.Divide the solution getting above-mentioned imide amination polymer on a small quantity, add METHYLPYRROLIDONE, form the solution of polyimide fluidized polymer concentration 10 % by weight, the soltion viscosity of mensuration is 68mPas.

The allotment of < liquid crystal aligning agent and evaluation >

Embodiment 1

[allotment of liquid crystal aligning agent]

METHYLPYRROLIDONE and ethylene glycol butyl ether is added in the solution of the imide amination polymer (PI-1) obtained containing above-mentioned synthesis example 4, formation solution composition is METHYLPYRROLIDONE: the solution of ethylene glycol butyl ether=65:35 (weight ratio), solid component concentration 4 % by weight, by the strainer in 1 μm, aperture, it is filtered, allotment liquid crystal aligning agent.

[manufacture of liquid crystal cell]

Use liquid crystal orientation film printing press (Japan's description printing (Co., Ltd.) manufactures), the liquid crystal aligning agent of above-mentioned allotment is coated on the transparent electrical pole-face with the glass substrate of the transparency electrode formed by ito film, on the hot plate of 80 DEG C, prebake is after 1 minute, cure 10 minutes after on the hot plate of 200 DEG C, thus form average film thickness film (liquid crystal orientation film).Repeat this operation, obtain the substrate that a pair (2 pieces) have liquid crystal orientation film on nesa coating.

Then, in the respective outer rim a pair with liquid crystal orientation film of aforesaid substrate, after the epoxy resin binder of the alumina balls of coating containing diameter 3.5 μm, make liquid crystal orientation film in the face of the crimping that overlaps to ground, tackiness agent is solidified.Then, from liquid crystal injecting port, between a pair substrate, after filling nematic liquid crystal (メルク society manufactures, MLC-6608), with acrylic acid or the like Photocurable adhesive encapsulated liquid crystals inlet, vertical alignment-type liquid crystal box is manufactured.

[evaluation of liquid crystal cell]

(1) evaluation of voltage retention

To above-mentioned liquid crystal cell, at 70 DEG C, apply the voltage of 30 seconds 1V, remove the voltage retention after applying at 1V, at 70 DEG C, measure with the frame period 167 milliseconds, the voltage retention of this liquid crystal cell is 98%.

(2) sunproof evaluation

To above-mentioned liquid crystal cell under the white fluorescent lamp of 100 watts, configure with the distance of 5cm, irradiate after 500 little time, and above-mentioned when similarly again measuring voltage retention, the voltage retention of rayed after 500 hours is good, is 94%.

(3) evaluation of LCD alignment

With similarly above-mentioned, at 2 pieces of polaroids of laminating up and down of liquid crystal cell, to make its direction of polarized light mutually orthogonal, manufacture liquid crystal display device.During to this liquid crystal display device visual observation, when not applying voltage, light does not spill, and liquid crystal aligning agent (vertical orientated property) is good.

Embodiment 2 and 3 and comparative example 1

Except in above-described embodiment 1, the solution containing imide amination polymer shown in table 1 is used to replace beyond the solution containing imide amination polymer (PI-1) respectively, similarly allocate liquid crystal aligning agent with above-described embodiment 1, manufacture liquid crystal cell and liquid crystal display device, evaluate.

Evaluation result is as shown in table 1.

[table 1]

Claims

1. a liquid crystal aligning agent, this liquid crystal aligning agent comprises at least a kind of polymkeric substance in the group being selected from and being made up of polyamic acid and imide amination polymer thereof, this polyamic acid is obtained by tetracarboxylic dianhydride and diamine reactant, it is characterized in that: aforementioned diamines comprises the compound shown in following formula (A2)

X in formula (A2) ⁶be respectively Sauerstoffatom, ^*-OCO-, following formula (X ⁶-1) group shown in, methylene radical or carbonatoms are the alkylidene group of 2 ~ 6,

Formula (X ⁶-1) in, a is the integer of 1 ~ 12, and b is the integer of 0 ~ 5,

Wherein, hereinbefore, the connecting key with " * " combines with the phenyl ring with hydroxyl.

2. the liquid crystal aligning agent described in claim 1, wherein the compound shown in above formula (A2) is the compound shown in following formula (A2-1),

X in formula (A2-1) ⁶with the X in above formula (A2) ⁶definition identical.

3. the liquid crystal aligning agent described in claim 1 or 2, wherein above-mentioned tetracarboxylic dianhydride contains 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride.

4. a liquid crystal orientation film, is characterized in that: the liquid crystal aligning agent described in any one of claims 1 to 3 is formed.

5. a liquid crystal display device, is characterized in that: have the liquid crystal orientation film described in claim 4.

6. a polyamic acid, this polyamic acid is obtained by tetracarboxylic dianhydride and the diamine reactant containing the compound shown in formula (A2) described in claim 1 or 2.

7. an imide amination polymer, this polymkeric substance is formed by the polyamic acid dehydration closed-loop that tetracarboxylic dianhydride and the diamine reactant containing the compound shown in formula (A2) described in claim 1 or 2 obtain.

8. the compound shown in formula (A2) described in claim 1 or 2.